TW201033737A - Radiation-sensitive resin composition, interlayer insulating film and the preparation method thereof - Google Patents

Abstract

This invention provides a radiation-sensitive resin composition which can show excellent evenness of film thickness even if using silt coating method as a coating method, and an interlayer insulating film having high radiation-sensitivity, and having development margin capable of forming good pattern sharp even exceeding the most preferable developing time; and an interlayer insulating film having various performances such as high heat resistance, high solvent resistance, high transparency and low dielectric constant, and the like. A laminated isolation film formed by the said resin composition is also provided. The radiation-sensitive resin composition for forming a laminated isolation film comprises: (A) alkali soluble resin; (B) 1, 2-quinonediazide compound, and (C) the specific polymer having silicone chain. The laminated isolation film is formed by the radiation-sensitive resin composition for forming a laminated isolation film.

Description

201033737'. TECHNICAL FIELD OF THE INVENTION The present invention relates to a radiation sensitive resin composition, an interlayer insulating film, and a method of manufacturing the same. [Prior Art] Electronic components such as a thin film transistor (hereinafter referred to as "TFT") type liquid crystal display element and a magnetic head element, an integrated circuit element, and a solid-state image sensor element are usually used for wiring between layers arranged in a layer. Insulation 'Set the interlayer insulation ❹ film. The radiation-sensitive resin composition is widely used as a material for forming the interlayer insulating film, and a material having a small number of steps and a high flatness is required for obtaining a necessary pattern shape (see Patent Document 1 and Patent Document 2). ). In the above-mentioned electronic component, for example, a TFT-type liquid crystal display device is manufactured by a step of forming a transparent electrode film on the interlayer insulating film and forming a liquid crystal alignment film thereon, and thus the interlayer insulating film is formed in the transparent electrode film. It is subjected to the temperature conditions and is subjected to the resist stripping liquid used in the formation of the electrode pattern, and therefore, it must have sufficiently good resistance thereto. The interlayer insulating film thus obtained, in the developing step at the time of its formation, even if the development time is only slightly more than the optimum time, the developer permeates easily between the pattern and the substrate to cause detachment, and therefore, development must be strictly controlled. Time, and the yield of the product is very problematic. In recent years, in the field of TFT-type liquid crystal display devices, there is a trend of large-screening, high-brightness, high-definition, rapid response, and thinning. 201033737 is required as a composition for forming an interlayer insulating film. The high 'sensitivity and the formed interlayer insulating film' require high performance such as low dielectric constant and high light transmittance which are superior to the prior art. Thus, when the interlayer insulating film is formed of the radiation sensitive resin composition, it is required to have high sensitivity as the composition 'and 'requires that in the developing step in the forming step, even when the developing time exceeds the predetermined time' The pattern is detached, and the good adhesion is exhibited, and the interlayer insulating film formed therefrom has high heat resistance, high solvent resistance, low dielectric constant, high transmittance, and the like. However, the radiation sensitive resin composition satisfying this requirement has hitherto been unknown. Moreover, with the trend of large-screen televisions and the reduction in production cost in recent years, the size of substrate glass used in the manufacture of substrates with color filters is increasing in size. Therefore, in the coating step of the radiation sensitive resin composition which is performed when the interlayer insulating film is formed on the substrate, it has been difficult to employ the spin coating method which has been widely used in the past, and the coating method is replaced by spraying the composition by the slit nozzle. So-called slot die coating method of coating. This gastric seed coating method has an advantage of being able to reduce the amount of the composition required for coating as compared with the spin coating method, and is also advantageous for reducing the production cost of the liquid crystal display element. However, in the slit die coating method, the coating nozzle is swept in a certain direction in the adsorption state of the vacuum adsorption substrate, and then the support pin held in the cavity for vacuum adsorption is lifted. The substrate is lifted up and transferred from the coating station to the next step. Therefore, in a series of steps, there are cases in which a mark caused by holes for vacuum adsorption, a mark caused by a support pin, and a strip-like spot appearing in the direction of the coating nozzle are formed, thereby becoming a shape. A barrier to high flatness as described above is achieved. CITATION LIST Patent Literature Patent Literature 1: JP-A-2001-354822 (Patent Document 2) Japanese Laid-Open Patent Publication No. JP-A No. Hei No. Hei No. Hei. The purpose of the invention is to provide a radiation-sensitive resin composition which exhibits excellent film thickness uniformity and high ray sensitivity even in the development step, even if the slit coating method is used as the coating method. It has a development margin capable of forming a good pattern shape even beyond an optimum development time, and an interlayer insulating film excellent in various properties such as high heat resistance, high solvent resistance, high light transmittance, low dielectric constant, and the like method. The above objects and advantages of the present invention, first, are achieved by a radiation sensitive resin composition comprising: (A) an alkali-soluble resin; (Β) 1,2·醌diazide compound (hereinafter referred to as "a compound" (B) "); and (C) a compound represented by the following formula (1) by (cl) (hereinafter referred to as "compound (cl)"), (c2) a compound represented by the following formula (2) (hereinafter referred to as "compound (c2)") and (c3) a polymerizable unsaturated compound having a group represented by the following formula (3) (hereinafter referred to as "compound (c3)")) Copolymer (hereinafter referred to as "copolymer (C)"). 201033737 CH2 = CRiCOO-CaH2«-CpF2P + i (l〇) (In the formula (1°), R1 is a hydrogen atom or a methyl group, a is an integer of 0 to 6, and β is an integer of 1 to 20). CH2 = CR2COO-(CyH2Y-〇)a-R3 (2°) (In the formula (2°), R2 is a hydrogen atom or a methyl group, R3 is an alkyl group having 1 to 12 carbon atoms, and γ is 2 or 3 , a is the number of repeating units, and the average number 値 is 1~3 0).

R7

I

Si—(3) R8 (In the formula (3), R4, R5, R6, R7 and R8 are each independently an alkyl group having 1 to 20 carbon atoms, a phenyl group or a formula represented by the following formula (4) The group, b is an integer from 〇~3). ❹ Π10 \ R9 Si 〇4 —Si—〇—— (4) \ R11 / :R11

(In the formula (4), R9, R1G and R & from independently an alkyl group or a phenyl group having a carbon number, and c is an integer of 0 to 3) The above objects and advantages of the present invention are obtained by using the above-described radiation. The inter-layer green _ formed by the _ resin composition is a good result. 201033737 The above objects and advantages of the present invention are, in a third, achieved by a method of forming an interlayer insulating film comprising the following steps, (1) a step of applying the above-described radiation sensitive resin composition onto a substrate to form a coating film, ( 2) a step of irradiating at least a portion of the coating film with radiation, (3) a developing step, and (4) a heating step. The above objects and advantages of the present invention, and fourthly, are achieved by an interlayer insulating film formed by the above method. According to the present invention, it is possible to provide a radiation sensitive resin composition which exhibits excellent film thickness uniformity even with a slit die coating method as a coating method, and has high ray sensitivity in the developing step. It has a development margin capable of forming a good pattern shape even if the optimum development time is exceeded, and can provide an interlayer insulating film excellent in various properties such as high heat resistance, high solvent resistance, high light transmittance, and low dielectric constant. Production method. [Embodiment] 形态W Mode for Carrying Out the Invention Hereinafter, the present invention will be specifically described. <(A) Alkali-soluble resin> The (A) alkali-soluble resin contained in the radiation-sensitive resin composition of the present invention is used as long as it is a developing solution (preferably an alkali developing solution) used in the development step described below. There is no particular limitation on the soluble alkali-soluble resin. As such (A) alkali-soluble resin, an alkali-soluble resin having at least one selected from the group consisting of a carboxyl group and a carboxylic anhydride group is preferable, and it is suitable for use in 201033737, for example, containing (al) selected from unsaturated carboxylic acids and not At least one of the group consisting of saturated carboxylic anhydrides (hereinafter referred to as "compound (a 1), ') and (a2) a polymerizable unsaturated compound having an epoxy group (hereinafter referred to as "compound (a2)'') A copolymer of a monomer (hereinafter referred to as "copolymer (A)"). The copolymer (A) may be a copolymer of a monomer composed of the above compound (ai) and the compound (a2) or may contain (a3) other than the above compound (al) and compound (a2). A copolymer of a monomer of a polymerizable unsaturated compound (hereinafter referred to as "compound a3"), and the latter is preferable. The copolymer (A) can be produced by subjecting the monomer as described above to a radical polymerization in a solvent, preferably in the presence of a polymerization initiator. [Compound (al)] The copolymer (A) used in the present invention preferably contains 5 to 40% by mass based on the total of the repeating units derived from the compounds (al), (a2) and (a3). It is preferable to contain 5 to 25% by mass of a constituent unit derived from the compound (al). When the ratio of the constituent unit is 5 to 40% by mass, various radiation-sensitive linear resin compositions having higher levels of performance such as radiation sensitivity, developability, and storage stability can be obtained. The compound (a1) is at least one selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic anhydrides, and examples thereof include monocarboxylic acids, dicarboxylic acids, acid anhydrides of dicarboxylic acids, and monocarboxylic acids of polycarboxylic acids. A methyl (meth) decyloxyalkyl] ester, a mono(meth) acrylate of a polymer having a carboxyl group and a hydroxyl group at both terminals, a polycyclic compound having a carboxyl group, an acid anhydride thereof, and the like. As a specific example, the monocarboxylic acid may, for example, be acrylic acid, methacrylic acid, crotonic acid or the like; and the 201033737 dicarboxylic acid may, for example, be maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid or the like; Examples of the acid anhydride of the carboxylic acid include an acid anhydride of a compound exemplified as the above dicarboxylic acid; and a mono[(meth)acryloxyalkylalkyl] ester of a polyvalent carboxylic acid, for example, succinic acid mono [2-(methyl) a propylene oxyethyl ester, a mono [2-(methyl) propylene methoxyethyl] phthalate, etc.; a mono(meth) acrylate of a polymer having a carboxyl group and a hydroxyl group at both ends © For example, a mono(meth)acrylate of ω-carboxypolycaprolactone or the like; a polycyclic compound having a carboxyl group and an acid anhydride thereof may, for example, be 5-carboxybicyclo[2.2.1]hept-2-ene, 5 , 6-dicarboxybicyclo[2.2.1]hept-2-ene, 5-carboxy-5-methylbicyclo[2.2.1]hept-2-ene, 5-carboxy-5-ethylbicyclo[ 2.2.1] Hept-2-ene, 5-carboxy-6-methylbicyclo[2·2·1]hept-2-ene, 5-carboxy-6-ethylbicyclo[2.2.1]g- 2-ene, 5,6-dicarboxybicyclo[2.2.1]hept-2-ene anhydride, and the like. Among them, an acid anhydride of a monocarboxylic acid or a dicarboxylic acid is preferably used, and acrylic acid, methacrylic acid, and maleic anhydride are particularly preferably used in terms of copolymerization reactivity, solubility in an aqueous alkali solution, and easy availability. These compounds (al) can be used singly or in combination. (Compound (a2)) The copolymer (A) used in the present invention preferably contains 10 to 80% by mass based on the total amount of the repeating units derived from the compounds (al), (a2) and (a3). It contains 30 to 80% by mass of a constituent unit derived from the compound (a2). When the ratio of the constituent unit is 10 to 80% by mass, heat resistance and solvent resistance of the interlayer insulating film-10-201033737 and radiation sensitivity of the radiation-sensitive resin composition can be obtained at a higher level. Composition. The compound (a2) is a polymerizable unsaturated compound having an epoxy group, and examples of the epoxy group include an epoxy group (having a 1,2-epoxy structure) and an oxetanyl group (having 1,3-). Epoxy structure) and the like. As the polymerizable unsaturated compound having an epoxy group, for example, glycidyl acrylate, glycidyl methacrylate, α-glycidyl acrylate, α-n-propyl acrylate glycidyl ester, α-® acrylonitrile shrinkage can be used. Glyceride, 3,4-epoxybutyl acrylate, 3,4-epoxybutyl methacrylate, 6,7-epoxyheptyl acrylate, 6,7-epoxyglycol acrylate Base ester, 6,7-epoxy ester of α-ethyl acrylate, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, methacrylic acid- 3,4· Cyclohexyl ester and the like. Among them, preferred is glycidyl methacrylate 6,7-epoxyheptyl acrylate, o-vinyl benzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl condensed base. Ether, 3,4-epoxycyclohexyl methacrylate, etc.; as the unsaturated compound having an oxetanyl group, 3-(acryloxymethyl)oxetane, 3-( Propylene methoxymethyl 3 methyl oxetane, 3-(acryloxymethyl)-3-ethyloxacyclo, 3-(acryloxymethyl)-2-phenyl oxa Cyclobutane, 3-(2-propoxyethyl)oxetane, 3-(2-propenyloxyethyl)-2-ethylcyclobutane, 3-(2-propenyloxy) Ethyl ethyl)-3-ethyloxetane, propylene methoxyethyl)-2-phenyl oxetane, 3-(methyl propylene styrene stable. Butyl propyl methyl heptyl glycerol epoxy, methyl glycerin such as g)-2-cyclobutenoxa oxa 3-(2-oxyl

