JP2009229567A - Radiation sensitive resin composition, interlayer dielectric, and microlens, and method of producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a radiation sensitive resin composition with which an interlayer dielectric having high surface hardness, excellent heat resistance and solvent resistance, and further having low dielectric constant can be formed, and with which a microlens with an excellent melted shape can be formed. <P>SOLUTION: The radiation sensitive resin composition includes: a copolymer of a mixture of unsaturated compounds containing at least one selected from a group comprising an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride, and an unsaturated compound having an oxetanyl group; a 1,2-quinonediazide compound; and a carboxylic acid with a molecular weight of ≤1,000. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a radiation-sensitive resin composition, an interlayer insulating film and a microlens, and methods for producing them.

  In general, in an electronic component such as a thin film transistor (hereinafter referred to as “TFT”) type liquid crystal display element, magnetic head element, integrated circuit element, solid-state imaging element, etc., an interlayer is used to insulate between wirings arranged in layers. An insulating film is provided. As a material for forming an interlayer insulating film, a radiation-sensitive resin composition characterized in that an interlayer insulating film having a sufficient number of steps and sufficient flatness can be obtained to obtain an interlayer insulating film having a required pattern shape The thing is widely used (refer patent document 1 and patent document 2).

  In general, microlenses having a lens diameter of about 5 to 100 μm, or those microlenses are used as an optical system material for an on-chip color filter such as a facsimile, an electronic copying machine, a solid-state image sensor, or an optical fiber connector. A regularly arranged microlens array is used. To form a microlens or microlens array, after forming a lens pattern, the pattern is melt-flowed by heat treatment and used as it is as a lens, or by dry etching using the melt-flowed lens pattern as a mask. A method for transferring a lens shape to a base is known. For the formation of the lens pattern, a radiation sensitive resin composition having a feature that a microlens having a desired radius of curvature is obtained is widely used (see Patent Document 3 and Patent Document 4).

These interlayer insulating films and microlenses or microlens arrays are required to have various performances such as high heat resistance, high solvent resistance, high transparency, and adhesion to the substrate. In recent years, TFT-type liquid crystal display elements have been trended toward larger screens, and high sensitivity is required as a composition for producing an interlayer insulating film used therefor. Furthermore, in recent years, the demand for a touch panel display, whose demand is rapidly increasing due to the widespread use of mobile terminals, requires the strength of the panel as compared with a normal display. Reinforcement is desired.
The present applicant has already included a copolymer of a specific monomer having an oxetanyl group, so that the interlayer insulation is excellent in various performances such as heat resistance, solvent resistance, transparency, and adhesion to the substrate. It discloses that a radiation-sensitive resin composition capable of forming a film and a microlens is obtained (see Patent Document 5). However, such a radiation sensitive resin composition has room for further improvement in terms of sensitivity and strength of a cured film formed therefrom.
JP 2001-354822 A JP 2001-343743 A JP-A-6-18702 JP-A-6-136239 JP 2001-330953 A

  The present invention has been made based on the above situation. Therefore, an object of the present invention is to provide a radiation-sensitive composition having high sensitivity.

  Another object of the present invention is to form an interlayer insulating film having a high surface hardness, excellent heat resistance and solvent resistance, and having a low dielectric constant when used in the production of an interlayer insulating film. When using for manufacture of this, it is providing the radiation sensitive resin composition which can form the micro lens which has a favorable melt shape.

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

  Still other objects and advantages of the present invention will become apparent from the following description.

According to the present invention, the above objects and advantages of the present invention are as follows.
[A] Copolymerization of an unsaturated compound mixture comprising (a1) at least one selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride, and (a2) an unsaturated compound having an oxetanyl group Coalescence (hereinafter sometimes referred to as “copolymer [A]”),
[B] A radiation-sensitive resin composition comprising a 1,2-quinonediazide compound (hereinafter sometimes referred to as “[B] component”), and [C] a carboxylic acid having a molecular weight of 1,000 or less. Achieved by things.

The objects and advantages of the present invention are secondly:
This is achieved by a method for forming an interlayer insulating film or a microlens, which includes the following steps in the order described below.
(1) The process of forming the coating film of said radiation sensitive composition on a board | substrate,
(2) A step of irradiating at least a part of the coating film with radiation,
(3) The process of developing the coating film after irradiation, and (4) The process of heating the coating film after development.

The radiation sensitive resin composition of the present invention has high radiation sensitivity. The interlayer insulating film produced from the above composition has high surface hardness, excellent solvent resistance and heat resistance, and a low dielectric constant, and can be suitably used as an interlayer insulating film for electronic parts.
Moreover, the microlens manufactured from the said composition is excellent in solvent resistance and heat resistance, has a favorable melt shape, and can be used suitably as a microlens of a solid-state image sensor.

  Hereinafter, the radiation sensitive resin composition of this invention is explained in full detail.

Copolymer [A]
The copolymer [A] used in the present invention contains at least one selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic anhydride (hereinafter referred to as “compound (a1)”), and an oxetanyl group. It can manufacture by carrying out radical polymerization of the unsaturated compound mixture containing the unsaturated compound which it has (henceforth "compound (a2)") in presence of a polymerization initiator in a solvent.
The compound (a1) is an unsaturated carboxylic acid and / or unsaturated carboxylic acid anhydride having radical polymerizability, such as monocarboxylic acid, dicarboxylic acid, dicarboxylic acid anhydride, polyvalent carboxylic acid mono [(meth)]. Acryloyloxyalkyl] ester, mono (meth) acrylate of a polymer having a carboxyl group and a hydroxyl group at both ends, a polycyclic compound having a carboxyl group, and anhydrides thereof.

Specific examples thereof include monocarboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid;
Examples of dicarboxylic acids include maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid and the like;
As anhydrides of dicarboxylic acids, for example, anhydrides of the compounds exemplified as the above dicarboxylic acids;
Examples of mono [(meth) acryloyloxyalkyl] esters of polyvalent carboxylic acids such as succinic acid mono [2- (meth) acryloyloxyethyl] and phthalic acid mono [2- (meth) acryloyloxyethyl];
Examples of the mono (meth) acrylate of a polymer having a carboxyl group and a hydroxyl group at both ends, such as ω-carboxypolycaprolactone mono (meth) acrylate;
Examples of the polycyclic compound having a carboxyl group and anhydrides thereof include 5-carboxybicyclo [2.2.1] hept-2-ene and 5,6-dicarboxybicyclo [2.2.1] hept-2-ene. 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] hept-2-ene, 5,6-dicarboxybicyclo [2.2.1] And hept-2-ene anhydride.
Of these, monocarboxylic acid and dicarboxylic acid anhydrides are preferably used, and acrylic acid, methacrylic acid, and maleic anhydride are particularly preferably used because of their copolymerization reactivity, solubility in alkaline aqueous solutions, and availability. . These compounds (a1) are used alone or in combination of two or more.

  Compound (a2) is an unsaturated compound having an oxetanyl group having radical polymerizability, such as 3- (methacryloyloxymethyl) oxetane, 3- (methacryloyloxymethyl) -3-ethyloxetane, 3- (methacryloyloxymethyl). ) -2-methyloxetane, 3- (methacryloyloxymethyl) -2-trifluoromethyloxetane, 3- (methacryloyloxymethyl) -2-pentafluoroethyloxetane, 3- (methacryloyloxymethyl) -2-phenyloxetane, 3- (methacryloyloxymethyl) -2,2-difluorooxetane, 3- (methacryloyloxymethyl) -2,2,4-trifluorooxetane, 3- (methacryloyloxymethyl) -2,2,4,4- Tetrafluorooxetane, 3- (me Acryloyloxyethyl) oxetane, 3- (methacryloyloxyethyl) -3-ethyloxetane, 2-ethyl-3- (methacryloyloxyethyl) oxetane, 3- (methacryloyloxyethyl) -2-trifluoromethyloxetane, 3- (Methacryloyloxyethyl) -2-pentafluoroethyloxetane, 3- (methacryloyloxyethyl) -2-phenyloxetane, 2,2-difluoro-3- (methacryloyloxyethyl) oxetane, 3- (methacryloyloxyethyl) -2 2,4-Trifluorooxetane, 3- (methacryloyloxyethyl) -2,2,4,4-tetrafluorooxetane, and the like.

Of these, 3- (acryloyloxymethyl) -2-methyloxetane, 3- (acryloyloxymethyl) -3-ethyloxetane, 3- (methacryloyloxymethyl) -2-methyloxetane, 3- (methacryloyloxymethyl) -3-Ethyloxetane or the like is preferably used from the viewpoint of polymerizability.
These compounds (a2) may be used alone or in combination of two or more.

