WO2005101124A1 - Radiation-sensitive resin composition, interlayer insulation film, microlens and process for producing them - Google Patents

Abstract

A radiation-sensitive resin composition that exhibits high radiation sensitivity, having such a development margin that desirable pattern configuration can be formed even when the optimum development time is exceeded in the development step, that is capable of easily forming a patterned thin film excelling in adherence and reduces the amount of sublimed matter occurring at firing, and that is appropriately usable in production of an interlayer insulation film or microlens. There is provided a radiation-sensitive resin composition comprising carboxylated epoxidized polymer (A) exhibiting a ratio of, as measured by gel permeation chromatography, weight average molecular weight (Mw) in terms of polystyrene to number average molecular weight (Mn) in terms of polystyrene, Mw/Mn, of 1.7 or below, and 1,2-quinonediazide compound (B).

Description

 Radiation-sensitive resin composition, interlayer insulating film and microlens, and method for producing the same

 The present invention relates to a radiation sensitive resin composition, an interlayer insulation film and a microlens, and a method for producing them. Background art

 In electronic components such as thin film transistors (hereinafter referred to as “TFTs”) type liquid crystal display elements, magnetic head elements, integrated circuit elements, solid-state image pickup elements, etc. An insulating film is provided. As a material for forming the interlayer insulating film, a radiation-sensitive resin composition is widely used because it is preferable that the number of steps for obtaining the required pattern shape be small and the material have sufficient flatness. JP 2001-354822 and JP-A 2001-343743).

 Among the above electronic components, for example, a TFT type liquid crystal display element is manufactured through the steps of forming a transparent electrode film on the above interlayer insulating film and further forming a liquid crystal alignment film on it, The insulating film is exposed to high temperature conditions in the step of forming a transparent electrode film and exposed to a stripping solution of a resist used for forming a pattern of the electrode, so sufficient resistance against these is required. .

 In recent years, in TFT liquid crystal display devices, there are trends such as larger screen size, higher brightness, higher definition, faster response, thinner thickness, etc., and a composition for forming an interlayer insulating film used therefor is high. The interlayer insulating film to be formed is required to have higher performance than ever in the low dielectric constant, high transmittance and the like.

On the other hand, as an optical system material for on-chip color imaging optical systems such as facsimiles, electronic copying machines, solid-state imaging devices, etc. or optical fiber connectors 3 to 100 2 A microlens having a lens diameter of about m, or a microlens array in which the microlenses are regularly arranged is used.

 To form a micro lens or micro lens array, a resist pattern corresponding to the lens is formed, and then heat treatment is performed to cause melt flow and use as it is as a lens, or melt flow lens There is known a method of transferring a lens shape onto a base by dry etching with the pattern as a mask. Radiation-sensitive resin compositions are widely used for the formation of the lens pattern (see Japanese Patent Application Laid-Open Nos. 6-180702 and 6-126323).

 By the way, the element on which the above-described microlens or microlens array is formed is then coated with a planarizing film and an etching resist film in order to remove various insulating films on the bonding pad which is a wiring formation portion. The resist is exposed and developed using a desired mask to remove the etching resist on the bonding pad portion, and then, the planarization film and various insulating films are removed by etching to expose the bonding pad portion. Therefore, solvent resistance and heat resistance are required in the step of forming a planarizing film and the coating film of the etching resist and the etching process for the microlens or the microlens array.

 The radiation sensitive resin composition used to form such a micro aperture lens is highly sensitive, and the micro lens formed therefrom has a desired radius of curvature, high heat resistance, high Transmittance is required.

 Also, in the interlayer insulating film and microlens thus obtained, in the developing step when forming them, if the developing time is slightly more than the optimum time, the developer penetrates between the pattern and the substrate. Therefore, it is necessary to strictly control the development time, and there is a problem in the yield of the product.

As described above, in forming the interlayer insulating film or the microlens from the radiation sensitive resin composition, the composition is required to have high sensitivity, and the developing time in the developing process during the forming process is a predetermined time. Even if it becomes more excessive, it shows good adhesion without peeling of the pattern, and the interlayer insulating film formed from it is high. Heat resistance, high solvent resistance, low dielectric constant, high transmittance etc. are required. In the case of forming a microlens, furthermore, good melt shape (desired curvature radius), high heat resistance, high solvent resistance and high transmittance are required as the microlens, but such The radiation sensitive resin composition which satisfies the requirement was not known conventionally.

 It is feared that the above-mentioned sublimate generated at the time of firing to form the interlayer insulating film and the micro lens contaminates the device in the process line, and a radiation-sensitive resin composition in which the generated sublimate is reduced is desired. It was Disclosure of the invention

 The present invention has been made based on the above circumstances. Therefore, an object of the present invention is to provide a pattern having high radiation sensitivity, a development margin capable of forming a good pattern shape even if it exceeds the optimum development time in the development process, and a pattern having excellent adhesion. It is an object of the present invention to provide a radiation-sensitive composition capable of easily forming a porous thin film and having reduced sublimation products generated at the time of firing.

 Another object of the present invention is to form an interlayer insulating film having high heat resistance, high solvent resistance, high transmittance, and low dielectric constant when used for forming an interlayer insulating film, and for forming a microlens. It is an object of the present invention to provide a radiation-sensitive resin composition which forms a micro-lens having a high transmittance and a good melt shape when used, and in which a sublimate generated at the time of firing is reduced.

 Still another object of the present invention is to provide a method for forming an interlayer insulating film and a micro lens using the above radiation sensitive resin composition.

 Still another object of the present invention is to provide an interlayer insulating film and a microlens formed by the method of the present invention.

 Other objects and advantages of the present invention will become apparent from the following description. According to the invention, the above objects and advantages of the invention are:

(A) The ratio (Mw / Mn) of polystyrene-equivalent weight average molecular weight (Mw) to polystyrene equivalent number average molecular weight (Mn), which has a force propoxy group and an epoxy group and is measured by gel permeation chromatography Polymers which are less than 1.7, Biny (B) 1, 2-quinone diazide compound

The present invention is achieved by a radiation sensitive resin composition characterized by containing

 The above objects and advantages of the present invention are secondly:

The invention is achieved by a method of forming an interlayer insulating film or a microlens characterized in that the following steps are performed in the order described below.

 (1) forming a coating film of the above radiation sensitive resin composition on a substrate,

 (2) irradiating at least a part of the crucible with radiation;

 (3) Development process, and

 (4) Heating process.

 Furthermore, the above objects and advantages of the present invention are thirdly:

This is achieved by the interlayer insulating film and the microphone lens formed by the above method. Brief description of the drawings

 FIG. 1 is a schematic view showing the cross-sectional shape of the microphone lens. BEST MODE FOR CARRYING OUT THE INVENTION

 Hereinafter, the radiation sensitive resin composition of the present invention will be described in detail.

Copolymer (A)

 The copolymer (A) used in the present invention is preferably (al) unsaturated carboxylic acid and Z or unsaturated carboxylic acid anhydride (hereinafter sometimes referred to as "compound (al)") ,,,

(a 2) Epoxy group-containing unsaturated compound (hereinafter sometimes referred to as “compound (a2)”),

and

(a 3) Preferably, a polymerizable mixture containing unsaturated compounds other than the (a 1) component and the (a 2) component (hereinafter, sometimes referred to as “compound (a 3) J”) is subjected to living radical polymerization can get. For example, the copolymer (A) is produced by living radical polymerization of a polymerizable mixture containing a compound 1), a compound (a 2) and a compound (a 3) in a solvent in the presence of a polymerization initiator be able to.

 The carboxyl group and epoxy group possessed by the copolymer (A) thus obtained are derived from the complex compound (al) and the compound (a 2), respectively.

 Various initiator systems for living radical polymerization have been proposed. For example, TEMPO system discovered by Ge orges et al., An initiator system composed of a combination of copper bromide and bromine-containing ester compounds proposed by Matyjasz ews ki et al., Proposed by Higa shimura et al. An initiator system composed of a combination of carbon tetrachloride and a ruthenium (II) complex, Thiocarboic described in JP-A 2000-515181, JP-A 2002-500251 and JP-A 2004-518773. A combination of a ruthio compound and a radical initiator is preferably used.

 As a suitable living polymerization initiator system for obtaining the polymer (A) of the present invention, a system in which the growth terminal is not inactivated is appropriately selected depending on the type of monomer used, but in consideration of the polymerization efficiency etc. And preferably a combination of a thiocarboxylthio compound and a radical initiator. Here, examples of the thiocarbothio compounds include dithioesters, dithiocarbonates, trithiocarponates, xanthates and the like.

Specific examples thereof include compounds represented by the following formulae.

l.0C00 / S00Zdf / X3d 丽 sooz OAV

l.0C00 / S00Zdf / X3d 丽 sooz OAV

Among these, cumyl diisocyanate, S-cyano-methyl-S-dodecyl trithiocarponate, pyrazole-di-dicarboxylic acid, fluoromethyl ester, di-thio ester used in the following synthesis example 5 and used in the following synthesis example 6 Mention may be made of xanthate.

 Moreover, as a radical initiator, what is generally known as a radical polymerization initiator can be used, and, for example,, 2'-azobisisoptyronitrile, 2, 2, 2-azobis ((2, 4- Azo compounds such as dimethylvaleronitrile), 2,2 monoazobis- (4-methoxy-2, 4-dimethylvaleronitrile); benzoyl peroxide, lauroyl beroxide, t-butyl peroxypipalate, 1, 1, 1 And organic peroxides such as monobis (t-butylperoxy) cyclohexane; hydrogen peroxide; redox type initiators comprising these peroxides and a reducing agent, and the like.

 These polymerization initiators can be used alone or in combination of two or more.

The amount of the thiocarboxyl thio compound used is preferably 1 to 10, 000 parts by weight, more preferably 10 to 1, 000 parts by weight, per 100 parts by weight of the polymerization initiator. The amount of the radical polymerization initiator used is preferably 0.01 to 100 parts by weight, and more preferably 0.1 parts by weight, per 100 parts by weight of the monomer mixture containing the epoxy group-containing polymerizable unsaturated compound. It is 1 to 10 parts by weight. Above living radio There are no particular limitations on the polymerization temperature during the loop polymerization, but it is preferably 0 ° C. to 1000 ° (:, and more preferably 10 ° to 85 ° C.).