201033737 Methyl)oxetane, 3-(methacryloxymethyl)-2-methylbutane, 3-(methacryloxymethyl)-3-ethyloxa Cyclobutane, propylene oxymethyl)-2-phenyl oxetane, 3-(2-methylpropoxyethyl) oxetane, 3-(2-methylpropene Oxyloxyethyl)-2oxetane, 3-(2-methylpropenyloxyethyl)-3-ethyloxaline, 3-(2-methylpropenyloxyethyl) These compounds (a2) such as 2-phenyloxetane may be used singly or in combination. [Compound (a3)] The copolymer (A) used in the present invention preferably contains 1 to 50 masses, particularly preferably 5 to 50, based on the total amount of the repeating units derived from the compounds (a 1) and (a3). The mass % is a constituent unit derived from the compound (a3). When the ratio of the constituent unit is from 1 to 50% by mass, the heat resistance and solvent resistance of the formed insulating film and the radiolucent sensitization of the radioactive resin group wiped in the alkali aqueous solution at a higher level can be obtained. Things. The compound (a3) is not particularly limited as long as it is a radical polymerizable unsaturated material. As the compound (a3), for example, an alkyl methacrylate, an alkyl acrylate, a methacrylyl ester, a methacrylate having a hydroxyl group, a cycloalkyl acrylate, an aryl acrylate, an aryl acrylate can be used. , an unsaturated dicarboxylic acid diester, an unsaturated compound, a maleimide compound, an unsaturated aromatic 1 conjugated diene; an unsaturated compound having a phenolic hydroxyl group represented by the following formula (I); having tetrahydrofuran a skeleton, a furan skeleton, a tetrahydropyran skeleton, a heterocyclic 3-(methene-ethyl:cyclobutane (a2)%, when the interlayer is a lipid group, a cycloalkylmethylbicyclic-substrate, pyridyl Iso-12-201033737 Skeleton or an unsaturated compound of the skeleton represented by the following formula (II); and other unsaturated compounds.

(In the formula (I), RI is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R11 to RVI are the same or different, and are a hydrogen atom, a hydroxyl group or an alkyl group having 1 to 4 carbon atoms. The bond, -C00-, or -CONH-, m is an integer of 〇~3, wherein at least one of 'RU~RVI is a hydroxyl group.

(II) As a specific example thereof, examples of the alkyl methacrylate include methyl methacrylate, ethyl methacrylate, methacrylic acid n-butyl ester, and sec-butyl methacrylate. Tert-butyl methacrylate, 2-ethylhexyl methacrylate, isodecyl methacrylate, methyl -13 - 201033737 n-dodecyl enoate, tridecyl methacrylate And n-octadecyl methacrylate or the like; examples of the alkyl acrylate include methyl acrylate and isopropyl acrylate; and examples of the cycloalkyl methacrylate include cyclohexyl methacrylate. 2-methylcyclohexyl methacrylate, tricyclo[5.2.1.0''6]nonane-8-yl methacrylate, tricyclo[5.2.1.0''6]nonane-8-yloxy methacrylate Ethyl ethyl ester, isobornyl methacrylate, etc.; as a methacrylate having a hydroxyl group, for example, hydroxymethyl methacrylate, 2-hydroxyethyl methacrylate, 3-hydroxypropyl methacrylate Ester, 4-hydroxybutyl methacrylate, diethylene glycol monomethyl Acrylate, 2,3-dihydroxypropyl methacrylate, 2-methylpropenyloxyethyl glycoside, 4-hydroxyphenyl methacrylate, etc.; as a cycloalkyl acrylate, for example, acrylic acid Cyclohexyl ester, 2-methylcyclohexyl acrylate, tricyclo[5.2.1.02'6]nonane-8-yl acrylate, tricyclo[5.2.1.0''6]nonane-8-yloxy B Examples of the aryl methacrylate include phenyl methacrylate and benzyl methacrylate; and the aryl acrylate may, for example, be benzo acrylate. a base ester, a benzyl acrylate or the like: Examples of the unsaturated dicarboxylic acid diester include diethyl maleate, diethyl fumarate, diethyl itaconate, and the like; as a bicyclic unsaturated compound, For example, a bicyclo[2.2.1]heptane-14-201033737-2-ene, a 5-methylbicyclo[2.2.1]hept-2-ene, a 5-ethylbicyclo[2.2.1]heptan-2-diene 5-methoxybicyclo[2 2丨]heptane 2,ethoxy 5-cyclo[2 2丨]hept-2-pyrene, 5,6-dimethoxybicyclo[2 2丨] Geng-2_ene, etc.; as Malay The amine compound may, for example, be N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-(4-hydroxyphenyl)maleimide. , N-(4-hydroxybenzyl)maleimide, N-succinimide-3-maleimidobenzoate, N-ammonium imino-4-malay Iminobutyrate, N-succinimide-6-maleimidohexanoate, N-succinimide-3-maleimidopropionate, N- (9-Aridinyl), quinone, etc.; as the unsaturated aromatic compound, for example, phenethyl styrene, α-methyl styrene, m-methyl styrene, p-methyl styrene, vinyl Toluene, p-methoxystyrene, etc.; as a conjugated diene, for example, fluorene, 3-butane, isoprene, 2,3-dimethyl-1,3-butane, etc.; The unsaturated compound ' ® having a phenolic skeleton represented by the above formula (I) may, for example, be a compound represented by the following formula (I-D to (1 to 5); -15-201033737

(I-l) (1-2) -16- 201033737

R1 Ο

»11 R1 (1-4)