  The copolymer [A] used in the present invention is a copolymer of the above-mentioned compounds (a1) and (a2) and another unsaturated compound copolymerizable with these compounds (hereinafter referred to as “compound (a3)”). The compound (a3) is not particularly limited as long as it is an unsaturated compound having radical polymerizability, but is an unsaturated compound having an oxiranyl group (hereinafter referred to as “compound (a3-1)”). And a compound (a3) other than the compound (a3-1) (hereinafter referred to as “compound (a3-2)”).

  Examples of the compound (a3-1) include glycidyl acrylate, glycidyl methacrylate, glycidyl α-ethyl acrylate, glycidyl α-n-propyl acrylate, glycidyl α-n-butyl acrylate, acrylic acid 3,4- Epoxybutyl, methacrylic acid-3,4-epoxybutyl, acrylic acid-3,4-epoxycyclohexyl, methacrylic acid-3,4-epoxycyclohexyl, acrylic acid-3,4-epoxycyclohexylmethyl, methacrylic acid-3,4 -Epoxycyclohexylmethyl, acrylic acid-6,7-epoxyheptyl, methacrylic acid-6,7-epoxyheptyl, α-ethylacrylic acid-6,7-epoxyheptyl, o-vinylbenzylglycidyl ether, m-vinylbenzylglycidyl Ether, p-vinylben Such as glycidyl ether, and the like. Among these, glycidyl methacrylate, 3,4-epoxycyclohexyl methacrylate, 3,4-epoxycyclohexylmethyl methacrylate, methacrylic acid-6,7-epoxyheptyl, o-vinylbenzyl glycidyl ether, m-vinylbenzyl Glycidyl ether, p-vinylbenzyl glycidyl ether and the like are preferably used from the viewpoint of increasing the copolymerization reactivity and the heat resistance and surface hardness of the resulting interlayer insulating film or microlens. These compounds (a3-1) may be used alone or in combination of two or more.

  Examples of the compound (a3-2) include methacrylic acid alkyl ester, methacrylic acid cyclic alkyl ester, acrylic acid alkyl ester, acrylic acid cyclic alkyl ester, methacrylic acid aryl ester, acrylic acid aryl ester, unsaturated dicarboxylic acid diester, and hydroxyl group. Methacrylic acid ester, bicyclo unsaturated compound, maleimide compound, unsaturated aromatic compound, conjugated diene, tetrahydrofuran skeleton, furan skeleton, tetrahydropyran skeleton, pyran skeleton, unsaturated compound having (poly) alkylene glycol skeleton, phenolic Mention may be made of unsaturated compounds having a hydroxyl group and other unsaturated compounds.

Specific examples thereof include methacrylic acid alkyl esters such as methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate, t-butyl methacrylate, 2-ethylhexyl methacrylate, isodecyl methacrylate, n-lauryl methacrylate, Tridecyl methacrylate, n-stearyl methacrylate, etc .; as cyclic alkyl esters of methacrylic acid, for example, cyclohexyl methacrylate, 2-methylcyclohexyl methacrylate, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl methacrylate (hereinafter referred to as “cyclohexyl methacrylate”) , “Dicyclopentanyl methacrylate”), tricyclo [5.2.1.0 ^2,6 ] decan-8-yloxyethyl methacrylate, Boronyl methacrylate, etc .; Examples of acrylic acid alkyl esters include methyl acrylate, ethyl acrylate, n-propyl acrylate, i-propyl acrylate, n-butyl acrylate, sec-butyl acrylate, t-butyl acrylate, etc .; acrylic acid cyclic alkyl ester As, for example, cyclohexyl acrylate, 2-methylcyclohexyl acrylate, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl acrylate (hereinafter referred to as “dicyclopentanyl acrylate”), tricyclo [5. 2.1.0 ^2,6 ] decan-8-yloxyethyl acrylate, isoboronyl acrylate, etc .; As an acrylic acid aryl ester, for example, phenyl acrylate, benzyl acrylate, etc. Methacrylic acid aryl ester, for example, phenyl methacrylate, benzyl methacrylate, etc .; unsaturated dicarboxylic acid diester, for example, diethyl maleate, diethyl fumarate, diethyl itaconate, etc .; methacrylic acid ester having a hydroxyl group, for example, hydroxymethyl Methacrylate, 2-hydroxyethyl methacrylate, 3-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, diethylene glycol monomethacrylate, 2,3-dihydroxypropyl methacrylate, 2-methacryloxyethylglycoside and the like;
Examples of the bicyclo unsaturated compound include bicyclo [2.2.1] hept-2-ene, 5-methylbicyclo [2.2.1] hept-2-ene, and 5-ethylbicyclo [2.2.1]. Hept-2-ene, 5-hydroxybicyclo [2.2.1] hept-2-ene, 5-carboxybicyclo [2.2.1] hept-2-ene, 5-hydroxymethylbicyclo [2.2. 1] Hept-2-ene, 5- (2-hydroxyethyl) bicyclo [2.2.1] hept-2-ene, 5-methoxybicyclo [2.2.1] hept-2-ene, 5-ethoxy Bicyclo [2.2.1] hept-2-ene, 5,6-dihydroxybicyclo [2.2.1] hept-2-ene, 5,6-dicarboxybicyclo [2.2.1] hept-2 -Ene, 5,6-di (hydroxymethyl) Bicyclo [2.2.1] hept-2-ene, 5,6-di (2-hydroxyethyl) bicyclo [2.2.1] hept-2-ene, 5,6-dimethoxybicyclo [2.2. 1] hept-2-ene, 5,6-diethoxybicyclo [2.2.1] hept-2-ene, 5-hydroxy-5-methylbicyclo [2.2.1] hept-2-ene, 5 -Hydroxy-5-ethylbicyclo [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-hydroxymethyl-5-methylbicyclo [2.2.1] hept-2-ene, 5-carboxy-6-methylbicyclo [2.2.1] hept 2-ene, 5-carboxy-6-ethylbicyclo [2.2.1] hept-2-ene, 5,6-dicarboxybicyclo [2.2.1] hept-2-ene anhydride (hymic acid anhydride), 5-t-butoxycarbonylbicyclo [2 2.1] hept-2-ene, 5-cyclohexyloxycarbonylbicyclo [2.2.1] hept-2-ene, 5-phenoxycarbonylbicyclo [2.2.1] hept-2-ene, 5, 6-di (t-butoxycarbonyl) bicyclo [2.2.1] hept-2-ene, 5,6-di (cyclohexyloxycarbonyl) bicyclo [2.2.1] hept-2-ene and the like;
Examples of maleimide compounds include N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N- (4-hydroxyphenyl) maleimide, N- (4-hydroxybenzyl) maleimide, N-succinimidyl-3-maleimidobenzoate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidocaproate, N-succinimidyl-3-maleimidopropionate, N- (9-acridinyl) maleimide and the like;
As unsaturated aromatic compounds, for example, styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, p-methoxystyrene, etc .; as conjugated dienes, for example, 1,3-butadiene, isoprene, 2 As unsaturated compounds containing a tetrahydrofuran skeleton, for example, tetrahydrofurfuryl (meth) acrylate, 2-methacryloyloxy-propionic acid tetrahydrofurfuryl ester, 3- (meth) acryloyl As unsaturated compounds containing a furan skeleton, for example, 2-methyl-5- (3-furyl) -1-penten-3-one, furfuryl (meth) acrylate, 1-furan- 2-butyl-3-en-2-one, 1 Furan-2-butyl-3-methoxy-3-en-2-one, 6- (2-furyl) -2-methyl-1-hexen-3-one, 6-furan-2-yl-hex-1- En-3-one, acrylic acid 2-furan-2-yl-1-methyl-ethyl ester, 6- (2-furyl) -6-methyl-1-hepten-3-one, etc .; containing tetrahydropyran skeleton Examples of unsaturated compounds include (tetrahydropyran-2-yl) methyl methacrylate, 2,6-dimethyl-8- (tetrahydropyran-2-yloxy) -oct-1-en-3-one, and tetrahydropyran 2-methacrylate. 2-yl ester, 1- (tetrahydropyran-2-oxy) -butyl-3-en-2-one, etc .; unsaturated compounds containing a pyran skeleton include, for example, 4- (1, 4-dioxa-5-oxo-6-heptenyl) -6-methyl-2-pyrone, 4- (1,5-dioxa-6-oxo-7-octenyl) -6-methyl-2-pyrone, etc .;
Examples of unsaturated compounds having a (poly) alkylene glycol skeleton include polyethylene glycol (n = 2 to 10) mono (meth) acrylate and polypropylene glycol (n = 2 to 10) mono (meth) acrylate;
Examples of unsaturated compounds having a phenolic hydroxyl group include 4-hydroxybenzyl (meth) acrylate, 4-hydroxyphenyl (meth) acrylate, o-hydroxystyrene, p-hydroxystyrene, α-methyl-p-hydroxystyrene, N- (4-hydroxybenzyl) (meth) acrylamide, N- (3,5-dimethyl-4-hydroxybenzyl) (meth) acrylamide, N- (4-hydroxyphenyl) (meth) acrylamide and the like;
Examples of other unsaturated compounds include acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, and vinyl acetate.