 Depending on the initiator system, after polymerization using an ester compound (a 1 ') in which the group of the compound (al) is appropriately protected by a protecting group so as to prevent the polymerization initiator from being inactivated, deprotection may be performed. The copolymer (A) can also be obtained by

 The copolymer (A) used in the present invention is a polymerization unit derived from the compound (al), a polymerization unit derived from each of the compounds (al), (a 2) and (a 3) or The content is preferably 5 to 40% by weight, particularly preferably 10 to 30% by weight, based on the total of the repeating units. If a copolymer having less than 5% by weight of this polymerization unit is used, it becomes difficult to dissolve in an aqueous alkaline solution during the development step, while a copolymer exceeding 40% by weight becomes too soluble in an aqueous solution. There is a tendency.

 The compounds (al) are radically polymerizable unsaturated carboxylic acids and Z or unsaturated carboxylic acid anhydrides, and examples thereof include monocarboxylic acids, dicarboxylic acids, anhydrides of dicarponic acids, monocarboxylic acids of polyvalent carboxylic acids [(meth) (Acryloyloxyalkyl) ester, mono (meth) acrylates of polymers having a hydroxyl group and a hydroxyl group at each of both ends, polycyclic compounds having a carboxyl group, and anhydrides thereof and the like can be mentioned. .

 Specific examples of these include monocarboxylic acids such as acrylic acid, methacrylic acid and crotonic acid;

As dicarboxylic acids, for example, maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid etc .;

As anhydrides of dicarboxylic acids, for example, acid anhydrides of the above compounds exemplified as the above dicarboxylic acids;

Examples of mono-[(meth) acrylic acid alkyl] esters of polyvalent carboxylic acids such as succinic acid mono [2- (meth) acrylic acid], fumaric acid mono [2-

(Meta) Acralloy mouth kichetil] etc;

Mono (meta) of the polymer having a power propoxyl group and a hydroxyl group at each of both ends As an acrylate, for example, ω-Carboxy poly strength prolactone mono (meth) relay soot etc;

For example, 5-carpoxybicyclo [2. 2. 1] Hep! ^ 1-ene, 5, 6- dicarpoxybisic acid [2. 2. 1) Hep! 2-en, 5-force propoxy 1-5-methylbicyclo [2. 2. 1] Hepto 2-en, 5-force lupoxy-5-ethylbicyclo [2. 2. 1] Hepto 2-en , 5-force propoxy-6-methylbicyclo [2.2. 1] heptene, 5- carboxy-6-ethylbicyclo [2.2. 1] hepto-2-ene, 5, 6-dicarpoxybicyclo [ 2.2.1] Heptow 2-en anhydride etc. are mentioned respectively.

 Among these, monocarboxylic acids and anhydrides of dicarboxylic acids are preferably used. In particular, acrylic acid, methacrylic acid and maleic anhydride are copolymerizable, and in view of solubility in alkaline aqueous solution and easy availability. It is preferably used. These are used alone or in combination.

The protective group for protecting the carboxyl group of the compound (al) is not particularly limited and those known as a protective group for a l-hydroxyl group can be used. For example, a trialkylsilyl group, a monoalkoxyalkyl group, a cyclic monoalkoxyalkyl group and the like can be mentioned. More specifically, for example, 卜 methylsilyl, dimethylbutylsilyl,

1-1-ethoxyethyl, 1-1 proboxycetyl, tetrahydrofuranilile, tetrahydrobranil, trifenylmethyl and the like.

 The copolymer (A) used in the present invention is obtained by adding a polymerization unit derived from the compound (a 2) to a total of polymerization units derived from the compounds (al), (a 2) and (a 3) The content is preferably 10 to 70% by weight, particularly preferably 20 to 60% by weight. If this polymerized unit is less than 10% by weight, the heat resistance and surface hardness of the resulting interlayer insulating film and the micro lens tend to be lowered, while if the amount of this polymerized unit is more than 70% by weight Storage stability of the resin composition tends to decrease.

The compound (a 2) is an epoxy group-containing unsaturated compound having radical polymerization. Examples thereof include glycidyl acrylate, glycidyl methacrylate, glycidyl α-ethyl butyrate, glycidyl α-η-propyl acetate, glycidyl グ リ シ ジ -butyl acrylate, acrylic acid-3, 4-epoxybutyl, methacryl 1-, 3-, 4-epoxybutyl, 1-, 6-, 7-epoxyheptyl acrylate, 1-methacrylic acid 6, 7-epoxyheptyl, α-ethyl acrylate, 6, 7-epoxyheptyl, ο-vinylbenzyl dalysyl ether And m-vinylbenzyl daricidyl ether, p-vinylbenzyl glycidyl ether and the like. Among these, glycidyl methacrylate, methacrylic acid mono 6,7-epoxyheptyl, op-vinylbenzyl glycidyl ether, 3, 4-epoxycyclohexyl methacrylate, etc. are copolymerizable and an interlayer insulating film obtained or obtained It is preferably used from the viewpoint of enhancing the heat resistance and surface hardness of the microlens. These are used alone or in combination.

 The copolymer (A) used in the present invention is a polymer unit derived from the compound (a 3), and a compound (al), (a 2) and (a 3) Preferably, it is 5 to 70% by weight, particularly preferably 5 to 50% by weight, based on the total. If this polymerization unit is less than 5% by weight, the storage stability of the radiation sensitive resin composition tends to decrease, while if it exceeds 70% by weight, the development step in the formation of the interlayer insulating film or the micro lens May become difficult to dissolve in aqueous solution.

 The compound (a 3) is not particularly limited as long as it is a radically polymerizable unsaturated compound, and examples thereof include methacrylic acid alkyl esters, acrylic acid alkyl esters, methacrylic acid cyclic alkyl esters, and meta compounds having a hydroxyl group. Acrylic acid ester, cyclic acrylic acid alkyl ester, methacrylic acid aryl ester, acrylic acid aryl ester, unsaturated dicarboxylic acid diester, bicyclo unsaturated compound, maleimide compound, unsaturated aromatic compound, conjugated diene Saru.

As specific examples of these, as methacrylic acid alkyl ester, for example, methyl Methacrylate, n-butyl methacrylate, sec-butyl methacrylate, sec-butyl methacrylate, 2-ethylhexyl methacrylate, isodecyl methacrylate, n-lauryl methacrylate, tridecyl methacrylate, n-stearyl methacrylate, etc. ;

As acrylic acid alkyl ester, for example, methyl acrylate, isopropyl acrylate and the like;

As methacrylic acid cyclic alkyl esters such as cyclohexyl meth click Relay preparative cyclohexane, Kishirumetakurire Ichito to 2 methylcyclohexane, tricyclo [5.2.2 1.0 ^{2 '6]} decane one 8-Irumetakurire Ichito, tricyclo [5. 2. 1 ² 0 ^{6 6} ] dexan-1-hydroxylatel methacrylate, isopolonil methacrylate, etc .; As a meta-acrylic acid ester having a hydroxyl group, for example, hydroxymethyl methacrylate, 2-hydroxy ethyl methacrylate, 3-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, diethylene glycol monomethacrylate, 2, 3-dihydroxypropyl methacrylate, 2-methacrylic acid xichetildalycoside, 4-hydroxyphenyl methacrylate, etc .; As an alkyl ester For example hexyl § chestnut rate cyclohexane, cyclohexyl § chestnut rate to 2-methylcyclohexyl, tricyclo [5.2.2 1.0 ^2.6] decane one 8-Iruakurireto, tricyclo [5.2.2 1.0 ^{2 '6]} decane (I) 8-Irooxyethyl acrylate, isoporonyl acrylate, etc .; Methacrylic acid aryl ester such as phenyl methacrylate, benzyl methacrylate etc .;

As acrylic acid aryl esters, such as phenyl acrylate, benzyl acrylate and the like;

As unsaturated dicarponic acid diesters, for example, jetyl maleate, diethyl ether fumarate, jetyl itaconate, etc .;

As a bicyclo unsaturated compound, for example, bicyclo [2. 2. 1] hepto-2_ ene, 5-methylbicyclo [2. 2. 1] hepto-2-ene, 5- ethylbicyclo [2. 2. 1] hepto 2 — En, 5 — Methoxybicyclo [2. 2. 1] Heptor 2 — En, 5-Ethoxybicyclo [2. 2. 1] Heptone 2-ene, 5, 6-dimethoxybicyclo [2. 2. 1] Heptone 2-en, 5, 6- Jetoxybicyclo [2. 2. 1] Hept-2-ene, 5-butyoxycarboxylbicyclo [2. 2. 1] Hept-2-ene, 5-cyclohexylbicyclic bicyclo [2. 2. 1] Heptow 2- En, 5-phenoxy group-bicyclo [2. 2. 1] Heptor 2-en, 5, 6-di (t- butoxycarponyl) bicyclo [2. 2. 1] Hep 1 ^ 1 2-en , 5, 6-Di (cyclohexy l-oxonyl) bicyclo [2. 2] Hepto-2-en, 5-(2 '-hydroxy-ethyl)-bicyclo [2. 2] Hepto-2-en 5,6-Dihydroxybicyclo [2. 2. 1] Hepto-2-en, 5, 6-di (hydroxymethyl) bicyclo [2. 2. 1] Hepto-2-en, 5, 6-di (2 '— Hydroxy Chill) bicyclo [2. 2. 1] hept-2 -ene, 5-hydroxy 5-methylbicyclo [2. 2. 1] hepto-2-ene, 5-hydroxy-5-ethylbicyclo [2. 2. 1] Heptto-2-en, 5-hydroxymethyl-5-methylbicyclo [2. 2. 1] Heptone 2-ene, etc .;

As a maleimide compound, for example, phenyl maleimide, cyclohexyl maleimide, benzyl maleimide, N-succinimidyl mono-3-maleimido benzoate, N-succinimidyl mono 4_maleimidobutyrate, N-succinimidyl mono 6-maleimidocaproate, N-succinimidyl (I) 3-maleimidopropionate, N- (9-acridinyl) maleimide etc.

Examples of unsaturated aromatic compounds include styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyl toluene, p-methoxystyrene and the like; and as a conjugated gene, for example, 1,3-butadiene, isoprene, 2, 3 — Dimethyl — 1, 3 — Butadiene etc;

Other unsaturated compounds include, for example, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide and vinyl acetate.