(1-5) -17- 201033737 (wherein η in the formula (I-1) and the formula (I-3) is an integer of 1 to 3, and R1, R11, Riii, Riv in the formula (I-5), The definitions of rv and Rvi are the same as in the above formula (I). Examples of the unsaturated compound having a tetrahydrofuran skeleton include tetramethyl decyl methacrylate, 2-(meth) propylene methoxy-tetrahydro decyl propionate, and 3-(methyl) propylene hydride. Oxytetrahydrofuran-2-one or the like; as the unsaturated compound having a furan skeleton, for example, 2-methyl-5-(3-furyl)-1-penten-3-one, cesium (meth)acrylate Base ester, 1-furan-2-butyl-3-en-2-one, 1·furan-2-butyl-3-methoxy-3-ene-2-one, 6-(2-furanyl) -2-methyl-1·hexen-3-one, 6-furan-2-yl-hex-1-en-3-one, 2-furan-2-yl-1-yl (meth)acrylate a base-ethyl ester, 6-(2-furyl)-6-methyl-1-hepten-3-one, etc.; as the unsaturated compound having a tetrahydropyran skeleton, for example, (meth)acrylic acid (tetrahydropyran-2-yl)methyl ester, 2,6-dimethyl-8-(tetrahydropyran-2-yloxy)-oct-1-en-3-one, 2-( Tetrahydropyran-2-yl methacrylate, 1-(tetrahydropyran-2-yloxy)-butyl-3-en-2-one, etc.; as an unsaturated compound having a pyran skeleton, For example, 4-(1,4-dioxa-5- can be cited Generation-6-heptenyl)-6-methyl-2-pyrone' 4-(1,5-dioxa-6-oxo-7-octenyl)-6-methyl-2- Examples of the unsaturated compound which has a skeleton represented by the above formula (II) include, for example, polyethylene glycol mono(meth)acrylate having a polymerization degree of 2 to 10, and a polymerization degree of 2 to 10 Propylene glycol mono(meth)acrylate or the like; Examples of the other unsaturated compound include acrylonitrile, methacrylonitrile, acrylamide, methacrylamide, and the like. -18- 201033737 Among them, alkyl methacrylate, methacrylic acid cycloalkyl ester, cycloalkyl acrylate, maleic imine compound, unsaturated aromatic compound, and the above formula are preferably used. An unsaturated compound of a phenolic hydroxyl group represented by I), an unsaturated compound having a tetrahydrofuran skeleton, a furan skeleton, a tetrahydropyran skeleton, a ruthenium skeleton or a skeleton represented by the above formula (II), from copolymerization reactivity and alkali In terms of solubility of the aqueous solution, it is particularly preferred to use styrene, tert-butyl methacrylate, tricyclo[5.2.1.〇2,6]decane-8-yl ester, p-methoxy group. Styrene, 2-methylcyclohexyl acrylate, N_ ® phenyl maleimide, N-cyclohexylmaleimide, tetrahydrofurfuryl (meth) acrylate, polyethylene glycol (η = 2~10) mono(meth)acrylate, 3-(meth)acryloxytetrahydrofuran-2-one, 4-hydroxybenzyl (meth)acrylate, 4-hydroxyphenyl (meth)acrylate In the group consisting of o-hydroxystyrene, p-hydroxystyrene, and α-methyl-p-hydroxystyrene Less - kind. These compounds (a3) can be used singly or in combination. As a preferable specific example of the copolymer (A) used in the present invention, for example, methacrylic acid/trimethyl methacrylate [5.2.1.0''6] decane-8-yl ester / 2-methylcyclohexyl acrylate can be cited. Ester/glycidyl methacrylate/styrene copolymer, methacrylic acid/tetrahydrofurfuryl methacrylate/glycidyl methacrylate/N-cyclohexylmaleimide/dodecyl methacrylate Base ester / α-methyl-p-hydroxystyrene copolymer, styrene / methacrylic acid / glycidyl methacrylate / methacrylic acid (3-ethyloxetan-3-yl ester) / a tricyclo[5.2.1.02,6]decane-8-yl ester copolymer of methacrylic acid or the like. The polystyrene-equivalent weight average molecular weight (hereinafter referred to as "M w") measured by gel permeation chromatography of the copolymer (Α) used in the present invention is preferably -19-201033737 2xl 〇 3 to lxl 〇 5, more It is preferably 5xl03~5xl04. If the Mw is less than 2 Å, the development margin may be insufficient, and the resulting coating film ratio may be lowered, and the pattern shape and heat resistance of the obtained interlayer insulating film may be poor. On the other hand, if it exceeds lxlO5, the sensitivity 1 will appear and the pattern shape will deteriorate. Further, the molecular weight distribution (hereinafter, "Mw/Mn", wherein the Μη is a polystyrene-equivalent number average molecular weight for gel permeation of the copolymer (A)) is preferably 5.0 or less, and is 3.0 or less. If Mw/Mn exceeds 5.0, the pattern shape of the obtained layer film may be deteriorated. The radiation-sensitive resin containing the copolymer (A) as described above does not cause development residue during development, and the pre-pattern shape can be easily formed. The solvent to be used in the preparation of the copolymer (A) may, for example, be a glycol dialkyl ether, a propylene glycol alkyl ether acetate, a propylene glycol alkyl ether ester, a ketone or an alkoxy propionate. Ο As a specific example thereof, as the diethylene glycol dialkyl ether, for example, diglyme, diethylene glycol diethyl ether, or diethylene glycol ethyl methyl acid may be used as the propylene glycol alkyl ether acetate. For example, propylene glycol acetate, propylene glycol diethyl ether acetate, propylene glycol propyl ether acetate, and the like; and examples of the alkoxypropion acid ester include 3-methoxypropionic acid. Among them, preferred are diethylene glycol dialkyl ether, propylene glycol alkyl ether ethyl acetate alkoxy propionate, and particularly preferably diethylene glycol dimethyl ether, diethylene glycol methyl ether, propylene glycol diethyl ether acetate, propylene glycol. Methyl ether acetate, 3·1 03, the residual change: lower, called the better spectral composition, such as dipropionic acid enumeration; etc.: methyl ether methyl ester, ethyl - methoxy 20- 201033737 Methyl propionate. As the polymerization initiator used in the preparation of the copolymer (A), a polymerization initiator which is generally known as a radical polymerization initiator can be used. For example, 2,2'-azobisisobutyronitrile, 2,2'-azobis-(2,4-dimethylvaleronitrile), 2,2'-azobis-(4-methoxy) An azo compound such as benzyl-2,4·dimethylvaleronitrile. In the preparation of the copolymer (A), a molecular weight regulator for adjusting the molecular weight can also be used. Specific examples thereof include mercaptan such as n-hexyl mercaptan, n-octyl mercaptan, n-dodecyl mercaptan, tridodecyl mercaptan, and mercaptoacetic acid; dimethyl xanthone sulfide; diisopropyl Xanthene ketones such as ketone ketone disulfide; terpinolene, α-methyl styrene dimer, and the like. <Compound (Β)> The compound (Β) used in the present invention is a 1,2-quinonediazide compound capable of generating a carboxylic acid by irradiation with a ray, and a phenolic compound or an alcoholic compound (hereinafter referred to as " A condensate of a parent core ") with 1,2-naphthoquinonediazide sulfonium halide. Examples of the mother nucleus include trihydroxybenzophenone, tetrahydroxybenzophenone, pentahydroxybenzophenone, hexahydroxybenzophenone, and (polyhydroxyphenyl)alkane. Specific examples of the trihydroxybenzophenone include 2,3,4-trihydroxybenzophenone and 2,4,6-trihydroxybenzophenone; and tetrahydroxybenzophenone includes 2 , 2',4,4'-tetrahydroxybenzophenone, 2,3,4,3'-tetrahydroxybenzophenone, 2,3,4,4'-tetrahydroxybenzophenone, 2,3,4 , 2'-tetrahydroxy-4'-methylbenzophenone, 2,3,4,4'-tetrahydroxy-3'-methoxybenzophenone, etc.; -21- 201033737 as pentahydroxybenzophenone, For example, 2,3,4,2',6'-pentahydroxybenzophenone or the like can be mentioned; as the hexahydroxybenzophenone, for example, 2,4,6,3',4',5'-hexahydroxydi can be mentioned. Benzophenone, 3,4,5,3',4',5'-hexahydroxybenzophenone, etc.; (polyhydroxyphenyl) alkane, for example, bis(2,4-dihydroxyphenyl)methane, Di(p-hydroxyphenyl)methane, tris(p-hydroxyphenyl)methane, 1,1,1·tris(p-hydroxyphenyl)ethane, bis(2,3,4-trihydroxyphenyl)methane, 2 ,2-bis(2,3,4·trihydroxyphenyl)propane, 1,1,3-tris(2,5-dimethyl-4-hydroxyphenyl)-3-phenylpropane, 4,4 '-[1-[4-[1-[4-Hydroxyphenyl]-1- Ethylethyl]phenyl]ethylidene]bisphenol, bis(2,5-dimethyl-4-hydroxyphenyl)-2-hydroxyphenylmethane, 3,3,3',3'-tetra Base-1,1'-spirobisindole_5,6,7,5',6',7'-hexaol, 2,2,4-trimethyl-7,2',4'-trihydroxy yellow In addition to the above, a 1,2-naphthoquinonediazidesulfonamide such as 2,3,4-tri3, which is obtained by changing the ester bond of the parent core exemplified above to a guanamine bond, may be suitably used. Hydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonamide and the like. Among these cores, 2,3,4,4'-tetrahydroxybenzophenone, 4,4'-[1-[4-[1-[4-hydroxyphenyl]-1-methyl-B is preferred Phenyl]ethylidene]bisphenol. As the 1,2-naphthoquinonediazidesulfonium halide, 1,2-naphthoquinonediazidesulfonium chloride is preferred. As a specific example thereof, 1,2-naphthoquinonediazide-4- chlorobenzene and 1,2-naphthoquinone-5-sulfonyl chloride can be cited. Among them, hydrazine, 2 naphthoquinonediazide-5-sulfonyl chloride is preferably used. In the condensation reaction, a ruthenium equivalent to 30 to 85 mol%, more preferably 50 to 7 mol%, and 2 naphthoquinone-22-201033737 may be used with respect to the number of hydroxyl groups in the mother nucleus. Nitrosulfuronium halide. The condensation reaction can be carried out by a known method. These compounds (B) may be used alone or in combination of two or more. The use ratio of the compound (B) is preferably 5 to 100 parts by mass, more preferably 1 to 50 parts by mass, per part by mass of the (A) alkali-soluble resin. When the ratio is 5 to 100 parts by mass, the difference between the solubility of the irradiated portion and the unirradiated portion with respect to the aqueous alkali solution as the developing solution is large, so that the pattern is good, and the heat resistance and solvent resistance of the obtained interlayer insulating film are obtained. Good sex

<Copolymer (C)> The copolymer (C) in the present invention is a copolymer of a polymerizable unsaturated compound containing the above compound (cl), compound (c2) and compound (c3), and is in the present invention. The resin composition for forming an interlayer insulating film functions as a surfactant having a high surface tension reducing performance, and even if used at a small ratio, the surface smoothness of the coating film can be improved, so that the formation can be remarkably improved. The film thickness uniformity of the interlayer insulating film. The copolymer (C) preferably contains (c4) a polymerizable unsaturated compound having a group having 1 to 8 carbon atoms in addition to the above compound (cl), compound (c2) and compound (c3) (hereinafter referred to as More preferably, the copolymer of the polymerizable unsaturated compound of the "compound (c4)") contains (c5) a molecule in addition to the above compound (c1), compound (c2), compound (c3) and compound (c4). A copolymer of a polymerizable unsaturated compound having two or more unsaturated bonds (hereinafter referred to as "compound (c 5),)) is particularly preferably a compound (cl) or a compound (c2) a copolymer of a polymerizable unsaturated compound composed of the compound (c3), the compound (c4), and -23-201033737 compound (c5). The group in the above formula (1°) - CaH2tt- is a methylene group or an alkane a methylidene group or a linear or branched alkylene group, when the group -CaH2a• is asymmetric, the bonding direction does not matter. The number of carbon atoms a of the group -C„H2a- is preferably 2 to 4 . Specific examples of the group -CaH2a- include, for example, 1,2-extended ethyl group, 1,2-propanyl group, 1,3-propanyl group, 1,4-tert-butyl group, and the like. 1,2-extended ethyl or 1,3-propanyl, particularly preferably 1,2-extended ethyl. The group CPF2P+1 in the above formula (1°) is a linear or branched fluoro-extension W alkyl group having a carbon number β of from 1 to 2 0, preferably from 4 to 12, particularly preferably 8 . The group CPF2P+1 is preferably a linear fluoroalkylene group. The compound (cl) in the present invention is preferably a compound represented by the following formula (1), CH2 = CR1COO-CH2CH2C8Fi7 (1) (In the formula (1), R1 is the same as defined in the above formula (1°) ). Specific examples thereof include compounds represented by the following formulas (cl-1) and (Cl-2). Reference CH2 = CHCO〇CH2CH2(CF2)7CF3 (cl - 1) CH2 = C(CH3)COOCH2CH2(CF2)7CF3 (cl - 2) The group in the above formula (2°)-(:γΗ2γ- is linear Or a branched alkyl group. When the group -ϋγΗ2γ• is asymmetric, the direction of bonding does not matter. As a specific example of the group -(:γΗ2γ-, for example, 1,2-extended ethyl and 1, 2-propyl group, preferably 1,2-extended ethyl group. The compound (c2) may be a mixture of compounds having a repeating number of units a in the above formula (2°). The average number of a is 1 ~30, preferably -24-201033737 2~20, particularly preferably 4~12. The enthalpy of a can be calculated by calculating the polystyrene-equivalent number average molecular weight of the compound (c2) by gel permeation chromatography. The compound (c2) in the present invention is preferably a compound represented by the following formula (2): CH2 = CR2C00-(C2H40)aR3 (2) In the formula (2), R2 and R3 are respectively the above formula The definition in (2°) is the same, and the average number 重复 of the number of repeating units a is 4 to 12. Φ As such a compound (c2), a commercially available product can be applied, and as an example thereof, for example, Shin-Nakamura NK-ester Μ - 40G, Μ - 90G, AM - 90G produced by Industrial Co., Ltd.; B lemmer - PME-200, PME-400, PME- 5 5 0, etc. produced by Nippon Oil Co., Ltd. In the formula (3), when R5 and R6 are each present in plurality, each R5 may be the same 'may be different, and each R6 may be the same or different. In addition, in the above formula (4), when Ri and Rii When there are a plurality of R1Q, each R1Q may be the same 'may be different', and each R11 may be the same or different. As the compound (c3), it is preferred that each of R4, R5 and R6 in the above formula (3) is a carbon atom. A polymerizable unsaturated compound having an alkyl group or a phenyl group of 1 to 20, and each of which has a group represented by the above formula (4), and R8 is preferably a compound of the following formula (c; Compound represented by 3 — 1}.