Among these, methacrylic acid alkyl ester, methacrylic acid cyclic alkyl ester, acrylic acid cyclic alkyl ester, maleimide compound, unsaturated aromatic compound, tetrahydrofuran skeleton, furan skeleton, tetrahydropyran skeleton, pyran skeleton, (poly) alkylene glycol skeleton The unsaturated compound which has and the unsaturated compound which has phenolic hydroxyl group are used preferably. Among them, styrene, t-butyl methacrylate, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl methacrylate, p-methoxystyrene, 2-methylcyclohexyl acrylate, N-phenylmaleimide, N-cyclohexylmaleimide, Tetrahydrofurfuryl (meth) acrylate, polyethylene glycol (n = 2 to 10) mono (meth) acrylate, 3- (meth) acryloyloxytetrahydrofuran-2-one, 4-hydroxybenzyl (meth) acrylate, 4-hydroxyphenyl ( Of these, meth) acrylate, o-hydroxystyrene, p-hydroxystyrene, and α-methyl-p-hydroxystyrene are particularly preferable from the viewpoint of copolymerization reactivity and solubility in an aqueous alkali solution. These compounds (a3-2) are used alone or in combination of two or more.

The copolymer [A] used in the present invention is a copolymer of the compounds (a1), (a2) and (a3-2) and the compounds (a1), (a2), (a3-1) and (a3- The copolymer of 2) is preferred, and the latter copolymer is more preferred.
When the copolymer [A] used in the present invention is a copolymer of the compounds (a1), (a2) and (a3-2), a structural unit derived from the compound (a1), from the compound (a2) The structural unit derived and the structural unit derived from the compound (a3-2) are converted into the compound (a1) based on the sum of the repeating units derived from the compounds (a1), (a2) and (a3-2). 5 to 40 wt% per compound (a2), and 5 to 85 wt% per compound (a3-2), preferably 10 to 30 wt% per compound (a1) More preferably, the content is 30 to 50% by weight per compound (a2) and 20 to 60% by weight per compound (a3-2).

  When the copolymer [A] used in the present invention is a copolymer of the compounds (a1), (a2), (a3-1) and (a3-2), a structural unit derived from the compound (a1) A structural unit derived from the compound (a2), a structural unit derived from the compound (a3-1), and a structural unit derived from the compound (a3-2) are represented by the compounds (a1), (a2), (a3). -1) and (a3-2) based on the sum of the repeating units derived from 5a to 40% by weight per compound (a1), 5 to 50% by weight per compound (a2), per compound (a3-1) 5 to 50% by weight and preferably 5 to 85% by weight per compound (a3-2), 10 to 30% by weight per compound (a1), 5 to 30% by weight per compound (a2), 20-5 per a3-1) It is further preferred to contain 10 to 70 wt% per weight% and the compound (a3-2).

Preferable specific examples of the copolymer [A] used in the present invention include, for example, methacrylic acid / tricyclo [5.2.1.0 ^2,6 ] decan-8-yl methacrylate / glycidyl methacrylate / 2-methyl. Cyclohexyl acrylate / N- (3,5-dimethyl-4-hydroxybenzyl) methacrylamide copolymer, methacrylic acid / glycidyl methacrylate / 1- (tetrahydropyran-2-oxy) -butyl-3-en-2-one / N-cyclohexylmaleimide / p-methoxystyrene / 3-ethyl-3-methacryloyloxymethyloxetane / N- (3,5-dimethyl-4-hydroxybenzyl) methacrylamide copolymer, methacrylic acid / tricyclo [5.2 1.0 ^2,6 ] decan-8-yl methacrylate / styrene / N-sulfur Enylmaleimide / N- (4-hydroxyphenyl) methacrylamide copolymer, methacrylic acid / glycidyl methacrylate / tricyclo [5.2.1.0 ^2,6 ] decan-8-yl methacrylate / n-lauryl methacrylate / 3 -Methacryloyloxytetrahydrofuran-2-one / N- (4-hydroxyphenyl) methacrylamide copolymer, methacrylic acid / glycidyl methacrylate / styrene / 2-methylcyclohexyl acrylate / 1- (tetrahydropyran-2-oxy) -butyl -3-en-2-one / 4-hydroxybenzyl methacrylate copolymer, methacrylic acid / glycidyl methacrylate / tricyclo [5.2.1.0 ^2,6 ] decan-8-yl methacrylate / p-methoxystyrene / 4-hydroxybenzyl Methacrylate copolymer, methacrylic acid / tricyclo [5.2.1.0 ^2,6 ] decan-8-yl methacrylate / glycidyl methacrylate / styrene / p-vinylbenzyl glycidyl ether / tetrahydrofurfuryl methacrylate / 4-hydroxyphenyl Methacrylate copolymer, methacrylic acid / glycidyl methacrylate / N-cyclohexylmaleimide / α-methyl-p-hydroxystyrene / tetrahydrofurfuryl methacrylate copolymer, methacrylic acid / glycidyl methacrylate / N-cyclohexylmaleimide / 3-ethyl- 3-methacryloyloxymethyloxetane / 3-methacryloyloxytetrahydrofuran-2-one / tetrahydrofurfuryl methacrylate / 4-hydroxyphenyl methacrylate copolymer Methacrylic acid / glycidyl methacrylate / 3-ethyl-3-methacryloyloxymethyloxetane / tetrahydrofurfuryl methacrylate / N-phenylmaleimide / α-methyl-p-hydroxystyrene copolymer, methacrylic acid / glycidyl methacrylate / 3 -Ethyl-3-methacryloyloxymethyloxetane / tricyclo [5.2.1.0 ^2,6 ] decan-8-yl methacrylate / N-cyclohexylmaleimide / n-lauryl methacrylate / α-methyl-p-hydroxystyrene copolymer Examples include coalescence.

The copolymer [A] used in the present invention has a polystyrene-equivalent weight average molecular weight (hereinafter referred to as “Mw”), preferably 2 × 10 ³ to 1 × 10 ⁵ , more preferably 5 × 10 ^{3 to} 5 × 10. ^4. If the Mw is less than 2 × 10 ³ , the development margin may not be sufficient, the remaining film ratio of the resulting film may decrease, the pattern shape of the resulting interlayer insulating film or microlens, heat resistance, etc. On the other hand, if it exceeds 1 × 10 ⁵ , the sensitivity may be lowered or the pattern shape may be inferior. The molecular weight distribution (hereinafter referred to as “Mw / Mn”) is preferably 5.0 or less, more preferably 3.0 or less. If Mw / Mn exceeds 5.0, the pattern shape of the resulting interlayer insulating film or microlens may be inferior. The radiation-sensitive resin composition containing the copolymer [A] can easily form a predetermined pattern shape without causing a development residue during development.
[A] The copolymer is synthesized, for example, by polymerizing the unsaturated compound (a1), the unsaturated compound (a2), and the unsaturated compound (a3) in an appropriate solvent in the presence of a radical polymerization initiator. can do.

  Examples of the solvent used for the polymerization include alcohol, ether, ethylene glycol ether, ethylene glycol alkyl ether acetate, diethylene glycols, propylene glycol monoalkyl ether, propylene glycol alkyl ether acetate, propylene glycol alkyl ether propionate, and aromatic. There may be mentioned hydrocarbons, ketones, esters and the like.

Specific examples of these solvents include alcohol, methanol, ethanol, benzyl alcohol, 2-phenylethanol, 3-phenyl-1-propanol, etc .; ether, tetrahydrofuran, etc .; ethylene glycol ether, ethylene glycol monomethyl ether, ethylene Glycol monoethyl ether, etc .; ethylene glycol alkyl ether acetate, ethylene glycol methyl ether acetate, ethylene glycol ethyl ether acetate, ethylene glycol n-propyl ether acetate, ethylene glycol n-butyl ether acetate, etc .; diethylene glycols, diethylene glycol monomethyl ether, diethylene glycol Monoethyl ether, diethylene Glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether;
As propylene glycol monoalkyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether, etc .; as propylene glycol alkyl ether acetate, propylene glycol methyl ether acetate, propylene Glycol ethyl ether acetate, propylene glycol n-propyl ether acetate, propylene glycol n-butyl ether acetate, etc .; as propylene glycol alkyl ether propionate, propylene glycol methyl ether propionate, propylene glycol ethyl ether propionate, propylene glycol n- Propi Ether propionate, propylene glycol n- butyl ether propionate; aromatic hydrocarbons, toluene, xylene and the like; as ketone, methyl ethyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone and the like;
Examples of esters include methyl acetate, ethyl acetate, propyl acetate, butyl acetate, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, methyl hydroxyacetate, hydroxy Ethyl acetate, hydroxybutyl acetate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, methyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, propyl 3-hydroxypropionate, butyl 3-hydroxypropionate, 2-hydroxy -3-methylbutanoate, methyl methoxyacetate, ethyl methoxyacetate, propyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, propyl ethoxyacetate, butyl ethoxyacetate, propoxy Methyl acetate, ethyl propoxyacetate, propyl propoxyacetate, butyl propoxyacetate, methyl butoxyacetate, ethyl butoxyacetate, propyl butoxyacetate, butylbutoxyacetate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, 2-methoxypropionic acid Propyl, butyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, propyl 2-ethoxypropionate, butyl 2-ethoxypropionate, methyl 2-butoxypropionate, ethyl 2-butoxypropionate Propyl 2-butoxypropionate, butyl 2-butoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, 3-methoxypropyl Butyl pionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, propyl 3-ethoxypropionate, butyl 3-ethoxypropionate, methyl 3-propoxypropionate, ethyl 3-propoxypropionate, 3-propoxypropionate Examples thereof include esters such as propyl acid, butyl 3-propoxypropionate, methyl 3-butoxypropionate, ethyl 3-butoxypropionate, propyl 3-butoxypropionate, and butyl 3-butoxypropionate.

  Of these, ethylene glycol alkyl ether acetate, diethylene glycols, 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, and propylene glycol methyl ether acetate are particularly preferable. preferable.

As the polymerization initiator used for the production of the copolymer [A], those generally known as radical polymerization initiators can be used. For example, 2,2′-azobisisobutyronitrile, 2,2′-azobis- (2,4-dimethylvaleronitrile), 2,2′-azobis- (4-methoxy-2,4-dimethylvaleronitrile) Azo compounds such as; benzoyl peroxide, lauroyl peroxide, t-butyl peroxypivalate, organic peroxides such as 1,1′-bis- (t-butylperoxy) cyclohexane; and hydrogen peroxide. When a peroxide is used as the radical polymerization initiator, the peroxide may be used together with a reducing agent to form a redox initiator.
In the production of the copolymer [A], a molecular weight modifier can be used to adjust the molecular weight. Specific examples thereof include halogenated hydrocarbons such as chloroform and carbon tetrabromide; mercaptans such as n-hexyl mercaptan, n-octyl mercaptan, n-dodecyl mercaptan, tert-dodecyl mercaptan and thioglycolic acid; dimethylxanthogen sulfide And xanthogens such as diisopropylxanthogen disulfide; terpinolene, α-methylstyrene dimer and the like.

[B] Component The [B] component 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 nucleus”). And a condensate of 1,2-naphthoquinonediazide sulfonic acid halide can be used.
Examples of the mother nucleus include trihydroxybenzophenone, tetrahydroxybenzophenone, pentahydroxybenzophenone, hexahydroxybenzophenone, (polyhydroxyphenyl) alkane, and other mother nuclei.

Specific examples thereof include trihydroxybenzophenone such as 2,3,4-trihydroxybenzophenone and 2,4,6-trihydroxybenzophenone;
Examples of tetrahydroxybenzophenone include 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 .;
Examples of pentahydroxybenzophenone include 2,3,4,2 ′, 6′-pentahydroxybenzophenone;
Examples of hexahydroxybenzophenone include 2,4,6,3 ′, 4 ′, 5′-hexahydroxybenzophenone, 3,4,5,3 ′, 4 ′, 5′-hexahydroxybenzophenone and the like;
Examples of (polyhydroxyphenyl) alkanes include bis (2,4-dihydroxyphenyl) methane, bis (p-hydroxyphenyl) methane, tri (p-hydroxyphenyl) methane, and 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) -3-phenylpropane, 4,4 '-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol, bis (2,5-dimethyl- 4-hydroxyphenyl) -2-hydroxyphenylmethane, 3,3,3 ′, 3′-tetramethyl-1,1′-spirobiindene-5 6,7,5 ′, 6 ′, 7′-hexanol, 2,2,4-trimethyl-7,2 ′, 4′-trihydroxyflavan and the like;
As other mother nucleus, for example, 2-methyl-2- (2,4-dihydroxyphenyl) -4- (4-hydroxyphenyl) -7-hydroxychroman, 2- [bis {(5-isopropyl-4-hydroxy- 2-methyl) phenyl} methyl], 1- [1- (3- {1- (4-hydroxyphenyl) -1-methylethyl} -4,6-dihydroxyphenyl) -1-methylethyl] -3- ( 1- (3- {1- (4-hydroxyphenyl) -1-methylethyl} -4,6-dihydroxyphenyl) -1-methylethyl) benzene, 4,6-bis {1- (4-hydroxyphenyl) -1-methylethyl} -1,3-dihydroxybenzene.

Further, 1,2-naphthoquinone diazide sulfonic acid amides in which the ester bond of the mother nucleus exemplified above is changed to an amide bond, such as 2,3,4-trihydroxybenzophenone-1,2-naphthoquinone diazide-4-sulfonic acid amide, etc. Are also preferably used.
Among these mother nuclei, 2,3,4,4′-tetrahydroxybenzophenone, 1,1,1-tri (p-hydroxyphenyl) methane, 1,1,1-tri (p-hydroxyphenyl) ethane, 4,4 ′-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol is preferred.

The 1,2-naphthoquinone diazide sulfonic acid halide is preferably 1,2-naphthoquinone diazide sulfonic acid chloride. Specific examples thereof include 1,2-naphthoquinone diazide-4-sulfonic acid chloride and 1,2-naphthoquinone diazide. -5-sulfonic acid chloride can be mentioned, and among these, 1,2-naphthoquinonediazide-5-sulfonic acid chloride is preferably used.
In the condensation reaction, 1,2-naphthoquinonediazide sulfonic acid halide corresponding to 30 to 85 mol%, more preferably 50 to 70 mol% is used with respect to the number of OH groups in the phenolic compound or alcoholic compound. be able to.
The condensation reaction can be carried out by a known method.

These [B] components can be used alone or in combination of two or more. [B] component is used in an amount of 5 to 100 parts by weight, preferably 100 parts by weight of copolymer [A], preferably 10 to 50 parts by weight. When this ratio is less than 5 parts by weight, the amount of acid generated by irradiation with radiation is small, so the difference in solubility in an alkaline aqueous solution that is a developer between the irradiated part and the unirradiated part is small, and patterning is difficult. Tend to be. In addition, since the amount of acid involved in the reaction with the copolymer [A] decreases, sufficient heat resistance and solvent resistance may not be obtained. On the other hand, if this ratio exceeds 100 parts by weight, a large amount of unreacted [B] component remains after irradiation for a short time, so that the effect of insolubilization in the alkaline aqueous solution is too high and development is performed. Tend to be difficult

[C] component [C] component used by this invention is a single compound which does not have molecular weight distribution of molecular weight 1,000 or less, Preferably it is C1-C40, More preferably, it is 3-30. Carboxylic acid. By containing such a component [C], the radiation sensitivity of the radiation-irradiated portion in the alkali developer can be promoted, and the radiation sensitivity of the radiation sensitive resin composition can be increased, and the radiation sensitive resin composition is further formed. The curability of the cured film can also be increased. When the number of carbon atoms exceeds 40, it becomes difficult to obtain the desired effect of the present invention.
Examples of the [C] component used in the present invention include aliphatic carboxylic acids, alicyclic carboxylic acids, and aromatic carboxylic acids. These carboxylic acids may have a substituent in the aliphatic group, alicyclic group or aromatic group.

Examples of the aliphatic carboxylic acid include:
Saturated aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, caproic acid, diethyl acetic acid, enanthic acid, caprylic acid, furan carboxylic acid;
Oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, brassylic acid, methylmalonic acid, ethylmalonic acid, dimethylmalonic acid, methylsuccinic acid, tetramethylsuccinic acid , Saturated aliphatic dicarboxylic acids such as cyclohexanedicarboxylic acid, itaconic acid, citraconic acid, maleic acid, fumaric acid, mesaconic acid;
Saturated aliphatic tricarboxylic acids such as tricarballylic acid, aconitic acid, camphoric acid;
Succinic acid mono [2- (meth) acryloyloxyethyl], ω-carboxypolycaprolactone mono (meth) acrylate, monoesterified product of pentaerythritol triacrylate and succinic acid, monoester of pentaerythritol trimethacrylate and succinic acid Unsaturated fatty monocarboxylic acids such as monoesterified products of dipentaerythritol pentaacrylate and succinic acid, monoesterified products of dipentaerythritol pentamethacrylate and succinic acid, and the like;
Examples of the alicyclic carboxylic acid include
Cyclohexyl carboxylic acid, 1,2-cyclohexyl carboxylic acid, cyclopentyl acetic acid, 1-adamantane carboxylic acid, 2-adamantane carboxylic acid, 3-hydroxy-1-adamantane carboxylic acid, 1,3-adamantane dicarboxylic acid, 3-methoxy-1 -Adamantanecarboxylic acid, 3-ethoxy-1-adamantanecarboxylic acid, 3-butoxy-1-adamantanecarboxylic acid, 3-acetoxy-1-adamantanecarboxylic acid, 3-bromo-1-adamantanecarboxylic acid, 3-acetyl-1 -Adamantanecarboxylic acid, adamantyl acetic acid, cholic acid, chenodeoxycholic acid, dehydrocholic acid, deoxycholic acid, lithocholic acid, 3-acetoxydeocholic acid, 3-butylcarbonyloxydeoxycholic acid, 2,3-norbornanedicarboxylic acid Alicyclic monocarboxylic acids such as tricyclodecane acid;
Examples of the aromatic carboxylic acid include
Aromatic monocarboxylic acids such as benzoic acid, salicylic acid, 4-methylsalicylic acid, acetylsalicylic acid, 2,4,5-trimethoxybenzoic acid, toluic acid, cumic acid, hemelitic acid, mesitylene acid;
Aromatic dicarboxylic acids such as phthalic acid, isophthalic acid, 4-methoxy-isophthalic acid, terephthalic acid;
Trivalent or higher aromatic polycarboxylic acids such as trimellitic acid, trimesic acid, merophanic acid, and pyromellitic acid;
Can be mentioned. These carboxylic acids can be used alone or in combination of two or more.

Among these carboxylic acids, unsaturated aliphatic monocarboxylic acids, alicyclic monocarboxylic acids, aromatic monocarboxylic acids from the viewpoints of solubility in solvents, development margin of the resulting radiation-sensitive resin composition, and storage stability. An acid is preferable, and unsaturated aliphatic monocarboxylic acid and aromatic monocarboxylic acid are more preferable from the viewpoint of sensitivity of the radiation-sensitive resin composition and curability of the resulting cured film.
The proportion of the component [C] used is preferably 0.001 to 50 parts by weight, more preferably 1 to 20 parts by weight, and further preferably 1 to 10 parts by weight with respect to 100 parts by weight of the copolymer [A]. is there. If this ratio is less than 0.001 part by weight, the desired effect may not be obtained, while if it exceeds 50 parts by weight, the residual film ratio, heat resistance and development margin may be reduced.

Other Components The radiation-sensitive resin composition of the present invention contains the above-mentioned copolymers [A], [B] and [C] as essential components, but [D] a heat-sensitive acid as necessary. Product compound, [E] Polymerizable compound having at least one ethylenically unsaturated double bond (excluding [C] component), [F] Epoxy resin other than copolymer [A], [G] A surfactant or [H] adhesion assistant can be contained.
[D] The heat-sensitive acid generating compound can be used to improve heat resistance and hardness. Specific examples thereof include known onium salts such as sulfonium salts, benzothiazonium salts, ammonium salts, and phosphonium salts.
The proportion of the component [D] used is preferably 20 parts by weight or less, more preferably 5 parts by weight or less with respect to 100 parts by weight of the copolymer [A]. When the amount used exceeds 20 parts by weight, precipitates may be deposited in the coating film forming step, which may hinder the coating film formation.

Examples of the polymerizable compound having at least one ethylenically unsaturated double bond as the component [E] include a known monofunctional (meth) acrylate, bifunctional (meth) acrylate, or trifunctional or higher (meth). An acrylate can be mentioned preferably. Of these, trifunctional or higher functional (meth) acrylates are preferably used, and trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, and dipentaerythritol hexa (meth) acrylate are particularly preferable.
[E] The use ratio of the component is preferably 50 parts by weight or less, more preferably 30 parts by weight or less with respect to 100 parts by weight of the copolymer [A].
By including the [E] component at such a ratio, the heat resistance, surface hardness, etc. of the interlayer insulating film or microlens 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 the substrate.

The epoxy resin other than the copolymer [A] as the [F] component (hereinafter sometimes referred to as “F component”) is not limited as long as the compatibility is not affected. Preferably, bisphenol A type epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, cyclic aliphatic epoxy resin, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, heterocyclic epoxy resin, glycidyl methacrylate ) Polymerized resins and the like can be mentioned. Of these, bisphenol A type epoxy resins, cresol novolac type epoxy resins, glycidyl ester type epoxy resins and the like are particularly preferable.
The proportion of the component [F] used is preferably 30 parts by weight or less with respect to 100 parts by weight of the copolymer [A]. By containing the component [F] at such a ratio, the heat resistance and 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 ratio exceeds 30 parts by weight, the film thickness uniformity of the coating film may be insufficient when a coating film of the radiation sensitive resin composition is formed on the substrate.

The copolymer [A] also includes what can be referred to as an “epoxy resin”, but differs from the [F] component in that it has alkali solubility. [F] component is alkali-insoluble.
In the radiation sensitive resin composition of the present invention, a surfactant which is the above [G] component can be used in order to further improve the coating property. As the [G] surfactant that can be used here, fluorine-based surfactants, silicone-based surfactants, and nonionic surfactants can be suitably used.

  Specific examples of the fluorosurfactant include 1,1,2,2-tetrafluorooctyl (1,1,2,2-tetrafluoropropyl) ether, 1,1,2,2-tetrafluorooctylhexyl ether. , Octaethylene glycol di (1,1,2,2-tetrafluorobutyl) ether, hexaethylene glycol (1,1,2,2,3,3-hexafluoropentyl) ether, octapropylene glycol di (1,1 , 2,2-tetrafluorobutyl) ether, hexapropylene glycol di (1,1,2,2,3,3-hexafluoropentyl) ether, sodium perfluorododecyl sulfonate, 1,1,2,2,8 , 8,9,9,10,10-decafluorododecane, 1,1,2,2,3,3-hexafluorodecane, fluoroalkylbenzene Sodium sulfonates; fluoroalkyloxyethylene ethers; fluoroalkylammonium iodides, fluoroalkylpolyoxyethylene ethers, perfluoroalkylpolyoxyethanols; perfluoroalkylalkoxylates; fluorinated alkyl esters be able to. Examples of these commercially available products include BM-1000, BM-1100 (manufactured by BM Chemie), MegaFuck F142D, F172, F173, F183, F178, F191, F191 (and above, Dainippon Ink). Chemical Industries, Ltd.), Fluorad FC-170C, FC-171, FC-430, FC-431 (above, manufactured by Sumitomo 3M), Surflon 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 EF301, 303, and 352 (manufactured by Shin-Akita Kasei Co., Ltd.).

  Examples of the silicone surfactant include DC3PA, DC7PA, FS-1265, SF-8428, SH11PA, SH21PA, SH28PA, SH29PA, SH30PA, SH-190, SH-193, SZ-6032 (above, Toray Dow Corning)・ Silicon Co., Ltd.), TSF-4440, TSF-4300, TSF-4445, TSF-4446, TSF-4460, TSF-4442 (above, GE Toshiba Silicone Co., Ltd.) are commercially available. You can list what you have.

  Examples of the nonionic surfactant include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, and polyoxyethylene oleyl ether; polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, and the like. Polyoxyethylene aryl ethers; polyoxyethylene dialkyl esters such as polyoxyethylene dilaurate and polyoxyethylene distearate; (meth) acrylic acid copolymer polyflow Nos. 57 and 95 (manufactured by Kyoeisha Chemical Co., Ltd.) Etc. can be used.

These surfactants can be used alone or in combination of two or more.
These [G] surfactants are 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]. [G] If the amount of the surfactant used exceeds 5 parts by weight, the coating film may be easily formed when the coating film is formed on the substrate.

  In the radiation sensitive resin composition of the present invention, an adhesion assistant as the [H] component can also be used in order to improve the adhesion to the substrate. As such [H] adhesion assistant, a functional silane coupling agent is preferably used, and examples thereof include a silane coupling agent having a reactive substituent such as a carboxyl group, a methacryloyl group, an isocyanate group, and an epoxy group. . Specifically, trimethoxysilylbenzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane and the like. Such [H] 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 [A]. In the case where the amount of the adhesion assistant exceeds 20 parts by weight, there may be a case where development residue is likely to occur in the development process.

Radiation-sensitive resin composition The radiation-sensitive resin composition of the present invention is a uniform mixture of the above-mentioned copolymer [A], [B] and [C] components and other components optionally added as described above. To be prepared. Usually, the radiation-sensitive resin composition of the present invention is preferably used in a solution state after being dissolved in an appropriate solvent. For example, preparing a radiation-sensitive resin composition in a solution state by mixing the copolymer [A], [B] and [C] components and other optionally added components in a predetermined ratio. Can do.
As a solvent used for the preparation of the radiation sensitive resin composition of the present invention, each component of the copolymer [A], [B] and [C] components and other components optionally blended is uniformly dissolved. And what does not react with each component is used.
As such a solvent, the thing similar to what was illustrated as a solvent which can be used in order to manufacture copolymer [A] mentioned above can be mentioned.

  Among such solvents, alcohol, glycol ether, ethylene glycol alkyl ether acetate, ester and diethylene glycol are preferably used from the viewpoints of solubility of each component, reactivity with each component, ease of film formation, and the like. . Among these, benzyl alcohol, 2-phenylethyl alcohol, 3-phenyl-1-propanol, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol dimethyl ether, propylene glycol monomethyl ether, Purpylene glycol monomethyl ether acetate, methyl methoxypropionate, and ethyl ethoxypropionate can be particularly preferably used.

  Furthermore, in order to improve the in-plane uniformity of the film thickness together with the solvent, a high boiling point solvent can be used in combination. Examples of the high boiling point solvent that can be used in combination include N-methylformamide, N, N-dimethylformamide, N-methylformanilide, N-methylacetamide, N, N-dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, and benzylethyl ether. , Dihexyl ether, acetonyl acetone, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, phenyl Examples include cellosolve acetate. Of these, N-methylpyrrolidone, γ-butyrolactone, and N, N-dimethylacetamide are preferable.

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 used is 50% by weight or less, preferably 40% by weight or less, more preferably 30% by weight or less, based on the total amount of the solvent. can do. If the amount of the high-boiling solvent used exceeds this amount, the coating film thickness uniformity, sensitivity, and residual film rate may decrease.
When the radiation-sensitive resin composition of the present invention is prepared in a solution state, components other than the solvent in the solution (that is, the copolymer [A], [B] and [C] components and other optionally added) The ratio of the total amount of the components can be arbitrarily set according to the purpose of use, the value of the desired film thickness, etc., but is preferably 5 to 50% by weight, more preferably 10 to 40% by weight, Preferably it is 15 to 35% by weight.
The composition solution thus prepared can be used after being filtered using a Millipore filter having a pore size of about 0.2 μm.

Production of Interlayer Insulating Film and Microlens Next, a method for producing the interlayer insulating film and microlens of the present invention using the radiation sensitive resin composition of the present invention will be described. The method for manufacturing an interlayer insulating film or microlens of the present invention includes the following steps in the order described below.
(1) The process of forming the coating film of the radiation sensitive composition of this invention on a board | substrate,
(2) A step of irradiating at least a part of the coating film with radiation,
(3) The process of developing the coating film after irradiation, and (4) The process of heating the coating film after development.

(1) Step of forming a coating film of the radiation-sensitive composition of the present invention on a substrate In the step (1), the composition solution of the present invention is applied to the substrate surface, preferably by pre-baking. The solvent is removed to form a coating film of the radiation sensitive resin composition.
Examples of the types of substrates that can be used include glass substrates, silicon wafers, and substrates on which various metals are formed.
The method of applying the composition solution is not particularly limited, and an appropriate method such as a spray method, a roll coating method, a spin coating method (spin coating method), a slit die coating method, a bar coating method, an ink jet method, or the like is employed. be able to. In particular, a spin coating method and a slit die coating method are preferable. Prebaking conditions vary depending on the type of each component, the proportion of use, and the like. For example, it can be set at 60 to 110 ° C. for about 30 seconds to 15 minutes.
The film thickness of the coating film to be formed is, for example, 3 to 6 μm when the interlayer insulating film is formed, and 0.5 to 3 μm, for example, when the microlens is formed, as the value after pre-baking. preferable.

(2) Step of irradiating at least a part of the coating film In the step (2), the developer is irradiated with radiation through a mask having a predetermined pattern on the formed coating film. The patterning is performed by removing the irradiated portion using the development process. Examples of the radiation used at this time include ultraviolet rays, far ultraviolet rays, X-rays, and charged particle beams.
Examples of the ultraviolet rays include g-line (wavelength 436 nm), i-line (wavelength 365 nm), and the like. Examples of the far ultraviolet light include KrF excimer laser. Examples of X-rays include synchrotron radiation. Examples of the charged particle beam include an electron beam.
Among these, ultraviolet rays are preferable, and radiation containing g-line and / or i-line is particularly preferable.
The exposure amount, 50~1,500J / ^{m 2} In the case of forming an interlayer insulating film, in the case of forming a micro-lens is preferably set to 50~2,000J / ^{m 2.}

(3) Development process Examples of the developer used in the development process include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, ammonia, ethylamine, n-propylamine, diethylamine, diethylaminoethanol, di-acid. N-propylamine, triethylamine, methyldiethylamine, dimethylethanolamine, triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, pyrrole, piperidine, 1,8-diazabicyclo [5,4,0] -7-undecene An aqueous solution of an alkali (basic compound) such as 1,5-diazabicyclo [4,3,0] -5-nonane can be used. In addition, an aqueous solution obtained by adding an appropriate amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant to the aqueous alkali solution described above, or various organic solvents that dissolve the composition of the present invention can be used as a developing solution. Furthermore, as a developing method, for example, an appropriate method such as a liquid piling method, a dipping method, a rocking dipping method, a shower method, or the like can be used. The development time at this time varies depending on the composition of the composition, but can be, for example, 30 to 120 seconds.

(4) Heating step (3) Performed as described above (3) After the development step, the patterned thin film is preferably rinsed, for example, by washing with running water, and more preferably irradiated with radiation from a high-pressure mercury lamp or the like. (After post-exposure), the 1,2-quinonediadito compound remaining in the thin film is decomposed, and then the thin film is heated (post-baked) with a heating device such as a hot plate or an oven. Then, the thin film is cured. The exposure amount in the post-exposure step is preferably about 2,000 to 5,000 J / m ² . Moreover, the baking temperature in this hardening process is 120-250 degreeC, for example. Although heating time changes with kinds of heating apparatus, for example, when performing heat processing on a hotplate, it can be set to 30 to 90 minutes when performing heat processing in oven, for example. At this time, a step baking method or the like in which a heating process is performed twice or more can also be used.
In this manner, a patterned 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 microlens manufactured as described above have high surface hardness and excellent heat resistance, solvent resistance, and the like, as will be apparent from Examples described later.

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

Microlens The microlens of the present invention formed as described above is excellent in solvent resistance and heat resistance and has a good melt shape, and can be suitably used as a microlens for a solid-state imaging device.
The shape of the microlens of the present invention is a semi-convex lens shape as shown in FIG.

Synthesis Examples, Examples and Comparative Examples are shown below to describe the present invention more specifically. However, the present invention is not limited to the following examples.

Synthesis example 1
A flask equipped with a condenser and a stirrer was charged with 7 parts by weight of 2,2′-azobis (2,4-dimethylvaleronitrile) and 220 parts by weight of propylene glycol monomethyl ether acetate. Subsequently, 22 parts by weight of methacrylic acid, 28 parts by weight of dicyclopentanyl methacrylate, 50 parts by weight of 3-ethyl-3-methacryloyloxymethyloxetane and 3 parts by weight of α-methylstyrene dimer were charged, and gently stirring was started while replacing with nitrogen. It was. The temperature of the solution was raised to 70 ° C. and heated at this temperature for 4 hours to obtain a polymer solution containing the copolymer [A-1]. The obtained polymer solution had a solid content concentration of 31.1% by weight, the polymer had a weight average molecular weight of 17,200, and a molecular weight distribution (ratio of weight average molecular weight / number average molecular weight) of 1.9. It was. In addition, a weight average molecular weight and a number average molecular weight are polystyrene conversion average molecular weights measured using GPC (Gel permeation chromatography (HLC-8020 manufactured by Tosoh Corporation)).

Synthesis example 2
A flask equipped with a condenser and a stirrer was charged with 7 parts by weight of 2,2′-azobis (2,4-dimethylvaleronitrile) and 220 parts by weight of diethylene glycol ethyl methyl ether. Subsequently, 13 parts by weight of methacrylic acid, 50 parts by weight of glycidyl methacrylate, 10 parts by weight of 3-ethyl-3-methacryloyloxymethyloxetane, 10 parts by weight of cyclohexylmaleimide and 17 parts by weight of tetrahydrofurfuryl methacrylate were charged and gently stirred while replacing with nitrogen. Started. The temperature of the solution was raised to 70 ° C. and heated at this temperature for 4 hours to obtain a polymer solution containing the copolymer [A-2]. The obtained polymer solution had a solid content concentration of 32.1% by weight, a weight average molecular weight of 18,200, and a molecular weight distribution of 1.8.

Synthesis example 3
A flask equipped with a condenser and a stirrer was charged with 7 parts by weight of 2,2′-azobis (2,4-dimethylvaleronitrile) and 200 parts by weight of diethylene glycol ethyl methyl ether. Subsequently, 11 parts by weight of methacrylic acid, 12 parts by weight of cyclohexylmaleimide, 9 parts by weight of α-methyl-p-hydroxystyrene, 50 parts by weight of glycidyl methacrylate, 10 parts by weight of 3-ethyl-3-methacryloyloxymethyloxetane, tetrahydrofurfuryl methacrylate 8 parts by weight and 3 parts by weight of α-methylstyrene dimer were charged, and gently stirring was started while replacing with nitrogen. The temperature of the solution was raised to 70 ° C. and heated at this temperature for 5 hours to obtain a polymer solution containing the copolymer [A-3]. The resulting polymer solution had a solid content concentration of 32.4% by weight, a weight average molecular weight of 18,200, and a molecular weight distribution of 2.1.

Synthesis example 4
A flask equipped with a condenser and a stirrer was charged with 8 parts by weight of 2,2′-azobis (2,4-dimethylvaleronitrile) and 220 parts by weight of diethylene glycol ethyl methyl ether. Subsequently, 10 parts by weight of styrene, 20 parts by weight of methacrylic acid and 20 parts by weight of 3-ethyl-3-methacryloyloxymethyloxetane, 30 parts by weight of glycidyl methacrylate, 20 parts by weight of tetrahydrofurfuryl acrylate, 4.0 parts by weight of α-methylstyrene dimer Was slowly stirred while replacing nitrogen. The temperature of the solution was raised to 70 ° C. and heated at this temperature for 5 hours to obtain a polymer solution containing the copolymer [A-4]. The resulting polymer solution had a solid content concentration of 32.0% by weight, a weight average molecular weight of 18,100, and a molecular weight distribution of 1.9.

Comparative Synthesis Example 1
A flask equipped with a condenser and a stirrer was charged with 7 parts by weight of 2,2′-azobis (2,4-dimethylvaleronitrile) and 220 parts by weight of diethylene glycol methyl ethyl ether. Subsequently, 23 parts by weight of methacrylic acid, 47 parts by weight of dicyclopentanyl methacrylate, 20 parts by weight of glycidyl methacrylate and 2.0 parts by weight of α-methylstyrene dimer were charged, and the mixture was gently stirred while replacing with nitrogen. 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-1R]. The resulting polymer solution had a solid content concentration of 32.8% by weight, a weight average molecular weight of 24,000, and a molecular weight distribution of 2.3.

Example 1
Preparation of Radiation Sensitive Resin Composition 100 parts by weight of copolymer [A-1] obtained in Synthesis Example 1 (in terms of solid content) and 4,4 ′-[1- [4- [1] as component [B] -[4-Hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol (1 mol) and 1,2-naphthoquinonediazide-5-sulfonic acid chloride (2 mol) (4,4 ′-[ 1- [4- [1- [4-Hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol-1,2-naphthoquinonediazide-5-sulfonic acid ester) 20 parts by weight, [C] 5 parts by weight of adamantanecarboxylic acid and 5 parts by weight of γ-methacryloxypropyltrimethoxysilane are mixed and propylene glycol monomethyl ether is mixed so that the solid content concentration becomes 30% by weight. Was dissolved in acetate, the solution of the radiation-sensitive resin composition was filtered through a Millipore filter having a pore size 0.5μm to (S-1) was prepared.

Examples 2-12, Comparative Examples 1-2
In Example 1, as [A], [B], [C], [H], and [G] component, the kind and quantity as described in Table 1 were used, and it carried out similarly to Example 1, and using it. The solutions (S-2) to (S-12), (S-1R) and (S-2R) of the radiation sensitive resin composition were prepared.

Example 13
In Example 10, it was dissolved in diethylene glycol ethyl methyl ether / propylene glycol monomethyl ether acetate = 6/4 (weight ratio) so that the solid concentration was 20% by weight, and SH-28PA (Toray Industries, Inc.) was used as a surfactant. A solution (S-13) of a radiation sensitive resin composition was prepared in the same manner as in Example 10 except that Dow Corning Silicone Co., Ltd.) was added.

In Table 1, the abbreviation of each component has the following meaning.

[B-1]: 4,4 ′-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol (1.0 mol) and 1,2-naphthoquinonediazide Condensate of -5-sulfonic acid chloride (2.0 mol) [C-1]: 2-adamantanecarboxylic acid [C-2]: Benzoic acid [C-3]: Mono of pentaerythritol triacrylate and succinic acid Esterified product [C-4]: cyclohexanedicarboxylic acid [H-1]: γ-methacryloxypropyltrimethoxysilane [G-1]: silicone surfactant (trade name SH-28PA, Toray Dow Corning Silicone ( Made by Co., Ltd.)

<Evaluation of interlayer insulating film>
Examples 14 to 26, Comparative Examples 3 to 4
Using the radiation-sensitive resin composition prepared as described above, various characteristics as an interlayer insulating film were evaluated as follows.

[Evaluation of sensitivity]
For Examples 14 to 25 and Comparative Examples 3 to 4 on a silicon substrate, the compositions shown in Table 2 were applied using a spinner, and then prebaked on a hot plate at 100 ° C. for 2 minutes. A coating film having a thickness of 4.0 μm was formed. For Example 26, coating was performed with a slit die coater, the pressure was reduced to 0.5 Torr at room temperature over 15 seconds, the solvent was removed, and then prebaked on a hot plate at 100 ° C. for 2 minutes to obtain a film thickness of 4. A 0 μm coating film was formed.
The obtained coating film was exposed using a PLA-501F exposure machine (extra-high pressure mercury lamp) manufactured by Canon Inc. through a mask having a pattern of 3.0 μm line and space (10 to 1). After exposure by varying the time, development was performed by a puddle method with a 0.40 wt% tetramethylammonium hydroxide aqueous solution at 25 ° C. for 80 seconds. Next, the substrate was washed with ultrapure water for 1 minute and dried to form a pattern on the silicon substrate. At this time, the minimum exposure amount necessary for the space line width to be 0.3 μm was examined. This minimum exposure amount is shown in Table 2 as sensitivity.

[Evaluation of development margin]
For Examples 14 to 25 and Comparative Examples 3 to 4 on a silicon substrate, the compositions shown in Table 2 were applied using a spinner, and then prebaked on a hot plate at 100 ° C. for 2 minutes. A coating film having a thickness of 4.0 μm was formed. For Example 26, coating was performed with a slit die coater, the pressure was reduced to 0.5 Torr at room temperature over 15 seconds, the solvent was removed, and then prebaked on a hot plate at 100 ° C. for 2 minutes to obtain a film thickness of 4. A 0 μm coating film was formed.
Using the PLA-501F exposure machine (extra-high pressure mercury lamp) manufactured by Canon Inc. through a mask having a 3.0 μm line and space (10 to 1) pattern on the obtained coating film, the above After performing exposure with the exposure amount corresponding to the sensitivity value investigated in “[Sensitivity evaluation]”, the solution is accumulated in a 0.40% by weight tetramethylammonium hydroxide aqueous solution at 25 ° C. with the development time as a variable. Developed by the method. Next, the substrate was washed with ultrapure water for 1 minute and then dried to form a pattern on the silicon substrate. At this time, the development time necessary for the line width to be 3 μm is shown in Table 2 as the optimum development time. Further, when the development was further continued from the optimum development time, the time until the 3.0 μm line pattern was peeled off was measured and shown in Table 2 as a development margin.

[Evaluation of solvent resistance]
For Examples 14 to 25 and Comparative Examples 3 to 4 on a silicon substrate, the compositions shown in Table 2 were applied using a spinner, and then prebaked on a hot plate at 100 ° C. for 2 minutes. A film was formed. For Example 26, coating with a slit die coater was performed, and the pressure was reduced to 0.5 Torr over 15 seconds at room temperature. After removing the solvent, a coating film was formed by prebaking on a hot plate at 100 ° C. for 2 minutes. did.
Each of the obtained coating films was exposed using a PLA-501F exposure machine (extra-high pressure mercury lamp) manufactured by Canon Co., Ltd. so that the integrated irradiation amount was 3,000 J / m ² . Was heated at 220 ° C. for 1 hour to obtain a cured film having a thickness of about 3.0 μm. The film thickness (T1) of the obtained cured film was measured. And after immersing the silicon substrate in which this cured film was formed in the dimethyl sulfoxide temperature-controlled at 70 degreeC for 20 minutes, the film thickness (t1) after immersion of the said cured film was measured, and the film thickness change rate by immersion {| T1-T1 | / T1} × 100 [%] was calculated. The results are shown in Table 2.
In addition, since the patterning was unnecessary in the solvent resistance evaluation, the development step was omitted, and only the coating film forming step, the radiation irradiation step, and the heating step were performed for evaluation.

[Evaluation of heat resistance]
A cured film was formed on a silicon substrate in the same manner as in the above “[Evaluation of solvent resistance]”, and the thickness (T2) of the obtained cured film was measured. Next, the substrate with the cured film was additionally baked in a clean oven at 240 ° C. for 1 hour, and then the film thickness (t2) after the additional baking of the cured film was measured, and the film thickness change rate {| t2- T2 | / T2} × 100 [%] was calculated. The results are shown in Table 2.

[Evaluation of relative permittivity]
On the polished SUS304 substrate, for Examples 14 to 25 and Comparative Examples 3 to 4, the compositions shown in Table 2 were applied using a spinner, and then prebaked on a hot plate at 100 ° C. for 2 minutes. As a result, a coating film having a thickness of 3.0 μm was formed. For Example 26, coating was performed using a slit die coater, the pressure was reduced to 0.5 Torr at room temperature over 15 seconds, the solvent was removed, and the film was then baked on a hot plate at 100 ° C. for 2 minutes to obtain a film thickness of 3.0 μm The coating film was formed.
Each of the obtained coating films was exposed using a PLA-501F exposure machine (extra-high pressure mercury lamp) manufactured by Canon Co., Ltd. so that the integrated irradiation amount was 3,000 J / m ² . A cured film was formed on the substrate by heating at 220 ° C. for 1 hour. A Pt / Pd electrode pattern was formed on the cured film by vapor deposition to prepare a sample for measuring dielectric constant. About the obtained sample, the relative dielectric constant in the frequency of 10 kHz was measured by CV method using the HP16451B electrode and HP4284A precision LCR meter by Yokogawa Hewlett-Packard Co., Ltd. The results are shown in Table 2.
In addition, since the patterning was unnecessary in evaluation of a dielectric constant, the image development process was abbreviate | omitted, and only the coating-film formation process, the radiation irradiation process, and the heating process were performed for evaluation.

[Evaluation of storage stability]
The composition solution was warmed and stored in an oven at 40 ° C. for 1 week, and the storage stability was evaluated by measuring the change in viscosity before and after the warmed storage. The viscosity change rate at this time is shown in Table 1. When the rate of change is less than 5%, the storage stability is good, and when it is 5% or more, the storage stability is poor.

[Evaluation of surface hardness]
A cured film was formed on a silicon substrate in the same manner as in the above “[Evaluation of solvent resistance]”, and the obtained cured film was measured for pencil hardness by the 8.4.1 pencil scratch test of JIS K-5400-1990. It was measured. The results are shown in Table 2.

<Performance evaluation as a micro lens>
Examples 27-39, Comparative Examples 5-6
Using the radiation-sensitive resin composition prepared as described above, various characteristics as a microlens were evaluated as follows. For the evaluation of solvent resistance and heat resistance, refer to the results of performance evaluation as the interlayer insulating film.

[Evaluation of sensitivity]
Each composition shown in Table 3 was applied onto a silicon substrate using a spinner, and then prebaked on a hot plate at 100 ° C. for 2 minutes to form a coating film having a thickness of 2.0 μm. Using the NSR1755i7A reduced projection exposure machine (NA = 0.50, λ = 365 nm) manufactured by Nikon Corporation, exposure is performed with the exposure time varied through a pattern mask having a predetermined pattern on the obtained coating film. After that, the film was developed with a 0.40% by weight tetramethylammonium hydroxide aqueous solution at 25 ° C. for 1 minute. Next, the substrate was rinsed with ultrapure water and dried to form a pattern on the silicon substrate. The minimum exposure required for the space line width of 0.8 μm line and space pattern (1 to 1) to be 0.8 μm was examined. This minimum exposure amount is shown in Table 3 as sensitivity.

[Evaluation of development margin]
Each composition shown in Table 3 was applied onto a silicon substrate using a spinner and then pre-baked on a hot plate at 100 ° C. for 2 minutes to form a coating film having a thickness of 2.0 μm. Using the NSR1755i7A reduction projection exposure machine (NA = 0.50, λ = 365 nm) manufactured by Nikon Corporation through a pattern mask having a predetermined pattern on the obtained coating film, the above “[sensitivity evaluation]” After exposure with an exposure amount corresponding to the sensitivity value examined in this way, the film was developed with a 0.40 wt% aqueous tetramethylammonium hydroxide solution at 25 ° C. for 1 minute. It was rinsed with water and dried to form a pattern on the silicon substrate. Table 3 shows the development time necessary for the space line width of 0.8 μm line and space pattern (one to one) to be 0.8 μm as the optimum development time. Further, when the development was further continued from the optimum development time, the time until the pattern having a width of 0.8 μm was peeled was measured and shown in Table 3 as a development margin.

[Formation of microlenses]
Each composition shown in Table 3 was applied onto a silicon substrate using a spinner and then pre-baked on a hot plate at 100 ° C. for 2 minutes to form a coating film having a thickness of 2.0 μm. Using the NSR1755i7A reduction projection exposure machine (NA = 0.50, λ = 365 nm) manufactured by Nikon Corporation through a pattern mask having 4.0 μm dots and 2.0 μm space pattern on the obtained coating film. After exposure at an exposure amount corresponding to the sensitivity value investigated in the above “[Sensitivity evaluation]”, a liquid piling method at 25 ° C. for 1 minute in a 0.40 wt% tetramethylammonium hydroxide aqueous solution. Developed with. Next, the substrate was rinsed with ultrapure water and dried to form a pattern on the silicon substrate. Thereafter, further exposure was performed using a PLA-501F exposure machine (extra-high pressure mercury lamp) manufactured by Canon Inc. so that the integrated irradiation amount was 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 flow the pattern to form a microlens.

  Table 3 shows the size (diameter) and cross-sectional shape of the bottom (surface contacting the substrate) of the formed microlens. It can be said that the microlens bottom portion is good when it is larger than 4.0 μm and smaller than 5.0 μm. When this dimension is 5.0 μm or more, the adjacent lenses are in contact with each other, which is not preferable. Further, the cross-sectional shape is good when it is a semi-convex lens shape as shown in (a) in the schematic diagram shown in FIG. 1, and it is bad when it is on a substantially trapezoidal shape as shown in (b).

It is a schematic diagram of the cross-sectional shape of a micro lens.

Claims (7)

[A] Copolymerization of an unsaturated compound mixture comprising (a1) at least one selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride, and (a2) an unsaturated compound having an oxetanyl group Coalescence,
[B] A radiation-sensitive resin composition comprising a 1,2-quinonediazide compound and [C] a carboxylic acid having a molecular weight of 1,000 or less. [C] The radiation-sensitive resin composition according to claim 1, wherein the carboxylic acid having a molecular weight of 1,000 or less is an unsaturated aliphatic monocarboxylic acid, an alicyclic monocarboxylic acid, or an aromatic monocarboxylic acid. [A] The copolymer is an unsaturated compound copolymer comprising the (a1) component, the (a2) component, and the (a3-1) unsaturated compound having an oxiranyl group. The radiation sensitive resin composition described in 1.   The radiation-sensitive resin composition according to any one of claims 1 to 3, which is used for producing an interlayer insulating film. The manufacturing method of the interlayer insulation film characterized by including the following processes in the order as described below.
(1) The process of forming the coating film of the radiation sensitive composition of Claim 4 on a board | substrate,
(2) A step of irradiating at least a part of the coating film with radiation,
(3) A step of developing the coated film after irradiation, and (4) a step of heating the coated film after development.   The radiation-sensitive resin composition according to any one of claims 1 to 3, which is used for producing a microlens. The manufacturing method of the micro lens characterized by including the following processes in order of description below.
(1) The process of forming the coating film of the radiation sensitive composition of Claim 6 on a board | substrate,
(2) A step of irradiating at least a part of the coating film with radiation,
(3) A step of developing the coated film after irradiation, and (4) a step of heating the coated film after development.

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