Among them, alkyl methacrylate ester, cyclic alkyl methacrylate Ester, bicyclo unsaturated compounds, unsaturated aromatics, conjugated diene is preferably use Irare, especially styrene, t _ butyl methacrylate, tricyclo [5.2.2 1.0 ^{2 '6]} decane one 8-methacrylate And p-methoxystyrene, 2-methylcyclohexyl acrylate, 1,3-butadiene, and bicyclo [2.2. 1] hepto-2-ene are particularly preferred in view of copolymerization reactivity and solubility in an aqueous alkali solution. preferable. These are used alone or in combination.

Preferred specific examples of the copolymer (A) used in the present invention include, for example, methacrylic acid / styrene / tricyclo [5. 2. 2.0 ² ' ⁶ ] decane-18-yl methacrylate glycidyl methacrylate / tetrahydro Furfuryl methacrylate copolymer, methacrylic acid Z styrene Z tricyclo [5. 2. 0 ^{2 6} ] decan _ 8-yl methacrylate Z glycidyl methacrylate / p-bibenzyl glycidyl ether Z tetrahydroful Furyl methacrylate copolymer, methacrylic acid Z styrene / tricyclo [5. 2. 0 ^{2 6} ] decane-18-yl methacrylate glycidyl methacrylate Z polyethylene glycol monomethacrylate copolymer, evening acrylic acid / styrene / tricyclo [5.2.2 1.0 ^2.6] decane one 8-I methacrylate / glycidyl methacrylate / polypropylene grayed Li Over monomethyl methacrylate copolymer. .

The copolymer (A) used in the present invention has a polystyrene equivalent weight average molecular weight (hereinafter referred to as "Mw") and a polystyrene equivalent number average molecular weight (hereinafter referred to as "Mn") which are measured by gel permeation chromatography. The ratio of (MwZMn) is 1.7 or less, preferably 1.5 or less. When MwZMn exceeds 1.7, the pattern shape of the obtained interlayer insulating film or microlens may be inferior. Further, Mw is ^{preferably, 2X 10 3 ~1 X 10 5} , more preferably ^{5 X 10 3 ~5 X 10 4} . If Mw is less than 2 × 10 ³ , development may not be sufficient, and the residual film ratio of the resulting film may decrease, or the pattern shape of the interlayer insulating film or microlens obtained. And heat resistance etc. may be inferior. On the other hand, when the Mw exceeds 1 × 10 ⁵ , the sensitivity may be lowered or the pattern shape may be inferior. Moreover, Mn is preferably 1.2 × 10 ³ to 1 × 10 ⁵ , more preferably 2. 9 X 1 0 ³ to 5 X 1 0 ⁴ The radiation sensitive resin composition containing the above-mentioned copolymer [A] can easily form a predetermined pattern without development residue when developing.

 Furthermore, the amount of residual monomer measured by gel permeation chromatography of the copolymer (A) used in the present invention is preferably less than 5.0%, more preferably less than 3.0%. Particularly preferably, it is less than 2.0%. By using such a copolymer having a residual monomer content, it is possible to obtain a protective film in which the sublimate at the time of firing is reduced.

 In the present invention, the copolymer (A) can be used alone or as a mixture of two or more.

 Examples of the solvent used for producing the copolymer (A) include alcohols, ethers, glycol ethers, ethylene glycol alkyl ether esters, diethylene glycol, propylene glycol monoalkyl ethers and propylene. Examples include glycol alkyl ether acetate, propylene glycol alkyl ether propionate, aromatic hydrocarbon, ketone, ester and the like.

 Specific examples of these include alcohols such as methanol, ethanol, benzyl alcohol, 2-phenylethyl alcohol, 3-phenyl-1-propanol, etc .;

For example, as tetrahydrofuran, such as tetrahydrofuran;

As glycol ether, for example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether and the like;

Ethylene glycol alkyl ether acetates such as methyl cellulose ether acetate, ethyl cellulose ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monoethyl ether acetate, etc .; diethylene glycols such as dimethylene glycol monomethyl ether, diethylene glycol Monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol jetyl ether, diethylene glycol ether Chill ether etc;

As propylene daryl monoalkyl ether, for example, propylene glycol mono methyl ether, propylene glycol mono ether, propylene glycol mono propyl ether, propylene daryl mono butyl ether, etc .;

As propylene glycol alkyl ether acetate, for example, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, propylene glycol alkyl ether acetate, etc .;

For example, propylene glycol glycol ether terpropionate, propylene glycol ether ether propionate, propylene glycol isopropyl ether propionate, propylene ether alcoholyl ether Propionate etc;

As aromatic hydrocarbons, for example, toluene, xylene etc .;

As ketones, for example, methyl ethyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone and the like;

As an ester, for example, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, methyl hydroxyacetate, hydroxy Acetyhyl acetate, Butyl hydroxyacetate, Methyl lactate, Ethyl lactate, Propyl lactate, Methyl 3-hydroxypropionate, Methyl 3-hydroxypropionate, Propyl 3-hydroxypropionate, Butyl 3-hydroxypropionate, 2- Hydroxy methyl 3-methylbutanoate, methyl methoxyacetate, ethyl methoxyacetate, propyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, propyl ethoxyacetate, butyl ethoxyacetate Methyl propoxy acetate, propoxy acetate Echiru, propoxy acetate propyl, propoxy acetate heptyl, methyl butoxy acetate, butoxy acetate Echiru, butoxy propyl acetate, butoxy acetate heptyl, 2-methyl methoxypropionate, 2 —Methyl methoxypropionate, propyl 2-methoxypropionate, butyl 2-methoxypropionate, methyl 2-ethoxypropionate, 2_ethoxypropionoethyl, 2_propyl ethoxypropionate, 2-ethoxypropionate butyl 2-Methyl 1-butoxypropionate, ethyl 2-butoxypropionate, propyl 2-butoxypropionate, butyl 2-butoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, Butyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, propyl 3-ethoxypropionate, butyl 3-ethoxypropionate, methyl 3-propoxypropionate, 3-propoxypropionic acid Esters such as chill, propyl 3-propoxypropionate, butyl 3-propoxypropionate, methyl 3-butoxypropionate, ethyl 3-butyoxypropionate, propyl 3-butoxypropionate, butyl 3-butoxypropionate, and the like It can be mentioned.

 Among these, ethylene glycol alkyl ether acetate, diethylene glycol, propylene glycol monoalkyl ether and propylene glycol alkyl ether acetate are preferable, and among them, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, propylene glycol methyl ether Propylene glycol monoether acetate is particularly preferred.

 (B) Ingredient

 The component (B) used in the present invention is a 1,2-quinonediazide compound that generates a carboxylic acid upon irradiation with radiation, and is a phenolic compound or an alcoholic compound (hereinafter referred to as "mother core"), 1,1, A condensate of 2-naphthoquinone diazide sulfonic acid halide can be used.

Examples of the mother nucleus include trihydroxybenzophenone, tetrahydrobenzobenzoone, pendent hydroxybenzophenone, hexahydroxybenzophenone, (polyhydroxyphenyl) alkane, and other mother nuclei. As specific examples of these, as trihydroxybenzophenone, for example, 2, 3, 4-trihydroxybenzophenone, -2, 4, 6-trihydroxybenzophenone, etc .;

As tetrahydroxybenzophenone, for example, 2,2 ′, 4,4′-tetrahydroxybenzophenone, 2,3,4,3′-tetrahydroxybenzophenone, 2,3,4,4, -tetrahydroxybenzo Phenoone, 2, 3, 4, 2, 2-, 4-hydroxy, 4-methyl-penta-phenone, 2, 3, 4, 4, tetrahydro-x_3, mono-methoxy-benzophenone, etc .;

As pentahydroxybenzophenone, for example, 2, 3, 4, 2 ', 6, monopentahydroxybenzophenone etc .;

As hexahydroxybenzophenone, for example, 2, 4, 6, 3 ', 4', 5, 5-hexahydroxybenzophenone, 3, 4, 5, 3 ', 4', 5'- hexahydroxybenzo. Huenon et al .;

 Examples of (polyhydroxyphenyl) alkanes include bis (2,4-dihydroxyphenyl) methane, bis (p-hydroxyphenyl) methane, tri (P-hydroxyphenyl) methane, 1,1,1 tri (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) Mono-phenylpropane, 4, 4, 1 [1 1 [1 1 [1 [4 Hydroxyphenyl] 1 1 methylethy] phenyl] phenylidene] bis phenol Bis (2,5-dimethyl-4-hydroxyphenyl) -2-hydroxyphenylmethane, 3,3,3 ', 3,3-tetramethyl-1,1, -s-pyrobiindene 5,6,7,5', 6 ,, 7 'one Hexanol, 2, 2, 4-preparative Rimechiru one 7, 2 ', 4' single-trihydroxyflavan, and the like;

As other mother nucleus, for example, 2-methyl-2- (2, 4-dihydroxyphenyl), one-one (4-hydroxyphenyl), one 7-hydroxychroman, 2- [bis {(5-isopropyl) 4-hydroxy] — 2-Methyl) phenyl} methyl], 1- [1- (3- {1- (4-hydroxyphenyl) 1 1 1 methylethyl} 1 4, 6—Dich Droxyphenyl) 1-methylethyl] 1-3-(1-(1- {1-(4-hydoxyphenyl) 1-1-methylethyl)-1, 4-dihydroxyphenyl)-1 -methylethyl) benzene, 4, 6- bis { One (4-hydroxyphenyl) one

1-Methylethil} Examples include 1, 3-dihydroxybenzene.

 In addition, 1, 2-naphthoquinonediazide sulfonic acid amides in which the ester bond of the mother nucleus exemplified above is changed to an amide bond, for example, 2, 3, 4-trihydroxybenzophenone 1, 1-1-naphthoquinonediazide-4-sulfone Acid amides and the like are also suitably used.

 Among these mother nuclei, 2, 3, 4, 4'-tetrahydroxybenzophenone, 4, 4, 4- [1- [4- [1- [4-hydroxyphenyl] _1-methylethy] phenyl] ethyridylene Bisphenol is preferred.