Rsi 2)d Η (cc=o ο R12 IC=CH2 (C3-1 ) -25- 201033737 (In the formula (c3-l), RSi is a group represented by the above formula (3), and R12 is a hydrogen atom or The methyl group, d is an integer of 1 to 3. Specific examples of the compound (C3) include compounds represented by the following general formulae (c3 to 1-1) to (c3 to 1-3).

-26- 201033737

Η

I C—C=CH〇

II o (C3-1-2)

(In the above formula, Me is a methyl group, Ph is a phenyl group, and r, s, and t are each an integer of 0 to 3). The compound (c4) may, for example, be an alkyl (meth)acrylate having an alkyl group having 1 to 8 carbon atoms, and specific examples thereof include methyl methacrylate and 2-ethylhexyl acrylate. Wait. Specific examples of the above compound (c5) include, for example, both ends of butanediol for carrying out A-27-201033737

The acrylated compound may, for example, be a polyethylene glycol having a polymerization degree of from 1 to 20, a polypropylene glycol having a polymerization degree of from 1 to 20, or the like. As the above-mentioned compound (c5), a commercially available product 'as a specific example thereof' can be used, for example, NK ester 1G, NK ester 2G, NK ester 3G, NK ester 4G, NK ester 9G produced by Shin-Nakamura Chemical Industry Co., Ltd. , NK ester 14G, NK ester 23G, etc. The copolymer (C) in the present invention is a copolymerized product of a polymerizable unsaturated compound containing the compound (cl), the compound (c2) and the compound (c3) as described above. Here, the use ratio of each compound with respect to the total amount of the polymerizable unsaturated compound is 10 to 55 wt% for the compound (cl) and 10 to 50 wt% for the compound (c2), for the compound (c3) , is .5 to 45 wt%. The copolymer (C) is preferably a copolymer of a polymerizable unsaturated compound containing the compound (c4) in addition to the compound (cl), the compound (c2) and the compound (c3). In this case, the use ratio of each compound with respect to the total amount of the polymerizable unsaturated compound is 20 to 50% by weight for the compound (cl) and 15 to 40% by weight for the compound (c2), for the compound ( C3) 'is 10 to 30% by weight, and for compound (c4)' is 20 to 35% by weight. The copolymer (C)' is more preferably a copolymer of a polymerizable unsaturated compound containing a compound (c5) in addition to the compound (cl), the compound (c2), the compound (c3), and the compound (c4). A copolymer of a polymerizable unsaturated compound composed of a compound (cl), a compound (c2), a compound (c3), a compound (c4) and a compound (c5). In this case, the use ratio of each compound is 25 to 35 wt% with respect to the compound (cl) and 20 to 30 wt% with respect to the compound (c2) with respect to the total amount of the polymerizable unsaturated compound, for the compound (c3) It is 15 to 20% by weight, 25 to 35% by weight for the compound (c4) of -28 to 201033737, and 1 to 5% by weight for the compound (C5). The weight average molecular weight (Mw) of the copolymer (C) is preferably from 5,000 to 25,000, more preferably from 1,000,000 to 25,000, particularly preferably from 15,000 to 25,000. The molecular weight distribution Mw/Mn of the copolymer (C) is preferably from 1 to 10, more preferably from 2 to 4. The preparation method of such a copolymer (C) is not particularly limited, and a solution polymerization method, a bulk polymerization method, or the like can be employed according to a known polymerization method such as a radical polymerization method, a cationic polymerization method, an anionic polymerization method, or the like. The preparation is carried out by an emulsion polymerization method or the like, and the radical polymerization method in the solution is industrially preferable because of its simplicity. The polymerization initiator to be used in the preparation of the copolymer (C) may, for example, be a peroxide such as benzamidine peroxide or bismuth peroxide; or an azo such as azobisisobutyronitrile or phenylazotriphenylmethane. Compounds, etc. The preparation of the copolymer (C) can be carried out in any of the presence or absence of a solvent, and is preferably carried out in the presence of a solvent from the viewpoint of workability. Examples of the solvent include an alcohol, a ketone, an ester, an alkyl Φ ester of a monocarboxylic acid, a polar solvent, an ether, propylene glycol and an ester thereof, a halogenated hydrocarbon, an aromatic hydrocarbon, and a fluorinated inert liquid. Examples of the alcohol include ethanol, isopropanol, n-butanol, isobutanol, and third butanol. Examples of the ketone include acetone, methyl ethyl ketone, methyl isobutyl ketone, and methyl alcohol. Examples of the ester include methyl acetate, ethyl acetate, butyl acetate, methyl lactate, ethyl lactate, and butyl lactate. Examples of the alkyl ester of the monocarboxylic acid include, for example, alkyl esters. 2-hydroxypropionic acid -29- 201033737 Methyl ester, ethyl 2-hydroxypropionate, propyl 2-hydroxypropionate, butyl 2-hydroxypropionate, methyl 2-methoxypropionate, 2-methoxy Ethyl propyl propionate, propyl 2-methoxypropionate, butyl 2-methoxypropionate, etc.; as the above polar solvent, for example, dimethylformamide, dimethyl hydrazine, N- Methylpyrrolidone or the like; examples of the ether include methyl cellosolve, cellosolve, butyl cellosolve, butyl carbitol, ethyl cellosolve acetate, tetrahydrofuran, dioxane, and the like; Examples of the propylene glycol and the ester thereof include, for example, propylene glycol, propylene glycol monomethyl ether, and propylene glycol monomethyl ether acetate. The ester, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether acetate, etc., and the halogenated hydrocarbon may, for example, be 1,1,1-trichloroethane or chloroform; and the aromatic hydrocarbon may, for example, be mentioned. Benzene, toluene, xylene, etc., and examples of the fluorinated inert liquid include perfluorooctane and perfluorotri-n-butylamine, and any of them may be used. In the preparation of the copolymer (C), a chain transfer agent such as decanedithiol, 2-mercaptoethanol, ethyl decylacetate or octyl thioglycolate may be further used as needed. In the radiation sensitive resin composition of the present invention, the use ratio of the copolymer (C) is preferably 0.01 to 3 parts by mass, more preferably 0.05 to 2 parts by mass, per 100 parts by mass of the (A) alkali-soluble resin. Here, when the copolymer (C) is used in a ratio of 0.01 to 3 parts by mass, the coating film formed by the slit die coating method has a good mold thickness uniformity. If the cerium exceeds 3 parts by mass, a film crack is likely to occur in the coating film, and the film thickness uniformity of the formed interlayer -30-201033737 may be impaired. <Other components> The radiation sensitive resin composition of the present invention contains the copolymer (A), the compound (B) and the copolymer (C) as described above as essential components, and may further contain (D if necessary) a heat-sensitive acid generating compound, (E) a polymerizable compound containing at least one ethylenically unsaturated double bond (hereinafter referred to as "(E) component"), and (F) an epoxy resin other than the copolymer (A) (hereinafter) It is called "(F) component"), (G) adhesion aid, (H) radical trapping agent, etc. m [(D) heat-sensitive acid generating compound] The (D) heat-sensitive acid generating compound is a compound which generates an acid by heating, and may be contained in the radiation sensitive resin composition of the present invention in order to improve heat resistance and hardness. Specific examples thereof include key salts such as an onium salt, a benzothiazole key salt, an ammonium salt, and a scale salt. Specific examples of the onium salt include an alkyl phosphonium salt, a benzyl phosphonium salt, a dibenzyl phosphonium salt, and a substituted benzyl phosphonium salt. Among them, an onium salt and a benzoxadiazole salt are preferably used, and 4-ethyloxyphenyl dimethyl hexafluoroarsenate, benzyl-4-hydroxyphenylmethyl hexafluorophosphate is particularly preferably used. Phosphate, benzyl-4-hydroxyphenylmethylphosphonium hexafluoroantimonate, 4-ethoxycarbonylphenylbenzylmethylphosphonium hexafluoroantimonate, dibenzyl-4-hydroxyphenyl 0 oxime Hexafluoroantimonate, 4-acetoxyphenylbenzyl hexafluoroantimonate, 3-benzylbenzothiazole hexafluoroantimonate. As their commercial products, 'SunaidSI-L85, Sunaid SI-L110, SunaidSI-L145, SunaidSI-L150, SunaidSI-L160 (Sanxin Chemical Industry Co., Ltd.), etc. - 31-201033737 (D) heat-sensitive production The use ratio of the acid compound is preferably 0.1 to 10 parts by mass, more preferably 5 to 5 parts by mass, per 100 parts by mass of the (A) alkali-soluble resin. When the amount is in the range of 0.1 to 1 part by mass, precipitates are not precipitated in the coating film forming step, and an interlayer insulating film having good hardness can be formed. [Component (E)] As the polymerizable compound having at least one ethylenically unsaturated double bond as the component (E), for example, a monofunctional (meth) acrylate, a difunctional (meth) acrylate, or a trifunctional group can be used. The above (meth) acrylate or the like. ^ The above-mentioned monofunctional (meth) acrylate may, for example, be 2-(methyl)propenyloxyethyl-2-hydroxypropylbutyrate or the like. As a commercial product thereof, for example, Aronix M-101, Aronix M-111, Aronix®-114 (above produced by East Asia Synthetic Co., Ltd.); KAYARAD TC-110S, KAY ARAD TC-120S (above by Japanese chemical) (Stock) production); Viscoat 158, Viscoat 23 1 1 (above produced by Osaka Organic Chemical Industry Co., Ltd.), etc. Examples of the above difunctional (meth) acrylate include ethylene bisphenol (meth) acrylate, 1,6-hexane diol di(meth) acrylate, and 1,9 decylene diol ( Methyl) acrylate, polypropylene glycol di(meth) acrylate, tetraethylene glycol di(meth) acrylate, bis(phenoxyethanol) quinone di(meth) acrylate vinegar, and the like. As their commercial products, for example, Aronix®-210, Aronix®-240, Aronix®-6200 (above produced by East Asia Synthetic Co., Ltd.); KAYARAD HDDA, KAYARAD HX-220, KAYARAD R-604 (above) Nissan Chemical Co., Ltd.); Viscoat 260, Viscoat 3 12, Viscoat 3 3 5 HP (above produced by Osaka Organic Chemical Industry Co., Ltd.), etc. Examples of the above trifunctional or higher (meth) acrylate include -32-201033737 such as trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, and tris((meth)propene).醯 oxyethyl) phosphonate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and the like. As its commercial products, for example, Aronix®-309, Aronix®-400, Aronix®-405, Aronix®-450, Aronix®-7100, Aronix®-8030, Aronix®-8060, (the above is synthesized by East Asia) (production)); KAYARAD TMPTA, KAYARAD DPHA, KAYARAD DPCA-20, KAYARAD DPCA-30, KAYARAD DPCA-60, KAYARAD DPCA-120 (above produced by Nippon Kayaku Co., Ltd.); Viscoat 295, Viscoat 300, Viscoat 3 60, Viscoat GPT, Viscoat 3PA, Viscoat 400 (above produced by Osaka Organic Chemical Industry Co., Ltd.). Among them, a trifunctional or higher (meth) acrylate is preferably used, and among them, trimethylolpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(methyl) are particularly preferred. Acrylate. These monofunctional, difunctional or trifunctional or higher (meth) acrylates may be used singly or in combination. The use ratio of the component (E) is preferably 50 parts by mass or less, more preferably 1 to 50 parts by mass, still more preferably 3 to 30 parts by mass, per 100 parts by mass of the (A) alkali-soluble resin. When the use ratio of the component (E) is from 1 to 50 parts by mass, the heat resistance, surface hardness and the like of the obtained interlayer insulating film can be further improved. [Component (F)] The epoxy resin other than the copolymer (A) as the component (F) is a resin having an epoxy group (preferably an epoxy group), and as long as it is to the present invention -33 - 201033737 There is no limitation on the compatibility of the other components contained in the radiation sensitive resin composition. Preferred examples of the component (F) include bisphenol A epoxy resin, phenol novolak epoxy resin, cresol novolac epoxy resin, cyclic aliphatic epoxy resin, and glycidyl ester epoxy resin. A glycidylamine type epoxy resin, a heterocyclic epoxy resin, a resin obtained by (co)polymerization with glycidyl methacrylate, and the like. Among them, a bisphenol A type epoxy resin, a cresol novolac type epoxy resin, a glycidyl ester type epoxy resin, and the like are particularly preferable. The use ratio of the component (F) is preferably 30 parts by mass or less, more preferably 1 to 30 parts by mass, per 100 parts by mass of the (A) alkali-soluble resin. By containing the component (F) in a ratio of 1 to 30 parts by mass, the heat resistance and surface hardness of the interlayer insulating film can be further improved. Further, the copolymer (A) may also be referred to as a bird "epoxy resin", but the copolymer (A) is different from the component (F) in terms of alkali solubility. The component (F) is alkali-insoluble. [(G) Adhesive Aid] In the radiation sensitive resin composition of the present invention, in order to further improve the adhesion to the substrate, (G) an adhesion aid may be used. As such a (G) binder, a functional decane coupling agent is preferably used, and examples thereof include a reactive substituent such as a carboxyl group, a methacryl group, an isocyanate group or an epoxy group (preferably an epoxy group). a functional decane coupling agent. Specifically, for example, trimethoxydecyl benzoic acid, γ-methyl propylene methoxy propyl trimethoxy decane, vinyl triethoxy decane, vinyl trimethoxy decane, γ-isocyanate propyl may be mentioned. Triethoxy decane, γ-glycidoxypropyl-34-201033737 dimethoxy sand, β-(3,4-epoxycyclohexyl)ethyltrimethoxy chopping, etc. The (G) adhesion aid is preferably used in an amount of 20 parts by mass or less, more preferably ido parts by mass, still more preferably 3 to 15 parts by mass, per part by mass of the (a) alkali-soluble resin. When the ratio of use of the (G) adhesion aid is from 1 to 20 parts by mass, the adhesion to the substrate is the best. [(H) radical scavenger] The (H) radical scavenger may be used to further improve the storage stability of the resulting radiation-sensitive resin composition and to increase the film thickness of the interlayer insulating film formed. Used for uniform purposes. As such a (H) radical scavenger, for example, a hindered phenol compound, a hindered amine compound, an alkylphosphonate, a sulfur atom-containing compound (excluding an alkylphosphonate compound), or the like can be used. As a specific example thereof, as the hindered phenol compound, for example, pentaerythritol tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], thiodiethylidene 2-[3- (3,5-di-t-butyl-4-hydroxyphenyl)propionate], octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, Ο W 1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene, 1:^-hexane-1,6-di Bis[3-(3,5-di-t-butyl-4-hydroxyphenylpropionate decylamine)], 3,3',3'',5',5''-penta-t-butyl -(»,〇1',(1''-(mesitylene-2,4-triyl)tri-p-cresol, 4,6-di(octylthiomethyl)-o-cresol, 4,6 - bis(dodecylthiomethyl)-o-cresol, ethyl bis(oxyethyl) bis[3-(5-t-butyl-4-hydroxy-m-tolyl)propionate] , hexyl bis[3-(3,5-di-t-butyl-4-phenylphenyl)propionate], 1,3,5-tris(3,5-di-t-butyl-4- Hydroxybenzyl)-1,3,5-tritrap-2,4,6-(1Η,3Η,5Η)-trione, 1,3,5-tri-35- 201033737 • .

[(4-Tertibutyl-3-hydroxy-2,6-dimethylphenyl)methyl]-1,3,5-tri-trap-2,4,6-(1Η,3Η,5Η)-trione 2,6-di-tert-butyl-4-(4,6-di(octylthio)-1,3,5-tri-2-ylamine)phenol, 1,3,5-tris (3', 5,-Di-tert-butyl-4'-hydroxybenzyl)isocyanuric acid and the like.

As a commercial item thereof, for example, ADK STAB AO-20, ADK STAB AO-30, ADK STAB AO-40, ADK STAB AO-50,

ADK STAB AO- 60, ADK STAB AO- 70, ADK STAB AO — 80, ADK STAB AO — 3 3 0 (above produced by ADEKA); f| sumilizer GM ' sumilizer GS ' sumilizer MDP — S ' sumilizer BBM — S, sumilizer WX — R, sumilizer GA — 80 (above produced by Sumitomo Chemical Co., Ltd.); IRGANOX 1010, IRGANOX 1 03 5, IRGANOX 1 076, IRGANOX 1 098, IRGANOX 1135, IRGANOX 1 3 3 0, IRGANOX 1 726, IRGANOX 1 425WL > IRGANOX 1 520L 'IRGANOX 245 'IRGANOX 259 'IRGANOX 3114, IRGANOX 565, IRGAMOD 295 (above produced by Ciba Japan); Yoshinox BHT, Yoshinox BB, Yoshinox 2246G, ◎

Yoshinox 425, Yoshinox 250 'Yoshinox 93 0 'Yoshinox SS, Yoshinox TT, Yoshinox 917, Yoshinox 314 (above produced by API).

The hindered amine compound may, for example, be tetrakis(2,2,6,6-tetramethyl-4-acridinyl) 1,2,3,4-butanetetracarboxylate or di(1-octyloxy). Base-2,2,6,6-tetramethyl-4-acridinyl) sebacate, bis(1,2,2,6,6-pentamethyl-4-acridinyl)[[3 , 5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]methyl]butyl malonate, etc., as a commercial product thereof, for example, ADK STAB LA-36-201033737 - 52, ADK STAB LA-57, ADK STAB LA-62, ADK STAB LA-67, ADK STAB LA-63P, ADK STAB LA-68LD, ADK STAB LA-77, ADK STAB LA-82, ADK STAB LA-87 ( The above is produced by ADEKA (share); sumilizer 9A (produced by Sumitomo Chemical Co., Ltd.); CHIMASSORB 119FL, CHIMASSORB 2020FDL, CHIMASSORB 944FDL, TINUVIN 622LD, TINUVIN 123, TINUVIN 144, TINUVIN 765, TINUVIN 770DF (above by Ciba specialty chemicals Company production) and so on. As the above alkylphosphonate compound, for example, butylenebis {2-t-butyl-5-methyl-p-phenylene}-? ,? ,? -tetra-tridecyl bis(phosphine), di(octadecyl)pentaerythritol diphosphite, 2,2'-methylenebis(4,6-di-t-butyl-1-phenyl Oxy)(2-ethylhexyloxy)phosphorus, tris(2,4-di-t-butylphenyl)phosphite, 3,9-di(2,6-di-t-butyl-4 -Methylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, etc., as a commercial product thereof, for example, ADK STAB PEP-4C , ADK STAB PEP-8, ADK STAB PEP-8W, ADK STAB PEP-24G, ADK STAB PEP-36, ADK STAB HP-10, ADK STAB 2112, ADK STAB 260, ADK STAB 522A, ADK STAB 1178, ADK STAB 1 5 00, ADK STAB C, ADK STAB 1 3 5 A ' ADK STAB 3010, ADK STAB TPP (above produced by ADEKA); IRGAFOS 168 (produced by Ciba specialty chemicals) and the like. Examples of the sulfur atom-containing compound include pentaerythritol tetrakis(3-dodecylthiopropionate), bis(propionate-n-tridecyl) sulfide, and -37-201033737 thiodiethylene. In addition to bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], a thioether can also be used. As a commercial item of the thioether, for example, ADK STAB AO - 412S ' ADK STAB AO - 503 (above produced by ADEKA); sumilizer TPL - R, sumilizer TPM, sumilizer TPS, sumilizer TP - D, sumilizer MB can be cited. (The above is produced by Sumitomo Chemical Co., Ltd.); IRGANOX PS 800FD, IRGANOX PS802FD, IRGANOX 1035 (produced by Ciba specialty chemicals); DLTP, DSTP, DMTP, DTTP (produced by API) ©etc. Such (H) radical scavengers may be used singly or in combination of two or more. The (Η) radical scavenger may be used in a ratio of 15 parts by weight or less based on 100 parts by mass of the alkali-soluble resin, and may be in the range of 0.01 to 15 parts by mass, and further preferably 1 to 10 parts by mass. The use of the range is effective in that the effect of the (Η) radical scavenger can be effectively exhibited without impairing the radiation sensitivity of the obtained radiation sensitive resin composition. <Radiation-sensitive linear resin composition> ❹ The radiation-sensitive resin composition of the present invention may be obtained by using the above-mentioned (Α) alkali-soluble resin, compound (Β) and copolymer (C), or (Α) alkali-soluble resin, The compound (Β) and the copolymer (C) and the other components as described above are uniformly mixed and prepared. The radiation sensitive resin composition of the present invention is preferably used in the form of a solution dissolved in a suitable solvent. For example, by mixing the (Α) alkali-soluble resin, the compound (Β) and the copolymer (C), and optionally other components at a certain ratio, a radiation-sensitive resin composition in a solution state can be prepared. -38- 201033737 As a solvent which can be used for preparation of the radiation sensitive resin composition of the present invention, it is possible to uniformly dissolve (A) an alkali-soluble resin, a compound (B) and a copolymer (C), and optionally other components. a solvent in which each component is not reacted with each component. As such a solvent, the same solvent as exemplified as the solvent which can be used for the preparation of the above copolymer (A) can be mentioned. In such a solvent, alcohol, ethylene glycol® ether, ethylene glycol alkyl ether acetate is preferably used from the viewpoints of solubility of each component, reactivity with each component, easiness of formation of a coating film, and the like. , esters and diethylene glycol. Among them, benzyl alcohol, 2-phenylethanol, 3-phenyl-1-propanol, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol can be preferably used. Diethyl ether, diethylene glycol ethyl methyl ether, diglyme, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, methyl methoxypropionate, ethyl ethoxy propionate. In order to improve the in-plane uniformity of the film thickness, it is also possible to use a high boiling point solvent together with the above solvent. Examples of the hydrazine boiling point solvent which can be used include 0, for example, N-methylformamide, N,N-dimethylformamide, N-methylformamide, N-methylacetamide, N, N-dimethylacetamide, N-methylpyrrolidone, methylmeridene, benzylidene acid, dihexyl ether, acetone acetone, isophorone, hexanoic acid, octanoic acid, 1-octanol, 1-nonanol, acetic acid vinegar, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, phenyl cellosolve acetate Wait. Among them, preferred are Ν_methylpyrrolidone, γ-butyrolactone, hydrazine, hydrazine-dimethylacetamide. As the solvent of the radiation sensitive resin composition of the present invention, when a high boiling point solvent is used, the amount thereof is preferably from 1 to 4 Å by mass to 39 to 201033737%, more preferably from 3 to 30% by mass based on the total of the solvent. . When the amount of the high boiling point solvent is i-40% by mass, the film thickness uniformity of the coating film is good, and the pattern is also good. When the radiation sensitive resin composition of the present invention is formulated into a solution state, components other than the solvent (ie, (A) alkali-soluble resin, compound (B), and copolymer (C) and optionally added are added to the solution. The ratio of the total amount of other components may be arbitrarily set depending on the purpose of use and the desired film thickness, etc., preferably 5 to 50% by mass, more preferably 10 to 40% by mass, still more preferably 15 ~35 mass%. The composition solution thus prepared can also be filtered by a micropore filter having a pore size of about 2 μm or the like and then supplied. <Method of Forming Interlayer Insulating Film> Next, a method of forming an interlayer insulating film using the radiation sensitive resin composition of the present invention will be described. The method of forming the interlayer insulating film of the present invention is characterized in that the following steps are included in the following order. (1) a step of forming a coating film of the radiation sensitive resin composition of the present invention on a substrate, (2) a step of irradiating at least a part of the coating film, (3) a developing step, and (4) a heating step. [(1) Step of Forming Coating Film of Radiation-Sensitive Resin Composition of the Present Invention on Substrate] In the step (1), the radiation-sensitive resin composition of the present invention is applied to the surface of the substrate. The solvent is removed by prebaking to form a coating film, and the coating film is cured by post-baking. -40-201033737 The type of the substrate which can be used for the formation of the interlayer insulating film is, for example, a glass substrate, a tantalum sheet, and a substrate on which various metals are formed on the surface. The coating method of the resin composition solution is not particularly limited, and may be, for example, a spray coating method, a roll coating method, a spin coating method (spin coating method), a slit die coating method, a bar coating method, an inkjet method, or the like. The method is particularly preferably a spin coating method or a slit die coating method. In particular, when the slit die coating method is employed, the advantageous effects of the present invention can be exerted to the utmost extent, and therefore it is preferable. ❹

The conditions for prebaking and post-baking are appropriately set depending on the type of each component, the use ratio, and the like. The prebaking can be carried out, for example, at 70 to 90 ° C for about 1 to 15 minutes. The post-baking can be carried out by using a suitable heating means such as a hot plate or a clean oven. The temperature for post-baking is preferably from 120 to 25 °C. As the post-baking time, when a heating plate is used as the heating means, it is preferably carried out for 5 to 30 minutes, and when a clean oven is used as the heating means, it is preferably carried out for 30 to 90 minutes. The thickness of the coating film thus formed is preferably from 0.1 to 8 μm, more preferably from 0.1 to 6 μm, and even more preferably from 〇.·ι to 4 μηι. [(2) Step of irradiating at least a part of the coating film] In the step (2), the formed coating film is irradiated with a ray by a mask having a predetermined pattern. As the rays which can be used at this time, for example, ultraviolet rays, far ultraviolet rays, and the like can be listed. Examples of the ultraviolet rays include a g line (wavelength of 4 6 nm), an i line (wavelength of 3 6 511111), and the like. Examples of the far ultraviolet rays include KrF quasi-molecular lasers and the like. Among them, ultraviolet rays are preferred, and particularly preferably, rays of at least one bright line selected from the group consisting of g-line and i-line are selected from -41 to 201033737. The irradiation amount of the rays is preferably from 1 5 00 to 3 000 J/m 2 . Further, when the radiation sensitive resin composition of the present invention is used, even when the irradiation amount of the radiation is 2000 J/m 2 or less, a desired pattern can be formed even when the enthalpy is 1 700 J/m 2 or less. It is also possible to form the advantages of the desired pattern. [(3) Developing Step] Then, in the step (3), the coating film after the irradiation ray ® is developed by using a developing solution, and the irradiated portion is removed to form a pattern. As the developing solution used in the developing step, for example, an aqueous solution of a base (basic compound) such as sodium hydroxide, potassium hydroxide, sodium carbonate, tetramethylammonium hydroxide or tetraethylammonium hydroxide can be used. Further, an aqueous solution of a water-soluble organic solvent such as methanol or ethanol or a surfactant, or various organic solvents in which the composition of the present invention is dissolved may be added to the aqueous alkali solution as a developing solution. As the developing method, for example, a suitable method such as a flow spread coating method, a dipping method, a shaking dipping method, or a rinsing method can be employed. The development time varies depending on the composition of the radiation sensitive resin composition, and may be, for example, 30 to 120 seconds. Further, in the previously known radiation sensitive resin composition, if the development time exceeds the optimum enthalpy by more than 20 to 25 seconds, the formed pattern may fall off, so that the development time must be strictly controlled, and the feeling of the present invention is In the case of the radiation-linear resin composition, even if the time exceeding the optimum development time reaches 30 seconds or more, a good pattern can be formed, and there is an advantage in the product yield of -42-201033737. After the (3) development step, a rinsing treatment such as running water washing is preferably performed, and it is preferred to irradiate (post-exposure) the entire surface of the patterned coating film by using a high-pressure mercury lamp or the like in the patterned coating film. The residual (B) 1,2-quinonediazide compound is subjected to decomposition treatment. The amount of radiation exposure in the post-exposure step is preferably about 2,000 to 5,000 J/m2. [(4) Heating step] Finally, in the step (4), the patterned coating film is subjected to a curing treatment by heat treatment (post-baking treatment) using a heating device such as a hot plate or a supply box. The heating temperature in the step (4) is, for example, 120 to 250 °C. The heating time varies depending on the type of the heating machine. For example, it may be 5 to 30 minutes when heat-treated on a hot plate, and may be 30 to 90 minutes when heat-treated in an oven. In this case, a stepwise baking method or the like which performs two or more heating steps may be employed. Thus, a pattern-like film corresponding to the target interlayer insulating film can be formed on the surface of the substrate. <Interlayer insulating film> It is understood from the following examples that the interlayer insulating film formed as described above is excellent in adhesion to a substrate, excellent in heat resistance, solvent resistance, transparency, and the like, and has a low dielectric constant. Therefore, it can be suitably used as an interlayer insulating film of various electronic products. [Examples] Hereinafter, the present invention will be more specifically described by way of Examples, but the present invention is not limited to these Examples. In addition, the weight of the polymer - 43 - 201033737, the average molecular weight (Mw) and the number average molecular weight (Μη) ) was determined by gel permeation chromatography (GPC) using the following conditions. Measuring device: "H L C 8 2 2 0 system" manufactured by Τ 〇 s 〇 h (share) Separation column: TSK gel GMHhr-N manufactured by Tosoh (strand) is connected in series

Column temperature: 40 °C Elution solvent: tetrahydrofuran (produced by Wako Pure Chemical Industries, Ltd.) Flow rate: 1.0 ml/min® Sample concentration: 1.0% by mass Sample injection amount: ΙΟΟμιη Detector: Differential refractometer standard substance : Monodisperse polystyrene In addition, the solution viscosity of the radiation sensitive resin composition was measured at 30 ° C using a Ε-type viscometer manufactured by Tokyo Keiki Co., Ltd. <Synthesis of Copolymer (A)> Synthesis Example 1 ❹ To a flask equipped with a cooling tube and a stirrer, 7 parts by weight of 2,2'-azobis(2,4-dimethylvaleronitrile) and 200 parts by weight of diethylene glycol ethyl methyl ether were added. Continue to add 16 parts by weight of methacrylic acid, 16 parts by weight of tricyclo[5.2.1.0''6]nonane-8-yl methacrylate, 20 parts by weight of 2-methylcyclohexyl acrylate, 40 parts by weight of methacrylic acid Glycidyl ester, 1 part by weight of styrene and 3 parts by weight of α-methylstyrene dimer were slowly stirred after replacement with nitrogen. The temperature of the solution was raised to 70 ° C, and the temperature was maintained for 4 hours to obtain a polymer solution containing the copolymer (A-1). -44 - 201033737 The copolymer (A-1) had a polystyrene-equivalent weight average molecular weight (Mw) of 8,000 and a molecular weight distribution (Μw/Mn) of 2.3. Further, the solid content concentration of the polymer solution prepared here (the ratio of the weight of the polymer contained in the polymer solution to the total weight of the polymer solution, the same hereinafter) was 34.4% by weight. Synthesis Example 2 '8 parts by weight of 2,2'-azobis(2,4-dimethylvaleronitrile) and 220 parts by weight of diethylene glycol ethylmethyl group were added to a flask equipped with a cooling tube and a stirrer ether. Continue to add 11 parts by weight of methacrylic acid, 12 parts by weight of tetrahydrofurfuryl methacrylate, 40 parts by weight of glycidyl methacrylate, 15 parts by weight of N-cyclohexylmaleimide, 10 parts by weight of methacrylic acid The dodecyl ester, 10 parts by weight of α-methyl-p-hydroxystyrene, and 3 parts by weight of the α-methylstyrene dimer were slowly stirred after replacement with nitrogen. The temperature of the solution was raised to 70 ° C, and the temperature was maintained for 5 hours to obtain a polymer solution containing a copolymer (Α-2). The copolymer (A-2) had a polystyrene-equivalent weight average molecular weight (Mw) of 8,000 and a molecular weight distribution (Mw/Mn) of 2.3. Further, the solid content concentration of the polymer solution prepared here was 31.9% by weight»<Synthesis of Copolymer (C)> Synthesis Example 3 Into a glass flask equipped with a stirring device, a condenser and a thermometer, it was added as ( Cl) 28.4 parts by mass of the compound represented by the above formula (cl-1), 20.7 parts by mass of NK-esterM-90G (trade name, manufactured by Shin-Nakamura Chemical Co., Ltd.) as the compound (c2), as the compound (c3) 18.1 parts by mass of the compound represented by the following formula (c3 - -45 - 201033737 1-1 - 1), 5.9 parts by mass of methyl methacrylate as the compound (c4), and 23.5 parts by mass of 2-ethylhexyl acrylate, 3.4 parts by mass of a compound in which both ends of butanediol of the compound (c5) were methacrylated, and 414 parts by mass of isopropanol as a solvent were added as a polymerization initiator under reflux in a nitrogen stream. 0.7 parts by mass of 2,2,-azobisisobutyronitrile and 4 parts by mass of dodecylmercaptan as a chain transfer agent were copolymerized at 75 ° C for 8 hours to obtain a copolymer (c-1). )The solution. Then, use an evaporator at 7 〇. (: The solvent was removed under heating, ® was used to separate the copolymer (C-1). The obtained copolymer (C-1) had a number average molecular weight Mn of 2,800, a weight average molecular weight Mw of 50,000, and a molecular weight distribution (Mw/Mn). ) is 1.9.

Me·

Me

•Si—Ο

Me I o—c—c=ch2II o (C3-1-1-1 )

Me (Me is a methyl group in the above formula). -46 201033737 Synthesis Example 4 In the above Synthesis Example 3, a copolymer (C-2) was obtained in the same manner as in Synthesis Example 3 except that the amount of dodecyl mercaptan as a chain transfer agent was changed to 1 part by mass. ). The obtained copolymer (C-2) had a number average molecular weight Μη of 4,700, a weight average molecular weight Mw of 11 Å, and a molecular weight distribution (Mw/M η) of 2.3. Synthesis Example 5 In the same manner as in Synthesis Example 3, in the above-mentioned Synthesis Example 3, the dodecyl-based mercaptan as the chain transfer agent was not used, and the copolymerization temperature and time were 73 ° C and 1 Torr, respectively. The operation was carried out to obtain a copolymer (C-3). The obtained copolymer (C-3) had a number average molecular weight Μη of 5,600, a weight average molecular weight Mw of 21,000, and a molecular weight distribution (Mw/Mn) of 3.8. Synthesis Example 6 To a glass flask equipped with a stirring device, a condenser and a thermometer, 39.4 parts by mass of a compound represented by the above formula (cl-1) as a compound of (cl), and NK-esterM- as a compound of (c2) were added. 303.6 (manufactured by Shin-Nakamura Chemical Co., Ltd.) 31.6 parts by mass, 29.0 parts by mass of the compound represented by the above formula (c3-1 to 1-1) as the compound (c3), and 414 parts by mass of isopropanol as a solvent in nitrogen In the stream, 0.7 parts by mass of azobisisobutyronitrile as a polymerization initiator and 4 parts by mass of dodecylmercaptan as a chain transfer agent were added under reflux, and then refluxed at 75 ° C for 8 hours to carry out copolymerization. A solution containing the copolymer (C-4) was obtained. Then, the solvent was removed by heating at 70 ° C with an evaporator to separate the copolymer (C-4). The molecular weight of the obtained copolymer (C-4) having a number average molecular weight of 3,000 Å -47 - 201033737 and an average molecular weight of 6,000. Further, the molecular weight distribution (Μ w/Mn) was 2.0. Synthesis Example 7 28.4 parts by mass of a compound represented by the above formula (cl-1) as a compound of (cl) was added to a glass flask equipped with a stirring device, a condenser and a thermometer, and NK-ester M-90G as a compound of (c2) (manufactured by Shin-Nakamura Chemical Co., Ltd.) 20.7 parts by mass, 21.5 parts by mass of the compound represented by the above formula (c3 - 1 - 1 - 1) as the compound (c3), and methyl methacrylate 5.9 as the compound (c4) 2 parts by mass of 2-ethylhexyl acrylate and 4 14 parts by mass of isopropanol as a solvent, and 2,2'-azo two as a polymerization initiator were added under reflux in a nitrogen stream. 0.7 parts by mass of isobutyronitrile and 4 parts by mass of dodecylmercaptan as a chain transfer agent were copolymerized at 75 ° C for 8 hours to obtain a solution containing the copolymer (C - 5 ). Then, the solvent was removed by heating at 7 ° C with an evaporator to separate the copolymer (C -5) » The obtained copolymer (C-5) had a number average molecular weight Μη of 2,600 and a weight average molecular weight Mw of 5000. Further, the molecular weight distribution (Mw/Mn) was 1.9.实施 Example 1 [Preparation of a radiation-sensitive resin composition] The content of the copolymer (A-1) corresponding to 100 parts by mass (solid content) of the copolymer (A) was synthesized in the above Synthesis Example 1. a solution of the copolymer (A-1), 30 parts by mass of 4,4'-[1-[4-[1-[4-hydroxyphenyl]-methylethyl]phenyl]phenylene as a compound of (B) a condensate of bisphenol (1.0 mol) with 12-naphthoquinonediazide-5-sulfonyl chloride (2.0 mol) (B-1), and 5 parts by mass of (C) copolymer The copolymer obtained in the above Synthesis Example 3 (c-indole was mixed with -48-201033737, and after adding diethylene glycol methyl ethyl ether as a solvent, it was filtered with a membrane filter having a pore size of 0.2 μm to prepare a feeling. Radiation-linear resin composition (S-1) [Evaluation of performance as interlayer insulating film] (1) Appearance evaluation of coating film On a 550x650 mm chrome-plated glass, a slot die coater (Tokyo Chemical Industry Co., Ltd.) was used. (manufactured by the company), model "TR6321 05 - CL") coated with the above-mentioned radiation-sensitive resin composition (S-1), set to a pressure of 1000 Pa, at After removing the solvent under vacuum, it was prebaked at 90 ° C for 2 minutes to form a coating film having a film thickness of Ι.Ομιη. The coating film was visually observed under a sodium lamp to observe the appearance. At this time, the entire film was smoked. The smudges are called "smoke spots", and the plaques originating from the proximate pins in the pre-baking furnace are called "pins", and their appearance is investigated. When these plaques are basically not visible, the evaluation is "good". When any of these marks can be seen slightly, the evaluation is “slightly unqualified”, and when it can be clearly seen, the evaluation is “failed.” The evaluation results are listed in Table 1. (2) Sensitivity Evaluation was carried out by coating hexamethyldioxane (HMDS) on a 550 x 650 mm chrome-plated glass and heating it at 60 ° C for 1 minute to form HMDS. After the HMDS treatment, chromium was formed. On the glass of the film, the above-mentioned radiation-sensitive resin composition (S-1) was applied by a slot die coater ("TR63 2 1 0 5 - CL", and the pressure reached was set to 100 Pa, and the solution was removed under vacuum. - 201033737 after the agent, Prebaking at 90 ° C for 2 minutes to form a film having a film thickness of 3.0 μm. Using a MPA-600FA exposure machine manufactured by Canon, masking with a line of 3.0 μm and a gap (1〇 to 1) The mold was irradiated with radiation as a variable, and the developed film was irradiated with a tetramethylammonium hydroxide aqueous solution having a concentration shown in Table 1, and developed by a flow spread coating method at 25 ° C. When a developer having a tetramethylammonium hydroxide concentration of 0.4% by mass was used, it was 80 seconds, and when it was 2.38 mass. /. The developer ^ is 50 seconds. Next, it was rinsed with ultrapure water for 1 minute, and then dried to form a pattern on a glass substrate on which a chromium film was formed by HMDS treatment. At this time, the amount of exposure required to completely dissolve the gap and pattern of the 3. Ομιη line and the gap (10 to 1) was investigated. The sensitivity is listed in Table 1. When the enthalpy is 2000 J/m2 or less, the sensitivity can be considered to be good, and when it is 1700 J/m2 or less, the sensitivity can be considered to be excellent. (3) Evaluation of development margin e The glass in which the chromium film was formed was subjected to HMDS treatment in the same manner as in the above "(2) Evaluation of sensitivity". On the glass on which the chrome film was formed after the HMDS treatment, the above-mentioned radiation-sensitive resin composition (S-1) was applied by a slit die coater ("TR632105-CL"), and the pressure reached was set to i〇〇pa. After removing the solvent under vacuum drying, it was prebaked at 90 ° C for 2 minutes to form a coating film having a film thickness of 3.0 μm. The ΜΡ Α — 600 FA exposure machine manufactured by Canon was passed through with 3 · 0 μm The line and gap (10 to 1) pattern of the mask is exposed to the exposure film corresponding to the sensitivity 测定 measured in "(2) Sensitivity Evaluation" on -50-201033737, and then, using Table 1 The hydrogen v-ammonium aqueous solution of the indicated concentration was developed with a development time as a variable, and developed under a flow spread of 25 t. Next, it was subjected to ultrapure water for 1 minute and then dried, and chromium formation was formed after treatment with HMDS. At this time, the preferred development time required to make the line width of the line 3.0 μη is listed in Table 1. And, when the development is continued from the optimum development, the measurement is continued until the 3. Ομπι line/pattern is peeled off. This time is listed as the development margin 1. When the 値 is 30, the development margin can be considered as good. (4) Evaluation of solvent resistance on a 550x650 mm chrome-plated glass, produced by Tokyo Chemical Industry Co., Ltd., model number TR632105 - The above-prepared radiation sensitive resin composition (S - 1 ) was set to 100 Pa, and the solvent was removed under vacuum, and then at 90 ° C to form a coating film. Using an MPA machine manufactured by Canon, The coating film was heated at 2200 ° C for 1 hour at a cumulative irradiation amount of 9000 J/m 2 to form a cured film having a film thickness of 3.0 μm formed thereon. Here, the obtained cured film was measured. Film thickness (Τ1). Then, the chrome film glass substrate of the cured film was immersed at a temperature of 7 ° C for 20 minutes, and the film thickness (t1) of the cured film was measured again, resulting in a film thickness change rate {|tl- Tl|/Tl}xl00 [%]. The coating oxidized tetramethyl coating method is applied in: running water, the filming time of the film is the time of the most time, and when the film is over, the coating is applied by the slit die. CL") coated with a pressure of pre-baked 2 points 600FA exposure light, then glass in the chrome film The immersion results will be calculated from the immersion results listed in Table-51-201033737. 1. When the enthalpy is 5% or less, the solvent resistance can be considered to be good. (5) Evaluation of heat resistance and the above "( 4) Evaluation of Solvent Resistance In the same manner, a cured film having a film thickness of 3.Ομη was formed on the glass on which the chromium film was formed. The film thickness (Τ2) of the cured film obtained here was measured. Then, the curing was formed. The chrome-plated glass substrate of the film was placed in a clean oven. After additional heating at 240 ° C for 1 hour, the thickness (t2) of the cured film was measured again, and the film thickness change rate caused by additional heating was calculated {|t2 - Τ 2| / Τ2}χ100 [%]. The results are shown in Table 1. When the enthalpy is 5% or less, the heat resistance can be considered to be good. (6) Evaluation of transparency In the above "(4) Evaluation of solvent resistance", a glass substrate "NA35 (manufactured by NH Techno Glass Co., Ltd.)" of 550 x 650 mm was used instead of the chromium film. The same operation was carried out except for the glass substrate to form a cured film on the glass substrate. Using a spectrophotometer "150-20 type double beam (manufactured by Hitachi, Ltd.), a glass-glass substrate having no protective film was used as a reference, and the light transmittance of the glass-based raft having the cured film was measured in the wavelength range of 400 to 800 nm. The lowest transmittance at this time is shown in Table 1. When the enthalpy is 90% or more, the transparency can be considered to be good. (7) Evaluation of film thickness uniformity and the above "(6) Evaluation of transparency Similarly, a cured film was formed on the glass substrate. The film thickness was measured at 20 measurement points of the cured film, and film thickness uniformity was obtained according to the following formula. Film thickness uniformity (%) = (coating film thickness) The maximum uniformity is 値100/((the average thickness of the coating film at 20 points) χ2) -52- 201033737 If the uniformity of the coating film thickness obtained in this way is 1% or less, the uniformity can be considered to be good. The above 20 measurement points are determined as follows: that is, the range from the long side and the short side of the substrate (550 x 650 mm) is inwardly 50 mm, and the inner area (4 5 Ox 5 50 mm) is used as the measurement area. In the area, on the straight line in the long side direction and the short side direction, Do not determine 10 points (20 points in total) every 40 mm, and use it as a measurement point. (8) Evaluation of relative dielectric constant The surface is flattened by polishing with a sisal polishing wheel (hemp polishing wheel) On the SUS 304 substrate, the above-mentioned radiation-sensitive resin composition (S-1) was applied by a spin coating method, and the pressure reached was set to 100 Pa, and the solvent was removed under vacuum, followed by prebaking at 90 °C. In minutes, a coating film having a film thickness of 3.0 μm was formed. The resulting coating film was exposed to a cumulative irradiation amount of 9000 J/m 2 using an MPA-600FA exposure machine manufactured by Canon, and the substrate was placed in a clean oven. After heating at 220 ° C for 1 hour, a cured film was formed on the SUS substrate, and a Pt/Pd electrode pattern was formed on the cured film by a vapor deposition method to prepare a sample for measuring a dielectric constant. The relative dielectric constants of the HP 1 645 1 B electrode and the HP 4284A precision LCR meter manufactured by Yokogawa Hewlett-Packard Company were measured by the CV method at a frequency of 10 kHz. The results are shown in Table 1. When the 値 is 3.9 or less, the dielectric constant can be determined Examples 2 to 7 and Comparative Examples 1 to 3 [Preparation of Radiation-sensitive Resin Composition] -53- 201033737 In Example 1, the types and amounts of the respective components other than the radiation-sensitive resin composition were respectively The radiation sensitive resin compositions (S - 2) to (S - 7) and (s - 1) to (S-3) were prepared in the same manner as in Example 1 except as shown in Table 1. Evaluation was carried out using these compositions. B-1 as compound (B) used in these examples and comparative examples is 4,4'-[1-[4-[1-[4-hydroxyphenyl]-1-methylethyl] A condensate of phenyl]ethylene]bisphenol (1·〇mol) and 1,2-naphthoquinonediazide-5-sulfonyl chloride (2.0 mol). In Comparative Examples 1 and 2, the following surfactant was used in place of the copolymer (C) » c-1 (Comparative Example 1): Polyoxyalkylene surfactant (produced by Dow Coming Toray Co., Ltd.) Trade name: SH — 193). C-2 (Comparative Example 2): Fluorine-based surfactant (ΝΕΟ S (manufacturing), trade name: FTERGENT 222F) Further, in Comparative Example 3, the copolymer (C) and the surfactant were not used. [Evaluation of Performance as Interlayer Insulating Film] In Example 1, except that the above-described radiation-sensitive resin compositions (S-2) to (S-7) and (s-1) to (s-3) were respectively used. Various evaluations were carried out in the same manner as in Example 1 except that the radiation sensitive resin composition (S-1) was used. The evaluation results are shown in Table 1. -54 - 201033737

Example 7 • (1 < 8 4 Β - 1 1 〇 0.50 1 〇 good 0.40 1650 Ο CS CN ON 0.58 〇S Example 6 1 - Η 1 < 8 Γ · Η Β - 1 inch 1 U 0.50 1 〇 Good 0.40 1680 § VJl CS CN) Os un 实施 Example 5 Α—2 8 1 Η Β —1 r—Η 1 u 0.50 1 〇 Good: 2.38 1_ 1680 Ο CS (N w-» as 0.60 〇Example 4 1 < 8 τ -1 Β-1 ! • Η ί U 0.30 1 〇good ί 0.40 1680 § Ο CS CN v〇ON οο ^Γί ο VO Example 3 1 <: s ι Η Β — 1 C-3 0.50 1 〇 good 0.40 1690 g Ο <N 05 ON ί 0.73 vy-> cn Example 2 1 < 8 rH Β-1 C-2 0.50 1 〇 Good 0.40 1650 g ο CN CS V-) ON ι— VO VO Example 1 1—Η t C 8 »—Η Β —1 Calving 1 U 0.50 1 〇Good 1 ! 0.40 1 Brain g CN CnJ as 0.62 un Charging W Usage (mass) Jun P Price and Quantity) Job 0w]| m Dosage (parts by mass) Μ P Dosage (parts by mass) Developer concentration (% by mass) Optimum development time (seconds) i Development margin (seconds) Kirin change rate W mmmimc%) 1- Transparency (%) film thickness uniformity (%) relative dielectric constant Click on Ife to strike ti 绁m Aluminum & 1 ιϋηπΐ ιρτ fQ ύ S mmm 5Γ <- M ¥ I mm Age intrusion m I m 鼹m is mm ΦΚ m 胆- cn' S in' ΚΟ bo 201033737 Table 2 Ο Ο Comparative Example 1 Comparative Example 2 Comparative Example 3 Copolymer (A) Surface A-1 A-1 A-1 The amount of inertia is 100 100 100 潍 (B) Surface B-1 B-1 B- 1 Dosage (part by mass) 30 30 30 Copolymer (C) Draw — — — Dosage (part by mass) 0 0 0 Surfactant face c-1 c-2 — Dosage (part by mass) 0.30 0.30 0 (1) Appearance of the film Evaluation is slightly unqualified, unqualified, unqualified (2) Sensitivity evaluation Developer's degree (% by mass) 0.40 0.40 0.40 Sensitivity (J/m2) 1740 1740 1710 (3) Development margin evaluation Best development time (seconds) 80 80 80 (4)瞧Formulation evaluation film thickness change rate (%) 2 2 3 (5) Heat resistance evaluation 2 2 2 (6) Transparency and transparency (%) 95 95 95 (7) Film thickness average H4 Evaluation film thickness uniformity (%) 1.33 2.50 4.86 (8) Relative dielectric Evaluation of Constant Relative Dielectric Constant 3.5 3.5 3.5 Examples 8 to 10 In Example 1, after mixing the (Α) copolymer, the (Β) compound, and the (C) copolymer, before adding the solvent, relative to 100 A part by mass of the copolymer (A), and further added 2 parts by mass of 1,3,5-tris (3', 5'-di in Example 8

Tert-butyl-4'-hydroxybenzyl)isocyanuric acid (trade name "ADK STAB AO-20", produced by ADEKA Co., Ltd.), further added in Example 9 to 2-56-201033737 parts by mass 1, 3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene (trade name "ADK STAB AO-330", produced by ADEKA) Further, 2 parts by mass of di(octadecyl)pentaerythritol diphosphite (trade name "ADK STAB PEP-8" 'produced by ADEKA Co., Ltd.) was further added to Example 10. In the same manner as in Example 1, the radiation sensitive resin compositions (S-8) to (S-10) were prepared and evaluated. As a result, in all of Examples 8 to 10, the appearance of the coating film was "good", and the sensitivity, development margin, solvent resistance, heat resistance, transparency, and relative dielectric constant were all the same as in Example 1. value. Further, the film thickness uniformity was 0.45% in Example 8, 0.48% in Example 9, and 0.43% in Example 10. [Circular Simple Description] None. [Main component symbol description] None.

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Claims (1)

201033737 ' VII. Patent application scope: 1. A radiation sensitive resin composition characterized by: (A) an alkali-soluble resin; (B) 1,2-quinonediazide compound; and (C) containing (cl) a compound represented by the following formula (1°), (〇2) a compound represented by the following formula (2°), and (c3) a polymerizable unsaturated compound having a group represented by the following formula (3); Copolymer of a polymerizable unsaturated compound, CH2 = CR1COO-CaH2a-CpF2p + 1 (1°) (In the formula (1°), R1 is a hydrogen atom or a methyl group, a is an integer of 0 to 6, and β is 1 An integer of -20, CH2 = CR2COO-(CrH2y-〇)a-R3 (2°) (In the formula (2°), R2 is a hydrogen atom or a methyl group, and R3 is an alkyl group having 1 to 12 carbon atoms. , γ is 2 or 3, a is the number of repeating units, and the average number 値 is 1 to 30), R4 Ο Λ R5 1 R7 I 1 Si 0— 1 Si (3) R6 R8 (In the formula (3), R 4 , R 5 , R 6 , R 7 and R 8 are each independently an alkyl group having 1 to 20 carbon atoms, and benzene. Or a group represented by the following formula (4), b is an integer of 0 to 3), -58- 201033737 / R10 \ R10 h \ i R9-fi; i - Ο -] - Si - O - (4 \ R11 Λ R11 (In the formula (4), R9, R1G and R11 are each independently an alkyl group or a phenyl group having 1 to 2 carbon atoms, and c is an integer of 0 to 3). 2. The radiation sensitive resin composition according to claim 1, wherein the (C) copolymer contains (c4) in addition to the above compound (cl), compound (c2) and chemical complex (c3). A copolymer of a polymerizable unsaturated compound having a polymerizable unsaturated compound having an alkyl group having 1 to 8 carbon atoms. 3. The radiation sensitive linear resin composition according to claim 2, wherein the (C) copolymer is contained in addition to the above compound (cl), compound (c2), compound (e3) and compound (c4) (c5) a copolymer of a polymerizable unsaturated compound having a polymerizable unsaturated compound having two or more unsaturated bonds in a molecule. Φ 4 The radiation-sensitive resin composition of the third aspect of the invention is in which the compound (cl) is a compound represented by the following formula (1): the compound (c2) is represented by the following formula (2) The compound, and the (C) copolymer is composed of 25 to 35 mass% of the compound (cl), 20 to 30 mass% of the compound (c2), 15 to 2 mass% of the compound (c3), and 25 to 35 mass% of the compound (c4). And a copolymer of a polymerizable unsaturated compound composed of 1 to 5 mass% of the compound (c 5) 'CH2 = CR1COO-CH2CH2C8Fi7 (1) In the formula (1), R1 is the same as defined in the above formula (1°), -59- 201033737 CH2 = CR2C00-(C2H40)aR3 (2) (In the formula (2), R2 and R3 are the same as defined in the above formula (2), and the average number of repeating units a is 4 to 12). 5. The radiation sensitive resin composition according to any one of claims 1 to 4, wherein (A) the alkali-soluble resin is a group comprising (ai) selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic anhydrides. A copolymer of at least one of (a2) a monomer having a polymerizable unsaturated compound having an epoxy group. 6. An interlayer insulating film' characterized by being formed of a radiation-sensitive resin composition according to any one of claims 1 to 5 of the patent application. 7. A method of forming an interlayer insulating film, comprising the steps of: (1) coating a radiation sensitive resin composition according to any one of claims 1 to 5 on a substrate a step of forming a coating film, (2) a step of irradiating at least a portion of the coating film, (3) a developing step, and (4) a heating step. 8. An interlayer insulating film which is characterized by the method of claim 7 of the patent application. -60-201033737 IV. Designation of representative drawings: (1) The representative representative of the case is: None. (2) A brief description of the symbol of the representative figure: 〇, , ❹ 5. If there is a chemical formula in this case, please reveal the chemical formula that best shows the characteristics of the invention: