TW201229666A - Radiation-sensitive resin composition, cured film, array substrate of liquid crystal display device, method for forming cured film and method for forming array substrate of liquid crystal display device - Google Patents

Abstract

The present invention provides a radiation-sensitive resin composition and cured film as interlayer insulating film, protective film or spacer. The radiation-sensitive resin composition not only make low-temperature-burning and storage stability coexist but also has high radiation sensitivity. The cured film is suitable for use in flexible display and has excellent surface hardness, resistance to solvent and relative dielectric constant. The radiation-sensitive resin composition comprises [A] copolymer having (A1) structure unit containing carboxyl groups and (A2) structure unit containing epoxy groups, [B] quinone diazide compound and [C] at least one curing agent selected from group comprising compounds represented by formula (1) and formula (2), tertiary amine, amine salt, phosphonium salt, amidine salt, amide compound, ketimine compound, blocked isocyanate compound, imidazole ring-containing compound and clathrate.

Description

201229666 6. TECHNOLOGICAL FIELD OF THE INVENTION [Technical Field] The present invention relates to a radiation sensitive linear resin composition, a cured film, an 曰β one-day θ.., an array substrate of a member, a method of forming a cured film, and a liquid crystal A method of forming an array substrate of a display element. [Prior Art] In recent years, flexible displays such as electronic paper have become widespread. For the substrate of the flexible display, a plastic substrate of polyethylene terephthalate has been studied. Since the substrate is elongated or contracted upon heating, there is a problem that it is a function of the display, and thus the temperature of the manufacturing process in which the flexibility is developed is lowered. One of the procedures requiring the highest temperature when manufacturing a flexible display is a step of firing by heating an interlayer insulating film, and the firing step is being sought to achieve a low temperature. In the present case, a material for forming a cured film such as an interlayer insulating film is used, and a number of steps for obtaining a necessary pattern shape is small, and a radiation-sensitive resin composition which can obtain a surface hardness is widely used. As the radiation sensitive resin composition, a radiation-sensitive resin composition containing a copolymer of an unsaturated m acid and/or an anhydride thereof, an epoxy group-containing unsaturated compound, or the like is known. The composition thereof makes it possible to obtain the surface hardness as a cured film by the reaction of a thiol group and an epoxy group (refer to Japanese Laid-Open Patent Publication No. 2001-354822). However, in the case of the interlayer insulating film, in order to increase the surface hardness to a level which can be practically required by the art, a firing step exceeding 200 ° C is required. Therefore, a strategy of crosslinking reaction by adding an amine compound used as a hardener for an epoxy-based material even under low overflow is also considered, and the addition of the general 201229666 aminated a substance may cause It reacts with the epoxy group present in the composition over time, thereby reducing storage stability. In addition, a technique of a coating liquid for a gate insulating film of a flexible display which can be cured by a polyimine precursor which can be cured by low-temperature firing has been developed (see Japanese Patent Laid-Open Publication No. 2009-4394). However, the ruthenium coating liquid does not have the ability to form a pattern by exposure and development, so that it is impossible to form a fine pattern. Further, since the curing reactivity is insufficient, the interlayer insulating film or the like obtained is hardened for a period of 1 hour or longer, and a satisfactory level is not obtained. Further, in the process of the flexible display, there is a shape in which a laminate is formed on the upper layer of the interlayer insulating film. In this case, it is required to have solvent resistance to a solvent used for forming a laminate in which an interlayer insulating film is applied to a relative dielectric constant. Based on this situation, it is highly desirable to develop a radiation sensitive resin composition suitable for producing a cured film for a flexible display. [PRIOR ART DOCUMENT] [Patent Document 1] JP-A-2001-354822 (Patent Document 2) JP-A-H07-4394 [Summary of the Invention] [Problems to be Solved by the Invention] Sense of radiation, as an inter-sheet insulating film, a protective film, or the present invention, based on the above i, 浩,: brother Pinshan

A cured film of a protective film or spacer. The object of the present invention is 201229666 [Means for Solving the Problem] The invention for solving the above problems is: a radiation sensitive resin composition containing: [A] having (A1) a structural unit having a carboxyl group and an epoxy group-containing structure a copolymer of a unit (hereinafter, also referred to as "[A] copolymer"); [B] an azide compound; and [C] a compound represented by the following formula (1): i, the following formula (2) a compound, a tertiary amine compound, an amine salt, a scale salt, a phosphonium salt, a guanamine compound, a ketimine compound, a blocked isocyanate compound, a compound, and a chelating compound. At least one hardener selected from the group (hereinafter sometimes referred to as "[C] hardener").

(In the formula (1), ~ Han 6 Jiumin are each independently a hydrogen atom, a group or an amine group. Among them, Rlp6j;, at least one of the electron withdrawing groups R is a charge and R 丨 R R6 At least . ^ The electron group 'Ding Qiao is one amine group. The other 201229666 or part of the hydrogen atom of the above amine group may be substituted by an alkyl group having 1 to 6 carbon atoms. In the formula (2), each of 'R7~6 Independently, it is a hydrogen atom, an electron withdrawing group or an amine group, wherein at least one of R7 to R16 is an amine group. Further, all or a part of hydrogen atoms of the above amine group may be an alkyl group having 1 to 6 carbon atoms. Substituting A for a single bond, a carbonyl group, a carbonyloxy group, a carbonylmethylene group, a sulfinyl group, a sulfonyl group, a methylene group or an alkylene group having 2 to 6 carbon atoms. All or a part of the hydrogen atoms of the alkyl group may be substituted by a cyano group, a halogen atom or a fluoroalkyl group.) The radiation sensitive resin composition contains, in addition to the [A] copolymer, the [B] quinonediazide compound, [C;] hardener selected from the above specific compounds, while having high radiation sensitivity, also for [A] copolymer The epoxy group or the like which acts as an effective hardening catalyst has both storage stability and low-temperature firing. In addition, since the cured film formed of the radiation-sensitive linear mooncake composition is excellent in surface hardness, solvent resistance, and relative dielectric constant, it is suitably used as an interlayer insulating film, a protective film, or a separator of a flexible display. Form the material. A preferred [c] hardener is represented by the above formula (1) and formula (2).

For dielectric constants, etc. The protective film or separator as described above is suitable for forming a cured film as an interlayer insulating film because the radiation-sensitive resin composition has a desired effect. The liquid crystal alignment agent of the above-mentioned liquid crystal alignment agent is a liquid crystal alignment agent containing a radiation-sensitive polymer having a photo-alignment group, or a liquid crystal alignment agent containing a polyimide having no photo-alignment group. The method for forming a cured film of the present invention comprises: (1) a step of forming a coating film of the radiation sensitive resin composition on a substrate; (2) a step of irradiating at least a part of the coating film with radiation; (3) passing a step of developing the coating film by the radiation irradiation; and (4) a step of firing the coating film subjected to the above development. When the cured film is formed by the above-described steps using the S-ray radiation-reducing resin composition, the pattern is formed by exposure and development by sensitization, so that a fine and delicate pattern can be easily formed. Further, the cured film formed using the S-ray radiation-reducing resin composition has sufficient surface hardness or the like even if it is fired at a low temperature. The firing temperature in the step (4) in the forming method is preferably 20 〇〇c or less. In addition to the ability to form a fine pattern of radiation, since the firing at such a low temperature can be performed, the forming method is suitable for forming a cured film such as an interlayer insulating film on a plastic substrate of a flexible display. The present invention also encompasses a cured film formed of the radiation sensitive resin composition as an interlayer insulating film, a protective film or a separator. Further, "burning" in the present specification means heating the cured film to obtain the required strength. Further, "radiation" irradiated during exposure is a concept including visible light, ultraviolet light, ultraviolet light, xenon radiation, charged particle beam, and the like. [Effects of the Invention] 201229666 The radiation-sensitive resin composition according to the present invention has a low-temperature firing and storage stability, and has a radioactive linear resin composition and a conjugated radiation. It is an interlayer insulating film excellent in surface hardness, solvent resistance, and relative density for a flexible display, and a cured film as a protective film or a separator. [Embodiment] [Formation for Carrying Out the Invention] <Sensitive Radiation Resin Composition> The radiation sensitive resin composition of the present invention contains a [Α] copolymer, a [Β] quinonediazide compound, and [c] hardener. Further, optional components may be contained as long as the effects of the present invention are not impaired. Hereinafter, various components will be described in detail. 77 < [Α] copolymer> [Α] The copolymer is at least one monomer selected from the group consisting of unsaturated carboxylic acid and unsaturated carboxylic acid needle (Ai, hereinafter, sometimes referred to as " (Α1) a compound formed by copolymerization of an epoxy group-containing unsaturated compound (hereinafter sometimes referred to as "(Α2) compound)"). For the [Α] copolymer, for example, the compound (A1) which provides a carboxyl group-containing structural unit and the (A 2) compound which provides an epoxy group-containing structural unit can be subjected to the presence of a polymerization initiator in a solvent. Copolymerization to manufacture. Further, (A3) a hydroxyl group-containing unsaturated compound (hereinafter sometimes referred to as "(A3) compound") which provides a hydroxyl group-containing structural unit may be further added to form a copolymer. Further, in the production of the [A] copolymer, the compound (A4) may be further added together with the above (A丨) compound, (A2) compound and (A3) compound (provided from the above (Al), (A2) And (A3) a structural unit of the compound (A30), an unsaturated compound of a structural unit other than 201229666), forming a copolymer. [(Α1) compound] Examples of the (Α1) compound include an unsaturated monocarboxylic acid, an unsaturated dicarboxylic acid, an anhydride of an unsaturated dicarboxylic acid, and a mono[(meth)acryloxy group of a polyvalent carboxylic acid. Alkyl]ester, a mono(indenyl)acrylate of a polymer having a carboxyl group and a hydroxyl group at both ends, an unsaturated polycyclic compound having a carboxyl group, an anhydride thereof, and the like. Examples of the unsaturated monocarboxylic acid include acrylic acid, methacrylic acid, crotonic acid, and the like; Α For example, maleic acid and fumar y can be enumerated, for example, as the above-mentioned unsaturated ditinoic acid, which can be acid and lemon. Kang acid, mesaconic acid, itaconic acid, etc., in the case of unsaturated two-repulsive acid Xuan Xuan, the compound of the diacidic acid exemplified by Xuan et al; The appearance of vinegar is exemplified by, for example, acid mono[2_(methyl)(tetra)decyloxy. Formic acid mono [2-(methyl) propylene oxime oxime], etc.; η 丨 就 就 就 就 就 就 就 单 单 单 单 单 单 单 单 单 单 单 单 单 单 单 单 单 单 单 单 单 单 单 单Cyanine vinegar, etc.; omega fluorenyl... vinegar mono(methyl) propyl phenanthrene and its anhydride are exemplified by, for example, 5-carboxybicyclo[2.2. This is enough - women, 5,6 - two more 雔 [2.2.1] hept-2-ene, 5 绫 熳 熳 又 又 又 又 % % % % % 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 · Ethyl bicyclo [2 · 2.1] G · 2 · dilute, 4 base. 6. Methyl bicyclo [2 ^ hept-2-dilute, 5-nonyl winter ethyl bicyclo [2 · 2.] bicyclo [2.2. 1] Geng-2·enic anhydride and the like. '—Back group•11- 201229666 Among these, a monocarboxylic acid and a dicarboxylic acid anhydride are preferable, and acrylic acid and methacrylic acid are preferable from the viewpoints of copolymerization reactivity, solubility to an aqueous alkali solution, and ease of availability. maleic anhydride. These (A 1) compounds may be used singly or in combination of two or more. The total ratio of the (A 1) compound and the (A2) compound (optionally (A3) compound and (A4) compound) is preferably 5% by mass to 30% in terms of the ratio of use of the (A 1) compound. quality. /. More preferably, it is 1% by mass to 25% by mass. By using the ratio of the compound (A 1) in the above range, the solubility of the [A] copolymer in the aqueous alkali solution can be optimized, and the sensitivity is improved. Excellent radiation sensitive resin composition. [(A2) Compound] The compound (A2) is an epoxy group-containing unsaturated compound. The epoxy group can be exemplified by an oxiranyl group (1,2-epoxy structure) or an oxetane group (1,3-epoxy structure). Examples of the unsaturated compound having a % oxyethylene group include glycidyl acrylate, glycidyl methacrylate, 2-mercapto glycidyl thioglycolate, and α-ethyl acrylate shrinkage. Glyceride, α-glycidyl glycidyl ester, α_n-butyl acrylate glycidyl ester 3,4-epoxybutyl acrylate, methacrylic acid 3, butyl epoxide, propylene oxime 6,7 oxygen Heptyl ester, methacrylic acid 6,7-epoxyheptyl ester, .α-ethyl acrylate acid-6,7-epoxyheptyl ester, o-vinylbenzyl glycidyl ether, m-vinylbenzyl shrinkage Glycerol ether, p-vinylbenzyl glycidyl ether, 3,4-epoxycyclohexylmethyl methacrylate, and the like. Among these, from the viewpoint of improving copolymerization reactivity and solvent resistance of the cured film, etc., glycidyl methacrylate, 2-mercapto glycidyl methacrylate, thiol-12-201229666 acrylic acid- 6,7-epoxyheptenylbenzyl glycidyl, i θ '卩 vinyl benzyl glycidyl ether, m-acetyl 3,4-if t alkenyl benzyl glycidyl ether, decyl hexyl hexyl ester . In the case of an unsaturated compound having a heterocyclic ring, such as "°, it can be listed as a propylene oxymethyl methyl oxetane J % butadiene, 3 _ acetoxymethoxycyclobutane Sinter, 3 & s, 3-(acryloxycarbonyl)-3-ethyl oxa (propylene oxy oxime I. 3-( acetoxycarbonyl ketone) - fluoromethyl oxacyclohexane Dingyuan, oxymethyl)-2Γ2-2-pentafluoroethyl oxetane, 3-(propylene fluorene difluorooxetane/"heterocyclobutane, 3_(propylene oxime) Methyl) 2,2-butane, 3-(propadienyloxymethyl)-2,2,4·trifluorooxocyclo(propylene methoxymethyl, η 3-(2-propene) Bauxite)-2,2,4,4-tetrafluorooxetane, π-reduced oxyethyl) 氡)-2-ethyl-isomer ρ)-rolled % Butane, 3-(2- Propylene oxime ethyl acetonide % butane, 3 ring butyl sulphide, 3 ♦ propylene oxy-C-ethyl Aethyl oxapropoxyethyl propylene oxyethyl) _2 Oxyloxetane, 3-(2-ethyl)-2 2 _ ϋ 土 % 、, 3-(2-propenyl oxy), 2, ... a ring 炫, 3_(2_ Propyloxyethyltetrafluoro-(-propylene oxide) Ethyl ethyl)-2,2,4,4_ acrylates such as butyl ketone; 3-(methacryloxymethyloxymethyl)_2-methyl oxa " 3_(methylpropanyl)-3-acetonitrile oxaxane butane, 3_(methacryloxymethylethyloxetane, 3 尹 基 氧 氧 & amp & (methacryl醯oxyf-yl)-2•trifluoro-g^, 3_(methacryloxyl-methyl; “0277 helmet oxetane, 3 (methyl meth] rolling methyl) 2-fluoropenta Base 3 (methyl propyl ethoxymethyl) 2 _ phenyl oxetane-13- 201229666, 3-(methacryloxycarbonyl) 2,2-difluorooxetane , methacryloxymethyl) 2,2,4-trifluorooxetane, 3-(mercaptodecyloxymethyl)-2,2,4,4-tetrafluorooxa Cyclobutane, 3-(2- mercaptopropenyloxyethyl)oxetane, 3-(2-methacryloxyethylethyloxetane, 3-(2-indenyl) Propylene oxiranyl ethyl) _3_ethyl oxetane, 3-(2-methylpropenyloxyethyl)_2-trifluoromethyloxetane, 3-(2-mercapto Propylene oxiranyl ethyl) 2_pentafluoroethyl hydrazine, 3- (2-mercaptopropenyloxyethyl)_2_phenyloxetane, 3-(2-mercaptopropenyloxyethyl)_2,2-difluorooxetane, 3· (2_ mercaptopropenyloxyethyl)_2,2,4-trifluorooxetane, 3 (2-methacryloxyethyl)_2,2,4,4-tetrafluorooxa A thioglycolic acid vinegar such as cyclobutane. These (Α2) compounds may be used singly or in combination of two or more. The ratio of the (Α2) compound to be used is preferably 5% by mass based on the total of the (Α1) compound and the (Α2) compound (optionally (A3) compound and (Α4) compound). %, more preferably 丨〇 mass% ~ 5 〇 quality 3: %. By using the ratio of the (Α2) compound in the above range, a cured film having excellent solvent resistance and the like can be formed. [(A3) compound] In the case of the (Α3) compound, a (meth) group having a hydroxyl group, an unsaturated compound containing a condensed m represented by the following formula (3), and the like can be cited. 201229666

The formula (3), r 1 7 . Know that R丨8 to R22 are each independently: a wind atom or an alkyl group having 1 to 4 carbon atoms. base. γ is a single bond, a _c 〇〇 oxygen atom, a hydroxyl group or an alkane having 1 to 4 carbon atoms, and R18 to R22 or .C〇NH-°p is an integer of 〇3. One of the ^ and , one is a hydroxyl group. With respect to the above-mentioned (10)) acrylic acid having a hydroxyl group, it can be exemplified that (meth)acrylic acid, fluorenyl-acrylic acid-2_ thiophene-t 7 -rr 曰(fluorenyl)acrylic acid- 4-hydroxybutyl ester-alcohol (n=2~10) mono(indenyl)acrylic acid r曰, polypropylene glycol 2~丨〇)mono(indenyl)acrylate, (mercapto)acrylic acid·2,3·dihydroxy Acrylic, 2-methacryloxyethyl glucoside and the like. The unsaturated compound containing a desired hydroxyl group represented by the above formula (3), for example, a compound represented by the following formula (3-1) to formula (U-5), and the like, depending on the definition of hydrazine and hydrazine. -15- 201229666 R 17 〇

R20 In the above formula (3-1), 'q' is an integer of 1 to 3. The meaning in R1 is the same. X/R17

R 22 and the above formula (3)

R17 to R22 have the same meanings as in the above formula (3). In the above formula (3-2), R17

(3-3) In the above formula (3-3), r is an integer of 1 to 3. The meanings in R17 to R22 are the same. With the above formula (3) -16 - ZUlZZ^bbb X^R17

R20 In the above formula (3-4), r:X/R17 R22 has the same meaning as in the above formula (3) r22nAv/r18

R1a R20 <^>5) In the above formula (3-5), J\. ^ In these (A3) compound, the meaning is the same as in the above formula (3). Ester, mercapto hydroxy hydroxy _ preferably methacrylic acid 2-hydroxyethyl ethene, α-methyl-p-hydroxy stupid hydroxy styrene, p-hydroxybenzene, or a mixture of two ^ (3) Compounds can be isolated from 1 to above. The use of the (A3) compound is based on the (Α1) compound, the (A2) compound and the (/13) compound human 呻h from *, optionally the (A4) compound, as compared to humans from nm, λ] The total amount is preferably 5% by mass to 3 〇. / θ 0/ — · Berry / 〇, more preferably 10% by mass ~ 25 mass 罝 / 〇. The straw can be formed into a cured film having excellent solvent resistance and the like by using the compound (A3) in a ratio of the above. [(Α4) compound] -17-201229666 (A4) The compound is not particularly limited as long as it is an unsaturated compound other than the above (A1) compound, (A2) compound and (A3) compound. The (A4) compound can be exemplified by, for example, a chain styrene methacrylate, a carboxylic acid cyclic alkyl ester, an acrylic chain alkyl ester, a acryl cyclic alkyl acrylate, or an aryl methacrylate. Aryl acrylate, unsaturated dicarboxylic acid diester, bicyclic unsaturated compound, maleimide compound, unsaturated aromatic compound, conjugated diene, tetrahydrofuran skeleton, furan skeleton, tetrahydronane skeleton, piperazine An unsaturated structure of a skeleton, a skeleton represented by the following formula (4), and other unsaturated compounds.