 Further, as the 1, 2-naphthoquinone diazide sulfonic acid halide, preferred is 1, 2- naphthoquinone diazide sulfonic acid, and specific examples thereof include

Mention may be made of 2-naphthoquinonediazide-4-sulphonic acid chloride and 1,2-naphthoquinodiazido-5-sulphonic acid chloride, among which the use of 1,2-naphthoquinonediazide-5-sulphonic acid chelate can be mentioned. preferable. In the condensation reaction, it is preferably 30 to 85 mol%, more preferably 50 to 70 mol%, per 1 equivalent of OH group in the phenolic compound or the alcoholic compound. 2, 2-naphthoquinone diazide sulfonic acid halide can be used.

 The condensation reaction can be carried out by known methods.

 These (B) components can be used alone or in combination of two or more.

The proportion of component (B) used is preferably 5 to 1000 parts by weight, more preferably 10 to 50 parts by weight, per 100 parts by weight of the copolymer (A). If this ratio is less than 5 parts by weight, the difference in solubility between the irradiated part and the non-irradiated part in the aqueous Al-water solution as the developing solution may be small, which may make patterning difficult. Insufficient heat resistance and solvent resistance of interlayer insulating film or micro lens There is a case. On the other hand, when this ratio exceeds 100 parts by weight, the solubility in the aqueous solution of the above-mentioned aqueous solution in the irradiated part becomes insufficient, which may make it difficult to develop.

 Other ingredients

 The radiation-sensitive resin composition of the present invention comprises, if necessary, (C) a heat-sensitive acid-forming compound, (D) at least one, in addition to containing the above-mentioned copolymers (A) and (B). (E) an epoxy resin other than the copolymer (A), (F) a surfactant, or (G) an adhesion aid, etc. can be contained. .

 The (C) heat-sensitive acid-forming compound can be used to improve heat resistance and hardness. Specific examples thereof include ammonium salts such as sulfonium salts, benzothiazolium salts, ammonium salts, phosphonium salts and the like.

 Specific examples of the above sulfonium salts include alkyl sulfonium salts, benzyl sulfonium salts, dibenzyl sulfonium salts, substituted benzyl sulfonium salts and the like.

 Specific examples of these include, as alkylsulfonium salts, 4-acetophenyldimethylsulfoneme, hexafluoroantimonate, 4-acetoxyphenyldimethylsulfoneme as hexafluoroarsenene salt, and the like. , Dimethyl- 4 (phenyl sulfonyl) phenylsulfonyl, hexafluoroantimonate, Dimethyl- 1 (benzoxyloxy) phenyl sulfonium, hexaantimonate, Dimethyl 4-(benzoyloxy) phenyl Sulfonium Hexafluoro arsenate, Dimethyl- 3-chloro- 4-acetoxyphenyl sulfinium Hexafluoro anthramonate, etc .;

Benzyl-4-hydroxyphenylmethylsulfone as a benzylsulfonium salt, hydroxya-hydroxyantimonate, benzyl-4-hydroxyphenylmethylsulfone, hexafluorophospho-phenate, 4-acetoxyphenyl-pentyl methylsulfone Antimonate, benzyl-4-methoxyphenyl methyl sulfonium hexafluoroantimonate, benzyl-2-methi Roux 4-hydroxyphenyl methyl sulfonium hexathioantimonate, benzyl 3-chloro-4-hydroxyphenyl methyl sulfonium hexafluorinated alcohol, 4-methoxybenzyl 4-hydroxyphenyl methyl sulfonium hexafluoroboron Phosphate etc;

Dibenzyl 4-hydroxyphenyl sulfonium salt as a dibenzyl sulfonium salt, dibenzyl 4-hydroxyphenyl sulfonium hexafluorophosphate, 4-acetoxyphenyl dibenzyl sulfonium sulfate O b antimonate, hexa full O b antimonate to Jibenjiru 4-methoxy Hue Nils Ruhoniumu, dibenzyl - 3- chloro 4-hydrate hexa full O b arsenate titanate to Loki Schiff enyl sulfo Niu beam, dibenzyl - 3 main Chiru ₄ - Hydroxy-5-tert-tert-butylphenylsulfoneium hexafluoroantimonate, benzyl-4-methoxybenzyl-4-hydroxyphenylsulfoneium hexafluorophosphate and the like;

As substituted benzyl sulfonium salts, ρ-chlorobenzimidazole 4-hydroxyphenyl methyl sulfonium salt, p-nitrobenzyl-4-hydroxyphenyl methyl sulfonium salt Ro-antimonate, p--Ku-to-mouth benzene- 4-hydroxyphenyl methylsulfanium hexabasic acid, p-nitrobenzyl mono 3-methyl-4-hydroxyphenyl methyl sulfonium hemifloantimonate, 3, 5-dichlorobenzimidazole 4-hydroxyphenylmethylsulfoneium hexafluoroantimonate, O-cout oral benzyl-3-chloro-4-hydroxyphenylmethylsulfonium hexafluoro Each one can be listed, for example.

 As specific examples of the above benzothiazolium salts, 3-benzylbenzothiazolium, hexafluoroantimonate, 3-benzylbenzothiazolium hexafluorophosphate, 3-benzylbenzothiazolium Tetrafluoroborate, 3- (P-methoxybenzyl) benzothiazolium hexafluoroantimonate,

3-Benzyl-2-methylthiobenzothiazole hexafuroantimonate, 3-benzimidazole 5-chlorobenzazothiazole hexafurouroantimonate And benzil benzothiazolium salts.

 Among these, sulfonium salts and benzothiazolium salts are preferably used, and in particular, 4-acetoxyphenyl dimethyl sulfonium hexafluoroarcenet, benzyl-4-hydroxyphenylmethylsulfonium hexafluoroanantimonate, 4 Methyl acetoxylate phenylmethyl sulfonium: Hexafluoroantimonate, Dibenzyl 4-hydroxyphenyl sulfonium: Hexafluoroantimonate, 4-Acetoxyphenyl: Pentyl sulfonium Hexa fluoroa G, 3-Benzylbenzothiazolium hexafluoroanthomonate is preferably used.

 As these commercial products, San Aid S I-L 85, the same S I-L 110, the same S

1 1 L 1 45, the same S I-L 15 0, the same S I-L 16 0 (manufactured by Sanshin Chemical Industry Co., Ltd.), and the like.

 The proportion of the component (C) used is preferably, relative to 100 parts by weight of the copolymer (A),

The amount is 20 parts by weight or less, more preferably 5 parts by weight or less. When the amount used exceeds 20 parts by weight, precipitates may be precipitated in the coating film forming step, which may affect the formation of the coating film.

 Examples of the polymerizable compound (hereinafter sometimes referred to as “component D”) having at least one ethylenically unsaturated double bond which is the component (D) include, for example, monofunctional (membrane) acrylate, 2 The functional (meth) acrylate or the trifunctional or higher functional (meth) acrylate can be preferably mentioned.

Examples of the monofunctional (meth) acrylate include 2-hydroxy (meth) acrylate, carbitol (meth) acrylate, isopolonil (meth) acrylate, 3-methoxybutyl (meth) acrylate, 2- (meta Acryloyl oxethyl 2-hydroxypropyl phthalate and the like. As these commercial products, for example, Aronics M-101, M-111, M-114 (all, manufactured by Toagosei Co., Ltd.), KAYA R AD TC 1 1 0 S And TC- 120 S (above, manufactured by Nippon Kayaku Co., Ltd.), Biscoat 1 5 8 and 2 3 1 1 (above, made by Osaka Organic Chemical Industry Co., Ltd.), and the like. Examples of the above bifunctional (meth) acrylate include ethylene glycol (meth) acrylate, 1,6-hexanedi (meth) acrylate, 1,9-nonanediol di (meth) acrylate, polypropylene glycol di (meth) acrylate And tetraethylene glycol di (meth) acrylate, bisphenyl ethanol ethanol orange acrylate, bis phenoxy ethanol fluorene diacrylate and the like. As these commercial products, for example, ARONICS M-210, M-240, M- 6200 (above, manufactured by Toagosei Co., Ltd.), KA YARAD HDDA, HX- 220, and R- 604 (above, Nippon Kayaku Co., Ltd., Viscote 260, 312, and 335 HP (all manufactured by Osaka Organic Chemical Industry Co., Ltd.).

 Examples of (meth) acrylates having three or more functional groups include trimethylolpropantri (meth) acrylate, pentaerythritol tri (meth) acrylate, tri (meth) acrylate (physylate), phosphate, and pentaerythritol tetra (meth). Examples include acrylate, dipen erythritol, pentolate (meta) acrylate, dipen erythritol hexahydrate (meta) acrylate, and the like. Examples of commercially available products thereof include Aronics M-309, M-400, M-405, M-450, M-7100, M-8003, and M-8060 (above, Toagosei Co., Ltd.) ), KAYARAD TMPTA, DPHA, DPCA-20, DPCA-30, DPCA-60, DPCA-120 (above, Nippon Kayaku Co., Ltd. product), Viscote 295, 300, 360, Examples include GPT, 3PA, and 400 (above, Osaka Organic Chemical Industry Co., Ltd.).

 Among these, trifunctional or higher functional (meth) acrylates are preferably used, among which trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, and dipentene erythritol hexa (meth) acrylate are preferred. Particularly preferred.

These monofunctional, bifunctional or trifunctional or higher functional (meth) acrylates may be used alone or in combination. The proportion of component (D) used is preferably 50 parts by weight or less, more preferably 30 parts by weight or less, per 100 parts by weight of copolymer (A). It is.

 By containing the component (D) in such a proportion, the heat resistance, surface hardness and the like of the interlayer insulating film or the micropore lens obtained from the radiation sensitive resin composition of the present invention can be improved. When the amount used exceeds 50 parts by weight, film roughening may occur in the step of forming a coating film of the radiation sensitive resin composition on a substrate. The epoxy resin other than the copolymer (A) which is the component (E) (hereinafter sometimes referred to as "component E") is not limited as long as the compatibility is not affected, but is preferably Bisphenol A-type epoxy resin, phenol-type epoxy resin, cresol nopolac-type epoxy resin, cyclic aliphatic epoxy resin, glycidyl ester-type epoxy resin, glycidylamine-type epoxy resin, heterocyclic epoxy resin Resins, resins obtained by (co) polymerizing glycidyl methacrylate and the like can be mentioned. Among these, bisphenol A-type epoxy resin, cresol monopolar epoxy resin, daricidyl ester-type epoxy resin and the like are more preferable.

 The proportion of the component (E) used is preferably 30 parts by weight or less based on 100 parts by weight of the copolymer (A). By containing the component (E) in such a proportion, the heat resistance and the surface hardness of the protective film or insulating film obtained from the radiation sensitive resin composition of the present invention can be further improved. When this proportion exceeds 30 parts by weight, the film thickness uniformity of the coating film may be insufficient when forming a coating film of the radiation sensitive resin composition on a substrate. ■

 The copolymer (A) can also be referred to as "epoxy resin", but the copolymer (A) is different from the component (E) in that it has alkali solubility.

 In the radiation sensitive resin composition of the present invention, a surfactant which is the component (F) can be used to further improve the coating property. As the surfactant (F) that can be used here, for example, a fluorine-based surfactant, a silicone-based surfactant and a nonionic surfactant can be suitably used.

Specific examples of the fluorine-based surfactant include 1,1,2,2-tetrafluoro (butyl) (1,1,2,2-tetrafluoropropyl) ether, and 1,1,2,2-tetrafluorocyl. Xyl ether, keta ethylene glycol di (1, 1, 2, 2, 2-Tetrafulurobutyl) ether, Hexaethylene glycol (1, 1, 2, 2, 3, 3 _ Hexa- fluoropentyl) Ether, Octapropylene Glycol Di (1, 1, 2, 2-tetrafluoro) Mouth robutyl) ether, hexapropylene glycol di (1, 1, 2, 2, 3, 3-hexaflouropentyl) ether, perfluoro sodium dodecyl sulfonate, 1, 1, 2, 2, 8, 8, 9 9, 10, 10-Decaf mouth rhododecane, 1, 1, 2, 2, 3, 3-Hexaflorodecane and the like, sodium fluoroalkylbenzene sulfonate; fluoroalkyl oxyether ethers fluoro Fluoroalkyl ammonium monozide, fluoroalkylpolyoxyethylene ether, perfluoroalkyl polyoxyethanol; perfluoroalkyl alkoxylate; fluoroalkyl ester etc. It is possible to As these commercial products, BM-1000, BM-1100 (all, manufactured by BM Chemie), Megafac F 142 D, F 172, F 173, F 183, F 178, F 191, and F 191, respectively. Same F471 (more, Dainippon Ink and Chemicals, Inc.), Flora FC FC 170 C, FC 171, FC 430, FC 4 31 (Sumitomo Sliemm Co., Ltd.), Cerflon S 112 , S-113, S-131, S-141, S-145, S-382, SC-101, SC-102, SC-103, SC-104, SC-105 SC-106 (manufactured by Asahi Glass Co., Ltd.), F-top EF 301, 303, and 352 (manufactured by Shin-Akita Kasei Co., Ltd.).

 Examples of the silicone surfactant include DC3PA, DC7PA, FS-1265, SF-8428, SHI1PA, SH21PA> SH28PA, SH29PA, SH, 30PA, SH-190, SH-193, SZ- 6032 (more, Toray Dow Corning 'Silicone Co., Ltd.), TSF-4440, TSF-4300, TSF-4445, TSF-4446, TSF-4460, TSF-4452 (above, GE Toshiba Silicone Co., Ltd.) And those marketed under the trade names such as

As said nonionic surfactant, for example, polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl Polyoxyethylene alkyl ether such as ether; Polyoxyethylene alkyl phenyl ether, Polyoxy ethylene aryl ether such as polyoxy ethylene nonyl phenyl ether; Polyoxyethylene dilaurate, Polyoxy ethylene di stearate etc And (meth) acrylic acid copolymer polyflow No. 57, 95 (manufactured by Kyoeisha Chemical Co., Ltd.) and the like can be used.

 These surfactants can be used alone or in combination of two or more.

 The (F) surfactant is preferably used in an amount of 5 parts by weight or less, more preferably 2 parts by weight or less, based on 100 parts by weight of the copolymer (A). When the amount of the surfactant (F) used exceeds 5 parts by weight, the coating film may be easily peeled off when the coating film is formed on the substrate.

 The radiation-sensitive resin composition of the present invention can also use an adhesion assistant which is the component (G) in order to improve the adhesion to the substrate. As such (G) adhesion assistants, for example, functional silane coupling agents are preferably used. Examples thereof include silane coupling agents having reactive substituents such as carboxyl group, methacryloyl group, isocyanato group and epoxy group. More specifically, for example, trimethoxysilyl benzoic acid, r-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, biertrimethoxysilane, acid sodium tripropyltriethoxysilane, aglycidoxypropyl Trimethoxysilane, β- (3,4-epoxycyclohexyl) detritrimethoxysilane and the like can be mentioned. Such (G) adhesion assistant is preferably used in an amount of 20 parts by weight or less, more preferably 10 parts by weight or less, based on 100 parts by weight of the copolymer (Α). If the amount of adhesion promoter exceeds 20 parts by weight, the development residue may easily occur in the development process.

 Radiation sensitive resin composition

The radiation sensitive resin composition of the present invention can be prepared by uniformly mixing the above-mentioned copolymer (Α) and (Β) components and the other components optionally added as described above. Be prepared. The radiation sensitive resin composition of the present invention is preferably dissolved in a suitable solvent and used in a solution state. For example, the radiation-sensitive resin composition in a solution state can be prepared by mixing the components (A) and (B) and other components which are optionally added in a predetermined ratio.

 As solvents used for preparation of the radiation sensitive resin composition of the present invention, the components of the copolymers (A) and (B) and the other components which are optionally blended are uniformly dissolved, Those which do not react with the components are used.

 As such solvent, the same ones as exemplified as the solvent which can be used to produce the above-mentioned copolymer (A) can be mentioned.

 Among such solvents, in view of solubility of each component, reactivity with each component, easiness of coating formation, etc., for example, alcohol, glycol ether, ethylene glycol alkyl ether acetate, ester and ester Diethylene glycol is preferably used. Among these, for example, benzyl alcohol, 2-phenylethyl alcohol, 3-phenyl-l-propanol, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, dithiol ether glycol ether, diethylene glycol Particularly preferred are ethyl methyl ether, dimethylene glycol dimethyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, methyl methoxypropionate and ethyl ethoxypropionate.

Furthermore, in order to improve the in-plane uniformity of film thickness together with the above-mentioned solvent, a high boiling point solvent can be used in combination. Examples of high-boiling solvents that can be used in combination include N-methylformamide, N, N-dimethylformamide, N-methylformanilide, N-methylacetamide, N, N-dimethylacetoamide, N-methylpyrrolidone, Dimethyl sulfoxide, benzyl ethyl ether, dihexyl ether, acetonyl acetate, isophorone, caproic acid, purilic acid, one-year-old ctanol, 1-nonanal, benzyl acetate, ethyl benzoate, ketyl dithioate, jetyl maleate, There may be mentioned petiturolactone, ethylene carbonate, propylene carbonate and solvose acetate. Of these, N-methyl pyrrolidone, Quton, N, N-dimethylacetoamide is preferred.

 When a high boiling point solvent is used in combination as the solvent of the radiation sensitive resin composition of the present invention, the amount thereof used is preferably 50% by weight or less, more preferably 40% by weight or less, more preferably Can be less than 30% by weight. If the amount of the high boiling point solvent used exceeds this amount, the film thickness uniformity, sensitivity and residual film rate of the coating may be lowered.

 When the radiation sensitive resin composition of the present invention is prepared in the form of a solution, components other than the solvent occupied in the solution, that is, the components of the copolymers (A) and (B) and other components optionally added. The proportion of the total amount can be optionally set according to the purpose of use, the desired thickness of the film, etc. For example, 5 to 50% by weight, preferably 10 to 40% by weight, more preferably 1 5 to 35% by weight.

 The composition solution thus prepared can also be used after being filtered using Millipore filter having a pore diameter of about 0.2 m or the like.

 Formation of interlayer insulation film, micro lens

 Next, a method of forming the interlayer insulating film and the microlens of the present invention using the radiation sensitive resin composition of the present invention will be described. The respective methods of forming the interlayer insulating film and the micro lens according to the present invention can be implemented including the following steps in the order described below.

 (1) forming a coating film of the radiation sensitive resin composition of the present invention on a substrate,

(2) irradiating at least a part of the coating film with radiation;

 (3) Development process, and

 (4) Heating process.

 (1) A step of forming a coating of the radiation sensitive resin composition of the present invention on a substrate

 In the step (1), the composition solution of the present invention is applied to the surface of the substrate, and preferably the solvent is removed by prebaking to form a coating film of the radiation sensitive resin composition.

Examples of the type of substrate that can be used include a glass substrate, a silicon wafer, and a substrate having various metals formed on the surface thereof. The method for applying the composition solution is not particularly limited. For example, an appropriate method such as a spray method, roll coating method, spin coating method (spin coating method), slit die coating method, bar coating method, ink jet coating method, etc. In particular, spin coating and slit die coating are preferred. The conditions of the pre-baking depend on the type of each component, the ratio of use, and so on. For example, the temperature may be set to 60 to 110 ° C. for 30 seconds to 15 minutes.

 The film thickness of the coating film to be formed is, for example, 3 to 6 ^ m in the case of forming an interlayer insulating film and 0.5 to 5 in the case of forming a microlens as a value after prebaking. 3 m is preferred.

 () Irradiating at least a part of the coating

 In the step (2), the formed coating film is irradiated with radiation through a mask having a predetermined pattern. Thereafter, in the next step (3), patterning is carried out by developing with a developer to remove the irradiated part of the radiation. Examples of radiation used at this time include ultraviolet light, far ultraviolet light, X-rays, charged particle beams and the like.

 Examples of the ultraviolet light include g-ray (wavelength 4 3 6 nm) and i-ray (wavelength 3 6 5 nm). The far ultraviolet rays include, for example, a K r F excimer laser. Examples of X-rays include synchrotron radiation and the like. Examples of charged particle beams include electron beams and the like.

 Of these, ultraviolet light is preferred, and radiation containing, in particular, g-line and Z or i-line is preferred.

The exposure dose is, for example, 50 to 1, 500 J / m ² in the case of forming an interlayer insulating film, and, for example, 50 to 2, 0 0 in the case of forming a microlens. It is preferable to set it as 0 J Zm ² .

 (3) Development process

As a developing solution used for development processing, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium catechate, sodium metasilicate, ammonia, acetylamine, n-propylamine, getilamine, getilamino ester. G, n-Propylamine, triethylamine, methyl jetylamine, dimethylethanolamine, triethanolamine, tetramethyl ammonium hydroxide, tetraethyl ammonium hydroxide, pyrrole, piperidine, It is possible to use an aqueous solution of an alkali (basic compound) such as 1,8-diazabicyclo [5.4.0] mono-andecene, 1,5-diazabicyclo [4.3.0] mono-nonane. Further, an aqueous solution obtained by adding an appropriate amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant to an aqueous solution of the above-mentioned alkali, or various organic solvents capable of dissolving the composition of the present invention can be used as a developer. Further, as a development method, an appropriate method such as a liquid deposition method, a datebing method, a rocking immersion method, a shower method or the like can be used. The development time at this time depends on the composition of the composition, but can be, for example, 30 to 120 seconds.

 In the case of radiation-sensitive resin compositions known in the prior art, if the developing time exceeds the optimum value by about 20 to 25 seconds, the pattern formed will be peeled off, but it is necessary to control the developing time strictly. In the case of the radiation sensitive resin composition of the present invention, good pattern formation is possible even if the excess time from the optimum development time is 30 seconds or more, and there is an advantage in product yield.

 (4) Heating process

After the development step (3) carried out as described above, the thin film thus treated is preferably rinsed by running water, for example, and then the entire surface is preferably irradiated with radiation preferably by a high-pressure mercury lamp. After the decomposition treatment of the 1,2-quinonediazide compound remaining in the thin film by (post-exposure), the thin film is heated (post-baking treatment) by a heating device such as a hot plate or an oven. ) To cure the thin film. The exposure dose in the above-described post-exposure step is preferably about 2, 0 0 5 to 5 0 0 0 J Z m ² . Moreover, the heating temperature in this hardening process is 120-250 degreeC, for example. The heating time varies depending on the type of heating device. For example, when heat treatment is performed on a hot plate, for example, when heat treatment is performed in an oven for 5 to 30 minutes, for example, 3 0 to 9 0 It can be a minute. At this time, use a step bake method or the like that performs two or more heating steps. You can also

 In this way, a pattern-like thin film corresponding to the target interlayer insulating film or microlens can be formed on the surface of the substrate.

 The interlayer insulating film and the microphone lens formed as described above are excellent in adhesion, heat resistance, solvent resistance, transparency and the like, as will be apparent from the examples described later.

 Interlayer insulation film

 The interlayer insulating film of the present invention formed as described above has good adhesion to a substrate, is excellent in solvent resistance and heat resistance, has high transmittance, and is low in dielectric constant. It can be suitably used as an interlayer insulating film of electronic parts.

 Micro lens

 The lens of the present invention formed as described above has good adhesion to a substrate, is excellent in solvent resistance and heat resistance, and has high transmittance and good melt shape. It can be suitably used as a microlens of a solid-state imaging device. The shape of the microlens according to the present invention is a semi-convex lens shape as shown in FIG. 1 (a). Example

 The present invention will be described more specifically by showing synthesis examples and examples below, but the present invention is not limited to the following examples.

Measurement of Molecular Weight of Copolymer by Gel Permeation Chromatography> Device: GP C- 101 (manufactured by Showa Denko KK)

Columns: GPC-KF-801, GPC-KF-802, GPC-KF-804 and GPC-KF-804

Mobile phase: Tetrahydrofuran containing 0.5% by weight phosphoric acid.

 Example of synthesis of copolymer (A)

Synthesis example 1

In a flask equipped with a condenser and a stirrer, 1 part by weight of azobisisobutyronitrile, 4 parts by weight of cumyl dithiobenzoate and 50 parts by weight of diethylene glycol tributyl ether were charged. Subsequently, 20 parts by weight of styrene, 20 parts by weight of methacrylic acid, 20 parts by weight of tricyclo [5. 2. 0 ^{2 6} ] decane-18-yl methacrylate, and 40 parts by weight of glycidyl methacrylate were charged and nitrogen-exchanged. Stirring started quickly. The temperature of the solution is raised to 60 ° C., and this temperature is maintained for 24 hours, and then 3 parts by weight of azobisisoptyronitrile is added and stirring is carried out at 60 ° C. for another 4 hours. Diethylene glycol ethyl methyl ether 200 weight A part was added to obtain a solution of copolymer (A-1). The polystyrene equivalent weight average molecular weight (Mw) of the copolymer (A-1) was 10,000, the molecular weight distribution (Mw / Mn) was 1.4, and the residual monomer was 2.0% by weight. The solid concentration of the polymer solution was 29.8% by weight.

 Synthesis example 2

In a flask equipped with a condenser and a stirrer, 1 part by weight of azoisobutyronitrile, 4 parts by weight of cumyl dithiobenzoate and 50 parts by weight of diethylene diallyl ethyl ether were charged. Bow I Continuous Methacrylic Acid 16 parts by weight, Dalicidyl Methacrylate 18 parts by weight, Tricyclo [5. 2. 0 ^{2 6} !] Decane 1-yl methacrylate 6 parts by weight, p-vinylbenzyl glycidyl ether 30 parts by weight After 30 parts by weight of polyethylene glycol (n = 2) monomethacrylate was charged and replaced with nitrogen, stirring was gradually started. The temperature of the solution is raised to 60 ° C., and this temperature is maintained for 24 hours, and then 3 parts by weight of azobisisoptyronitrile is added, and stirring is carried out at 60 ° C. for another 4 hours. An additional 200 parts by weight was added to obtain a solution of the copolymer (A-2). The polystyrene equivalent weight average molecular weight (Mw) of the copolymer (A-2) was 11,000, the molecular weight distribution (Mw / Mn) was 1.3, and the residual monomer was 1.2% by weight. The solid concentration of the polymer solution obtained here was 30.1% by weight.

 Synthesis example 3

The copolymer according to Synthesis Example 1 except that, in the synthesis example 1, S-cyanomethyl-S-dodecyltrithiocarbonate was used instead of cumyl dithiobenzoate A solution of (A-3) was obtained. The polystyrene equivalent weight average molecular weight (Mw) of the copolymer (A-3) was 9,500, the molecular weight distribution (MwZMn) was 1.3, and the residual monomer was 1.5% by weight. The solid concentration of the polymer solution was 29.6% by weight. Synthesis example 4

 According to Synthesis Example 2 except that in Example 2 of the present invention, pyrazoyl dithio-1 dithiodibasic acid methyl ester is used in place of cumyldithiobenzoate, the copolymer (A-4) is contained. A polymer solution was obtained. The polystyrene conversion weight average molecular weight (Mw) of the copolymer (A-4) was 12,000, the molecular weight distribution (Mw / Mn) was 1.4, and the residual monomer was 1.3% by weight. The solid content concentration of the polymer solution was 29.7 weight.

 Synthesis example 5

 A polymer solution containing a copolymer (A-5) was obtained according to Synthesis Example 1 except that the following dithioester was used instead of cumyl dithiobenzoate in Synthesis Example 1. The polystyrene equivalent weight average molecular weight (Mw) of the copolymer (A-5) was 11,000, the molecular weight distribution (Mw / Mn) was 1.3, and the residual monomer was 1.4% by weight. The solids concentration of the polymer solution was 29.8% by weight.

Synthesis example 6

A polymer solution containing a copolymer (A-6) was obtained according to Synthesis Example 2 except that the following xanthate was used in place of cumyl dithiobenzoate in Synthesis Example 2. The polystyrene equivalent weight average molecular weight (Mw) of the copolymer (A-6) was 11,000, the molecular weight distribution (Mw / Mn) was 1.3, and the residual monomer was 1.5% by weight. The solids concentration of the polymer solution was 30.1% by weight.

Comparative synthesis example 1

 A flask equipped with a condenser and a stirrer was charged with 8 parts by weight of 2, 2, 2-azobis (2, 4-dimethylbareronitrile) and 220 parts by weight of diethylene glycol ethyl methyl ether. Subsequently, 20 parts by weight of styrene, 20 parts by weight of methacrylic acid, 40 parts by weight of glycidyl methacrylate and 20 parts by weight of phenylmaleimide were charged and nitrogen substitution was performed, and then stirring was gradually started. The temperature of the solution was raised to 70 ° C., and this temperature was maintained for 5 hours to obtain a polymer solution containing the copolymer (a-1).

 The polystyrene reduced weight average molecular weight (Mw) of the copolymer (a-1) was 7, 500, and the molecular weight distribution (Mw / Mn) was 2.4. The residual monomer was 5.8% by weight. The solid content concentration of the polymer solution obtained here was 30.6% by weight. Example 1

 Preparation of radiation sensitive resin composition

A solution containing the polymer (A-1) as the component (A) synthesized in the above Synthesis Example 1 is used as an amount corresponding to 100 parts by weight (solid content) of the polymer (A-1) and the component (B) 4,4,1 [1- [4- [1- [4-hydroxyphenyl] one-1-methylethyl] phenyl] phenylidene] bisphenol (1.0 mol) and 1,2-naphthoquinonediazide-5- Condensate of sulfonic acid chloride (2.0 mol) (B-1) 3 The mixture is mixed with 0 parts by weight, dissolved in diethylene glycol methyl ether so that the solid concentration becomes 30% by weight, and then filtered with a membrane filter of 0.2 m in diameter to obtain a radiation-sensitive resin composition The solution (S-1) was prepared.

 Examples 2-9, 11-14, Comparative Example 1

Preparation of radiation sensitive resin composition

 The procedure of Example 1 was repeated except that the types and amounts as described in Table 1 were used as the component (A) and the component (B) in Example 1, and a solution of a radiation sensitive resin composition was prepared. (S-2) to (S-9), (S-11) to (S-14) and (s-1) were prepared.

 In Table 1, the description of the component (B) in Example 8 indicates that two types of 1, 2-quinonediazide compounds, B-1 (20 parts by weight) and B-2 (15 parts by weight) were used in combination. it's shown.

 Example 10

 A composition was prepared in the same manner as in Example 1 except that the composition was dissolved in diethylene glycol ether so that the solid concentration would be 15% by weight, and the solution of the radiation-sensitive resin composition (S-10 ) Was prepared.

 In Table 1, abbreviations of the components indicate the following compounds.

 (B-1): 4, 4 '1 [1 1 [4- [1- [4-hydroxyphenyl] -1 1 methyl ethyl] phenyl] acetylidene] bis phenoyl (1.0 mol) and 1, 2 1 Condensate of naphthoquinone diazide-5-sulfonic acid chloride (2.0 mol)

(B-2): 4, 4'1 [1-[4 [1-[4- hydroxyphenyl] 1 1_ methylethyl] phenyl] acetylidene] bis phenol (1.0 mol) and 1,2 naphthoquinone diazide — 5-Condensate of sulfonic acid chloride (1.0 mol)

(B-3): 2, 3, 4, 4, 1-tetrahydroxybenzophenone (1.0 mol) and 1, 2-naphthoquinone diazide 5-sulfonic acid ester (2. 44 mol)

(B-4): 4, 4 '-[1-[4- [1 [4 [4 hydroxy phenyl] 1 1 methyl ethyl] phenyl] phenylidene] bis phenol (1. 0 mol) and 1, 2 naphtho Condensate of quinonediazide-4-sulfonic acid chloride (2.0 mol) (F): SH-28 PA (Toray · Dow Corning · Silicone Co., Ltd.) Table 1

Examples 15-28, Comparative Examples 2-4

Performance evaluation as interlayer insulation film

 Using the radiation sensitive resin composition prepared as described above, various properties as an interlayer insulating film were evaluated as follows. The compositions used in Comparative Examples 3 and 4 are all commercial products of a composition of m / p-cresol nopolac and 1,2-naphthoquinonediazide-5-sulfonic acid ester (manufactured by Tokyo Ohka Kogyo Co., Ltd.) ).

 Evaluation of sensitivity

The compositions described in Table 2 were coated on a silicon substrate using a spinner for Examples 15 to 27 and Comparative Examples 2 to 4 and a slit die for Example 28. The film was prebaked on a hot plate at 90 ° C. for 2 minutes to form a coating having a film thickness of 3.0 m. The obtained coating film is exposed by changing the exposure time with a PLA-501 F exposure machine (super high pressure mercury lamp) manufactured by Canon Inc. through a pattern mask having a predetermined pattern, and It was developed by a liquid deposition method at 25 ° C. for 90 seconds using an aqueous solution of tetramethyl ammonium hydroxide having a developer concentration described in Table 2. It was washed with running ultrapure water for 1 minute and dried to form a pattern on the wafer. 3. The amount of exposure required to completely dissolve the 0'm line 'and' space (10 to 1) space 'pattern was measured. This value is shown in Table 2 as sensitivity. ■ It can be said that the sensitivity is good when this value is less than 1,000 JZm ² .

 Evaluation of the development agent

 After the compositions described in Table 2 were coated on a silicon substrate using a spinner for Examples 15 to 27 and Comparative Examples 2 to 4 and a slit die coater for Example 28, 90 The film was prebaked on a hot plate at 2 ° C. for 2 minutes to form a coating having a thickness of 3.0 μm. The obtained coating film has a pattern of line 'and' space (10 to 1) of 3.0 m through a mask made by Canon Inc. PLA-501 F exposure machine (super high pressure mercury lamp Exposure is carried out at an exposure amount corresponding to the value of sensitivity measured in the above “Evaluation of sensitivity”, and the aqueous solution of tetramethyl ammonium hydroxide in the developer concentration shown in Table 2 is used at 25 ° C. , Developed for 90 seconds by immersion method. Next, it was washed with running ultrapure water for 1 minute, dried, and a pattern was formed on the wafer. At this time, the development time required for the line width to be 3 m is shown in Table 2 as the optimum development time. In addition, when the development was continued from the optimum development time, the time until the line pattern of 3.βm was peeled off was measured, and is shown in Table 2 as a development margin. When this value is 30 seconds or more, it can be said that the development margin is good. Evaluation of solvent resistance

After the compositions described in Table 2 were coated on a silicon substrate using a spinner for Examples 15 to 27 and Comparative Examples 2 to 4 and a slit die coater for Example 28, 90 ° The film was prebaked on a hot plate for 2 minutes at C to form a coating having a film thickness of 3.0 m. The resulting coating film was exposed to an integrated irradiation dose of 30,000 J / m ^{2 using a} PLA-501 F exposure apparatus (super high pressure mercury lamp) manufactured by Canon Inc., and this silicon substrate was placed in a clean oven. The film was heated at 220 ° C. for 1 hour to obtain a hard coating. The film thickness (T1) of the obtained cured film was measured. Then, the silicon substrate on which this cured film is formed is immersed in dimethyl sulfoxide controlled at 70 ° C. for 20 minutes, and then the thickness (t 1) of the cured film is measured, The rate of change {It1-T1I / Tl} x 100 [] was calculated. The results are shown in Table 2. this When the value is 5% or less, it can be said that the solvent resistance is good.

 In addition, since the patterning of the film to be formed is unnecessary in the evaluation of the solvent resistance, the radiation irradiation process and the development process are omitted, and only the coating film formation process, the post-baking process and the heating process are performed. Provided.

 Evaluation of heat resistance

 A cured film was formed in the same manner as the above-mentioned evaluation of solvent resistance, and the film thickness (T 2) of the obtained cured film was measured. Next, this cured film substrate is additionally baked at 240 ° C. for 1 hour in a clean oven, and then the film thickness (t 2) of the cured film is measured, and the film thickness change rate due to the additional baking {It2-T2IZT2} X100 [%] was calculated. The results are shown in Table 2. When this value is 5% or less, heat resistance can be said to be good.

 Transparency assessment

 A cured film was formed on the glass substrate in the same manner as in the above evaluation of the solvent resistance except that the glass substrate “Coating 7059 (manufactured by Koining Co., Ltd.)” was used instead of the silicon substrate. The light transmittance of the glass substrate having this cured film was measured at a wavelength of 400 to 800 nm using a spectrophotometer "150-20 type double beam (manufactured by Hitachi, Ltd.)". The values of the lowest light transmittance at that time are shown in Table 2. When this value is 90% or more, transparency can be said to be good.

 Evaluation of relative permittivity

The compositions described in Table 2 were coated on polished SUS 304 substrates using a spinner for Examples 15 to 27 and Comparative Examples 2 to 4 and a slit die coater for Example 28. Thereafter, it was pre-baked on a hot plate at 90 ° C. for 2 minutes to form a coating having a film thickness of 3.0 m. The obtained coating film was exposed to an integrated irradiation dose of 30,000 J / m ^{2 using a} Canon LA Co., Ltd. product PLA-501 F exposure machine (ultra high pressure mercury lamp), and this substrate was placed in a clean oven. A cured film was obtained by baking at 220 ° C. for 1 hour.

A PtZPd electrode pattern was formed on the hard solder film by vapor deposition to prepare a dielectric constant measurement sample. The substrate is at a frequency of 10 kHz, and an HP 16451 B electrode and an HP 4284 A pressure made by Yokogawa Hyoretto Packard Co., Ltd. The relative permittivity of the substrate was measured by a CV method using a John LCR meter. The results are shown in Table 2. When this value is 3.6 or less, it can be said that the dielectric constant is good.

 In addition, since the patterning of the film to be formed is unnecessary in the evaluation of the relative dielectric constant, the radiation irradiation process and the development process are omitted, and only the coating film formation process, the post baking process and the heating process are performed. did.

 Sublimate evaluation

The compositions described in Table 2 were coated on a silicon substrate using a spinner for Examples 15 to 27 and Comparative Examples 2 to 4 and using a slit die coater for Example 28. Thereafter, it was prebaked on a hot plate at 90 ° C. for 2 minutes to form a coating having a film thickness of 3.0 μm. The obtained coating film was exposed to an integrated irradiation dose of 3, 0 0 J / m ^{2 using a} Canon LA Co., Ltd. product made by PLA-501 F (ultrahigh pressure mercury lamp), and this silicon was The substrate was heated in a clean oven at 220 ° C. for 1 hour to obtain a cured film. A silicon wafer for cooling was attached at an interval of 1 cm above the obtained hard disk, and heated on a hot plate at 230 ° C. for 1 hour. After continuously treating twenty silicon substrates on which the above cured film was separately formed without replacing the cooling bare silicon wafer, the presence or absence of a sublimate adhering to the bare silicon was visually inspected. When no sublimate is confirmed, it can be said that the sublimate evaluation is good.

Table 2

Composition type Sensitivity evaluation Developer margin Solvent resistance Heat resistance Transparency Dielectric constant Raised substance Developer concentration

 Sensitivity (J / Optimum development Development after curing Curing curing Film thickness change Curing after curing Film thickness change

 Degree (weight (%)

 m)

The amount ^0/0) Time (seconds) Jin (s) film (Myuitaiota) (%) film (Myupaiiota) (%)

Example 1 5 (S-1) 0.5 550 60 30 2.3 1 2.3 1 92 3.5 Example "! 6 (S-2) 0.5 550 60 30 2.4 1 2.4 1 93 3.4

Example 1 F (S-3) 0.4 600 60 35 2.5 1 2.5 1 93 3.3 None Example 1 8 (S-4) 0.4 500 60 30 2.5 1 2.5 1 93 3.3

Example 1 9 (S-5) 0.4 600 70 30 2.5 1 2.5 1 93 3.4 Example 20 (S-6) 0.4 500 60 30 2.3 1 2.3 1 92 3.4

Example 21 (S-7) 2.38 600 60 35 2.3 1 2.3 1 91 3.5 Example 22 (S-8) 0.4 550 60 30 2.3 1 2.3 1 93 3.4

Example 23 (S-9) 0.4 500 60 35 2.4 1 2.4 1 93 3.3 None Example 24 (S-10) 0.5 600 60 30 2.3 1 2.3 1 92 3.4

Example 25 (S-1 1) 0.5 550 60 30 2.3 1 2.3 1 92 3.5 4-Example 26 (S-12) 0.5 500 60 30 2.4 1 2.4 1 93 3.4 None Example 27 (S-13) 0.5 550 60 30 2.3 1 2.3 1 92 3.3 Example 28 (S-14) 0.5 500 60 30 2.4 1 2.4 1 93 3.3

Comparative Example 2 (s-1) 0.4 700 60 15 2.4 2.4 94 3.3 Comparative Example 3 OFPR-800 2.38 2200 60 25 2 10 2 15 83 3.7 Comparative Example 4 OFPR-5000 2.38 2200 60 20 1.9 12 1.9 14 82 3.7 Yes

Examples 29 to 42, Comparative Examples 5 to 7

Performance evaluation as micro lens>

 The radiation-sensitive resin composition prepared as described above was used to evaluate various characteristics as a microphone lens as follows. For the evaluation of heat resistance and the evaluation of transparency, please refer to the above-mentioned results of the performance evaluation as interlayer insulation film (Table 2).

 Further, the compositions used in Comparative Examples 6 and 7 are all commercial products of a composition of m / p-cresol nopolac and 1,2-naphthoquinonediazide-5-sulfonic acid ester (manufactured by Tokyo Ohka Kogyo Co., Ltd.) ).

 Evaluation of sensitivity.

The compositions described in Table 3 were coated on a silicon substrate using a spinner for Examples 29 to 38, 40 to 42, and Comparative Examples 5 to 7 and using a slit die coater for Example 39. Thereafter, it was prebaked on a hot plate at 90 ° C. for 2 minutes to form a coating having a film thickness of 3.0 m. The exposure time is varied with a Nikon Corporation NSR 1755 17 A reduction projection aligner (NA = 0.50, λ = 365 nm) through a pattern mask having a predetermined pattern on the obtained coating film. It was exposed to light, and developed with a tetramethylammonium hydroxide aqueous solution having a developer concentration described in Table 3 by immersion for 1 minute at 25 ° C. It was rinsed with water and dried to form a pattern on the wafer. The exposure time required for the space line width of the 0.8 m line 'and' space pattern (1 to 1) to be 0.8 m was measured. This value is shown in Table 3 as sensitivity. It can be said that the sensitivity is good when this value is less than 2,500 J / m ² .

 Evaluation of the development agent

The compositions described in Table 3 were coated on a silicon substrate using a spinner for Examples 29 to 38, 40 to 42, and Comparative Examples 5 to 7 and using a slit die coater for Example 39. Thereafter, it was prebaked on a hot plate at 90 ° C. for 2 minutes to form a coating having a film thickness of 3.0 zm. Evaluation of the above-mentioned "sensitivity" with a Nikon NSR 1755 i 7 A reduction projection exposure machine (NA = 0.50, λ = 365 nm) through a pattern mask having a predetermined pattern on the obtained coating film Of the sensitivity measured in Exposure was carried out at an exposure amount corresponding to the value, and development was carried out with an aqueous solution of tetramethylammonium hydroxide having a developer concentration described in Table 3 at 25 ° (:, for 1 minute by liquid deposition method). After drying, a pattern was formed on the wafer 0.88 Development time required for the line width of the space line (one-to-one) space pattern to be 0.8 is defined as the optimum development time Table 3 In addition, when the development was continued from the optimum development time, the time (develop margin) until the pattern of width 0.8 was peeled off was measured, and the development margin is shown in Table 3. This value is 30. When it is more than a second, it can be said that the development margin is good.

 Evaluation of solvent resistance

After the compositions described in Table 3 were coated on a silicon substrate using a spinner for Examples 29 to 38, 40 to 42, and Comparative Examples 5 to 7 and using a slit die coater for Example 39. Precoating was performed on a hot plate at 90 ° C. for 2 minutes to form a coating having a film thickness of 3.0 m. The resulting coating film was exposed to an integrated irradiation dose of 30,000 JXm ^{2 using a} Canon A Corp. PL A-501 F exposure device (ultra high pressure mercury lamp), and this silicon substrate was exposed to a clean oven. The cured film was obtained by heating at 220 ° C. for 1 hour. The film thickness (T3) of the obtained cured film was measured. Then, after immersing the silicon substrate on which this cured film is formed in isopropyl alcohol whose temperature is controlled at 50 ° C. for 10 minutes, the film thickness (t 3) of the cured film is measured, and the film thickness change due to immersion. The rate {I t 3 − T 3 I / T 3} X 100 [%] was calculated. The results are shown in Table 3. When this value is 5% or less, it can be said that the solvent resistance is good.

 In addition, since patterning of the film to be formed is unnecessary in the evaluation of solvent resistance, the radiation irradiation process and the development process were omitted, and only the coating film formation process, the post-baking process and the heating process were performed.

 Formation of micro lens

The compositions described in Table 3 were coated on a silicon substrate using a spinner for Examples 29 to 38, 40 to 42, and Comparative Examples 5 to 7 and using a slit die for One Example for Example 39. Then, it was prebaked on a hot plate at 90 ° C. for 2 minutes to form a coating having a film thickness of 3.0 m. The obtained coating film 4.0 mdot · 2. Nikon Corporation NSR through a pattern mask having a 0 m space pattern

1755 17 A Exposure was carried out with an exposure amount corresponding to the value of sensitivity measured in the above “Evaluation of sensitivity” with a reduction projection exposure apparatus (NA: 0.20, λ = 365 nm), and the evaluation of sensitivity in Table 3 was performed. The solution was developed by immersion in an aqueous solution of tetramethyl ammonium hydroxide at the concentration described as the concentration of the developer at 25.degree. C. for 1 minute. Rinse with water and dry to form a pattern on Ueno. After that, exposure was performed using a PLA-501F exposure apparatus (super high pressure mercury lamp) manufactured by Canon Inc. so that the cumulative irradiation amount would be 3,000 J / m ² . Thereafter, the pattern was heated at 160 ° C. for 10 minutes on a hot plate and further heated at 230 ° C. for 10 minutes to melt the pattern to form a micro aperture lens.

Table 3 shows the dimensions (diameter) and cross-sectional shape of the bottom (surface in contact with the substrate) of the formed micro lens. The size of the bottom of the micro lens is good when it is greater than 4. O ^ m and less than 5.0 im. If this size is 5.0 // m or more, adjacent lenses are in contact with each other, which is not preferable. Further, in the schematic view shown in FIG. 1, the cross-sectional shape is good when it is a semi-convex lens shape as shown in (a), and it is bad when it has a substantially trapezoidal shape as shown in (b).

Table 3 Composition type Sensitivity evaluation Development margin Solvent resistance Micro lens shape

 Developer concentration

 Sensitivity Optimum development Developing mar Curing after curing Film thickness change Bottom dimensions

Degree (Heavy (J / m) (mm) cross-sectional shape amount ^0/0) Time (seconds) Jin (s) film (Myuitaiota) (%)

Example 29 (S-1) 0.5 620 60 30 2.3 1 4.2 On the semi-convex lens Example 30 (S-2) 0.5 690 60 30 2.4 1 4.3 On the semi-convex lens Example 31 (S-3) 0.4 670 60 35 2.5 1 4.3 Semi-Convex Lens Example 32 (S-4) 0.4 730 60 30 2.5 1 4.3 Semi-Convex Lens Example 33 (S-5) 0.4 620 70 30 2.5 1 4.3 Semi-Convex Lens Example 34 (S-6) 0.4 690 60 30 2.3 1 4.6 Example of a semi-convex lens Example 35 (S-7) 2.38 720 60 35 2.3 1 4.5 Example of a semi-convex lens Example 36 (S-8) 0.4 680 60 30 2.3 1 4.6 Example of semi-convex lens Example 37 (S- 9) 0.4 620 60 35 2.4 1 4.2 Semi-Convex Lens Top Example 38 (S-10) 0.5 620 60 35 2.3 1 4.2 Semi-Convex Lens Top Example 39 (S-11) 0.5 620 60 30 2.3 1 4.2 Semi Convex Lens Top Example 40 (S-12) 0.5 680 60 30 2.4 1 4.3 Example over semi-convex lens Example 41 (S-13) 0.5 660 60 30 2.3 1 4.2 Example over semi-convex lens Example 42 (S-14) 0.5 700 60 30 2.4 1 4.3 Semi-convex lens on the comparative example 5 (s-1) 0.4 840 60 15 2.4 3 4.4 semi-convex lens on the comparative example 6 OFPR-800 2.38 2800 60 25 2 8> 5.0 adjacent lens Contact, no shape observation Comparative example 7 OFPR-5000 2.38 3000 60 20 1.9 10> 5.0 adjacent lens contact, shape observation not possible

The radiation sensitive resin composition of the present invention has a high radiation sensitivity, and has a developing margin which can form a good pattern shape even if the optimum developing time is exceeded in the developing step. An excellent patterned thin film can be easily formed, and the sublimate generated at the time of firing is reduced.

 The interlayer insulating film of the present invention formed from the above composition has good adhesion to a substrate, is excellent in solvent resistance and thermal properties, has high transmittance, has a low dielectric constant, and is an interlayer of an electronic component. It can be suitably used as an insulating film.

 In addition, the microlens of the present invention formed from the upper composition has good adhesion to a substrate, is excellent in solvent resistance and heat resistance, has high transmittance and good melt shape, and is solid It can be suitably used as a microphone lens of an imaging element.

Claims

The scope of the claims

1. (A) The ratio (MwZMn) of a polystyrene equivalent weight average molecular weight (Mw) to a polystyrene equivalent number average molecular weight (Mn) which has an epoxy group and an epoxy group and is measured by gel permeation chromatography is 1. Polymer having 7 or less, and (B) 1, 2-quinonediazide compound

Radiation-sensitive resin composition characterized by containing. 2. The copolymer (A) is (a 1) unsaturated carboxylic acid and Z or unsaturated carboxylic acid anhydride,

 (a2) epoxy group-containing unsaturated compounds, and

 (a 3): unsaturated compounds other than the (a 1) component and the (a 2) component

The radiation sensitive resin composition according to claim 1, which is obtained by living radical polymerization of a polymerizable mixture containing

3. The radiation sensitive resin composition according to claim 1 or 2, wherein the copolymer (A) is a (co) polymer obtained by lipradical polymerization using a thiocarbothio compound as a control agent.

4. The radiation sensitive resin composition according to claim 1, which is for forming an interlayer insulating film.

5. A method for forming an interlayer insulating film, which comprises performing the following steps in the order described below.

 (1) forming a coating film of the radiation sensitive resin composition according to claim 1 on a substrate,

(2) irradiating at least a part of the coating film with radiation;

 (3) Development process, and

(4) Heating process.

6. An interlayer insulating film formed by the method of claim 5.

7. The radiation sensitive resin composition according to claim 1, which is for forming a micropore lens.

8. A method of forming a microphone lens characterized in that the following steps are included in the following description order.

 (1) forming a coating film of the radiation sensitive shelf effect composition according to claim 1 on a substrate,

(2) irradiating at least a part of the coating film with radiation;

 (3) Development process, and

 (4) Heating process.

9. A microlens formed by the method of claim 8.