In the above formula (4), R2 is a hydrogen atom or a fluorenyl group. s is an integer 1 of 1 or more. The fluorenyl methacrylate chain alkyl ester may, for example, be decyl methacrylate, ethyl methacrylate or decyl methacrylate - 2 butyl methacrylate. Tert-butyl methacrylate, 2-ethylhexyl methacrylate, isopropyl methacrylate, methyl propyl acrylate, laurel, tridecyl methacrylate, hydrazine The base acid is in the thirteen yards and the like. The cycloalkyl methacrylate may, for example, be cyclohexyl methacrylate, 2-methylcyclohexyl methacrylate or trimethyl sulfonate [5.2.1.02'6] 癸-8. - Stuffed, trimethoprimic [521〇26]癸-8-yloxyethyl ester, mercaptopropionic acid isobornyl vinegar, and the like. -18- 201229666 The acrylic chain alkyl ester may, for example, be methyl acrylate, ethyl acrylate, n-butyl acrylate, second butyl acrylate, tert-butyl acrylate or 2-ethylhexyl acrylate. Isodecyl acrylate, acrylic lauric vinegar, tridecyl acrylate, and octadecanoate. The cyclic alkyl acrylate may, for example, be cyclohexyl acrylate, 2-methylcyclohexyl acrylate, tricyclo[5.2.1.02'6] fluoren-8-ester, or tricyclohexyl acrylate [5.2.1.02]. '6] 癸-8-yloxyethyl ester, isobornyl acrylate, and the like. The aryl methacrylate may, for example, be phenyl methacrylate or benzyl methacrylate. The acryl aryl group S is exemplified by benzoic acid acrylate, benzyl acrylate or the like. The unsaturated dicarboxylic acid diester may, for example, be diethyl maleate, diethyl fumarate or diethyl itaconate. Examples of the bicyclic unsaturated compound include bicyclo [2.2.1] hept-2-ene, 5-methyl bicyclo [2.2.1] hept-2-ene, and 5-ethyl bicyclo [2.2.1] g. 2-ene, 5-methoxybicyclo[2.2.1]hept-2-ene, 5-ethoxybicyclo[2.2.1]hept-2-ene, 5,6-dimethoxybicyclo[2.2 .1]hept-2-ene, .5,6-diethoxybicyclo[2.2.1]hept-2-ene, 5-t-butoxycarbonylbicyclo[2.2.1]hept-2-ene, 5 - cyclohexyloxycarbonylbicyclo[2.2.1]hept-2-ene, 5-phenoxycarbonylbicyclo[2.2.1]hept-2-ene, 5,6-di(t-butoxycarbonyl)bicyclo[2.2. 1] Hept-2-ene, 5,6-di(cyclohexyloxycarbonyl)bicyclo[2.2.1]hept-2-ene, 5-(2'-hydroxyethyl)bicyclo[2.2.1]hept-2 -ene, 5,6-dihydroxybicyclo[2.2.1]hept-2-ene, 5,6-di(hydroxymethyl)bicyclo[2.2.1]hept-2-ene, 201229666 5,6-di ( 2,-Hydroxyethyl)bicyclo[2.2.1]hept-2-ene, hydroxy-5-methylbicyclo[2.2.Uhept-2-diene, 5-carbyl-5-ethylbicyclo[2 2 ^ Geng - olefin, 5-hydroxymethyl-5-methylbicyclo [2.2.1] g-2 - homing. Examples of the maleic imine compound include, for example, N-phenylmaleimine, N-cyclohexylmaleimide, N-based group, N-(4-hydroxyphenyl)malanium. Imine, N_(44f aryl) maleimide, N-saponin, iminoimide-3-maleimide, benzoic acid, _, N-sodium bromide, imine-4, Malay醯iminobutyrate, amber succinimide _6_maleimide caproate, N-succinimide-3 -maleimine propionic acid vinegar, n _(9 _ acridine Base) Maleidin and the like. The unsaturated aromatic compound may, for example, be styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene or p-methoxystyrene. Examples of the total amount of the dienes include hydrazine, 3-butadiene, isoprene, 2,3-dimethyl-i, 3-butadiene, and the like. Examples of the unsaturated compound containing a tetrahydrofuran skeleton include, for example, tetrahydroindenyl (meth) acrylate, 2-methacryloxy-propenyltetrahydrofurfuryl ester, and 3-(methyl) propylene.醯oxytetrahydrofuran-2-ketone and the like. Examples of the unsaturated compound containing a furan skeleton include, for example, 2-methyl-5-(3-indolyl)pentaene-3-enone, decyl (meth)acrylate, and 1-furan-2- Butyl-3-en-2-one, i • furan-2-butyl-3-methoxy-3-ene-2-one, 6-(2-furyl)_2_indolyl-丨-hexene_3 -ketone, 6-furan-2-yl-1-hex-1-en-3-one, 2-bromo-2-yl-ethyl-ethyl acrylate, 6-(2-»-furanyl)-6-methyl 1-heptene-3-one and the like. For the unsaturated compound containing a tetrahydrofuran skeleton, it can be listed as -20-201229666, such as methyl methacrylate (tetrahydropyran-2-yl) methyl ester, 2 6 dimethyl _8 (tetrahydrogen terminal) 2-yloxy)-octane] dilute _3, 2-methyl methic acid tetrahydropyran-2-yl ester, 1-(tetrahydropyran-2-yloxy)-butyl-3-ene-2- _ ketone and so on. The unsaturated compound containing a melane skeleton can, for example, be 4-(M-dioxa-5-oxy-6-heptenyl)_6-methyl-2-pyran, 4_(ι, 5_2 Oxa-6-oxyoctenyl)_6_mercapto-2-p-pyran. Examples of the other unsaturated compound include acrylonitrile methyl acrylonitrile, ethylene ethoxide, vinylidene chloride, propylene styrene, vinyl acetate and the like. t Among these (A4) compounds, preferred are mercaptoacrylic chain-chain alkyl fluorenyl carboxylic acid cyclic alkyl esters, maleimide compounds, tetrahydrofuran skeletons, furan skeletons, tetrahydropyranyl skeletons, The melane skeleton, the unsaturated compound of the skeleton represented by the above formula (4), the unsaturated aromatic compound, and the bupropion acid cyclic alkyl group. Among these, from the viewpoint of the solubility of the copolymerization reactivity to the aqueous solution, styrene, decyl methacrylate, butyl methacrylate, n-lauryl methacrylate, methyl propyl acrylate are preferred. Diluted tricyclo[5·2丄〇2'6]癸+vinegar, 曱methoxy styrene, propylene S 2 fluorenyl j-hexyl ester, Ν-phenyl maleimide, Ν_ring己iimide, tetrahydroindenyl (mercapto) acrylate vinegar, polyethylene glycol (η=2 bis(octa) mono(methyl) propyl vinegar, 3-(indenyl) propylene oxytetrahydroethylene (2) These (Α4) compounds may be used singly or in combination of two or more. In terms of the ratio of (Α4) compound, based on (Α1) compound, (Α2) compound, and (Α4) compound (and any The total of the selected compounds) is preferably from 10% by mass to 70% by mass, more preferably from 2% by mass to 6% by mass. - 21 - 201229666 5 ounces by means of the use of the compound (A4) The ratio is in the above-mentioned range, and a cured film excellent in solvent resistance and the like is formed. <Synthesis method of [A] copolymer> Into the "51 house agent [A] copolymer can be, for example, In the case where poly&in the presence of a solvent, the above (A1) compound and (a2) compound (optionally (compound and (A4) compound) are copolymerized to produce. 7 points used in the polymerization of the [A] copolymer can be exemplified by, for example, an alcohol, a glycol, a glycol thiol®^®&amp;&lt;2&gt; , diethylene glycol dialkyl bond, dipropyl monopropyl ether, propylene glycol monoalkyl ether, propylene glycol alkyl ether acetate, propylene glycol monoalkyl ether propionate, ketone, ester, etc. For example, the glycol ether may, for example, be ethylene glycol monomethyl hydrazine or ethylene glycol monoethyl ether; and the ethylene glycol alkyl ether acetate may, for example, be mentioned. Ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, etc.; as the diethylene glycol monoalkyl ether, for example, diethylene glycol monomethyl ether or diethylene glycol can be cited. Monoethyl ether or the like; as far as the monoethylene glycol dialkyl radical is concerned, for example, diethylene glycol didecyl ether, diethylene glycol diethyl ether, and two a diol ethyl fluorenyl hydrazine or the like; and a propylene glycol dialkyl group, for example, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, dipropylene glycol ethyl fluorenyl group, etc. The basal mystery can be, for example, propylene glycol methyl ether, propylene glycol ethyl hydrazine, propylene glycol propyl ether, propylene glycol butyl sulfonate, etc.; -22- 201229666 propylene glycol monoalkyl ether acetate, for example, propylene glycol monomethyl Ethyl ether acetate, propylene glycol monoethyl ether acetate, etc.; as the propylene glycol monoalkyl ether propionate, for example, propylene glycol methyl ether propionate, propylene glycol ethyl ether propionate, propylene glycol propyl ether Examples of the ketone include methyl ethyl ketone, cyclohexanone, 4-hydroxy-4-mercapto-2-pentanone, methyl isoamyl ketone, and the like; For example, ethyl acetate, butyl acetate, 3-methoxybutyl acetate, ethyl 2-hydroxypropionate, decyl 2-hydroxy-2-methylpropionate, and 2-hydroxy-2-mercaptopropionic acid Ester, butyl hydroxyacetate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, 2-ethoxyl Ethyl acetate, propyl 2-ethoxypropionate, butyl 2-ethoxypropionate, decyl 2-butoxypropionate, ethyl 2-butoxypropionate, 2-butoxypropane Acid propyl ester, butyl 2-butoxypropionate, decyl 3-methoxyoxypropionate, ethyl 3-methoxyoxypropionate, propyl 3-methoxypropionate, 3-methoxypropane Butyl acrylate, decyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, propyl 3-ethoxypropionate, butyl 3-ethoxypropionate, 3-propoxypropane曱 ester and the like. Among these solvents, preferred are 3-methoxy butyl acetate, ethylene glycol alkyl ether acetate, diethylene glycol monoalkyl ether, diethylene glycol dialkyl ether, propylene glycol monoalkyl ether, Propylene glycol alkyl ether acetate, more preferably 3-methoxybutyl acetate, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, propylene glycol monomethyl ether, propylene glycol monodecyl ether acetic acid ester. As the polymerization initiator used in the polymerization for producing the [A] copolymer, those generally known as radical polymerization initiators can be used. As the radical polymerization initiator, for example, 2,2'-even-23-201229666 nitrogen bisisobutyronitrile (AIBN), 2,2'-azobis gas double, methoxy group methyl group can be cited. 4, 曱 戍 戍 ) ) n n n n n ; ; ; ; ; ; ; ; ; ; ; 过 过 过 过 过 过 过 过 过 过 过 过 过 过 过 过 过 过 过 过 过 过 过 有机 有机 有机Peroxidation; when the oxide and reducing agent are used together as a two-agent, it can also be used as a deuterated reduction initiator. Once, for the polymerization of [Α] copolymer, in order to regulate the molecule The second aspect is to use a molecular weight modifier. The molecular weight modifier may, for example, be a functional hydrocarbon such as gas-like or carbon tetrabromide; n-hexyl mercaptan, n-octyl mercaptan, n-decyl mercaptan, and third tenth Mercaptans such as dialkyl mercaptan and mercaptoacetic acid; xanthogens such as dimethyl sulfide xanthogen and diisopropyl dithioxanthogen; and cappediene, dimercapto styrene dimer, and the like. The weight average molecular weight (Mw) of the [A] copolymer is preferably 1,000 to 30, and more preferably 5 Å to 2 Å. By making [A] a total The Mw of the substance is within the above range, and the sensitivity and developability of the radiation-sensitive resin composition can be improved. Further, the Mw and the number average molecular weight (?η) of the polymer in the present specification are condensed by the following conditions. GPC-101 (Showa Denko Co., Ltd.) Column: Connected to GPC-KF-8 (H, GPC-KF-802, GPC-KF-803 and GPC-KF-804 mobile phases) : tetrahydrogenation column temperature: 40 ° C flow rate: l.OmL / min sample concentration: 1 · 0 mass % -24- 201229666 sample injection amount: ΙΟΟμί detector: differential refractometer standard substance: monodisperse Polystyrene &lt;[B] Studed Diazide Compound> The [B] quinonediazide compound used in the radiation sensitive resin composition of the present invention is 1,2-quinone which produces carboxylic acid by irradiation of radiation. a diazide compound. For the 1,2-quinonediazide compound, a phenolic compound or an alcoholic compound (hereinafter referred to as "mother core") and a halogenated 1,2-naphthoquinonediazide sulfonate may be used. The condensate of the acid. For the above-mentioned mother nucleus, for example, trihydroxybenzophenone, tetrahydroxybenzophenone can be cited. Pentahydroxybenzophenone, hexahydroxydibenzophenone, (polyhydroxyphenyl)alkane, other mother nucleus, etc. Examples of the trihydroxybenzophenone include, for example, 2,3,4-trihydroxy Benzene ketone, 2,4,6-trihydroxybenzophenone, etc.; as the tetrahydroxydibenzophenone, for example, 2,2',4,4'-tetrahydroxybenzophenone, 2, 3,4,3'-tetrahydroxydibenzophenone, 2,3,4,4'-tetrahydroxydibenzophenone, 2,3,4,2'-tetrahydroxy-4'-mercaptobenzophenone Ketone, 2,3,4,4'-tetrahydroxy-3'-nonyloxybenzophenone, etc.; as the pentahydroxybenzophenone, for example, 2, 3, 4, 2', 6' can be cited. - pentahydroxybenzophenone or the like; in the case of hexahydroxybenzophenone, for example, 2,4,6,3',4',5'-hexahydroxybenzophenone, 3,4,5, 3', 4', 5'-hexahydroxybenzophenone, etc.; as the (polyhydroxyphenyl)alkane, for example, bis(2,4-dihydroxyphenyl)methane or bis(p-hydroxyphenyl) Methane, tris(p-hydroxyphenyl)decane, 1,1,1-tris(p-hydroxyphenyl)ethane, bis(2,3,4-trihydroxyphenyl)-25- 201229666 methane, 2, 2-bis(2,3,4-trihydroxyphenyl)propane, j!-yl-4-hydroxyphenyl)·3·phenylpropane, 3·bis(2,5-dimethyl)-1曱Ethylethyl]phenyl]ethylidene]bisphenol, bis[4-hydroxyphenylphenyl]-2-hydroxyphenylmethane, 3,3,3,3,_tetra-methyl-4- Hydroxy-5,6,7,5,6',7'-hexanol, 2,2,4-trimethyl-7,2,yl-1,1'-spirobifluorene; ,, 4', For the other parent core, trihydroxyflavan or the like can be exemplified by, for example, 2 hydroxyphenyl)-4-(4-hydroxyphenyl)-7-hydroxy stupyl-methyl-2' (2,4·di-1-[ 1-(3-{1-(4-hydroxyphenyl)-p-methylethyl} and hydrogenated piper, )-1-methylethyl]_3-(1-(3-{1-(4-) Stupid one base base}-4,6--transphenylyl)_ι_methylethyl)benzene, * 6) 1 methyl ethyl)-1-methylethyl}-1,3- Hydroxybenzene and the like. Hydroxybenzene in these mother nucleuses, preferably 2,3 4 4 , , tetrahetero 1,1,1-tris(p-hydroxyphenyl)ethane, diphenyl hydrazine ig, ]-ι-methyl Ethyl]phenyl]ethyl keto]bisphenol. U't 4-hydroxyphenyl muscle m ig ^ IU J / J ^ naphthoquinone diazide sulfonium gas. In the case of the bismuth, the 2-naphthalene roller is preferably a 1,2-naphthoquinonediazide~azide sulfonium I naphthoquinonediazide-5-sulfonyl chloride, etc. . In this case, 4 sulfonium chloride, 1,2 quinone diazide-5 - continued helium. More preferably, the ratio of 1,2 - in the condensation reaction of phenolic compounds or alcoholic diazide continued acid φ nucleus) and dentate naphthalene brewing should be 'relative to OHA in phenolic compounds or alcoholic compounds仓i·, &amp; ^ Lane number car father good use of the equivalent of 30~85 mol% 'better 50~7〇 Moer% dip h, _1,2-naphthalene diazide sulfonate acid. The condensation reaction can be carried out according to a known method. In the case of a bismuth azide compound, it is also suitable to convert the ruthenium of the above-mentioned nucleus to a guanamine sulfonate sulfonamide. For example, 2 fly 4 ^ Ding 0 Kun - vertical nitrogen - makeup cheek, such as 2,3,4-triaminobenzophenone-it naphthoquinone diazide-4 - acid decylamine and the like. k Some of the [B] quinonediazide compounds may be used alone or in combination of two or more. The ratio of use of the [B] quinone diazide compound in the radiation sensitive resin composition is preferably 5 parts by mass to 1 part by mass based on 1 part by mass of the [A] copolymer. More preferably, it is 1 part by mass to 5 parts by mass. When the ratio of use of the [B] quinone diazide compound is within the above range, the difference between the solubility of the aqueous solution and the unirradiated portion can be made large, and the patterning performance is good. Good solvent properties. &lt;[C] Hardener&gt; The [c] hardener contained in the radiation sensitive resin composition is a compound represented by the above formula (1), a compound represented by the above formula (2), a tertiary amine compound, and an amine salt. At least one selected from the group consisting of a squamous salt, a sulfonium salt, a guanamine compound, a ketimine compound, an ampho isocyanate compound, a compound containing a '&gt; rice bran ring, and a cage compound. The hardening agent selected from the specific compound described above may contain both storage stability and low-temperature firing. Hereinafter, various compounds will be described in detail. [The compound represented by the above formula (1) and the above formula (2)] The [C] hardener is preferably at least one selected from the group consisting of the compounds represented by the above formulas (1) and (2). By selecting the above specific compound having an amine group and an electron-deficient group as the [C] hardener, the -27-201229666 radiation-linear resin composition can have a higher level of storage stability and low-temperature firing, and The relative dielectric constant and the like of the obtained cured film can be further improved. In the above formula (1), R1 to R0 are each independently a hydrogen atom, an electron withdrawing group or an amine group. Here, at least one of Ri to R6 is an electron withdrawing group, and at least one of R1 to R6 is an amine group, and all or a nitrogen atom of the above amine group may be substituted with a group having 1 to 6 carbon atoms. In the above formula (2), R7 to R16 are each independently a hydrogen atom-electron group or an amine group. Wherein at least one of R7 to R16 is an amine group. Further, all or a part of the hydrogen atoms of the above amine group may be substituted by a group having 1 to 6 carbon atoms. The hydrazine is a bond, a benzyl group, a oxy group, a benzylidene group, a sulfinyl group, a sulfonyl group, an anthranylene group or an alkylene group having 2 to 6 carbon atoms. Wherein all or part of the hydrogen atoms of the above methylene and alkylene groups may be substituted by a cyano group, a halogen atom or a fluoroalkyl group. The electron withdrawing group represented by the above R1 to R16 may, for example, be a halogen atom, a cyano group, a nitro group, a trifluoromethyl group, a carboxyl group, a decyl group, an alkylsulfonyl group or an alkyl oxysulfonate. Base, dicyanovinyl, tricyanovinyl, sulfonyl, and the like. Among these groups, a nitro group, an alkyloxy group, and a trifluoromethyl group are preferred. As the group represented by A, an anthracenyl group which may be substituted by a fluoroalkyl group is preferred. The compound represented by the above formula (1) and formula (2) is preferably 2,2-bis(4-aminophenyl)hexafluoropropane or 2,3-bis(4-aminophenyl). Succinonitrile, 4,4'-diaminodibenzophenone, 4,4'-diaminophenyl benzoate, 4,4'-diaminodiphenyl hydrazine, 1,4-two Amino-2-gasbenzene, anthracene, 4-diamino-2-bromobenzene, 1,4-diamino-2-indenebenzene, 1,4-diamino-2-; &amp; Schottylbenzene 1,4 -Diamine-28- 201229666 Benz-2-trifluoromethyl stupid, 2,5-diaminobenzonitrile, 2,5-diaminophenylethyl, 2,5-diaminobenzene Citrate, 2,2'-di-diphenylaniline, 2,2,-dibromobenzamine, 2,2'-diiodobenzidine, 2'2,-dinitrobenzidine, 2,2, Bis(trifluoromethyl)benzidine, ethyl 3-aminobenzenesulfonate, 3,5-bistrifluorodecyl-nonylaminobenzene, 4-aminonitrobenzene, N,N-dimethyl 4_nitroaniline is more preferably 4,4'-diaminodiphenyl sulfone, 2,2-bis(4-aminophenyl)hexafluoropropane, 2,2'-bis(difluoromethyl) Benzidine, ethyl 3-aminobenzenesulfonate, 3,5-bistrifluorodecyl-1,2-diaminobenzene, 4-aminonitrobenzene, N,N-didecyl_4_ Nitroaniline. The compounds represented by the above formulas (1) and (2) may be used singly or in combination of two or more. The content ratio of the compound represented by the above formula (丨) and formula (2) is preferably from 1 part by mass to 20 parts by mass, more preferably from 1 part by mass to 1 part by mass of the [A] copolymer. 2 parts by mass to 1 part by mass. By making the content ratio of the compound represented by the above formulas (1) and (2) within the above range, the 6-sense radiation-sensitive linear resin composition can have a higher level of storage stability and low-temperature firing. [Tri-Amine Compound] If a general-purpose primary amine compound having a high reactivity and a bis-anthracene compound and an epoxy compound are coexistent, the nucleophilic action of the φ-butanamine on the epoxy group is stored in the composition solution. Leading to the hardening reaction may damage the quality of the treasure system. However, when the use of the tertiary amine is low in reactivity, even if it is present in the composition in combination with the epoxy compound, it has good storage stability. Formula (5) For the tertiary amine compound, at least one selected from the group consisting of compounds escaping may be used. -29- (5) 201229666 R24

I / N, R25 XR26 In the above formula (5), R24 to R26 are each independently an alkyl group of a carbon atom, an aryl group having 6 to 18 carbon atoms or a carbon number of 7 to 30. Among them, Han 24 and R25 can also be bonded to each other to form a ring structure together with the bond of the two. All of the hydrogen atoms of the above alkyl group, aryl group and aralkyl group may be substituted. The above-mentioned R24 to r26 have the above carbon atoms of 1 to 20. This exemplifies, for example, a linear or branched fluorenyl group, ethyl butyl amyl group, hexyl group, heptyl group, octyl group, decyl group, decyl group, undecyl group, tridecyl group, and fourteen. The alkylpentadecyl group heptadecyl group, octadecyl group, nonadecyl group, and eicosane are, for example, a phenyl group, and the aryl group having 6 to 18 carbon atoms represented by the above R24 to R26. Naphthyl and the like. The aryl group having 7 to 30 carbon atoms represented by the above R 4 to r20 may, for example, be a benzyl group or a phenethyl group. Examples of the primary amine compound include, for example, trimethylamine N,N dimethylbenzylamine, trisuccinylamine, tributyloctylamine-(dodecanyl)amine, tributyl sulfhydrylamine, Tris-N-methylaniline, N,N-diethylaniline, benzene Benzene N,N_-methyl-p-anisidine, N,N-didecyl N,N-dimethyl-4 _甲备甘_ Extraterrestrial methoxyaniline, N-phenylpiperidine, N-(4-yl)pyridine, N-branched soil-丨, 2,3,4-tetrahydroisoquineline, 6-Benzyl shoulder-7-oxime X 1 ) ·5 ^ ^ soil, 3,4-tetrahydroisoquinoline, hydrazine, Ν'-dimethylpiper number 1~20 Or base, propyl, laurel, hexadecane, etc. Amine, triamine, triamine, Ν-methylaniline, oxyphenyl hydrazine-phenyl, hydrazine, hydrazine - -30- 201229666 dimercaptocyclohexylamine, 2-dimethylamine Methyl phenol, 6 夂 methylamino fluorenyl phenol, and the like. Among these tertiary amine compounds, trioctylamine and 2-dimethylaminomethylbenzene are preferred. The tertiary amine compounds may be used singly or in combination of two or more. The content ratio of the tertiary amine compound in the radiation-sensitive resin k-form is more preferably 0.1 part by mass to 1 part by mass per part by mass of the [A] copolymer. .2 parts by mass to 5 parts of 4 parts. By setting the content ratio of the tertiary amine compound within the above specific range, the radiation sensitive resin composition can be combined at a high level of storage stability and fired at a low temperature. 1 [Amine salt and scaly salt] At least one selected from the group consisting of compounds represented by the following formula (6) can be used as the amine salt and the scaly salt. R27 1 + R28-A1—R30 Q- (6) R29 In the above formula (6), A1 is a nitrogen atom or a phosphorus atom. R27 to r3g are each independently a hydrogen atom, an alkyl group having a carbon number of 丨~汕, an aryl group having 6 to 18 carbon atoms or an aryl group having 7 to 30 atomic atoms. Among them, some or all of the hydrogen atoms of these groups may be substituted. Q- is a monovalent anion. The alkyl group having the number of carbon atoms &gt; 20 represented by the above R27~, for example, a linear or branched fluorenyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group or a heptyl group, Octyl, fluorenyl, fluorenyl, lauryl, decyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl octadecyl, nonadecane Base, eicosyl and the like. -31 - 201229666 The aryl group having 6 to 18 carbon atoms represented by the above R27 to R3 is, for example, a phenyl group or a naphthyl group. The aralkyl group having 7 to 3 carbon atoms represented by the above R27 to R30 may, for example, be a benzyl group or a phenethyl group. The monovalent anion represented by Q above may, for example, be a chloride ion, a odor ion, an iodide ion, a cyanide ion, a nitrate, a nitrite, a hypochlorite, a sulphate, a sulphate 'perchlorate, or the like. Perchloric acid, carbon hydrazine, dihydrogen phosphate, hydrogen sulfide ion, thiocyanate, carboxylate ' 酉夂 root, oxyanion, tetrafluoroborate, tetraarylborate, hexafluoroate Wait. When A is a nitrogen atom, that is, in the case of an ammonium salt, for example, tetramethylphosphonium chloride, tetrabutylammonium vapor, dodecyldimethylbenzylammonium chloride, octyldimethylamine gasification can be cited. Ammonium, mercaptotrimethylammonium vapor, dodecyltrimethylphosphonium chloride, tetradecyltrimethylammonium chloride, cetyltrimethyl chloride, decyl 9-dimethyldimethyl chloride Ammonium, cetyltrimethylammonium bromide, thruyltrimethylammonium hydride, thoryltriethylammonium hydride, gasified benzalkonium hydride, benzalkonium Based on vaporized ammonium, distearyl dimethyl vaporized money. When A is a phosphorus atom, that is, in the case of a scale salt, for example, tetraphenyl scale • tetraphenyl sulphonate, ^ - tetradentyl scale, tetrakis (p-phenyl) borate, tetraphenyl scale • Tetrakis(p-ethylphenyl)borate, tetraphenylphosphonium·tetra(p-oxyphenyl), tetraphenylscale·tetra(p-ethoxyphenyl)-penic acid: four Phenyl sulphate • tetra (p-tert-butoxyphenyl) succinate, tetraphenyl m-tolyl), tetraphenyl sulphate tetrakis (m-methoxyphenyl) Benzyl) phenyl sulphate. Tetrakis(p-tolyl)borate, tetra-32-201229666 (p-tolyl) scaly • tetra(p-tolyl)borate, tris(p-methoxyphenyl)phenyl hydrazine . Tetrakis(p-phenylphenyl)borate, tetraphenylphosphonium thiocyanate, butyltriphenylsulfate, methyltriphenylsulfate, p-tolyldiphenylsulfonate Cyanate 'benzyltriphenyl hexafluoroantimonate, p-benzylbenzyldiphenylphosphonium hexafluoroantimonate, p-methylbenzyltriphenyl hexafluoroantimony salt, p-methoxyl Benzyltriphenylphosphonium hexafluoroantimonate, α-methylbenzyltriphenylphosphonium hexafluoride Citrate, cinnamyltriphenyl hexafluoroantimonate, 2_ nitrosobenzyldiphenyl hexafluoroantimonate, iota naphthylmethyltriphenyl hexafluoroantimonate, 3 - trimethyl carbazinoalkyl _4_ trimethyl decyloxy benzyl di-base hexafluoroantimonate, p-methoxyl III (p-chlorophenyl) hexafluoroantimonate,曱oxyl group tris(p-methylphenyl) town hexafluoroantimony Ss•salt, cinnamyl di(p-chlorophenyl) hexafluoroantimonate-p-oxybenzyltriphenyl hexafluorophosphate Salt, 1_mercapto-yl-trisyl hexafluoroantimonate, lt-based benzyl-butyl diphenyl hexafluoroantimonate, 9-fluorenylmethyl·triphenyl sulphate Citrate, tetrabutyl sulphate, tris(T3) squamous tetraphenyl borate, di-tert-butyl fluorenyl tetraphenyl borate, p-phenylphenyl triphenyl Scale • Four (p-toluene) borate, tetraphenyl scale • tetrafluoroborate. Among these amine salts and squama salts, &lt;*&gt; muscle sputum j ^ gas salt. The amine salt and the scaly salt may be used singly or in combination of two or more phenyl sulfonium species. The content ratio of the amine salt and the scale in the radiation-sensitive resin composition is preferably 0.1 part by mass to 10 parts by mass, more preferably 0.5 part by mass to 5 parts by mass based on 100 parts by mass of the [Α] copolymer. Parts by mass. By making the content ratio of the amine salt and the scaly salt to the above-mentioned specific 笳囹1 target, it is possible to make the radiation-sensitive resin composition have a higher level of stability and low-temperature firing. -33- 201229666 [脒 salt] (7) indicates a compound. For the sulfonium salt, at least one selected from the group consisting of the salts of the following formula can be used.

(7)

In the above formula (7), m is an integer of 2 to 6. Among them, some or all of the hydrogen atoms which the alkylene group has may be substituted by an organic group. Further, the above-mentioned stretching group means both the stretching base in the tetrahydro 0 mil ring and the stretching base represented by (CH2) m in the formula (7). The above-mentioned exudyl group may be an organic group which may be a substituent, and examples thereof include a mercapto group, an ethyl group, an isopropyl group, a n-butyl group, a t-butyl group, a n-hexyl group and the like having 1 to 6 carbon atoms. Alkyl; hydroxyindenyl, 2-hydroxyethyl, 1-hydroxydiyl, 2-carboxypropyl, 3-hydroxypropyl, 2-hydroxyisopropyl, 3-hydroxy-t-butyl, 6_ a hydroxyalkyl group having 1 to 6 carbon atoms such as a hexyl group; a dimethylamino group, a methylethylamino group, a diethylamino group, a diisopropylamino group, a dibutylamino group, a third butyl group A diamine-based amino group having 2 to 12 carbon atoms such as a sulfhydryl group or a di-n-hexylamino group. The compound represented by the above formula (7) can be exemplified by 丨,5-diazabicyclo[4,3,〇]-nonene-5 (DBN), 1,5-diazabicyclo[4,4 ,0]_pinene-5,1,8-diazabicyclo[5,4,0]-undecene-7 (DBU), 5-hydroxypropan-34- 201229666 base-1,8-nitrogen Heterobicyclo[5,4,〇]-undecene_7,5-dibutylamino group_ι,8-diazabicyclo[5,4,0]-undecene-7 and the like. Among these, DBN and DBU are preferred. The acid used to form a salt of the compound represented by the above formula (7) can be exemplified by an organic acid and an inorganic acid. The organic acid may, for example, be a carboxylic acid, a monoalkyl carbonic acid, an aromatic transbasic compound, or a creatinic acid. Examples of the carboxylic acid include saturated fatty acids such as formic acid, acetic acid, 2-ethylhexanoic acid, and isovaleric acid; acrylic acid, crotonic acid, methacrylic acid, phthalic acid, and m-benzoic acid. Capric acid, fumaric acid, maleic acid 'palm oleic acid, oleic acid, linoleic acid, linolenic acid, isooleic acid, tung oil, arachidonic acid, cinnamic acid, naphthoic acid, benzoic acid, A Unsaturated carboxylic acid such as benzoic acid; gaseous acetic acid, cyanoacetic acid, dichloroacetic acid, trichloroacetic acid, trimethylacetic acid, fluoroacetic acid, bromoacetic acid, decyloxyacetic acid, thioglycolic acid, iodic acid, vinyl acetate L-substituted acetic acid such as acetic acid, phenylacetic acid or phenoxyacetic acid; dicarboxylic acid such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, sebacic acid, suberic acid or sebacic acid ; diolic acid, lactic acid, citric acid, d_tartaric acid, tartrate, anti-jk acid, mandelic acid, etc.; ketone carboxylic acid such as pyruvate, acetopropionate; 2-propionic acid, a carboxylic acid such as 3-propionic acid. As soon as the base is burned, it is A X, thank you, fire δ, which is enough to list, for example, methyl carbonate, ethylene carbonate, and the like. -35-201229666 The aromatic radical-based compound may, for example, be phenol, nonylphenol, catechol or naphthol. Examples of the sulfonic acid include octylbenzenesulfonic acid, butylbenzenesulfonate, anthracenesulfonic acid, benzoic acid, and fluorite. Examples of the inorganic acid include, for example, a tooth acid such as hydrochloric acid, hydrogen fluoride or bromine, carbonic acid; a perhydrohalogenated acid such as peroxy acid or perbromic acid; and the like.

Among these acids, 'preferably a carboxylic acid, an aromatic hydroxy compound, a sulfonium i' is a more preferred saturated fatty acid, an aromatic hydroxy compound, a sulfonic acid, and particularly preferably a sulfonic acid as a strong acid. Sulfonic acid, octyl sulfonic acid. As the onium salt, a salt of DBU and toluenesulfonic acid, a salt of DBU and octylbenzenesulfonic acid, a salt of DBN and nonylbenzene acid, a salt of DBN and octyl acid can be preferably used. The onium salt may be used singly or in combination of two or more. The content ratio of the onium salt in the radiation-sensitive resin composition is preferably from 10,000 parts by mass to 10 parts by mass, more preferably from 5 to 10 parts by mass, based on 100 parts by mass of the [A] copolymer. Backup. By making the content ratio of the pulse salt within the above specific range, the radiation sensitive resin composition can have a higher level of storage stability and low temperature firing. [Row Amine Compound] For the guanamine compound, at least one selected from the group consisting of compounds having a guanamine group represented by the following formulas (8) to (1 〇) can be used. 0 r31 c , N/, r32 &lt; δ)

I Η -36- 201229666

In the above formula (8), R31 and R32 each independently represent a hydrogen atom, a shin group having a carbon number of 1 to 12, a cyclohexyl group, a phenyl group, a 4 group, an ethylene group or a 2 - σ group. Among them, the above-mentioned stilbene, stupid and naphthyl group having 1 to 12 carbon atoms may be substituted by a condensing group having 1 to 6 carbon atoms, a halogen atom, a hydroxyl group, a thiol group or an ethylene group. In the above formula (9), R33 and R34 are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms or a cyclohexyl group, an anthracene group, an alkylene group having 2 to 12 carbon atoms, and a phenyl group. , stretching naphthyl or vinyl. Here, the above methylene group, an alkylene group having 2 to 12 carbon atoms, a phenylene group and a stilbene group may be substituted by an alkyl group having 1 to 6 carbon atoms or a halogen atom. In the above formula (10), R35 and R36 are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms or a cyclohexyl group; a3 is a methylene group, a carbon atom having 2 alkyl groups, a phenyl group, and a stretching group. Naphthyl or vinyl. Here, the above methylene group, an alkylene group having 2 to 12 carbon atoms, a phenylene group and a stilbene group may be substituted by an alkyl group having 1 to 6 carbon atoms or a halogen atom. The guanamine compound represented by the above formula (8) is a compound having one guanamine bond in the molecule. Specific examples thereof include, for example, acetamide, decyl-mercaptoacetamide, hydrazine-ethylacetamide, hydrazine-n-propyl acetamide, -37-201229666 N-isopropylacetyl hydrazine. Amine, N-n-butylethylamine, N-isobutyl N-tert-butylacetamide, N-n-hexylacetamide, N-n-octyl, N-n-dodecylacetamide, Propylamine, butylamine, pentamidine, octadecylamine, acetophenone, acetophenone, benzoic acid, m-acetamide, p-acetamide, phenol, m-ethyl Amidoxime phenol, p-acetamide phenol, acetamide dimethyl glutamate, acrylamide, benzamide, naphthylamine, isoniaceine guanamine, and the like. Among these, acetamide, N-mercaptoacetamide, and phthalic acid are used in terms of heat resistance and voltage holding ratio of a cured film which can be obtained by storage at room temperature. The compound represented by the above formulas (9) and (10) is a compound having a guanamine bond in the molecule. For specific examples thereof, it is possible to classify phthalic acid, m-xylamine, p-xylamine, succinimide, glutamine, hexamethyleneamine, heptamine, Indoleamine, indoleamine, maleic amine, fumarate, dimercapto-o-phthalamide, anthracene, Ν'-dimethyl-m-benzoquinone, Ν'-dimethyl · p-xylguanamine, hydrazine, Ν'-diethyl fluorenyl-hydrazine, Ν'-diethyl decyl-m-phenylenediamine, hydrazine, Ν'-diethyl fluorenyl-p-quinone, Ν' -dipropenyl-o-phenylenediamine, anthracene, Ν'-dipropenyl-inter-hydrazine, Ν'-dipropenyl-p-phenylenediamine, anthracene, Ν'-diethyl fluorenyl-extension ,Ν'-diethyl fluorenyl-propyl propylamine, hydrazine, Ν'-diethyl fluorenyl-arylene, hydrazine, Ν'-diethylhydrazine-hexamethylenediamine, hydrazine, Ν'-two醯···························~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~ Indoleamine, acetoinamide, iso-o-acetamide o-acetamide naphthalene, o-benzene in the stability of the guanamine, preferably have two actions such as o-propionamide, sin Oh, Ν, - guanamine, : phenylenediamine, phenylenediamine, phenylenediamine, &gt; bisdiamine, butyldiamine-dodecane, hydrazine, hydrazine, -diyldiamine, -38- 201229666 (4) Diphenyl fluorenyl-hexamethylene dialkyl methylene diamine, N, N, and two extracts - Benjia. Brewing base - docosaphthalene thiol-extension - 俨M soil - stretching Ethylenediamine, N,N,-, mononaphthalene: fluorenyldiyl-butylene (di), dodecylmethylenediamine, and the like. Earthworms, Ν'-naphthyl fluorenyl group - in these materials, t low temperature firing considerations, surface level storage stability and N, ... thiol diterpene dimethylamine, ... amine, sister sign Phenyldiamine, NN, _ diamine. The makeup ethyl-hexamethylene group, the sensation: = compound can be used alone or in combination of two or more. (2): The content of the guanamine compound in the resin composition is 100 parts by mass, preferably ❻·1 part by mass to 10 mass: °'5 parts by mass to 5 mass. The ratio of the content of the indoleamine compound to the above-mentioned special macrochrome can be made up of the radiation-sensitive resin composition, the storage stability of the π level, and the low-temperature firing. [Ketenimine compound], an imine compound can be obtained by a reaction of a ketone and an amine. For the sake of the scheme, for example, ethylmethyl hydrazine, isodecyl f methiriisobutyl methyl ketone, methyl tert-butyl ketone, ethyl butyl ketone, acetophenone butyl group, field basin 丄, "· Tertyl ketone, dipropyl ketone, 3-mercapto-2-hexanone, genus, 3-octyl, 4-octyl ketone, methylcyclohexyl ketone, methylcyclohexanone, etc. The diamine and the extension of both ends may, for example, be 2,5-dimethyl-2,5-hexanediamine or 1'4-bis(2-amino-2-methylpropyl) piperazine. Amino group-bound polypropylene glycol, B-39-201229666 diamine, tridecyldiamine, propylenediamine, tetramethylenediamine, dibutylene, pentamethylene two on the propyl branched carbon of the molecule Amine, hexamethylenediamine, heptadecyldiamine, octadecyldiamine, diethylidene triamine, tris-ethyltetramine, tetraethylamine, pentaethylhexamine, three Methylhexamethylenediamine, N-aminoethylpiperidinium, iminodipropylamine, methylimidopropylamine, h2n(ch2ch2o)2(ch2)2nh2 on amine nitrogen a diamine, 1,5-diamino-2-methylpentane, polyethylene , isophorone diamine, 1,3-diaminodecylcyclohexane (1,3BAC), cyclohexylamino-3-aminopropane, norbornane skeleton (NBDA), A compound represented by the following formula and the like. Amine subpenta group such as alkylamine 1-amine

-40- 201229666

Η2Ν ΝΗ η2ν νη2 \^\ νη2 Further, an amino alkoxydecane can be used as the amine. The amino alkoxy decane may, for example, be a compound represented by the following formula (丨i) (R gas R38 to WU (11). In the above formula, 'R37 is an alkyl group having 1 to 6 carbon atoms or a carbon atom. An alkoxy group having 1 to 6 or a monovalent decane-derived group. The caliper 38 is an alkylene group which may contain a nitrogen atom, and R39 is an alkoxy group. 11 is an integer of 〇~3. The alkyl group having 1 to 6 carbon atoms is preferably a fluorenyl 'ethyl group and a propyl group. The alkoxy group having 1 to 6 carbon atoms represented by R37 is preferably a methoxy group 'B. The oxy group and the propoxy group are preferably a decyloxy group in the case of the monovalent decane-derived group represented by R37. Among these, a decyloxy group and an ethoxy group are more preferred. The alkyl group which may contain a nitrogen atom, and the alkyl group of the alkyl group, and the alkyl group of the carbon atom, the alkyl group of the carbon atom, the alkyl group which does not contain a nitrogen atom, and the like: The propyl group is a group containing an imide group (_nh_) on a nicotine group represented by the above-mentioned nitrogen atom-free divalent hydrocarbon group in the above-mentioned nitrogen atom-free divalent hydrocarbon group. In this case, it is better to methylene and stretch. Propyl, -C2H4NH (: 3H6_.

Tk 3 9 - The alkoxy group represented by R is preferably an alkoxy group having 1 to 6 carbon atoms, more preferably a decyloxy group or an ethoxy group. The ketone imine containing oxime obtained by the reaction of a ketone and an amino alkoxy decane can be exemplified by a compound represented by the following formula (丨2) and a structural unit represented by the following formula (13). Polycondensate, etc. (R'

I (12) 'Si (R4Vv in the above formula (12), 'R4G and R41 are each independently a monovalent hydrocarbon group in which a part or all of hydrogen atoms may be substituted. Among them, and may also be formed together with the carbon atoms to which they are respectively bonded. Ring structure: R42 is an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms; r43 is an alkylene group which may contain a nitrogen atom. R44 is an alkoxy group. v is an integer of 〇~3 R48

/ I.

_____- si-〇, I R47 (13) R45^^R46 In the above formula (13), R45 and R46 are each independently a monovalent hydrocarbon group in which a part or all of hydrogen atoms may be substituted. Among them, R45 and R46 may also form a ring structure together with the carbon atoms to which they are respectively bonded. R47 is an alkylene group which may contain a nitrogen atom. R48 is an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms. -42-201229666 The terminal of the polycondensate having the structural unit represented by the above formula (13) may be bonded to an alkyl group having a carbon number of from 1 to 6 such as a hydrogen atom, a mercapto group, an ethyl group or a propyl group; methoxy group; An alkoxy group having 1 to 6 carbon atoms such as an oxy group or a propoxy group. Among these amines, a diamine having an alicyclic structure or an aromatic ring structure is preferred. As the suitable ketimine, a compound represented by the following formula (14) can be mentioned.

R50

(14) In the above formula (14), R49 to R52 are each independently a monovalent hydrocarbon group in which a part or all of hydrogen atoms may be substituted. Among them, the ruler 49 and the ruler 5 can also form a ring structure together with the carbon atoms to which they are respectively bonded. In addition, R5! and R52 may form a ring structure together with the carbon atoms to which they are respectively bonded. R53 is a divalent hydrocarbon group which may be substituted. The monovalent hydrocarbon group represented by R to R may, for example, be a monovalent aliphatic hydrocarbon group, a monovalent alicyclic hydrocarbon group or a monovalent aromatic hydrocarbon group. The aliphatic hydrocarbon group at the valence of the valence may, for example, be an alkyl group having a carbon number of 丨2 to 2 fluorene, an alkenyl group having 2 to 20 carbon atoms, or an alkynyl group having 2 to 2 carbon atoms. The i-valent alicyclic hydrocarbon group may, for example, be a cycloalkyl group having 3 to 2 carbon atoms. For example, the aryl group having a carbon number of 6 to 2 Å can be cited. The alkyl group having 1 to 20 carbon atoms is preferably an alkyl group having 1 to 12 carbon atoms, more preferably a carbon number; and an alkyl group having 1 to 6 carbon atoms. Preferred examples thereof include a methyl group, an ethyl group, an isopropyl group, a butyl group, an isobutyl-43-201229666 group, a second butyl group, a tert-butyl group, a pentyl group, and a diterpene group. Propyl, methylbutyl, 1,1 -didecylbutyl, hexyl. The alkenyl group having 2 to 20 carbon atoms is preferably an alkenyl group having 2 to 10 carbon atoms, more preferably an alkenyl group having 2 to 6 carbon atoms. Preferable specific examples include a vinyl group, an allyl group, a butenyl group, and a hexenyl group. The alkynyl group having 2 to 20 carbon atoms is preferably an alkynyl group having 2 to 10 carbon atoms, more preferably an alkynyl group having 2 to 6 carbon atoms. A preferred specific example is an ethynyl group or a propynyl group. The cycloalkyl group having 3 to 20 carbon atoms is preferably a cycloalkyl group having 3 to 12 carbon atoms, more preferably a cycloalkyl group having 3 to 8 carbon atoms. Preferred specific examples include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a 1-decylcyclopentyl group, a 1-ethylcyclopentyl group, and a cyclohexyl group. The aryl group having 6 to 20 carbon atoms is preferably an aryl group having 6 to 14 carbon atoms. Preferable specific examples include a phenyl group, a naphthyl group, a sulfhydryl group, and a fluorenyl group. More preferably, it is a phenyl group or a 2-naphthyl group, and a particularly preferred benzoic acid group. Examples of the divalent hydrocarbon group represented by R53 include a divalent aliphatic hydrocarbon group, a divalent alicyclic hydrocarbon group, a divalent aromatic hydrocarbon group, an alkylene-cycloalkylene group, an alkylene group, and a stretching ring. Alkyl-alkylene-cycloalkylene, alkylene-arylene-extended alkyl. The divalent aliphatic hydrocarbon group may, for example, be an alkylene group having 1 to 20 carbon atoms, an extended alkenyl group having 2 to 2 carbon atoms, or an extended alkynyl group having 2 to 2 carbon atoms. The divalent alicyclic hydrocarbon group may, for example, be a cycloalkylene group having 3 to 20 carbon atoms or a stretched cycloalkenyl group having 3 to 2 carbon atoms. The aromatic hydrocarbon group of 2 1 ja, for example, an aryl group having 6 to 2 carbon atoms may be mentioned. In the case of the above-mentioned alkyl group having 1 to 2 carbon atoms, the alkylene group having 1 to 12 carbon atoms is more preferably an alkyl group having 1 to 6 carbon atoms. Preferred specific examples include a methylene group, an ethyl group, a methyl group, a trimethylene group, a tetramethylene group, a pentamethylene group, and a hexamethylene group. In the case of the above-mentioned cycloalkylene group having 3 to 20 carbon atoms, a ring-shaped alkyl group having a carbon number of 3 to 12 is more preferably a ring-forming group having 3 to 6 carbon atoms. Preferred examples of the compound include a cyclopropyl group, a cyclopentene group, a cyclopentylene group, and a cyclohexylene group. Further, the ring-like base group having a carbon number of 3 to 2 Å is preferably a ring-opening group having 3 to 12 carbon atoms, more preferably a ring-opening alkenyl group having 3 to 6 carbon atoms. In a preferred specific example, a cyclobutenyl group, a cyclopentenyl group, and a cyclohexene group can be listed. The divalent aromatic hydrocarbon group having 6 to 18 carbon atoms may, for example, be an extended aryl group such as a stretched phenyl group, a stretched biphenyl group, an extended naphthyl group, a phenanthrenyl group or a fluorenyl group. In the case of a stretching base-extension ring base-extension base, it is preferably an alkyl group having 1 to 6 carbon atoms and a ring-opening alkyl group having 3 to 12 carbon atoms and having a carbon number of 6 The base is particularly preferably an alkylene group having 1 to 6 carbon atoms and an alkyl group having 3 to 6 carbon atoms and an alkylene group having 1 to 6 carbon atoms. In the case of a cycloalkyl-alkylene group, a cycloalkyl group is preferably a cycloalkyl group having a carbon number of from 3 to 2, and a carbon atom number of from 1 to 6 and a carbon atom number of from 3 to 丨. 2 is a cycloalkyl group, particularly preferably a cycloalkyl group having 3 to 6 carbon atoms - an alkyl group having a carbon number of 丨 1-6 and a ring-opening alkyl group having 3 to 6 carbon atoms. In the above-mentioned stretching group-extended aryl group-extension group, it is preferably a stretching group having a carbon number of 1 to 6 and an aryl group having 6 to 14 carbon atoms and having 1 to 6 carbon atoms. The base 'extra is a C 1 to 6 alkyl group-carbon number 6 to --45- 201229666 aryl group - an alkyl group having 1 to 6 carbon atoms. The method for producing a ketimine is particularly limited, and can be obtained, for example, by subjecting a ketone and an amine to a dehydration reaction under a sub heating condition at room temperature. As far as the reaction temperature is concerned, it is 20C~15 (TC, more preferably 5〇t:~11 (rc.'y in terms of reaction time, private society &amp; qt is preferably 2 hours). ～24小时, more preferably 2 hours to 5 hours. The ketimine can be obtained from commercially available products, and examples thereof include H 3 and H-30 (above, manufactured by Mitsubishi Chemical Corporation). The ketimine compound can be used alone or in combination. The use ratio of the ketimine compound in the radiation-sensitive resin composition is preferably 1 part by mass relative to the [A] copolymer by 1 part by mass. More preferably, it is 0.5 parts by mass to 5 parts by mass, and by making the content ratio of the ketimine compound within the above specific range, the radiation can be linearly known, and the product has more excellent storage stability and [Capping-type isocyanate compound] The blocked polyisocyanate compound is a temperature-inert substance which is formed by reacting an isocyanate group with a compound containing a reactive nitrogen (blocking agent), and has a blocking agent once heated. Resolving and regenerating isocyanate groups a material of a nature. By making the radiation-sensitive resin composition contain a blocked polyisocyanate, which can be used as an effective crosslinking agent, isocyanate-base crosslinking reaction can make the radiation-sensitive resin composition The product has a high level of storage stability and low-temperature firing. The blocked polyisocyanate compound can be a reaction of a polyisocyanate derived from an aliphatic or alicyclic diisocyanate and a compound having an active hydrogen (blocking agent) by a known reaction. -46- 201229666 For the diisocyanate δ, for example, tetradecyl monoisocyanate, pentane diisocyanate, hexamethylene diisocyanate (HDI), 2,2,4-tridecyl group can be cited. -1,6-diisocyanate hexane, 2,4,4-trimethyl-1,6-diisocyanate hexane, lysine diisocyanate, isophorone diisocyanate (IPDI), 1,3- Bis(isocyanatemethyl)cyclohexane, 4,4-dicyclohexylmethane diisocyanate, norbornene diisocyanate, toluene diisocyanate, 4,4,-diphenylmethane diisocyanate, hydrazine ,5·naphthalene diisocyanate, triterpenoid diisocyanate 'Dioxophenylisocyanate, 1,4-tetradecyl diisocyanate, 1,5-pentamethylene diisocyanate, hydrazine, hexamethylene diisocyanate, 3-isocyanate methyl _3,5, 5-tridecylcyclohexyl diisocyanate, etc. The commercially available product may, for example, be formed by blocking the isocyanate group with hydrazine of mercaptoethyl ketone, and examples thereof include DURANATE TPA-B80E and TPA. -B80X, E402-B80T, MF-B60XN, MF-B60X, MF-B80M (above, manufactured by Asahi Kasei Chemicals Co., Ltd.); For the formation of an isocyanate group by an active methylene group, a DURANATE MF- K60X (produced by Asahi Kasei Kogyo Co., Ltd.); For the end of the isocyanate compound having a (meth) acrylonitrile group, Karenz MOI-BP and Karenz MOI-BM (above 'Showa Denko') can be cited. Among these, DURANATE E4G2_B8 0T and MF-K60X exhibit high flexibility, and it is preferable to form a mixing system with other varieties so that the hardness can be freely controlled. -47- 201229666 The polyisocyanate derived from a diisocyanate may, for example, be an isocyanurate type polyisocyanate, a biuret type polyisocyanate, an amino phthalate type polyisocyanate or a urea phthalate type. Isocyanate, etc. From the viewpoint of curability, the isocyanurate type polyisocyanate is preferred. Examples of the terminal blocking agent include, for example, an alcohol compound, a compound, an active methylene compound, a thiol compound, and an acid hydrazine. An amine compound, an acid imine compound, and a β-sodium compound. The ratio of the α-based compound, the urea compound, the compound, the amine compound, the imine compound, the pyridine compound, and the like. Examples of the alcohol compound include methanol, ethanol, propanol, butanol, 2-ethylhexanol, thiol cellosolve, butyl cellosolve, methyl carbitol, benzyl alcohol, cyclohexanol, and the like. Examples of the compound to be used include, for example, benzophenone, mercaptobenzene, ethylphenol, butylphenol, nonylphenol, dinonylphenol, styrenated phenol, hydroxybenzoic acid ester, and the like; Examples of the methylene-based compound include dimethyl malonate, diethyl malonate, ethyl acetoacetate, ethyl acetate, ethyl acetate, and the like; For example, butyl mercaptan, dodecyl mercaptan, and the like; and examples of the acid amide compound include, for example, acetanilide, decylamine, ε-caprolactam, and δ-valeroguanamine. Γ-butylidene or the like; and examples of the acid quinone imine compound include amber imine, maleimide, and the like; -48-201229666 For the imidazole compound, for example, imidazole, 2_ For the pyrazole compound, for example, 3-methylpyrazole 3,5 can be cited. - Diterpenoid η is more than spit, 3,5-ethyl. More than saliva;

Examples of the urea-based compound include urea, sulfur-extension ethyl urea, and the like; μ; L, for the hydrazine-based compound, for example, formaldehyde oxime, ethyl acetate, acetone oxime, methyl ethyl ketone oxime, and cyclohexane Examples of the amine compound include, for example, dipyridylamine and °carbazole; and the imine compound may, for example, be an imine or imine; or a pyridyl compound; In other words, for example, 2_hydroxypyridin-2-light quinone may be mentioned. The blocked polyisocyanate compound can be used alone or in combination. The content ratio of the blocked polyisocyanate compound in the 6-ray radiation-sensitive linear resin composition is preferably 1 part by mass to 40 parts by mass, more preferably 3 mass, based on 1 〇〇 mass of the [A] copolymer. By making the content of the blocked polyisocyanate compound in the above ratio, the radiation-sensitive resin composition can have a higher level of stability and low-temperature firing [imidazole ring-containing compound]. For the imidazole ring-containing compound, at least one selected from the group consisting of compounds represented by the following (15) can be used. Methyl sputum, urea, aldoxime Aniline Polyethylene bite, two kinds of sour glutinous rice, part. Range Storage Statement -49-

201229666 A5 /R54

A6 In the above formula (15), each of A5, A6, A7 and R54 or a straight or cyclic group of ketone having 1 to 20 carbon atoms which may have a substituent. Further, A 6 and A 7 may be bonded to each other. The hydrocarbon group having 1 or a branched or cyclic group represented by A5, A6, A7 and R54 may, for example, be a mercapto group, an ethyl group, a n-propyl group or a different group. Propyl, n-butyl t-butyl, tert-butyl, n-pentyl, n-hexyl, yl, n-decyl, n-decyl, n-decyl, n-tridecyl, n-tetradecyl, N-pentadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl, an alkyl group having a dimer number of 1 to 20; a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group or the like a cycloalkyl group; a phenyl group, a fluorenylphenyl group, a benzyl group, a methylbenzyl group, a tricakisyl group, a naphthyl group, a fluorenyl group, a C 2 alkyl group having a carbon number of 6 to 20, a tricyclodecyl group, and a tetra Cyclododecane, methyladamantyl, ethyladamantyl, butyl gold having 6 to 20 butyl groups, and the like. The above hydrocarbon group may be substituted, and the substituent '' can be exemplified by a hydroxyl group; and independently a hydrogen original chain or a branched chain form a ring. -20 linear, benzyl, isobutyl, n-heptyl, n-octyl, n-hexadecyl, n-decene, etc. carbon atoms 3 to 20 f phenyl, 2, 4 , 6-aryl; base, adamantyl group, such as a carbon atom, a specific example -50-201229666 carboxyl group; a mercapto group, a 1-ethylidene group, a 2-hydroxyethyl group, a 1-hydroxypropyl group a 2-hydroxypropyl group, a 3-hydroxypropyl group, a 1-hydroxybutyl group, a 2-hydroxybutyl group, a 3-hydroxybutyl group, a 4-hydroxybutyl group, or the like, a hydroxyalkyl group having a carbon number of 4; An alkane having 1 to 4 carbon atoms such as ethoxy, n-propoxy, isopropoxy, n-butoxy, 2-methylpropoxy, 1-decylpropoxy or tert-butoxy Alkyl; cyano; 2-cyanoethyl, 3-cyanopropyl, 4-cyanobutyl, etc.; cyano group having 2 to 5 carbon atoms; oxime oxycarbonyl, ethoxy a oxyalkyl group having 2 to 5 carbon atoms such as a carbonyl group or a third butoxycarbonyl group; a carbon atom having 3 to 6 carbon atoms such as a methoxycarbonylmethoxy group, an ethoxycarbonylmethoxy group or a third butoxycarbonyloxy group; Alkoxycarbonylalkoxy; halogen atom such as fluorine or gas; fluoromethyl, trifluoromethyl, pentafluoroethyl Isofluoroalkyl and the like. The ring formed by the above-mentioned A6 and A7 being bonded to each other is preferably an aromatic ring or a saturated or unsaturated nitrogen-containing hetero ring having 2 to 20 carbon atoms. The ring formed when A and A are connected to each other is a benzene ring. Meter. The compound of the ring can be referred to as a compound represented by the following formula (16). RS5 R56

(16) R58 -51- 201229666 In the above formula (6), R54 and A5 have the same meanings as the above formula (5). Each of R55 to R58 is independently a linear, branched or cyclic hydrocarbon group having a carbon number which may have a substituent. Further, the hydrocarbon group represented by R55 to R58 may be the same as the hydrocarbon group of the above formula (15). In the case of the compound of 3 imidazole, 2-phenylbiimidazole and 2-methylmazole '2-methylbiimivir are preferred. The imidazole ring-containing compound can be used singly or in combination of two or more. The content of the compound containing the ring is as follows. The amount of the 〇 〇 mass portion relative to the [Α] copolymer is preferably 〇 · 1 part by mass to 10 parts by mass, more preferably. The content of the compound of the ring is: 2f parts to 5 parts by volume. The radiation-sensitive linear tree can be fired at a low temperature in the above specific garden. ^The product has a higher level of storage stability and [cage compound] The term "cage compound" in the present specification means a tetraterpenoid compound of the following formula (17) = or formula (10) The compound represented by the two cytotoxic acids is a compound formed by the t compound or the salivary compound.

OH R61 R66 (17)

X (18)201229666

COOH

COOH In the above formula (17), hydrazine is a single bond, a methylene group or an alkylene group having a carbon number of 2 to 6 and each of R is independently a hydrogen atom or an alkyl group having a carbon number of 丨 to 丨2, which may have a substitution. A phenyl group, a halogen atom or a hospitaloxy group having 1 to 12 carbon atoms. In the above formula (18), R67 is an alkyl group having a carbon number of 丨12 to 12, an alkoxy group having 1 to 12 carbon atoms, a nitro group or a hydroxyl group. The tetraphenol compound represented by the above formula (17) is preferably a compound represented by the above formula (17-1). By forming the tetraphenol compound represented by the above formula (17_丨), storage stability and low-temperature hardening can be further improved.

And X and R59 to R66 have the same meanings as in the above formula (17) in the above formula (17_1). -53- 201229666 For the four test compounds, there is no particular limitation on the σ I β 1ΝΦ compound. The above formula (1)-1) represents the chemical formula, which is, for example, 1,1,2,2 - hydrazine (4-hydroxybenyl)ethane, 1,1,2,2-industrial, (3-methyl-4-hydroxyphenyl)ethane, 1,1,2,2-indole ( 3,5-dimercapto-4-hydroxy floc, 7 w lean w ^ base) ethane, 1,1,2,2-indole (3- gas-4-hydroxyl)ethane, 1 1,1,2,2_肆ping (3,5_-indol-4-hydroxyphenyl)ethane, 1,1,2,2-indole (3-bromo-4-hydroxy which is poor 1 w. w „ Basic group) ethane, 1,1,2,2-anthracene (3,5-dibromo-based basic group), Ethylene, 1 〖 7 , , 丨, 2, 2 • 肆 (夂 butyl -4- -hydroxyphenyl)ethane, 1,1,2,2-indole (3,5_ _ first! ! . ^ - second butyl-4-hydroxyphenyl)ethane, 1,1,2,2 - 肆 (3-fluoro-4-hydroxy* 芏, , ^ ^ soil base) ethane, 1,1,2,2-anthracene (3,5-difluoro-4-hydroxyphenyl)ethane,虱1 , ^ Λ ^ ,, '2_肆(3_methoxy-4-hydroxyphenyl)ethyl pit, 1,1,2,2-anthracene (3,5-dimethyl gi ^ methoxyl) _4-hydroxyphenyl) Alkane, 1,1,2,2-砰U-chloro-5-methyl-4- via a smile, w Α 4 ,, Α ^ basic group) ethane, 1,1,2,2-肆(3-Bromo-5-methyl-4-mercaptophenyl)ethane, which is depleted of 1, 1, 2, 2-indole (3-methoxy-5-mercapto-4-hydroxyl) ethane , 1,1,2,2_肆( &amp; w ^ 1 , ping (t-butyl-5-methyl-4-hydroxyphenyl)ethane, 1,1,2,2-indole (3-翕ς 4 β 肆(3_1 gas _5-side _4-hydroxyphenyl)ethane, 1,1,2,2- ^风-5-benyl-4_ via a smile, benzene β base Ethane, U'2,2-肆[(4-hydroxy-3-3) base]ethane, lsl 3 3·肆肆Μ田甘μ gas ^ &amp; base) propane, 1,1,3 , 3-By-methyl 4-hydroxyphenyl) hydroxybenzine) propane, U,3,3-indole (3,5-dimethyl_4_operated base) propane, 1,1,3 3 Mf3 , , , , 3_肆(3-mur-4-hydroxyphenyl)propane, 夂 肆 (3,5-digas _4_ hydroxymei • 4, phenyl) propane: 1: ,1,3,3-肆(3-bromo, U,3,3.肆二漠·四七基phenyl)propane burning ^ ^^3,3^3Τ^,3^4(3^ { 9j — Methoxy-4·Zhengqi is poor, work 1,1,3,3-肆 (3_third-but | η... package basic Propane, _hydroxyphenyl)propane, 1,1,3,3-indole (3,5·-54· 201229666 di-tert-butyl-4-hydroxyphenyl)propane, 七七心肆(一)-hydroxybenzene Butane, 1,1,4,4-anthracene (3-methyl-4-hydroxyphenyl)butane, ^4,4-anthracene (3,5-dimethyl-4-hydroxyphenyl) Butane, ^, 夂 heart 肆 (1)-chloro-4-hydroxyphenyl) butane, 1,1,4,4-anthracene (3,5-dichloro-4-hydroxyphenyl)butane, ^4, 4-肆(3-oxo-4-hydroxyphenyl)butane, 丨^^肆(1). Dimethoxy- 4-hydroxyphenyl)butane, ^, seven anal sputum (3_ desert · 4 hydroxyphenyl) butane: 1,1,4,4-anthracene (3,5-dibromo 4-hydroxyphenyl)butane, anthracene, 4,4•indole (3_t-butyl-4-hydroxyphenyl)butane, ^, 宄 肆^: di-tert-butyl-hydroxybenzene Butane, 肆(4-carboxyphenyl)ethane, 肆(4-carboxyphenyl)ethane tetramethyl ester, 肆(4-carboxyphenyl)ethane tetraethyl ester, 肆carboxyphenyl Tetra-n-propyl ethane, tetrakis(4-carboxyphenyl)ethane tetradecyl ester, ruthenium (3,5-diindenyl-4-destrophenyl)ethane, ruthenium (3,5_ Dimethyl-4(nonylphenyl)ethylidene tetraacetate vinegar, hydrazine (3,5-dimethyl-4-yl)phenylethyl ethene tetraethyl vinegar, hydrazine (3,5-dimethyl Base_4_ cytosylphenyl) Ethylene tetra-n-propyl vinegar, ruthenium (3,5-dimethyl-4-ylcarboxyphenyl)ethane tetra-n- ate, ruthenium (4) carboxyphenyl) ethane tetrasodium Salt, cerium (4_carboxyphenyl)ethane tetrapotassium salt, cerium (3_carboxyphenyl)ethane, hydrazine (3-hydrazolyl) ethane tetramethyl vinegar, hydrazine (3- slow-base) 4,5-Dimethylphenyl) Ethylene, bismuth (3. decyl phenyl), Ethylene, tetraethyl, (3· benzylidene phenyl) 乙院四正propyl 酉 肆, 肆 (3-aminophenyl) Ethylene four-base vinegar, 肆 (3-carboxy-4,5-dimethylphenyl) B Alkane, anthracene (3·buxos-4,5-dimethylphenyl)ethenetetramethyl vinegar, hydrazine (3, yl·4,5·dimethylphenyl)ethyl=tetraethyl vinegar, hydrazine (3_Very _4,5-dimethylphenyl) ethene tetra-n-propyl': hydrazine (3,5-dimethyl-4-ylcarboxyphenyl) ethane tetrabenzyl ester, hydrazine (3 _Carboxylphenyl) Siyuan four sodium salt, bismuth (3_ slow phenyl) B hospital tetrapotassium salt and the like. In this case, use the imidazole compound of ^,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,, ::: is more excellent' and is better when it is heated. In the case of the compound represented by the above formula (2), there is a special limitation, for example, an acid, 5-hydroxyphthalic acid ^ Τ 5-methylphthalic acid, 5-decyloxy- ortho-carboxylic acid, 4-stone Xiaomou Hao岔φ ^ ^ self-violent ortho-dicarboxylic acid, 4-hydroxyphthalic acid, 4_ V-based Formic acid, 4_methythyl phthalic acid, etc. Among them, preferred is 5-nitro-o-zinomethyl k, 5-hydroxyphthalic acid. Since the miso compound knows that the above tetraphenolic compound or dicarboxylic acid compound forms a stable 籀a&amp; human, ^. t 〇 compound' thus increases the yarn of the radiation-sensitive resin composition at room temperature + Storage stability. Further, since the reactivity of the imidazolyl δ substance with the epoxy group is excellent, it is suitable for low-temperature hardening of 200 C or less. The glutinous rice is singular and s ' can be enumerated in the above-mentioned 0 m. The ringing. The compound represented by the above formula (15) described in the item of the object. The imidazole compound which is a group can be exemplified by, for example, imidazole, 2-methyl D-mazole, 2-ethylimidazole, 9 s igan, 2-isopropylimidazole. Sit, 2 - n-propyl i-a sitting, 2-burning &amp; _1H_ 2_heptacyl-1 - 唾 saliva, 1,2-dimercapto 2, 2_ethyl · 4 _ methyl ° m . Sitting, 2-phenyl-1 Η·Mimi, 4_methyl_2_benzene \1Η-flavor. Sitting, 2_phenyl_4_methyl taste. Sitting, l base 2_methylimidazole, ^ cyanoethyl-2-mercaptoimidazole, @@ 7 * ^ 土下生, 1._cyanoethyl·2-ethyl_4_曱Imidazole 1-disorganoethyl-2-11, Jt*- :Η· | , , ^ alkylimidazole, 1-cyanoethyl-2-phenylimidazole

1 murine ethyl-2-ethyl- 4· ® ·«· ik I soil 4-methyl-salt salicylate, 丨_cyanoethane-2 - eleven-burning microphone 0 sitting pen _ 瞒 瞒 本 本 本, 1-cyanoethyl-2-phenylimidazole-56- 201229666 trimellitate, 2,4-diamino-6-[2'-mercaptoimidazolyl- (1,)]-Ethyl_s_dimorphine, 2,4-amino--6-(2'-11-alkyl-based 0-square-s---ethyl-s-triple, 2,4 -diamino-6-[2'-ethyl-4.imidinyl-(1')]-ethyl-s-tripty, 2,4-diamino-6-[2'-methyl Imidazolyl-(丨')]-ethyl-s-triterpene isocyanurate adduct, 2-propenyl-flavored alpha-sodium isocyanate adduct, 2-mercapto-sodium-like isocyanuric acid Adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxyindenidazole, oxime-cyanoethyl-2-phenylene-4,5 _Bis(2-cyanoethoxy)methylimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 1-benzyl-2-phenylimidazolium hydrochloride, hydrazine Benzyl-2-phenylimidazole trimellitate and the like. Preferably, the imidazole compound has one or more substituents having from 1 to 6 carbon atoms. Since the imidazole compound is stably caged, it does not adversely affect the storage stability of the radiation sensitive resin composition, and has a small steric hindrance and excellent reactivity, and exhibits low-temperature curability at the time of cage disintegration. The imidazole compound having one or more substituents having 1 to 6 carbon atoms can be, for example, an imidazole compound having a substituent having one carbon atom number such as 2-mercaptoimidazole or 2-phenylimidazole; An imidazole compound having a carbon atom number of two substituents such as 6-methylimidazole, L2-dimethylimidazole, or 2phenyl-4-methyl-5-hydroxyindenidazole. There is no particular limitation on the method of cultivating the above imidazole compound by using the above-mentioned tetra-destination compound or the second-order nucleus &amp;# human carboxylic acid compound, and for example, it is exemplified in Japanese Patent Publication No. 7 (7) The method described, etc. -57- 201229666 In these σ-m β sit-in stability and sclerosis-promoting -5 - via 曱基米米&lt;7 sit. In view of the fact that the composition has a high level of storage, it is preferred that the 2-phenyl-4-methyl group is a compound of the above-mentioned imi-containing compound. In the case of the 3* sitting J, the compound represented by the above formula (16) and the like are described. Just like the taste. Sitting in combination with % t 1 and § can be exemplified by, for example, 2-indolyl half, &quot;linked imidazole, 5_曱... A violent oxazole _, methylbiimidazole, 6-mercaptoimidazole, 7-linked Imidazole, 2-methyl-6-indole _ ke k ^ T-based? ^ carbazole, 2-methyl-6-methylbiimidazole, 2-indolyl-5-mercaptoimidazole ^ 2 - Indole-5-methyl-linked saliva, 2_pr its methyl-linked glutinous rice, 2-methyl-&lt;^ soil~6~methyl_6-ethylbiimidazole, 2_ethyl azole, 2 - mercapto_5_ethylbiimidazole and the like. In this case, the Union has not been able to make a high level of storage hardening promotion from the composition. It is better to use 2-mercaptoimidazole, 2 methyl hydrazine, 2 -Methyl _5_methyl oxime. Methyl + the above biimidazole compound preferably has more than one carbon atom. Secondly, the tyrosine compound is stably caged, so that it does not ring: Erlic = mr stability... It can exhibit low temperature hardenability. The biimidazole compound having one or more substituents having 1 to 6 carbon atoms, and examples of the biimidazole compound having a substituent of one carbon atom, such as oxazole, may be exemplified. Sit compound; 2 • methyl _6_methyl carbamide, methyl-5-methyl odor. A compound such as a flavonoid having a substituent of two carbon atoms and having a number of 6 is used. The cage compound may be used singly or in combination of two or more. The content ratio of the -58-201229666 cage compound is preferably 0.1 parts by mass to 10 parts by mass, more preferably 0.5 parts by mass to 5 parts by mass, per 100 parts by mass of the [A] copolymer. The radiation-sensitive resin composition can have a higher level of storage stability and low-temperature firing by making the content ratio of the cage compound within the above specific range. &lt;Other optional components&gt; The radiation sensitive resin composition may be in a range that does not impair the effects of the present invention, if necessary, in addition to the above [A] copolymer, [B] diazide compound, and [c] hardener. It contains optional components such as a surfactant, an adhesion aid, a heat resistance enhancer, and a heat-sensitive acid generator. These optional components may be used singly or in combination of two or more. Hereinafter, various components will be described in detail. [Interacting Agent] The interface active agent is used to further improve the film formability of the radiation-sensitive resin composition. As the surfactant, for example, a fluorine-based surfactant, a polyoxymethylene-based surfactant, and other surfactants can be listed. In the case of a surfactant other than the surfactant, a compound having a fluoroalkyl group and/or a fluoroalkyl group at a terminal portion, a main chain and a side chain is preferred, and f 1 can be listed. Qa, for example, 1,1,2,2-tetrafluoro.n-octyl (u,2,2-w-propyl)ether, prepared, 1,2,2-tetrafluoro-n-octyl (n-hexyl) ether, six Ethylene (1,1,2,2,3 3-*^ _ ta, A, murine-n-pentyl) ether, octaethylene glycol di(mh fluoro-n-butyl) ether, hydrazine-sa, Propyl alcohol - (1,1,2,2,3,3-hexafluoro-n-pentyl)_-(,丨,2,2-tetra-n-butyl)ether, perfluoro-n-nine Yellow acid, 1 〇. 1 ^ , , , , 2,3,3-hexafluoro-n-decane, 1,1,2,2,8,8,9,9,10,10, -59- 201229666 ten gas - positive twelve burning And sodium fluoroalkyl benzoate, sodium fluorocarbonate, sodium fluoroalkylcarboxylate, diglycerol tetrakis(fluoroalkylpolyoxyethylene ether), fluoroalkyl ammonium iodide, fluoroalkyl betaine, Other fluoroalkyl polyoxyethylene ethers, perfluoroalkyl polyoxyethylenes, perfluoroalkyl alkoxides, fluoroalkyl carboxylates, and the like. Examples of commercially available products of the fluorine-based surfactant include BM-1000, BM-1100 (above, BM CHEMIE), MEGAFAC F142D, MEGAFAC F172, MEGAFAC F173 'MEGAFAC F183, MEGAFAC F178, MEGAFAC F191, MEGAFAC. F471, MEGAFAC F476 (above, Otsuka Ink Chemical Industry Co., Ltd.), Fluorad FC-170C, Fluorad FC-171, Fluorad FC-430, Fluorad FC-431 (above, Sumitomo 3M), surflon S-112, surflon S -113, surflon S-131, surflon S-141, surflon S-145, surflon S-3 82, surflon SC-101, surflon SC-102 'surflon SC-103, surflon SC-104 'surflon SC-105 'surflon SC-106 (above, Asahi Glass Co., Ltd.), EftopEF301, EftopEF303, Eftop EF 352 (above, New Akita Chemical Co., Ltd.), FTERGENT FT-100, FTERGENT FT-110, FTERGENT FT-140A, FTERGENT FT-150, FTERGENT FT-250 , FTERGENT FT-251, FTERGENT FT-300, FTERGENT FT-310, FTERGENT FT-400S, FTERGENT FTX-218, FTERGENT FTX-251 (above, NEOS).

For a commercially available product of a polyoxyxene-based surfactant, for example, TORAY SILICONE DC3PA, TORAY SILICONE DC7PA, TORAY SILICONE SH11PA, TORAY SILICONE SH21PA 'TORAY SILICONE SH28PA 'TORAY SILICONE -60- 201229666

SH29PA, TORAY SILICONE SH30PA, TORAY SILICONE SH-190, TORAY SILICONE SH-193, TORAY SILICONE SZ-6032, TORAY SILICONE SF-8428, TORAY SILICONE DC-57, TORAY SILICONE DC-190 (above, TORAY · DOW CORNING · SILICONE Company), TSF-4440, TSF-4300, TSF-4445, TSF-4446, TSF-4460, TSF-4452 (above, GE Toshiba Silicones), organic alkane polymer KP341 (Shin-Etsu Chemical Industries, Inc.) and the like. Examples of other surfactants include polyoxyethylene lauryl ether such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, and polyoxyethylene oleyl ether; and polyoxyethylene-n-octane Polyphenylene oxide aryl ether, polyoxyethylene-n-decylphenyl phthalate, etc.; polyoxyethylene dialkyl ester such as polyoxyethylene dilaurate vinegar, polyoxyethylene distearate, etc. Nonionic surfactant, (meth)acrylic copolymer P〇LYFl〇w No. 57, POLYFLOW No. 95 (above, Kyoeisha Chemical Co., Ltd.) and the like. The amount of the surfactant to be used is preferably 1.0 part by mass or less, more preferably 〇·7 part by mass or less, based on 1 part by mass of the [A] copolymer. If the amount of the surfactant used exceeds 丨.〇 by mass, film unevenness is likely to occur. '[Adhesive Aid] The adhesion aid is used to further improve the adhesion between the obtained pattern and the substrate. The adhesive auxiliary agent is preferably a functional decane coupling agent having a reactive functional group such as a carboxyl group, a methacryloyl group, a vinyl group, an isocyanate group or an oxiranyl group, and examples thereof include trimethoxy group. Formyl benzoic acid, γ-methacryloxypropyltrimethoxy-61 - 201229666 Shi Xi, Ethylene, Ethylene, Ethyl, Ethyl, Ethylene, Ethyl Cyanic acid propyl triethoxy decane, γ-glycidoxypropyltrimethoxy sulphide 'β-(3,4-epoxycyclohexyl)ethyltrimethoxy sulphur and the like. The amount of the adhesion aid to be used is preferably 20 parts by mass or less, and more preferably 15 parts by mass or less based on 1 part by mass of the [Α] copolymer. When the amount of the adhesion aid used exceeds 20 parts by mass, development residue is likely to occur [heat resistance improving agent] Examples of the heat resistance improving agent include *Ν((alkoxymethyl)glycolide compound, N_ (homoyloxymethyl) trimeric amine compound and the like. As the N-(alkoxyindenyl) glycoluril compound, for example, N'N'N, N•tetrakis(methoxymethyl)glycoluril, N, N, N, N, · IV can be cited. Ethoxymethyl)glycoluril, n,n,n',n,_tetra(n-propoxymethyl)glycoluril, Ν'Ν, Ν, N _tetrakis(isopropoxymethyl) glycoluril , N, N, N,, N, _ tetra (n-butoxy: yl) glycoluril, N, N, N, N,. tetra (t-butoxy fluorenyl) gland and the like. In the right! Of the ^(alkoxymethyl)glycoluric compounds, preferably N,N,N,,N,-tetrakis(methoxymethyl)glycolil. As the N-(alkoxymethyl) melamine compound, for example, N'n, N', n', n&quot;, n'4(^^&amp;)^u, n, n, N^ can be cited. N'N,N-hexa(ethoxymethyl)melamine, N,N,N,,N,,N,,,N _=(n-propoxymethyl)melamine, N'N,N,, N,,N,,,N,,-A(isopropyllactylmethyl)melamine, team; ^,,;^,;^,,,&gt;1,,-hexa(n-butoxycarbonyl) Melamine, N, N, N, N, N,, N,, -hexa(t-butoxymethyl)-melamine, and the like. Among the *N_(alkoxymethyl)melamine compounds, preferred are N,N,N,,N',N,',N,'-hexa(methoxymethyl)melamine-62-201229666. For the commercially available product, for example, NIKALAC N-2702, NIKALAC MW-30M (above, Sanwa Chemical Co., Ltd.), and the like can be cited. The amount of use of the heat resistance improving agent is preferably 50 parts by mass or less, more preferably 3 parts by mass or less based on 100 parts by mass of the [A] copolymer. If the blending amount of the heat resistance improving agent exceeds 5 Å by mass, the sensitivity may be lowered and the pattern shape may be deteriorated. [Thermal acid generator] The heat-sensitive acid generator is defined as a compound capable of releasing an acidic active material which acts as a catalyst when the [A] copolymer is hardened by heating. By using such a heat-sensitive acid generator, it is possible to promote the hardening reaction of the [A] copolymer in the heating step after development of the radiation-sensitive composition to form a cured film excellent in surface hardness and heat resistance. The heat-sensitive acid generator contains an ionic compound and a nonionic compound. In the case of an ionic compound, it is preferred that it does not contain heavy metals or dentate ions. Examples of the ionic heat-sensitive acid generator include triphenyl shovel, 1-dimethylthionaphthalene, 1-dimethylthio-4-hydroxynaphthalene, and 丄_dimercaptosulfur-4,7-. Dihydroxynaphthalene, 4-hydroxyphenyldimethylhydrazine, benzyl-4-hydroxyphenylhydrazinium, 2-mercaptobenzyl-4-hydroxyphenylmethylnickel, 2-mercaptopurinyl-4 B-based basic methyl sparse, 2-mercapto-based 4-phenylene phenyloxyphenyl sulfhydryl, their methylated acid salt, trifluoromethyl acid salt, camphor sulfonate, Toluene benzene sulfonate, hexafluorophosphate, and the like. In addition, as a commercially available product of a sulfhydryl salt, for example, SI-60, SI-80, SI-10〇, SI-11〇, SI-145, SI-15〇, SI-80L, SI- can be cited. 1〇〇L, SI-11〇l, SI-145L, SI-150L, SI-160L, SI-180L (above, Sanxin Chemical Industry Co., Ltd.). -63-201229666 The nonionic heat-sensitive acid generator may, for example, be a halogen-containing compound, a diazonium-sintering compound, an anthraquinone compound, a rhein vinegar compound, a carboxylate compound, a phosphate compound, or a sulfone sulfonium. An amine compound, a quinone trisalt compound or the like. The halogen-containing compound may, for example, be an alkyl group-containing hydrocarbon compound or a haloalkyl group-containing heterocyclic compound. Preferred examples of the halogen-containing compound include 1,1-bis(4-chlorophenyl)-2,2,2-trisethane and 2-phenyl-4,6-bis(trichloroanthracene). Base)-s-three tillage, 2-naphthyl-4,6-bis(trismethyl)-s-three clocks. Examples of the diazonium compound include bis(trifluoromethylsulfonyl)diazomethane, bis(cyclohexylsulfonyl)diazononane, and bis(phenylsulfonyl)diazomethane. , bis(p-tolylsulfonyl)diazononane, bis(2,4-xylsulfonyl)diazononane, bis(p-phenylsulfonyl)diazomethane,nonylsulfonium Base-p-phenylenesulfonyl diazomethane, cyclohexylsulfonyl (1,1-dimethylethylsulfonyl)diazononane, bis(1,1-dimethylethylsulfonyl) Diazomethane, phenylsulfonyl (phenylhydrazine) diazonium, and the like. The sulfone compound may, for example, be a β-ketosulfone compound, a β-sulfonylsulfone compound or a diaryldifluorene compound. As a preferable sulfone compound, 4-trityl hydrazine methyl sulfone, 2,4,6-triphenyl phenyl fluorenyl hydrazine, bis(phenylsulfonyl) decane, 4-chlorophenyl-4-mercaptophenyl di hard compound. Examples of the acid-reducing compound include, for example, a sulfonic acid sulfonate, a halogen-based acid-reactive acid S, an aryl acid vinegar, and an imido acid S. Preferred sulfonate compounds include benzoin p-toluenesulfonate, pyrogallate trisulphonate, and nitrobenzyl-9,10-diethoxyindole-2-sulfonate. -64 - 201229666, 2,6-di-diylbenzyl benzoate. The commercially available product of the imido lactone can be, for example, PAI-101, ΡΑΙ-1〇6 (above, Midori Kagaku Co., Ltd.), CGI-1311 (Ciba Speciality Chemicals Co., Ltd.), or the like. The carboxylic acid ester compound may, for example, be a carboxylic acid o-nitrophenyl ester or the like. In the case of the alkali quinone imine compound, for example, N-(tri-methyl-methyl-purine acid-oxyl) can be used as a succinic acid imide (trade name "SI-105", Midori Kagaku Co., Ltd.), N-(樟脑醯) Oxygen) boporil imine (trade name "sj _丨〇6", Midori Kagaku), N-(4-mercaptophenylsulfonyloxy) amber imine (trade name "SI-101" 'Midori Kagaku Co., Ltd.), N-(2-trifluoromethylphenyl sulfenyloxy) amber quinone imine, N-(4-fluorophenylphosphoniumoxy) amber quinone imine, N-(trifluoro Mercaptosulfonyloxy) phthalimide, N-(camphoric oxy) phthalic acid imine, n-(2-trifluoromethylphenylsulfonyloxy) ortho-benzene Dimethyleneimine, N-(2-fluorophenylsulfonyloxy) phthalimide, N-(trifluoromethylsulfonyloxy)diphenylmaleimide (trade name) "PI_105", Midori Kagaku Company), N-(camphor sulphate) diphenylmaleimide, 4-nonylphenylsulfonyloxy)diphenylmaleimide, N -(2-trifluoromethylphenylsulfonyloxy)diphenylmaleimide, N-(4-fluorophenyl fluorenyloxy) Phenylmaleimide, (4-fluorophenylsulfonyloxy)diphenylmaleimide, N_(phenylsulfonyloxy)bicyclo[2·2·l]hept-5-ene- 2,3-Dicarboxyindenine (trade name: NDI·100), Midori Kagaku Co., Ltd., N_(4-methylphenylsulfonyloxy)bicyclo[2.2.1]hept-5-ene-2,3 -Dicarboxy quinone imine (trade name "]^〇1-1〇1",

Midori Kagaku Company), N-(trifluorodecanesulfonyloxy)bicyclo[2 21] -65- 201229666 hept-5-ene-2,3-dicarboxy quinone imine (trade name "NDI-105", Midori 1^^@3]&lt;:11 company),&gt;1-(nonafluorobutanesulfonyloxy)bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyarmine ( Trade name "NDI-109", Midori Kagaku Co., Ltd., N-(camphorsulfonyloxy)bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyarmine (trade name "NDI-106" "Midori Kagaku Company", N-(camphorsulfonyloxy)-7-oxabicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinone imine, N-(trifluoromethyl) Sulfomethoxy)-7-oxabicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolimine, N-(4-nonylphenylsulfonyloxy)bicyclo[2· 2.1] Hept-5-ene-2,3-dicarboxy quinone imine, Ν-(4-mercaptophenylsulfonyloxy)-7-oxabicyclo[2.2.1]hept-5-ene-2 , 3-dicarboxy quinone imine, Ν-(2-trifluoromethylphenylsulfonyloxy)bicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinone imine, Ν-( 2-Trifluorodecylphenylsulfonyloxy)-7-oxabicyclo[2.2.1]hept-5-ene-2,3-dicarboxyarminemine, fluorene-(4-fluorophenylsulfonyl) Oxy) double ring [2.2.1] H--5-ene-2,3-dicarboxy quinone imine, Ν-(4-fluorophenylsulfonyloxy)-7-oxabicyclo[2.2.1]hept-5-ene -2,3-dicarboxy quinone imine, Ν-(trifluoromethylsulfonyloxy)bicyclo[2·2·1]heptane-5,6-oxo-2,3-dicarboxy quinone imine, Ν-( camphorsulfonyloxy)bicyclo[2.2.1]heptane-5,6-oxo-2,3-dicarboxy quinone imine, Ν-(4-methylphenylsulfonyloxy)bicyclo[ 2.2· 1]heptane-5,6-oxo-2,3·dicarboxy quinone imine, Ν-(2-trifluoromethyl phenylsulfonyloxy)bicyclo[2.2.1]heptane-5, 6-oxo-2,3-dicarboxy quinone imine, Ν-(4-fluorophenylsulfonyloxy)bicyclo[2.2.1]heptane-5,6-oxo-2,3-dicarboxy fluorene Amine, hydrazine (trifluoromethylsulfonyloxy) naphthoquinone imine (trade name "ΝΑΙ-105", Midori Kagaku), Ν-(camphorsulfonyloxy)naphthoquinone imine (product "NAI-106", Midori Kagaku Co., Ltd.), N-(4-methylphenylsulfonyloxy)naphthalene dioxime. The trade name "NAI-101"'Midori -66 - 201229666

Kagaku company), N-(phenylsulfonyloxy)naphthalene diimide (trade name "NAI-100", Midori Kagaku), N-(2-trifluoromethylphenylsulfonyloxy) Naphthyl imine, N-(4-fluorophenylsulfonyloxy)naphthalene diimide, N-(pentafluoroethylsulfonyloxy)naphthalene diimide, N-(seven Fluoropropylsulfonyloxy)naphthoquinone imine, N-(nonafluorobutoxysulfonyloxy)naphthoquinone imine (trade name "NAI·109"' Midori Kagaku), N-( Ethylsulfonyloxy)naphthoquinone imine, N-(propylsulfonyloxy)naphthoquinone imine, N-(butylsulfonyloxy)naphthalene diimide (trade name) "NAI-1004", Midori Kagaku Company), N-(pentylsulfonyloxy)naphthalene diimide, N-(hexyl decyloxy)naphthyldimethylimine, N-(heptylsulfonate)醯oxy)naphthyldimethylimine, N-(octylsulfonyloxy)naphthalene diimine, N-(fluorenyloxy)naphthalene diimine, and the like. Examples of other heat-sensitive acid generators include, for example, 1 _(4-n-butoxynaphthalen-1-yl)tetrahydro thiophene triacetate calcined acid salt, 1-(4,7-dibutoxygen). Tetrahydronaphthyl salt, such as 1,4-naphthyl)tetrahydrofuran. Among these heat-sensitive acid generators, from the viewpoint of the catalyst action of the [A] copolymer hardening reaction, it is more preferred to be benzyl-4-hydroxyphenylmethylphosphonium hexafluorophosphate, 1·(4,7·dibutyl) Oxy-1-naphthyl)tetrahydrothiophene trifluoromethanesulfonate, hydrazine-(trifluoromethylsulfonyloxy)naphthoquinone imine. The amount of the heat-sensitive acid generator to be used is preferably 0.1 part by mass to 10 parts by mass, more preferably 1 part by mass to 5 parts by mass, per 100 parts by mass of the [Α] copolymer. By using the amount of the heat-sensitive acid generator in the above range, the sensitivity of the radiation-sensitive composition can be optimized, and a cured film having high surface hardness while maintaining transparency can be formed. &lt;Preparation method of radiation sensitive resin composition&gt; -67- 201229666 The radiation sensitive resin composition of the present invention is uniformly obtained by using a substance, [B] quinonediazide compound, [C] hardener, and necessary components. Mixed and formulated. The radiation sensitive tree is preferably dissolved in a suitable solvent and used in the form of a solution. In the preparation of the radiation sensitive resin composition, a solvent which can uniformly dissolve the essential component and any component can be used. As such a solvent, a solvent exemplified as a solvent which can be used for producing the [A] copolymer can be listed. In this solvent, the formation of the film, the film formed by Rongxie early methyl 1, ethylene diethylene glycol mono-n-butyl scale, ether, diethylene glycol mono-n-ethyl alcohol early methyl bond, three , propylene glycol monoethyl ether, base bond, dipropylene glycol monomethanol mono-n-propyl propyl, dipropyl ether, tripropylene glycol monoethyl acetate ethylene glycol monomethyl glycol mono-n-propyl _, monool mono-hydrazine, Acidic mono-n-propyl bond, acetic acid _ thiol &amp; |, propylene glycolic acid 3-mercapto-3- methoxy butyl can be considered from the solubility and workability of each component, can be alcohol monoethyl ether , ethylene glycol monodiethylene glycol monomethyl ether, dipropyl ether, diethylene glycol mono-ethylene glycol monoethyl light, propylene dipropylene glycol mono-n-propyl ether, propyl ether, dipropylene glycol single B Polyglycol mono-n-butyl ether, tripropylene or the like (poly) alkylene glycol mono-3-yl ether, ethylene glycol monoethyl acetate ethylene glycol mono-n-butyl ether diethylene glycol monoethyl ether, Acetate glycol mono-n-butyl ether, vinegar monoethyl ether, acetic acid 3-methoxy group, etc. Acetate (poly) alkyl diterpene [A] copolymerized into any composition of the composition of the moon, used dissolution The agent 'does not recite the same as each of the above-mentioned solvents, such as ethyl propyl hydrazine, ethylene glycol monobutyl butyl sulphate, triol monomethyl ether diol mono-n-butyl ether, dipropylene Glycol monomethyl complete ethers; base ethers, acetic acid, acetic acid diacetic acid diglycolic acid propylene glycol monobutyl butyl, acetal monoalkyl ether -68-201229666; diethylene glycol dimethyl scales, Other ethers such as diethylene glycol decyl ethyl ether, diethylene glycol diethyl ether, tetrahydrofuran; mercapto ethyl ketone, cyclohexanone, 2-miketone, 3-heptanone, diacetone alcohol (4 Ketones such as -hydroxy-4-mercapto-2-one) and 4-hydroxy-4-methylhexan-2-one; propylene glycol diacetate, 1,3-butylene glycol diacetate, 1 , diacetate such as 6-hexanediol diacetate; alkyl lactate such as decyl lactate or ethyl lactate; ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, acetic acid Butyl ester, n-amyl formate, isoamyl acetate, n-butyl propionate, 3-mercapto-3-methoxybutyl propionate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate Ester, n-butyl butyrate Ethyl hydroxyacetate, ethyl ethoxyacetate, methyl 3-methoxyoxypropionate, ethyl 3-methoxyoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate Ester, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, ethyl acetate, ethyl acetate, ethyl 2-hydroxy-2-methylpropionate, 2-hydroxy-3- Other esters such as decyl decanoate and ethyl 2-oxobutanoate; aromatic hydrocarbons such as toluene and xylene; Ν-methylpyrrolidone, hydrazine, hydrazine-dimercaptoamine, hydrazine, hydrazine - guanamines such as dimercaptoacetamide. Among these solvents, propylene glycol monodecyl ether, propylene glycol monoethyl ether, ethylene glycol monodecyl ether, propylene glycol monodecyl ether, and the like are preferable from the viewpoints of solubility, pigment dispersibility, and coatability. Propylene glycol monoethyl ether acetate, 3-decyloxybutyl acetate, diethylene glycol didecyl ether, diethylene glycol methyl ethyl ether, cyclohexanone, 2-heptanone, 3-heptanone, 1 , 3- -69- 201229666 Butylene glycol diacetate, 1,6·hexanediol diacetate, ethyl lactate '3-methoxypropionate ethyl ester, 3_ethoxypropionate methyl ester, 3_Ethyl ethoxypropionate, 3-methyl-3-methoxybutylpropionate, n-butyl acetate, isobutyl acetate, n-amyl formate, isoamyl acetate, n-butyl propionate Ester, butyl succinate, isopropyl butyrate, n-butyl butyrate, ethyl pyruvate. The solvent may be used singly or in combination of two or more. Further, together with the above solvent, benzyl ethyl ether, di-n-hexyl ether, acetone acetone, isophorone, hexanoic acid, octanoic acid, 1-octyl alcohol, 1-nonanol, benzyl acetate may be used together. High boiling point solvents such as ethyl benzoate, diethyl oxalate, diethyl maleate, γ-caprolactone, ethylene carbonate, propylene carbonate, and ethylene glycol monophenyl ether acetate. The above-mentioned high-folk point &gt; granules may be used singly or in combination of two or more. The content of the solvent is not limited. From the viewpoint of coatability and stability of the radiation-sensitive resin composition to be obtained, it is preferred to add a total of various components other than the solvent to the radiation-sensitive resin composition. The concentration is from 5% by mass to 50% by mass, more preferably from 丄〇% by mass to 40% by mass. When the radiation-sensitive resin composition is formulated into a solution state, the solid content concentration (component other than the solvent in the composition solution) can be set to an arbitrary concentration depending on the purpose of use and the desired film thickness value (for example, 5% by mass). 50% by mass). A more preferable solid content concentration differs depending on the method of forming a film on the substrate, which will be described below. The thus-prepared composition solution is filtered using a micropore filter having a pore size of about 0.5 μm or the like, and then it can be used. &lt;Method for Forming Cured Film> The radiation-sensitive resin composition has both low-temperature firing and storage stability, and has high-sensitivity radioactivity, and can be formed as a surface hardness suitable for use as a flexible display. An interlayer insulating film, a protective film or a cured film of a separator excellent in solvent resistance and relative dielectric constant. - a method of forming a cured film of the present invention, comprising: (1) a step of forming a coating film of the radiation sensitive resin composition on a substrate; (2) a step of irradiating at least a part of the coating film with radiation; (3) a step of developing a coating film irradiated with the above-described radiation; and (4) a step of firing the coating film subjected to the above development. When the cured resin film is formed by the above-described steps, the pattern is formed by exposure and development by sensitization, and a fine and delicate pattern can be easily formed. Further, the cured film formed using the radiation sensitive resin composition has sufficient surface hardness and the like even when it is fired at a low temperature. Hereinafter, each step will be described in detail. [(1) Step] In this step, the solution of the radiation-sensitive resin composition is applied onto the surface of the substrate. Preferably, the solvent is removed by prebaking to form a coating film of the radiation-sensitive resin composition. The type of the substrate that can be used is, for example, a glass substrate, a tantalum sheet, a plastic substrate, and a substrate obtained by forming various metals on the surfaces of the substrates. Examples of the plastic substrate include a resin substrate formed of a plastic such as polyethylene terephthalate (PET), polybutylene terephthalate, polybutylene, polycarbonate, or polyimide. As the coating method, for example, a suitable method such as a spray coating method, a roll coating method, a -71-201229666 spin coating method (spin coating method), a slit die coating method, or a bar coating method can be employed. Among the above-mentioned coating method towels, it is preferably a spin coating method or a bar coating method. The pre-baking conditions may vary depending on the type of the components, the ratio of use, and the like, and may be set to, for example, from about 6 to about 9 minutes for about 30 seconds to about 1 minute. In terms of the film thickness of the coating film, it is preferably 〇·1μηι 8μιη, more preferably 〇~6 (four), particularly preferably 0.1 μπι~4μιη 〇 [(2) step] in this step. In the middle, the coating film formed by the step (1) is irradiated with radiation through a mask having a predetermined pattern. Examples of the radiation used at this time include ultraviolet rays, far ultraviolet rays, incident rays, charged particles, and the like. The ultraviolet light can be, for example, a g line (wavelength: 436 nm), Line (wavelength 365 nm) and the like. In terms of far ultraviolet rays, for example,

KrF excimer laser and so on. Examples of the x-ray radiation include a synchrotron radiation and the like. The charged particle beam can be, for example, an electron beam or the like. Among these radiations, ultraviolet rays are preferred, and ultraviolet rays of the g-line and/or i-line are particularly preferred in the ultraviolet rays. The exposure amount is preferably 3 〇 J/m 2 〜 l, 50 〇 J/m 2 . [(3) Step] In this step, the coating film irradiated with radiation by the step (2) is developed, and a portion irradiated with the radiation is irradiated to form a desired pattern. As the developer used in the development treatment, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium citrate, sodium metasilicate, aqueous ammonia, ethyl virgin, n-propylamine, diethylamine, and diethyl ether can be used. Aminoethanol, di-n-propylamine-72- 201229666, diethylamine, decyldiethylamine, dimethylethanolamine, triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, pyrrole , oxetidine, 丨8_diazabicyclo[5,4,0]-7-undecene, iota, 5-diazabicyclo[4,3, indole-5-decane, etc. (basic compound) Aqueous solution. Further, an aqueous solution formed by adding an appropriate amount of a water-soluble organic solvent such as methanol or ethanol to the surfactant, or an aqueous alkali solution containing a small amount of various organic solvents capable of dissolving the radiation-sensitive resin composition may be used as the aqueous solution. Developer solution. Further, as the developing method, an appropriate method such as a liquid-filling method (spin-on immersion method), a immersion method, a shaking impregnation method, or a spray method can be used. The development time varies depending on the composition of the radiation sensitive resin composition, and can be set, for example, to 3 sec to 1 2 sec. After the development step, the patterned coating film is subjected to a finishing rinsing treatment by running water washing, and then, it is preferable to perform total radiation irradiation (post exposure) using a high-pressure mercury lamp or the like to carry out residual film [b]. Decomposition treatment of quinonediazide compound. [(4) Step] In this step, the coating film is heated by a heating device such as a heating plate or an oven which is fired by the coating film developed in the step (3), and is subjected to a treatment (post-culture treatment). 'There is thus hardening of the coating film. After the above: The exposure amount in the first is preferably 2,0 〇〇J/m2 to 5, and 〇〇〇J/m2 or so. Further, the firing temperature in this step is preferably a fan. . In addition to the ability to form a fine pattern by radiation, the firing method can be suitably used at a low temperature to form a cured film such as an interlayer insulating film on a flexible display n: a plastic substrate. The firing temperature is preferably 120 (: ~ 180 (:, especially good for 12 〇. (: ~ 15 〇. (:. -73-201229666 during firing according to the type of heating equipment, &amp; + Ask 'For example, when the heat treatment is applied to the twisting plate, set it to 5 minutes to 4 minutes, '", 蛑#宁& 1 Λ, Ο Heat the temple in the upper and middle phases, and then change to 30 ~80 points, especially good in the crowning 3 0^4^ tv such as, ",, the upper 仃 仃 仃 仃 仃 仃 仃 仃 仃 仃 仃 仃 仃 仃 仃 仃 仃 仃 仃 仃 仃 , , , ^ ^ ^ ^ ^ ^ It is known that: [This method can form a pattern-like coating film corresponding to the target interlayer insulating film # cured film on the surface of the substrate έδ μ # & 。. &lt;Formation method of array substrate of liquid crystal display element> Liquid crystal The display element is formed by sealing a liquid crystal formed by bonding a color filter and an array substrate, and the liquid crystal array substrate of the present invention comprises the cured film of the present invention and laminated on the hard An alignment film formed of a liquid crystal alignment agent. [Step (7)] The method for forming an array substrate of the present invention has the above Steps (1) to (4), and (5) of the method for forming a cured film, the coating liquid is applied to the fired coating film, and the alignment agent is formed by heating at a temperature of 2 Å or less: if In the method of forming the array substrate, the array substrate including the alignment film for the liquid iridium alignment can be formed. The liquid crystal alignment agent preferably contains a radiation-sensitive polymer having a photo-alignment group (hereinafter, also referred to as " Radiation-sensitive linear polymer") a liquid crystal alignment agent or a liquid crystal alignment agent containing a polyimine (not known as "polyimine") having no photo-alignment group. As the coating method, for example, a suitable method such as a nozzle coating method, a roll coating method, a spin coating method (spin coating method), a slit coating method (slit coating method), a bar coating method, or an inkjet method can be employed. In each case, the coating is preferably a spin coating method or a slit coating method. Further, after coating the liquid crystal with -74-201229666, the coating surface is heated to form an alignment film. The daily alignment agent can be used at a low temperature ( For example, 2 〇〇 &lt; t or less) heating temperature In addition, the liquid crystal alignment may contain, for example, a curing agent, a curing catalyst promoter, an m-oxygen compound, a functional decane compound, an interface, a photosensitizer, etc. as a task. Eight 々 1 W is formed into a knife. Hereinafter, the radiation sensitive substance and the polyimine will be described in detail. <Sense Radiation Polymer> The photo-alignment group of the radiation-sensitive ruthenium polymer can be borrowed from the film: The U isotropic functional group' imparts anisotropy to the film by photoisomerization, and the photo-alignment group can be exemplified by, for example, containing azobenzene or diphenyl. Ethylene, keto-β-ketoester, spirulina m-spiroquinone, cinnamic acid, chalcone, basal bite, benzylidene 竿M ^ indanamide, coumarin, diphenyl group The selected photo-alignment group having a structure of at least one compound is such that ^^ m S ' is preferably derived from a group of the structure of cinnamic acid. a The radioactive alignment of the sensory group is bonded to the optical alignment: S ' is preferably a polymer which directly or by the ^ ^ ^ - D is a group. In the case of such a sensory polymer, S, the energy L L ^ ^ sentence exemplifies, for example, a polymer formed by bonding a poly(ortho) acid or a polyfluorene imide to a ^ e fluorene group. Further, as the radiation linear polymer &amp;&amp;&amp;&gt;, a polymer having a poly-proline acid 'amine and other polymers, and the other polymer having a photoalignment can be cited. In terms of the basic skeleton of the 贫 4 4 e 匕 polymer, it can be as described in the poly(methyl), the poly(methyl) acrylamide, the polyethylene, the above-mentioned liquidity, the hardening activity, and the hardening activity. The agent polymerization is carried out by light reaction or, in terms of α-imine styrene acetylene and oxime group. It is polymerized by tyrosine or the like, and is exemplified by a group of stimulating subgroups, -75- 201229666 polyolefin For the β-sensitive radioactive polymer such as polyorganosiloxane, it is preferably a polymer having a poly-proline, a poly-imine, or a polyorganosiloxane as a basic skeleton, and more preferably a polyorganism. The siloxane may be synthesized by a method as described in, for example, International Publication No. WO2009/0253 86. &lt;Polyimine&gt; Polyimine having no photo-alignment group may not have The polyamino acid dehydration ring closure of the photo-alignment group is synthesized by ruthenium imidization. The above-mentioned poly-branched acid can be made into a tetracarboxylic acid according to, for example, the method described in JP-A No. 20 10-97 188. The anhydride and the diamine are reacted to synthesize. The proguanilic acid as a precursor has a complete ruthenium imide formed by dehydration ring closure of the proline structure, and may also be a part of the structure of the tyrosine acid which is formed by dehydration and ring closure, and has a proline structure and a diamine ring. The quinone imide of the structure is preferably 30% or more, more preferably 50% or more, and 990/〇' is particularly preferably 65% or more and 99% or less. The imidization ratio indicates the amount of the proline structure relative to the amount of the quinone imine and the number of the quinone imine ring structure. The ratio of the number of the quinone imine ring structure is expressed by a percentage. The present invention is also suitable for inclusion. A color light ray having a film formed of an alignment film for liquid crystal alignment. The color filter is excellent in heat resistance, solvent resistance, voltage holding ratio, etc., and forms a two-dimensional film for use in such a color filter. The liquid crystal alignment agent preferably contains a radiation-sensitive polymerization [Example] -76 - 201229666 Hereinafter, the present invention will be described in detail based on examples, but the present invention is not construed as being limited to the embodiment. A] Synthesis of Copolymers > [Synthesis 1 ] In a flask equipped with a condenser and a stirrer, 7 parts by mass of 2,2'-azobis(2,4-dimethylvaleronitrile) and 22.0 parts by mass of diethylene glycol methyl ethyl ether were added. Then, 16 parts by mass of methacrylic acid as the compound (A1), 40 parts by mass of glycidyl methacrylate as the compound (A2), 10 parts by mass of styrene as the compound (A4), and 14 parts by mass are added. Tricyclo[meth] methacrylate [5.2.1.〇2'6]癸-8-ester, 20 parts by mass of 2-mercaptocyclohexyl acrylate vinegar, nitrogen substitution, while stirring slowly, the temperature of the solution is raised The polymerization was carried out at 70 ° C for 4 hours at this temperature to obtain a solution containing the copolymer (A_丨). The obtained polymer solution had a solid content concentration of 34.4%, a copolymer (eight-1) of ??\¥ of 8, and a 〇〇〇' molecular weight distribution (Mw/Mn) of 2.3. [Synthesis Example 2] In a flask equipped with a condenser and a stirrer, 8 parts by mass of 2,2'-azobis(2,4-dimethylvaleronitrile) and 220 parts by mass of diethylene glycol methyl group were added. Ethyl test. Next, 13 parts by mass of methyl methic acid as the (A 1) compound, and 40 parts by mass of glycidyl thioglycolate S, which is a compound of (A2), are added as a-methyl group of the (A3) compound. Styrene, 12 parts by mass of styrene as a compound of (A4), 12 parts by mass of tetrahydrofurfurylmethyl acrylate, 15 parts by mass of N-cyclohexylmaleimide and 1 〇 The mass was killed by lauryl methacrylate, and after nitrogen substitution, the temperature of the solution was raised to 70 while stirring slowly. (:, at this temperature, 5:77 - 201229666 hours, polymerization was carried out to obtain a solution containing the copolymer (A_2). The obtained polymer solution had a solid content concentration of 31.9%, and the Mw of the copolymer (A_2) was 8,0 0 0, the sub-quantity distribution (μ w / η η) was 2.3. [Comparative Synthesis Example 1] In a flask equipped with a condenser and a stirrer, 5 parts by mass of hydrazine and 220 parts by mass of propylene glycol monoterpene were added. Acetate vinegar, followed by adding 8 parts by mass of methyl methacrylate dilute broth, 20 parts by mass of methacrylic acid as (Α1) compound, while slowly stirring, raising the temperature of the solution to 80 ° C, The polymerization was carried out at this temperature for 5 hours to obtain a solution containing the copolymer (CA-1). The obtained polymer solution had a solid content concentration of 3 1.0%. The copolymer (CA-1) of the river was rated as 1〇. , 〇〇〇, molecular weight distribution (Mw / Mn) is 2.3 〇 &lt;Preparation of radiation sensitive resin composition &gt; [Example 1] Heavy polymer-containing copolymer (A-1) The solution, 30 parts by mass of (B-1), and 0.5 parts by mass (cl) of the azide compound Dihe '1*) Dan is added as a solvent of diethylene glycol methyl ethyl ether to a solid content concentration of 3 ~ J u by volume, and then filtered with a membrane filter having a pore size of 0.2 μm, thereby ashing A radiation sensitive resin composition. [Examples 2 to 13 and Comparative Examples 1 to 2] The various types and amounts of the long-term wire and the various components of the blade shown in Table 1 were added as the solvent-mixing ratio from the 'knife, and the hardener was used as the agent. The diol thiol ethyl ether was used to make a solid concentration of s$ 30% by mass, and then filtered through a membrane filter having a pore size of 0.2 μm to prepare respective radiation-sensitive resin compositions. Also, the _" of the shed φ + indicates that the -78-201229666 component is not used. The radiation-sensitive resin composition shown in Table 1 The details of the various components are shown below. &lt;[B] quinone diazide compound: :-hydroxyl stylyl] bis (1.0 mol) and 1,2-naphthyl diazide 4 condensate Β-2: 1,1,1 a condensate of tris(p-hydroxyphenyl)ethane and]-5-sulfonyl chloride (2.0 mol) &lt;[C] hardener&gt; C-1 : trioctylamine C - 2 . σ 〇米〇 sit C-3: tetramethyl chloride C-4. butyl triphenyl thiocyanate C-5: 1,8-diazabicyclo[5,4,0]-ten Monoethyl salt C-6 : Ν, Ν'-diethyl fluorenyl-p-phenylenediamine C-7 : Ν, Ν-bis(1,3-dimethylbutylidene) dimethyl C-8 : ΤΡΑ- Β80Ε (Asahi Kasei Chemicals cyanate, solid content 80%, effective isocyanic acid C-9: 4,4'-diaminodiphenyl stone C-10: ethyl 3-aminobenzenesulfonate C-1 1 : Cage compound c-1 formed by mixing 2:1 nitrophthalic acid and 2-phenyl-4-oxazole: f-ethyl group] used in the preparation of octylamine Ethyl bromide-5-sulfonyl chloride (2. 〇 Mo丨, 2 - Litchi azide-7 (DBU) toluene benzoic acid phenyl diamine, H DI type blocked isoester content 12.3 ° /〇) Methyl·5-hydroxyindolyl-79- 201229666

201229666 &lt;Evaluation&gt; The following evaluations were carried out on the prepared radiation sensitive resin composition and the carbide formed later, and the results are shown in Table 。. [Storage stability] The obtained radiation sensitive resin composition was placed in an oven at 4 Torr for 1 week, and the viscosity before and after heating was measured to determine the viscosity change rate. At this time, the viscosity change rate was taken as the storage stability, and when the 纟 was 5% or less, it was judged that the storage stability was good. When it exceeded 5%, it was judged that the storage stability was poor. The viscosity was measured at 25 ° C using an E-type viscometer (VISC0NIC ELD R, Toki Sangyo Co., Ltd.). [Sensitivity] All of the radiation-sensitive resin compositions prepared as the examples and the comparative examples were coated on a ruthenium substrate using a spin coater, and then prebaked on a hot plate at 9 〇t for 2 minutes to form a film thickness of 3 Å. Tu (four). On the obtained coating film, a predetermined amount of ultraviolet rays was irradiated with mercury through a mask having a line-to-space ratio pattern of a width of ΙΟμπι. Then, a developing solution consisting of tetramethylammonium hydroxide (% by mass) aqueous solution was used, and under 6 seconds, it was subjected to development at 8 seconds, and then washed with ultrapure water for 丨 minute water washing. At this time, the minimum ultraviolet ray irradiation i of the line-to-space ratio pattern in which Sauli was formed to have a width of 1 〇 μΐη was measured. When the amount is 850 J/m2, the sensitivity is judged to be good. No [solvent resistance] All of the radiation sensitive resin compositions prepared in the examples and comparative examples were coated on a tantalum substrate by a spin coater, and then prebaked on a hot plate at 90 ° C for 2 minutes to form a film thickness of 3 〇. The coating of μιη. On the obtained 2 membranes, the mercury-based lamp was used to achieve a cumulative exposure of 3, and the 〇〇〇J/m2 of the impotence was shot at -81-201229666. Then, for the germanium substrate', the example i

The film thickness (ti) was calculated from the following formula, and the cured film was measured for its solvent property. Film thickness change rate = {(tl - Tl) / Tl} xl 〇〇 (%) When the absolute value of the value is less than 5%, it is judged that the solvent resistance is excellent

The radiation sensitive linear resin composition of the film has sufficient hardenability. [Relative dielectric constant] All the radiation-sensitive resin compositions prepared as the examples and the comparative examples were coated on a SUS substrate by a spin coater, and then prebaked on a hot plate at 90 C for 2 minutes to form a film thickness of 3 〇μπι. Coating film. Using the MPA-600FA exposure machine of Can〇n Company, the cumulative exposure amount reached 9, 〇〇〇J/m2, and the obtained coating film was exposed, and the substrate was placed in a dust-free oven! 5 〇 t: Heating was performed for 30 minutes to form a cured film on the SUS substrate. A Pt/Pd electrode pattern was formed on the cured film by a vapor deposition method to prepare a sample for dielectric constant measurement. For the substrate with the electrode pattern, use Yokogawa.

Hewlett-Packard's HP1 645 1B electrode and HP4284A precision LCR meter (Precision LCR meter) measure the relative permittivity at the l〇kHz frequency by the 201229666 cv method. When the value is 39 or less, it is judged that the dielectric constant is good. As is apparent from the results of Table 1, the radiation sensitive resin composition of the present invention has high radiation sensitivity, and a cured film having high surface hardness can be obtained by heating at a low temperature and for a short period of time, and the cured film has excellent resistance. Solvent and relative dielectric constant. '[Industrial Applicability] According to the radiation sensitive resin of the present invention, it is possible to provide both low-temperature firing and storage stability, and the ancient, seismic, and sympathetic feelings. Radiation, w radiation linear resin composition, and suitable for shortening k, 'feeling' visual display of your * surface hardness, solvent resistance and relative dielectric constant. 9 as a hardened film of layer p, protective film or separator of double slow. s, interest film [simplified description] None. [Main component symbol description] No 0 -83-

Claims (1)

201229666 VII. Patent application scope: 1. A radiation sensitive resin composition comprising: [A] a copolymer having (A1) a carboxyl group-containing structural unit and (A2) an epoxy group-containing structural unit; [B] a quinonediazide compound; and [C] a compound represented by the following formula (1), a compound represented by the following formula (2), a tertiary amine compound, an amine salt, a scale salt, a phosphonium salt, a guanamine compound, The S-imine compound, the blocked isocyanate compound, the compound containing the oxime ring, and at least one hardener selected from the group of the cage compound, (2) In the formula (1), R1 to R6 are each independently a hydrogen atom, an electron withdrawing group or an amine group 'wherein at least one of R1 to R6 is an electron withdrawing group' and R1 to R6 At least one of them is an amine group, and all or a part of the hydrogen atoms of the above amine group may be substituted by an alkyl group having 1 to 6 carbon atoms, and -84-201229666 is a hydrogen atom and a pull electron. a group or an amine group, wherein at least one of R7 to R16 is an amine group, and all or a part of hydrogen atoms of the above amine group may be substituted by an alkyl group having 1 to 6 carbon atoms, and A is a single bond or a carbonyl group. a carbonyloxy group, a carbonylarylene group, an anthranylene group, a fluorenyl group, an anthranylene group or an alkylene group having 2 to 6 carbon atoms, wherein all or part of the hydrogen atom of the above methylene group and the alkylene group are present. It may be substituted by a cyano group, a dentate atom or a fluoroalkyl group. (2) A radiation sensitive linear resin composition of the following formula, wherein the [C] hardener is at least one selected from the group consisting of the compounds represented by the above formulas (1) and (7). 3. For example, the Radiation Resin Composition of the 1st or 2nd Division of the Patent Application No. 1 or 2 is used to form bamboo gas a 0a # &amp; _ for interlayer, 邑, Μ, 保护, protective film or isolation The 4' species of the substance is used as a hardened film of an interlayer insulating ruthenium, a protective film or a separator, which is formed of a radiation sensitive resin composition as described in the patent application section. A liquid crystal display element which is in contact with the material column substrate of the fourth aspect, which comprises the cured film of the fourth aspect of the patent application and an alignment film formed on the chemical film and formed of a liquid crystal alignment agent. (4) L Xuanji 6. As in the fifth paragraph of the patent application scope, the array substrate of the upper and lower components, wherein the liquid helium alignment agent is a radiation-sensitive linear water containing green W·taken 仏4 1 soil lumps A liquid crystal alignment agent of &amp; a liquid crystal alignment agent having a polyimine having no photo-alignment group. 7. A method for forming a cured film, comprising: (1) coating a substrate on a substrate such as a sensitizing radiation-85-201229666 linear resin composition of the third aspect of the patent scope of the patent, forming a coating film; 2) a step of irradiating at least a part of the coating film with radiation; (3) a step of developing a coating film irradiated with the radiation; and (4) a step of firing the coating film subjected to the development. The method for forming a cured film according to the seventh aspect of the invention, wherein the firing temperature in the step (4) is 2 〇 (Γ: 9. The method of forming an array substrate of a liquid crystal display element) The steps (1) to (4) and (5) having the seventh aspect of the invention are applied to the fired soil film, and the alignment is formed by heating at 200 ° C or lower. Step of film. -86- 201229666 IV. Designation of representative figure: (1) The representative figure of the case is: No. (2) Simple description of the symbol of the representative figure: None 0. If there is a chemical formula in this case, please reveal the most A chemical formula that shows the characteristics of the invention: