KR101421299B1 - Sensitive radiation-sensitive resin composition, an interlayer insulating film and a microlens, and a method for manufacturing the same - Google Patents

Abstract

(A3) a copolymer of a specific unsaturated compound other than the above (a1) and (a2), and a copolymer of a specific unsaturated compound having an alicyclic epoxy skeleton and a specific unsaturated compound other than the above (a1) B] 1,2-quinone diazide compound as a radiation-sensitive resin composition.

The radiation-sensitive resin composition has a high sensitivity to radiation and has a developing margin capable of still forming a good pattern shape even when a developing process is performed in excess of an optimum developing time in the developing process and also has a pattern An upper thin film can be easily formed, and is particularly preferably used for forming an interlayer insulating film or a microlens.

Sensitive radiation-sensitive resin composition, an interlayer insulating film, a micro lens

Description

TECHNICAL FIELD [0001] The present invention relates to a radiation-sensitive resin composition, an interlayer insulating film and a microlens, and a method of manufacturing the same,

The present invention relates to a radiation-sensitive resin composition, an interlayer insulating film and a microlens, and a method of manufacturing the same.

In an electronic component such as a thin film transistor (hereinafter referred to as " TFT ") type liquid crystal display element, a magnetic head element, an integrated circuit element, or a solid-state image pickup element, an interlayer insulating film is generally provided to insulate inter- . As the material for forming the interlayer insulating film, a radiation-sensitive resin composition is widely used because it is preferable that the number of processes for obtaining a necessary pattern shape is small and sufficient flatness is obtained (Japanese Patent Laid-Open Publication No. 2001-354822 and Japanese Patent Laid- 2001-343743).

Among the above electronic components, for example, a TFT type liquid crystal display element is manufactured by forming a transparent electrode film on the interlayer insulating film and further forming a liquid crystal alignment film thereon. Therefore, Since they are exposed to high temperature conditions in the forming process or are exposed to the stripping solution of the resist used for forming the pattern of the electrode, sufficient resistance to these is required.

In recent years, in TFT-type liquid crystal display devices, as a composition for forming an interlayer insulating film used in the trends such as a large-sized screen, a high brightness, a high-precision miniaturization, a high speed response and a thinness, Higher performance is demanded in the optical transmissivity and the like as compared with the prior art.

On the other hand, a microlens having a lens diameter of about 3 to 100 mu m as an optical system material of an imaging optical system or an optical fiber connector of an on-chip color filter such as a facsimile, an electronic copying machine, An array of microlenses is used.

In order to form a microlens or a microlens array, a method in which a resist pattern corresponding to a lens is formed and then subjected to a heat treatment to perform a melt flow and used as it is as a lens, or a method in which a lens pattern formed by a melt flow is used as a mask, And a method of transferring the lens shape to the lens. For the formation of the lens pattern, a radiation-sensitive resin composition is widely used (see Japanese Unexamined Patent Application Publication No. 6-18702 and Japanese Unexamined Patent Publication (Kokai) No. 6-136239).

After the formation of the microlenses or microlens arrays as described above, a planarizing film and a resist film for etching are applied to remove various insulating films on the bonding pads, which are wiring forming portions, Development is performed to remove the etching resist on the bonding pad portion, and then the flattening film and various insulating films are removed by etching to expose the bonding pad portion. Therefore, in the microlens or microlens array, solvent resistance and heat resistance are required in the film forming process and the etching process of the planarizing film and the etching resist.

The radiation-sensitive resin composition used for forming such a microlens is required to have a high sensitivity, a microlens formed therefrom having a desired radius of curvature, a high heat resistance, and a high light transmittance do.

In addition, the interlayer insulating film or microlens obtained in this way, when the development time is a little more than the optimal time in the developing step for forming them, if the excessive development occurs, the developing solution penetrates between the pattern and the substrate, It is necessary to strictly control the development time, and there is a problem in terms of the yield of the product.

As described above, when forming an interlayer insulating film or a microlens from a radiation-sensitive resin composition, a high sensitivity is required for the composition, and even when the developing time in the developing process during the forming process becomes excessively longer than the predetermined time, High dielectric constant, low dielectric constant, high light transmittance and the like are required for the interlayer insulating film formed therefrom. On the other hand, in the case of forming the microlenses, a good melt shape (desired curvature Radius), high heat resistance, high solvent resistance, and high light transmittance are required, but a radiation-sensitive resin composition satisfying such a requirement has not been known heretofore.

SUMMARY OF THE INVENTION The present invention has been made based on the above-described circumstances, and an object of the present invention is to provide a developing device which has a high sensitivity to radiation sensitivity and can still form a good pattern shape even if a developing process is performed in excess of an optimum developing time in the developing process Sensitive resin composition which is capable of easily forming a patterned thin film having an excellent adhesion to a substrate and a margin.

Another object of the present invention is to provide an interlayer insulating film having a high heat resistance, a high solvent resistance, a high light transmittance and a low dielectric constant when used for the formation of an interlayer insulating film, And to provide a radiation-sensitive resin composition capable of forming a microlens having a transmittance and a good melt shape.

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

It is still another object of the present invention 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 present invention, the above objects and advantages of the present invention are achieved by firstly,

[A] (a1) an unsaturated compound having a carboxyl group represented by the following formula (1)

(a2) an unsaturated compound having an alicyclic epoxy skeleton selected from the following formulas (2-1) to (2-3) and

(a3) at least one monomer selected from the group consisting of (a3) methacrylic acid alkyl esters, methacrylic acid cyclic alkyl esters, methacrylic acid cyclic alkyl esters, methacrylic acid esters having hydroxyl groups, acrylic acid cyclic alkyl esters, methacrylic acid aryl esters, A diester, a bicyclic unsaturated compound, a maleimide compound, an unsaturated aromatic compound, a conjugated diene; An unsaturated compound having a tetrahydrofuran skeleton, a furan skeleton, a tetrahydropyran skeleton, a pyran skeleton, a glycidyl skeleton, and a skeleton represented by Formula 3 below; A phenolic hydroxyl group-containing unsaturated compound represented by the following formula (4) and at least one unsaturated compound selected from the group consisting of acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide and vinyl acetate Copolymers and

And [B] a 1,2-quinonediazide compound.

(Wherein R represents hydrogen or a methyl group, and X represents a methylene group, an alkylene group having 2 or more carbon atoms, or a bivalent group represented by any one of the following formulas (1-1) to (1-6)

(Wherein X ¹ is each independently a methylene group or an alkylene group having 2 or more carbon atoms, and the bond on the right hand side of the formulas (1-1) to (1-6) is bonded to a carboxyl group)

(Wherein R ³ is a hydrogen atom or a methyl group, and n is a repeating number)

(Wherein R ⁴ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, a plurality of R ⁵ are each independently a hydrogen atom, a hydroxyl group or an alkyl group having 1 to 4 carbon atoms, X ² is a single bond, -COO- or -CONH- and m is an integer of 0 to 3, provided that at least one of R < ⁵ > is a hydroxyl group)

The objects and advantages of the present invention are secondly,

And the following steps are included in the order of the following description.

(1) a step of forming a coating film of the radiation-sensitive resin composition on a substrate

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

(3) Development process

(4) Heating process

The objects and advantages of the present invention are also, thirdly,

Is achieved by an interlayer insulating film or a microlens formed by the above method.

The radiation-sensitive resin composition of the present invention has a high sensitivity to radiation and has a developing margin capable of still forming a good pattern even when the developing process exceeds the optimum developing time in the developing process, An upper thin film can be easily formed.

The interlayer insulating film and the microlens formed from the radiation-sensitive resin composition of the present invention satisfy the various performances required for the interlayer insulating film and the microlens, respectively (recently more and more demanding performance).

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

- copolymer [A] -

The copolymer [A] can be produced by radical polymerization of the compound (a1), the compound (a2) and the compound (a3) in a solvent, preferably in the presence of a polymerization initiator.

The copolymer [A] used in the present invention can be obtained by copolymerizing the repeating unit derived from the compound (a1) with a repeating unit derived from the compound (a1), the compound (a2) and the compound (a3) By weight, preferably 5 to 40% by weight, particularly preferably 5 to 25% by weight. When a copolymer having a repeating unit of less than 5% by weight is used, it is difficult to dissolve in an alkali aqueous solution during the development process. On the other hand, a copolymer exceeding 40% by weight tends to have an excessively high solubility in an aqueous alkali solution.

The compound (a1) is a carboxyl group-containing unsaturated compound represented by the above formula (1). The alkylene group having 2 or more carbon atoms of X ^{1 in} the above general formula (1) and the above general formulas (1-1) to (1-6) is preferably an alkylene group having 2 to 6 carbon atoms, Ethylene group, 1,2-propylene group, 1,3-propylene group, 1,1-dimethyl-1,2-ethylene group, 2,2-dimethyl- Methylene-1,3-propylene group, 2-methyl-1,3-propylene group, 1,3-butylene group, 1,4-butylene group and 1,5-pentylene group. The cyclohexene ring in the formula (1-6) is preferably bonded at a position having a double bond between the carbon atoms at the 3-position and the 4-position with respect to -X ¹ -OCO- in the formula (1-6).

Among these compounds (a1), preferred are the following: 2-carboxyethyl (meth) acrylate, 2- (meth) acryloyloxyethylsuccinic acid, 2- (meth) acryloyloxyisopropylsuccinic acid, 2- (Meth) acryloyloxypropyl hexahydrophthalic acid, 2- (meth) acryloyloxyhexahydrophthalic acid, 2- (meth) acryloyloxyisopropylphthalic acid, 2- (Meth) acryloyloxypropyl-3,4,5,6-tetrahydrophthalic acid is copolymerizable and soluble in an aqueous alkali solution, Is advantageously used. These compounds (a1) are used alone or in combination.

The copolymer [A] used in the present invention can be obtained by copolymerizing the repeating unit derived from the compound (a2) with the repeating unit derived from the compound (a1), the compound (a2) and the compound (a3) Is contained in an amount of 10 to 80% by weight, particularly preferably 30 to 80% by weight. When the repeating unit is less than 10% by weight, the heat resistance, surface hardness and peel strength of the resultant interlayer insulating film or microlens tend to be lowered. On the other hand, when the amount of the repeating unit exceeds 80% by weight, The storage stability of the resin composition tends to be lowered.

The compound (a2) is an unsaturated compound having an alicyclic epoxy skeleton selected from the above formulas (2-1) to (2-3). As the compound (a2), for example, a methacrylate ester, an acrylate ester, a styrene compound, or a vinyl ether compound having an alicyclic epoxy skeleton are preferable, and methacrylate esters are particularly preferable. As the compound (a2), for example, a compound represented by the following formula may be mentioned as a preferable example.

(Wherein R ¹ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms and R ² is a divalent hydrocarbon group having 1 or more carbon atoms)

The bivalent hydrocarbon group having 1 or more carbon atoms in R ² is preferably a divalent hydrocarbon group having 1 to 6 carbon atoms, more preferably a divalent hydrocarbon group having 2 to 6 carbon atoms, particularly 1, 1-ethylene group, 1 Ethylene group, 1,2-propylene group, 1,3-propylene group, 1,1-dimethyl-1,2-ethylene group, 2,2- A 1,3-propylene group, a 2-methyl-1,3-propylene group, a 1,3-butylene group, a 1,4-butylene group or a 1,5-pentylene group is preferable.

Particularly preferred among the compounds (a2) are 3,4-epoxycyclohexylmethyl (meth) acrylate, 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decan-8-yl (meth) 2,3-epoxycyclopentylmethyl (meth) acrylate.

The copolymer [A] used in the present invention can be obtained by copolymerizing the repeating unit derived from the compound (a3) with the repeating unit derived from the compound (a1), the compound (a2) and the compound (a3) Contains 5 to 80% by weight, particularly preferably 10 to 60% by weight. When the repeating unit is less than 5% by weight, storage stability of the radiation-sensitive resin composition may be impaired. On the other hand, when the amount of the repeating unit exceeds 80% by weight, the heat resistance , Surface hardness or peel strength may be insufficient.

Specific examples of the compound (a3) include methacrylic acid alkyl esters such as methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate, t-butyl methacrylate, - ethylhexyl methacrylate, isodecyl methacrylate, n-lauryl methacrylate, tridecyl methacrylate, n-stearyl methacrylate and the like;

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

As the methacrylic acid cyclic alkyl ester, for example, cyclohexyl methacrylate, 2-methylcyclohexyl methacrylate, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl methacrylate, tricyclo [5.2. 1.0 ^2,6 ] decane-8- ^yloxyethyl methacrylate, isobornyl methacrylate and the like;

Examples of the methacrylic ester having a hydroxyl group include hydroxymethyl methacrylate, 2-hydroxyethyl methacrylate, 3-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, diethylene glycol monomethacrylate 2,3-dihydroxypropyl methacrylate, 2-methacryloxyethyl glycoside, 4-hydroxyphenyl methacrylate and the like;

Examples of the acrylic acid cyclic alkyl esters include cyclohexyl acrylate, 2-methylcyclohexyl acrylate, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl acrylate, tricyclo [5.2.1.0 ^2,6 ] Decane-8-yloxyethyl acrylate, isobornyl acrylate and the like;

As the methacrylic acid aryl esters, for example, phenyl methacrylate, benzyl methacrylate and the like;

As the acrylic acid aryl esters, for example, phenyl acrylate, benzyl acrylate and the like;

As the unsaturated dicarboxylic acid diester, for example, diethyl maleate, diethyl fumarate, diethyl itaconate and the like;

2.2.1] hept-2-ene, 5-methylbicyclo [2.2.1] hept-2-ene, 5-ethylbicyclo [2.2.1] hept- 2.2.1] hept-2-ene, 5-methoxybicyclo [2.2.1] 2-ene, 5,6-diethoxybicyclo [2.2.1] hept-2-ene, 5-t-butoxycarbonylbicyclo [2.2.1] hept- 2,6-di (t-butoxycarbonyl) bicyclo [2.2.1] hept-2-ene, 5-phenoxycarbonylbicyclo [2.2.1] hept- 2,1-hept-2-ene, 5,6-di (cyclohexyloxycarbonyl) bicyclo [2.2.1] hept-2-ene and 5- (2'-hydroxyethyl) bicyclo [2.2. (Hydroxymethyl) bicyclo [2.2.1] hept-2-ene, 5,6-dihydroxybicyclo [2.2.1] hept- , 5,6-di (2'-hydroxyethyl) bicyclo [2.2.1] hept-2-ene, 5-hydroxy- Hydroxy-5-ethylbicyclo [2.2.1] hept-2-ene, and 5-hydroxy-5-methyl-bicyclo [2.2.1] hept-2-ene;

Examples of the maleimide compound include N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N- (4-hydroxyphenyl) maleimide, N- (4-hydroxybenzyl) maleimide , N-succinimidyl-3-maleimide benzoate, N-succinimidyl-4-maleimide butyrate, N-succinimidyl-6-maleimide caproate, N- Pyranate, N- (9-acridinyl) maleimide, and the like;

As the unsaturated aromatic compound, for example, styrene,? -Methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, p-methoxystyrene and the like;

Examples of the conjugated diene include 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene and the like;

Examples of the unsaturated compound containing a tetrahydrofuran skeleton include tetrahydrofurfuryl (meth) acrylate, 2-methacryloyloxy-propionic acid tetrahydrofurfuryl ester, 3- (meth) acryloyloxytetrahydro Furan-2-one and the like;

As the unsaturated compound containing a furan skeleton, for example, 2-methyl-5-furan-3-yl-1-penten- 2-yl-2-methyl-1-hexen-3-one, 6-furan- 2-yl-1-en-3-one, 6-methyl-1-hepten- Etc;

As the unsaturated compound containing a tetrahydropyran skeleton, for example, (tetrahydropyran-2-yl) methyl methacrylate, 2,6-dimethyl-8- (tetrahydropyran- -En-3-one, 2-methacrylic acid tetrahydropyran-2-yl ester, 1- (tetrahydropyran-2-oxy) -butyl-3-en-2-

Examples of the unsaturated compound containing a pyran skeleton include 4- (1, 4-dioxa-5-oxo-6-heptenyl) -6- 6-oxo-7-octenyl) -6-methyl-2-pyrone;

As the unsaturated compound containing a glycidyl skeleton, for example, glycidyl acrylate, glycidyl methacrylate, glycidyl? -Ethyl acrylate, glycidyl? -N-propyl acrylate,? -N-butyl acrylate Glycidyl, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether and the like;

Examples of unsaturated compounds containing a skeleton represented by the above formula (3) include polyethylene glycol mono (meth) acrylate having a repeating number n of 2 to 10, polypropylene glycol mono (meth) acrylate having a repeating number n of 2 to 10 Rate etc;

Examples of the phenolic hydroxyl group-containing unsaturated compound represented by the formula (4) include the compounds represented by the following formulas (5) to (9), respectively.

(In the formulas (5) to (9), R ⁴ and R ⁵ have the same meanings as in the above formula (4), and m 'is an integer of 1 to 3)

Of these, methacrylic acid alkyl esters, methacrylic acid cyclic alkyl esters, maleimide compounds, and unsaturated aromatic compounds; A tetrahydrofuran skeleton, a furan skeleton, a tetrahydropyran skeleton, a pyran skeleton, a glycidyl skeleton, and a skeleton represented by Formula 3; The phenolic hydroxyl group-containing unsaturated compound represented by the above-mentioned formula (4) is preferably used, and in particular, styrene, t-butyl methacrylate, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl methacrylate, (Meth) acrylate, repeating number n = 2 to 10 (meth) acrylate, n-heptyl methacrylate, N-methylacrylamide, N-cyclohexylmaleimide, tetrahydrofurfuryl (Meth) acryloyloxytetrahydrofuran-2-one, 4-hydroxybenzyl (meth) acrylate, 4-hydroxyphenyl (meth) acrylate, o -Hydroxystyrene, p-hydroxystyrene or? -Methyl-p-hydroxystyrene are preferable in terms of copolymerization reactivity and solubility in an aqueous alkali solution. These compounds (a3) are used alone or in combination.

Specific preferred examples of the copolymer [A] used in the present invention include, for example, 2-methacryloyloxyethylphthalic acid / 3,4-epoxycyclohexylmethyl (meth) acrylate / styrene / tricyclo [5.2. 1.0 ^2,6] decane-8-yl (meth) acrylate, 2- (meth) acryloyloxyethyl hexahydrophthalic acid / 3,4-epoxycyclohexylmethyl (meth) acrylate / 4- (meth) acrylate (Meth) acryloyloxypropylhexahydrophthalic acid / 3,4-epoxycyclohexylmethyl (meth) acryloyloxytetrahydrofuran-2-one / styrene, (Meth) acryloyloxyethyl succinic acid / 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decan-8-yl (meth) acrylate / tricyclo [ 5.2.1.0 ^2,6 ] decan-8-yl (meth) acrylate / 4-hydroxyphenyl (meth) acrylate.

The polystyrene reduced weight average molecular weight (hereinafter referred to as "Mw") of the copolymer [A] used in the present invention is preferably 2 × 10 ³ to 1 × 10 ⁵ , more preferably 5 × 10 ³ to 5 × 10 ⁴ . If the Mw is less than 2 x 10 ³ , the developing margin may become insufficient, and the residual film ratio of the obtained film may decrease, and the pattern shape, heat resistance, etc. of the obtained interlayer insulating film or microlens may deteriorate, On the other hand, if it exceeds 1 × 10 ⁵ , the sensitivity may be lowered or the pattern shape may be deteriorated. The molecular weight distribution (hereinafter referred to as " Mw / Mn ") is preferably 5.0 or less, more preferably 3.0 or less. When Mw / Mn exceeds 5.0, the pattern shape of the resulting interlayer insulating film or microlens may be deteriorated. The radiation-sensitive resin composition containing the copolymer [A] can easily form a predetermined pattern shape without developing residue at the time of development.

Examples of the solvent used for preparing the copolymer [A] include alcohols, ethers, glycol ethers, ethylene glycol alkyl ether acetates, diethylene glycol, propylene glycol monoalkyl ethers, propylene glycol alkyl ether acetates, propylene glycol alkyl ethers Propionate, aromatic hydrocarbons, ketones, esters and the like.

Specific examples thereof include alcohols such as methanol, ethanol, benzyl alcohol, 2-phenylethyl alcohol, 3-phenyl-1-propanol and the like;

Ethers such as tetrahydrofuran;

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

As the ethylene glycol alkyl ether acetate, for example, methyl cellosolve acetate, ethyl cellosolve acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monoethyl ether acetate and the like;

As the diethylene glycol, for example, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether and the like;

As the propylene glycol monoalkyl ether, for example, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether and the like;

Examples of the propylene glycol alkyl ether propionate include propylene glycol methyl ether propionate, propylene glycol ethyl ether propionate, propylene glycol propyl ether propionate, and propylene glycol butyl ether propionate;

As the propylene glycol alkyl ether acetate, for example, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, propylene glycol butyl ether acetate and the like;

As aromatic hydrocarbons, for example, toluene, xylene and the like;

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

Examples of esters include esters such as methyl acetate, ethyl acetate, propyl acetate, butyl acetate, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy- Propyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, propyl 3-hydroxypropionate, 3-hydroxypropionate, 3-hydroxypropionate, propyl 3-hydroxypropionate, propyl 3-hydroxypropionate, Butyl methacrylate, methyl methoxyacetate, ethyl methoxyacetate, propyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, ethoxyacetic acid propyl, Propoxyacetic acid, propoxyacetic acid, propoxyacetic acid, propoxyacetic acid, propoxyacetic acid, Butyl methoxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, butyl 2-methoxypropionate, butyl 2-methoxypropionate, Ethoxypropionate, propyl 2-ethoxypropionate, butyl 2-ethoxypropionate, methyl 2-butoxypropionate, ethyl 2-butoxypropionate, propyl 2-butoxypropionate, 2-ethoxypropionate, Methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, 3- Ethoxypropionate, butyl 3-ethoxypropionate, methyl 3-propoxypropionate, ethyl 3-propoxypropionate, propyl 3-propoxypropionate, butyl 3-propoxypropionate, 3- Methyl 3-butoxypropionate, ethyl 3-butoxypropionate, propyl 3-butoxypropionate and butyl 3-butoxypropionate.

Of these, preferred are ethylene glycol alkyl ether acetates, diethylene glycol, propylene glycol monoalkyl ethers and propylene glycol alkyl ether acetates. Particularly preferred are diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, propylene glycol methyl ether, propylene glycol Ethyl ether, propylene glycol methyl ether acetate and methyl 3-methoxypropionate are preferable.

As the polymerization initiator used in the production of the copolymer [A], those generally known as radical polymerization initiators can be used. Azo compounds such as 2,2'-azobisisobutyronitrile, 2,2'-azobis- (2,4-dimethylvaleronitrile), 2,2'-azobis- (4-methoxy- 4-dimethylvaleronitrile); Organic peroxides such as benzoyl peroxide, lauroyl peroxide, t-butyl peroxy pivalate, and 1,1'-bis- (t-butyl peroxy) cyclohexane; And hydrogen peroxide. When the peroxide is used as the radical polymerization initiator, the peroxide may be used together with the reducing agent to form the redox type initiator.

In the production of the copolymer [A], a molecular weight regulator can be used to adjust the molecular weight. Specific examples thereof include halogenated hydrocarbons such as chloroform and carbon tetrabromide; mercaptan compounds such as n-hexylmercaptan, n-octylmercaptan, n-dodecylmercaptan, tert-dodecylmercaptan and thioglycolic acid; Xanthene compounds such as dimethylxanthogen sulfide and diisopropylxanthogen disulfide; Terpinolene,? -Methylstyrene dimer, and the like.

- [B] Component -

The component [B] used in the present invention is a 1,2-quinonediazide compound which generates a carboxylic acid upon irradiation with radiation, and is a phenolic compound or an alcoholic compound (hereinafter referred to as " , And condensates of 2-naphthoquinone diazidesulfonic acid halide can be used.

Examples of the mother nucleus include trihydroxybenzophenone, tetrahydroxybenzophenone, pentahydroxybenzophenone, hexahydroxybenzophenone, (polyhydroxyphenyl) alkane, and other parent nuclei.

Specific examples thereof include trihydroxybenzophenones such as 2,3,4-trihydroxybenzophenone, 2,4,6-trihydroxybenzophenone and the like;

Examples of the tetrahydroxybenzophenone include 2,2 ', 4,4'-tetrahydroxybenzophenone, 2,3,4,3'-tetrahydroxybenzophenone, 2,3,4,4'-tetrahydroxy Benzophenone, 2,3,4,2'-tetrahydroxy-4'-methylbenzophenone, 2,3,4,4'-tetrahydroxy-3'-methoxybenzophenone and the like;

As the pentahydroxybenzophenone, for example, 2,3,4,2 ', 6'-pentahydroxybenzophenone and the like;

As the hexahydroxybenzophenone, for example, 2,4,6,3 ', 4', 5'-hexahydroxybenzophenone, 3,4,5,3 ', 4', 5'-hexahydroxybenzophenone Phenon and the like;

(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- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] thiophene- Ethylidene] bisphenol, bis (2,5-dimethyl-4-hydroxyphenyl) -2-hydroxyphenylmethane, 3,3,3 ', 3'- tetramethyl-1,1'- 5,6,7,5 ', 6', 7'-hexanol, 2,2,4-trimethyl-7,2 ', 4'-trihydroxyflavone and the like;

(2,4-dihydroxyphenyl) -4- (4-hydroxyphenyl) -7-hydroxychroman, 2- [bis { 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) 4,6-bis {1- (4-hydroxyphenyl) -1-methylethyl} -1,3-dihydroxybenzene.

In addition, 1,2-naphthoquinone diazidesulfonic acid amides in which the above-mentioned ester bond of the mother nucleus is changed to an amide bond, such as 2,3,4-trihydroxybenzophenone-1,2-naphthoquinonediamine Sulfonic acid amide and the like are also preferably used.

Among these mother cells, 2,3,4,4'-tetrahydroxybenzophenone, 4,4 '- [1- [4- [1- [4-hydroxyphenyl] -1- methylethyl] phenyl] ethylidene ] Bisphenol is preferred.

As the 1,2-naphthoquinonediazide sulfonic acid halide, 1,2-naphthoquinonediazide sulfonic acid chloride is preferable, and specific examples thereof include 1,2-naphthoquinonediazide-4-sulfonic acid chloride and 1,2- And naphthoquinonediazide-5-sulfonic acid chloride. Of these, 1,2-naphthoquinonediazide-5-sulfonic acid chloride is preferably used.

In the condensation reaction, 1,2-naphthoquinonediazide sulfonic acid halide, which preferably corresponds to 30 to 85 mol%, more preferably 50 to 70 mol%, based on the number of OH groups in the phenolic compound or the alcoholic compound Can be used.

The condensation reaction can be carried out by a known method.

These [B] components may be used alone or in combination of two or more.

The proportion of the component [B] is preferably 5 to 100 parts by weight, more preferably 10 to 50 parts by weight, based on 100 parts by weight of the copolymer [A]. When the ratio is less than 5 parts by weight, the difference in solubility between the irradiated portion of the aqueous alkali solution and the unirradiated portion of the aqueous alkali solution becomes small, making patterning difficult. In addition, the heat resistance of the resulting interlayer insulating film or micro- The solvent resistance may be insufficient. On the other hand, when the proportion is more than 100 parts by weight, the solubility in the alkali aqueous solution becomes insufficient at the irradiated portion, so that it may become difficult to develop.

- Other ingredients -

The radiation-sensitive resin composition of the present invention contains the copolymer [A] and the component [B] as essential components, and if necessary, the thermosensitive acid generating compound [C] A polymerizable compound having an unsaturated double bond, an epoxy resin other than the [E] copolymer [A], an [F] surfactant or a [G] adhesion aid.

The [C] thermosensitive acid-generating compound can be used for improving heat resistance and hardness. Specific examples thereof include onium salts such as sulfonium salts, benzothiazonium salts, ammonium salts and phosphonium salts.

Specific examples of the sulfonium salt include an alkylsulfonium salt, a benzylsulfonium salt, a dibenzylsulfonium salt, and a substituted benzylsulfonium salt.

Specific examples thereof include alkylsulfonium salts such as 4-acetophenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium hexafluoroarsenate, dimethyl-4- (benzyloxycar (Benzoyloxy) phenylsulfonium hexafluoroantimonate, dimethyl 4- (benzoyloxy) phenylsulfonium hexafluoroantimonate, dimethyl-4- (benzoyloxy) phenylsulfonium hexafluoroarsenate, dimethyl -3-chloro-4-acetoxyphenylsulfonium hexafluoroantimonate and the like;

As the benzylsulfonium salt, for example, benzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, benzyl-4-hydroxyphenylmethylsulfonium hexafluorophosphate, 4-acetoxyphenylbenzylmethylsulfonium hexa Benzyl-2-methyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, benzyl-3-chloro-thiomorpholinomethane, benzyl-4-methoxyphenylmethylsulfonium hexafluoroantimonate, benzyl- 4-hydroxyphenylmethylsulfonium hexafluoroarsenate, 4-methoxybenzyl-4-hydroxyphenylmethylsulfonium hexafluorophosphate and the like;

Examples of dibenzylsulfonium salts include dibenzyl-4-hydroxyphenylsulfonium hexafluoroantimonate, dibenzyl-4-hydroxyphenylsulfonium hexafluorophosphate, 4-acetoxyphenyldibenzylsulfonium Dibenzyl-4-methoxyphenylsulfonium hexafluoroantimonate, dibenzyl-3-chloro-4-hydroxyphenylsulfonium hexafluoroarsenate, dibenzyl-3- Methyl-4-hydroxy-5-tert-butylphenylsulfonium hexafluoroantimonate, benzyl-4-methoxybenzyl-4-hydroxyphenylsulfonium hexafluorophosphate and the like;

As the substituted benzylsulfonium salts, for example, p-chlorobenzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, p-nitrobenzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, p -Chlorobenzyl-4-hydroxyphenylmethylsulfonium hexafluorophosphate, p-nitrobenzyl-3-methyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, 3,5-dichlorobenzyl- Hydroxyphenylmethylsulfonium hexafluoroantimonate, o-chlorobenzyl-3-chloro-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, and the like.

Specific examples of the benzothiazonium salts include 3-benzylbenzothiazonium hexafluoroantimonate, 3-benzylbenzothiazonium hexafluorophosphate, 3-benzylbenzothiazonium tetrafluoroborate, 3- (p-methoxybenzyl ) Benzothiazonium hexafluoroantimonate, 3-benzyl-2-methylthiobenzothiazonium hexafluoroantimonate, and 3-benzyl-5-chlorobenzothiazonium hexafluoroantimonate. Zonium salts.

Among them, sulfonium salts and benzothiazonium salts are preferably used, and in particular, 4-acetoxyphenyldimethylsulfonium hexafluoroarsenate, benzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, 4 -Acetoxyphenylbenzylmethylsulfonium hexafluoroantimonate, dibenzyl-4-hydroxyphenylsulfonium hexafluoroantimonate, 4-acetoxyphenylbenzylsulfonium hexafluoroantimonate, 3-benzyl Benzothiazolium hexafluoroantimonate is preferably used.

Examples of commercially available products thereof include Sun Aid SI-L85, SI-L110, SI-L145, SI-L150 and SI-L160 (manufactured by Sanshin Chemical Industry Co., Ltd.).

The proportion of the [C] component is preferably 20 parts by weight or less, more preferably 5 parts by weight or less, based on 100 parts by weight of the copolymer [A]. If the amount is more than 20 parts by weight, precipitates may precipitate in the coating film forming step, which may interfere with the coating film formation.

Examples of the [D] polymerizable compound having at least one ethylenically unsaturated double bond (hereinafter also referred to as "component [D]") include monofunctional (meth) acrylate, difunctional (meth) Or trifunctional or more (meth) acrylate.

Examples of the monofunctional (meth) acrylate include 2-hydroxyethyl (meth) acrylate, carbitol (meth) acrylate, isobornyl (meth) acrylate, 3-methoxybutyl Acrylate, 2- (meth) acryloyloxyethyl-2-hydroxypropyl phthalate, and the like. Examples of commercially available products thereof include Aronix M-101, M-111, M-114 (manufactured by TOAGOSEI CO., LTD.), KAYARAD TC-110S and CO-120S Ltd.), Viscot 158, and Copper 2311 (manufactured by Osaka Yuki Kagaku Kogyo Co., Ltd.).

Examples of the bifunctional (meth) acrylate include ethylene glycol (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol (meth) acrylate, Di (meth) acrylate, tetraethylene glycol di (meth) acrylate, bisphenoxyethanol fluorene diacrylate, and bisphenoxyethanol fluorene diacrylate. Examples of commercially available products thereof include Aronix M-210, M-240, M-6200 (manufactured by Toa Kosei Co., Ltd.), KAYARAD HDDA, copper HX-220 and copper R- (Manufactured by Kayaku Co., Ltd.), Viscot 260, Copper 312, Copper 335 HP (manufactured by Osaka Yuki Kagaku Kogyo Co., Ltd.) and the like.

Examples of the trifunctional or higher (meth) acrylate include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, tri ((meth) acryloyloxyethyl) (Meth) acrylate, dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate. Commercially available products thereof include Aronix M-309, M- KAYARAD TMPTA, Copper DPHA, Copper DPCA-20, Copper M-8060 (manufactured by TOAGOSEI CO., LTD.), Copper M-405, Copper M-450, Copper M-7100, Copper M- -30, DPCA-60, DPCA-120 (manufactured by Nippon Kayaku Co., Ltd.), Viscot 295, Copper 300, Copper 360, Copper GPT, Copper 3PA, Copper 400 (Manufactured by Nippon Polyurethane Industry Co., Ltd.).

Of these, trifunctional or more (meth) acrylates are preferably used, and trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate and dipentaerythritol hexa (meth) Particularly preferred.

These monofunctional, bifunctional or trifunctional (meth) acrylates are used alone or in combination. The proportion of the [D] component is preferably 50 parts by weight or less, more preferably 30 parts by weight or less, based on 100 parts by weight of the copolymer [A].

By including the [D] component in such a ratio, heat resistance and surface hardness of the interlayer insulating film or microlens obtained from the radiation sensitive resin composition of the present invention can be improved. When the amount is more than 50 parts by weight, film roughness may occur in the step of forming a coating film of the radiation-sensitive resin composition on the substrate.

The epoxy resin (hereinafter also referred to as "the [E] component") other than the [E] copolymer [A] is not limited as long as it does not affect compatibility. Preferred examples of the epoxy resin include bisphenol A type epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, cyclic aliphatic epoxy resin, glycidyl ester type epoxy resin, glycidylamine type epoxy resin, And resins obtained by (co) polymerization of cyydimethacrylate. Among them, bisphenol A type epoxy resin, cresol novolak type epoxy resin, glycidyl ester type epoxy resin and the like are particularly preferable.

The proportion of the component [E] is preferably 30 parts by weight or less, more preferably 1 to 20 parts by weight, based on 100 parts by weight of the copolymer [A]. By containing the [E] component in 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 the ratio is more than 30 parts by weight, uniformity of film thickness of a coating film may be insufficient when a coating film of a radiation-sensitive resin composition is formed on a substrate.

The copolymer [A] may also be referred to as an " epoxy resin ", but differs from the [E] component in that it has an alkali solubility. The [E] component is alkali-insoluble.

In the radiation-sensitive resin composition of the present invention, the [F] surfactant described above may be used to further improve the coatability. As the [F] surfactant usable herein, a fluorine-based surfactant, a silicon-based surfactant or a nonionic surfactant can be preferably used.

Specific examples of the fluorine-based surfactant 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 perfluorododecylsulfonate, 1,1,2 , 2,8,8,9,9,10,10-decafluorododecane, 1,1,2,2,3,3-hexafluorodecane, and the like, sodium fluoroalkylbenzenesulfonate; Fluoroalkyloxyethylene ethers; Fluoroalkyl ammonium iodide, fluoroalkyl polyoxyethylene ether, perfluoroalkyl polyoxyethanol; Perfluoroalkyl alkoxylates; Fluorine-based alkyl esters and the like. Examples of commercially available products thereof include BM-1000, BM-1100 (manufactured by BM Chemie), Megafac F142D, Copper F172, Copper F173, Copper F183, Copper F178, Copper F191, Copper F471 (Available from Sumitomo 3M Limited), Surflon S-112, S-113, S-113, and S-113 (manufactured by Sumitomo 3M Limited), Florad FC-170C, FC-171, FC- 131, S-141, S-145, S-382, SC-101, SC-102, SC-103, SC-104, SC- (Trade name, manufactured by Shin-Akita Kasei Co., Ltd.), and 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- (Commercially available from Momentive Performance Materials Japan Ltd.), TSF-4440, TSF-4300, TSF-4445, TSF-4446, TSF-4460 and TSF-4452 .

Examples of the nonionic surfactant include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether and polyoxyethylene oleyl ether; Polyoxyethylene aryl ethers such as polyoxyethylene octyl phenyl ether and polyoxyethylene nonyl phenyl ether; Polyoxyethylene dialkyl esters such as polyoxyethylene dilaurate and polyoxyethylene distearate; (Meth) acrylic acid-based copolymer Polyflow No.57 and 95 (manufactured by Kyoeisha Chemical Co., Ltd.) can be used.

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

These [F] surfactants are used preferably in an amount of 5 parts by weight or less, more preferably 0.01 to 2 parts by weight, based on 100 parts by weight of the copolymer [A]. When the amount of the [F] surfactant used is more than 5 parts by weight, film roughness of the coating film tends to easily occur when the coating film is formed on the substrate.

In the radiation sensitive resin composition of the present invention, a [G] adhesion aid may also be used to improve adhesion to a substrate. As the [G] adhesion aid, a functional silane coupling agent is preferably used, and examples thereof include silane coupling agents having reactive substituents such as a carboxyl group, a methacryloyl group, an isocyanate group, and an epoxy group. Specific examples include trimethoxysilylbenzoic acid,? -Methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane,? -Isocyanatepropyltriethoxysilane,? -Glycidoxypropyltrimethoxy Silane,? - (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and the like. The [G] adhesion aid is used in an amount of preferably 20 parts by weight or less, more preferably 10 parts by weight or less, based on 100 parts by weight of the copolymer [A]. When the amount of the adhesion-promoting agent exceeds 20 parts by weight, development residue tends to occur in the developing step.

- Radiation-sensitive resin composition -

The radiation sensitive resin composition of the present invention is produced by homogeneously mixing the copolymer [A] and the component [B] and other optional components that can be optionally added. 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 optionally other components in a predetermined ratio.

As the solvent used in the production of the radiation sensitive resin composition of the present invention, the components of the copolymers [A] and [B] and other components to be optionally compounded are uniformly dissolved, and those that do not react with each component are used .

Examples of such a solvent include the same solvents as those exemplified as solvents that can be used for producing the copolymer [A].

Among these solvents, alcohols, glycol ethers, ethylene glycol alkyl ether acetates, esters and diethylene glycols are preferably used in terms of solubility of each component, reactivity with each component, ease of forming a coating film, and the like. Of 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, di Ethylene glycol dimethyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, methyl methoxypropionate and ethyl ethoxypropionate are particularly preferably used.

In addition, a high boiling point solvent may be used in combination with the above solvent in order to increase the in-plane uniformity of the film thickness. Examples of the high boiling point solvents that can be used in combination include N, N-dimethylformamide, N-methylformanilide, N-methylacetamide, N, N-dimethylacetamide, Butanol, ethyl benzoate, diethyl oxalate, maleic anhydride, maleic anhydride, maleic anhydride, maleic anhydride, maleic anhydride, maleic anhydride, Propylene carbonate, phenyl cellosolve acetate, and the like can be given. Of these, N-methylpyrrolidone,? -Butyrolactone and N, N-dimethylacetamide are preferable.

When a high-boiling solvent is used as the solvent of the radiation-sensitive resin composition of the present invention, the amount of the solvent to be used is preferably not more than 50% by weight, preferably not more than 40% by weight, more preferably not more than 30% to be. If the amount of the high-boiling solvent used exceeds this amount, uniformity of film thickness, sensitivity and residual film ratio may be lowered.

When the radiation sensitive resin composition of the present invention is prepared in a solution state, the solid concentration (the sum of the components (copolymer [A] and [B] components other than the solvent occupying in the composition solution and the total amount of other components optionally added) Is preferably from 5 to 50% by weight, more preferably from 10 to 40% by weight, and still more preferably from 15 to 35% by weight, although it can be arbitrarily set depending on the purpose of use or the value of the desired film thickness.

The thus prepared composition solution may be filtered for use with a Millipore filter having a pore size of about 0.2 탆 and then used for use.

- Formation of interlayer insulating film, microlens -

Next, a method of forming an interlayer insulating film and a microlens of the present invention using the radiation sensitive resin composition of the present invention will be described. The method for forming an interlayer insulating film or a microlens of the present invention includes the following steps in the order described below.

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

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

(3) developing process, and

(4) Heating process

    - (1) Step of forming a coated film of the radiation sensitive resin composition of the present invention on a substrate -

In the step (1), the solution of the composition of the present invention is coated on the surface of the substrate, preferably by heat treatment (prebaking) to remove the solvent 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 substrates, and substrates on which various metals are formed.

The method of applying the composition solution is not particularly limited, and suitable methods such as a spraying method, a roll coating method, a rotation coating method (spin coating method), a slit die coating method, a bar coating method, , In particular, a spin coating method and a slit die coating method are preferable. Conditions for prebaking also differ depending on the kind of each component, the use ratio, and the like. For example, at 60 to 110 DEG C for 30 seconds to 15 minutes.

The film thickness of the formed coating film is preferably 3 to 6 占 퐉 in the case of forming an interlayer insulating film and 0.5 to 3 占 퐉 in the case of forming a microlens as a value after prebaking.

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

In the step (2), the formed coating film is irradiated with radiation through a mask having a predetermined pattern, and then subjected to development processing using a developer to remove the irradiated portion of the radiation to perform patterning. Examples of the radiation used at this time include ultraviolet rays, deep ultraviolet rays, X-rays, charged particle rays, and the like.

Examples of the ultraviolet ray include g-line (wavelength: 436 nm) and i-line (wavelength: 365 nm). Examples of the far ultraviolet ray include a KrF excimer laser. Examples of X-rays include synchrotron radiation. Examples of the charged particle beam include electron beams and the like.

Among these, ultraviolet rays are preferable, and radiation including g line and / or i line is particularly preferable.

The exposure dose is preferably 50 to 1,500 J / m2 in the case of forming an interlayer insulating film, and 50 to 2,000 J / m2 in the case of forming a microlens.

- (3) Developing process -

Examples of the developer used in the developing treatment include aqueous solutions such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, ammonia, ethylamine, n-propylamine, diethylamine, diethylaminoethanol, Amine, triethylamine, methyldiethylamine, dimethylethanolamine, triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, pyrrole, piperidine, 1,8-diazabicyclo [5.4.0] -7-undecene, 1,5-diazabicyclo [4.3.0] -5-nonane, or the like can be used. Further, an aqueous solution in which an appropriate amount of a water-soluble organic solvent such as methanol and ethanol or a surfactant is added to the aqueous alkali solution, or various organic solvents which dissolve the composition of the present invention may be used as a developer. As the developing method, suitable methods such as a puddle method, a dipping method, a swing dipping method, and a shower method can be used. The developing time at this time varies depending on the composition of the composition, but may be, for example, 30 to 120 seconds.

Further, in the conventionally known radiation-sensitive resin composition, when the developing time exceeds 20 to 25 seconds from the optimum value, the formed pattern is peeled off, so that it is necessary to strictly control the developing time. However, In the case of the composition, good pattern formation is possible even when the excess time from the optimum developing time is 30 seconds or more, which is advantageous in terms of product yield.

- (4) Heating process -

After the developing step (3) as described above, the patterned thin film is preferably subjected to a rinsing treatment by, for example, water washing, preferably by irradiating the entire surface with radiation by a high-pressure mercury lamp or the like Quinonediazide compound remaining in the thin film is subjected to decomposition treatment and then the thin film is subjected to a heat treatment (post-baking treatment) by a heating device such as a hot plate or an oven, . The amount of exposure in the post-exposure step is preferably about 2,000 to 5,000 J / m 2. The heating temperature in the post-baking treatment is, for example, 120 to 250 ° C. The heating time varies depending on the type of the heating apparatus. For example, the heating time may be 5 to 30 minutes in the case of performing heat treatment on the hot plate, and 30 to 90 minutes in the case of performing heat treatment in the oven. At this time, a step bake method in which two or more heating steps are performed may be used.

In this manner, a patterned thin film corresponding to a desired interlayer insulating film or microlens can be formed on the surface of the substrate.

- Interlayer insulating film -

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

- Micro lens -

The microlens of the present invention formed as described above has good adhesion to a substrate, excellent heat resistance and solvent resistance, and exhibits a high light transmittance and a good melt shape, and is preferably used as a microlens of a solid- Can be used. The shape of the microlens of the present invention is a semi-convex lens shape as shown in Fig. 1 (a).

Industrial Applicability As described above, the radiation sensitive resin composition of the present invention has a high sensitivity to radiation and has a developing margin capable of still forming a good pattern even if the developing process exceeds the optimum developing time in the developing process, The patterned thin film can be easily formed.

The interlayer insulating film and the microlens formed from the radiation-sensitive resin composition of the present invention satisfy the various performances required for the interlayer insulating film and the microlens, respectively (recently more and more demanding performance).

Hereinafter, the present invention will be described in more detail with reference to Synthesis Examples and Examples, but the present invention is not limited to the following Examples.

- Synthesis Example of Copolymer [A]

Synthesis Example 1

7 parts by weight of 2,2'-azobis (2,4-dimethylvaleronitrile) and 200 parts by weight of diethylene glycol ethyl methyl ether were fed into a flask equipped with a stirrer, a cooling tube and a stirrer. Subsequently, 25 parts by weight of 2-methacryloyloxyethyl phthalic acid, 45 parts by weight of 3,4-epoxycyclohexylmethyl methacrylate, 10 parts by weight of styrene, tricyclo [5.2.1.0 ^2,6 ] decan-8- 20 parts by weight of methacrylate and 3 parts by weight of? -Methylstyrene dimer were charged and purged with nitrogen, and stirring was started slowly. The temperature of the solution was raised to 70 캜 and maintained at this temperature for 4 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 10,000 and the molecular weight distribution (Mw / Mn) was 2.5. The solid content concentration of the polymer solution obtained here was 34.5% by weight.

Synthesis Example 2

A cooling tube and a stirrer, 8 parts by weight of 2,2'-azobis (2,4-dimethylvaleronitrile) and 220 parts by weight of diethylene glycol ethyl methyl ether were added. Subsequently, 13 weight parts of 2-methacryloyloxyethylhexahydrophthalic acid, 50 weight parts of 3,4-epoxycyclohexylmethyl methacrylate, 10 weight parts of 4-acryloylmorpholine, 3 weight parts of 3-methacryloyloxy 15 parts by weight of tetrahydrofuran-2-one, 12 parts by weight of styrene and 3 parts by weight of? -Methylstyrene dimer were charged and purged with nitrogen, and stirring was started slowly. The temperature of the solution was raised to 70 캜 and maintained at this temperature for 5 hours to obtain a polymer solution containing the copolymer [A-2].

The polystyrene reduced weight average molecular weight (Mw) of the copolymer [A-2] was 8,000 and the molecular weight distribution (Mw / Mn) was 2.3. The solid solution concentration of the polymer solution obtained here was 32.1% by weight.

Synthesis Example 3

A cooling tube and a stirrer, 8 parts by weight of 2,2'-azobis (2,4-diisobutylvaleronitrile) and 220 parts by weight of diethylene glycol ethyl methyl ether were charged. Subsequently, 20 parts by weight of 2-methacryloyloxypropyl hexahydrophthalic acid, 45 parts by weight of 3,4-epoxycyclohexylmethyl methacrylate, 10 parts by weight of N-cyclohexylmaleimide and 25 parts by weight of styrene were charged, After that, stirring was started slowly. The temperature of the solution was raised to 80 캜 and maintained at this temperature for 5 hours to obtain a polymer solution containing the copolymer [A-3].

The polystyrene reduced weight average molecular weight (Mw) of the copolymer [A-3] was 11,000 and the molecular weight distribution (Mw / Mn) was 2.8. The solid solution concentration of the polymer solution obtained here was 32.6% by weight.

Synthesis Example 4

A cooling tube and a stirrer, 8 parts by weight of 2,2'-azobis (2,4-dimethylvaleronitrile) and 220 parts by weight of diethylene glycol ethyl methyl ether were added. Subsequently, 15 parts by weight of methacryloyloxyethyl succinic acid, 50 parts by weight of 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decan-8-yl methacrylate, 50 parts by weight of tricyclo [5.2.1.0 ^2,6 ] decane -8-yl methacrylate (25 parts by weight) and 4-hydroxyphenyl methacrylate (10 parts by weight) were purged with nitrogen, and stirring was started slowly. The temperature of the solution was raised to 70 캜 and maintained at this temperature for 5 hours to obtain a polymer solution containing the copolymer [A-4].

The polystyrene reduced weight average molecular weight (Mw) of the copolymer [A-4] was 8,900 and the molecular weight distribution (Mw / Mn) was 2.4. The polymer solution thus obtained had a solid content concentration of 31.5% by weight.

Comparative Synthesis Example 1

A cooling tube and a stirrer, 8 parts by weight of 2,2'-azobis (2,4-dimethylvaleronitrile) and 220 parts by weight of diethylene glycol ethyl methyl ether were added. 18 parts by weight of methacrylic acid, 45 parts by weight of 3,4-epoxycyclohexylmethyl methacrylate, 10 parts by weight of styrene, 27 parts by weight of tricyclo [5.2.1.0 ^2,6 ] decan-8-yl methacrylate, After 3 parts by weight of? -methylstyrene dimer was added and replaced with nitrogen, stirring was started slowly. The temperature of the solution was raised to 70 캜 and maintained at this temperature for 4 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 8,800 and the molecular weight distribution (Mw / Mn) was 2.4. The solid concentration of the polymer solution obtained here was 31.9% by weight.

Comparative Synthesis Example 2

7 parts by weight of 2,2'-azobis (2,4-dimethylvaleronitrile) and 200 parts by weight of diethylene glycol ethyl methyl ether were fed into a flask equipped with a stirrer, a cooling tube and a stirrer. Then, 25 parts by weight of 2-methacryloyloxyethyl phthalic acid, 45 parts by weight of glycidyl methacrylate, 10 parts by weight of styrene, 20 parts by weight of tricyclo [5.2.1.0 ^2,6 ] decan-8-yl methacrylate And 3 parts by weight of the? -Methylstyrene dimer were introduced and replaced with nitrogen, and stirring was started slowly. The temperature of the solution was raised to 70 캜 and maintained at this temperature for 4 hours to obtain a polymer solution containing the copolymer [a-2].

The polystyrene reduced weight average molecular weight (Mw) of the copolymer [a-2] was 14,000 and the molecular weight distribution (Mw / Mn) was 2.5. The solid content concentration of the obtained polymer solution was 34.3% by weight.

- Preparation of radiation-sensitive resin composition -

Example 1

A solution containing the copolymer [A-1] synthesized in Synthesis Example 1 as a copolymer was added in an amount corresponding to 100 parts by weight (solid content) of the copolymer [A-1] Phenyl] ethylidene] bisphenol (1.0 mol) and 1,2-naphthoquinonediazide-5-sulfonic acid chloride (2.0 mol) were added to a solution of 1- [4- [1- [4- hydroxyphenyl] And 30 parts by weight of the condensate (B-1) having a solids content of 30% by weight were dissolved in diethylene glycol ethyl methyl ether and filtered through a membrane filter having a pore size of 0.2 탆, To prepare a resin composition (S-1).

Examples 2 to 4, Comparative Examples 1 and 2

Examples 1 and 2 were prepared in the same manner as in Example 1 except that the kind and amount described in the following Table 1 were used as the [A] component and the [B] component, respectively. In Examples 2 and 3, β- (3,4- (S-2) to (S-4) and (s-1) to (s-3) in the solution were prepared in the same manner as in Example 1, -2).

In Example 3, the two kinds of 1,2-quinonediazide compounds listed in Table 1 were used as the [B] component.

Example 5

In the same manner as in Example 1 except that the solvent was replaced by a mixed solvent of diethylene glycol ethyl methyl ether / propylene glycol monomethyl ether acetate (weight ratio: 6/4) and SH- 28PA (trade name, manufactured by Toray Dow Corning Silicones ) Was added in an amount of 0.1 part by weight to prepare a radiation-sensitive resin composition (S-5) in a solution in the same manner as in Example 1, except that the solid concentration of the composition solution was 20% by weight.

In Table 1, each abbreviation represents the following compound.

B-1: Synthesis of 4,4 '- [1- [4- [1- [4-hydroxyphenyl] -1- methylethyl] phenyl] ethylidene] bisphenol (1.0 mol) and 1,2-naphthoquinonediamine 5-sulfonic acid chloride (2.0 mol)

B-2: Synthesis of 4,4 '- [1- [4- [1- [4-hydroxyphenyl] -1- methylethyl] phenyl] ethylidene] bisphenol (1.0 mol) and 1,2-naphthoquinonediamine 5-sulfonic acid chloride (2.5 mol)

B-3: A condensate of 2,3,4,4'-tetrahydroxybenzophenone (1.0 mol) and 1,2-naphthoquinonediazide-5-sulfonic acid ester (2.44 mol)

E:? - (3,4-epoxycyclohexyl) ethyltrimethoxysilane

F: SH-28PA (trade name, manufactured by Toray Dow Corning Silicone Co., Ltd.)

- Evaluation of performance as an interlayer insulating film -

Examples 6 to 10, Comparative Examples 3 and 4

Using the radiation-sensitive resin compositions prepared in Examples 1 to 5 and Comparative Examples 1 and 2, various properties as an interlayer insulating film were evaluated as follows.

[Evaluation of Sensitivity]

On the silicon substrate, the compositions described in the following Table 2 were respectively applied to Examples 6 to 9 and Comparative Examples 3 to 4 using a spinner, and then prebaked on a hot plate at 90 캜 for 2 minutes to obtain a Thereby forming a coating film. In Example 10, the composition shown in Table 2 was applied by a slit die coater, and the solvent was removed by depressurization from normal pressure to 0.5 Torr for 15 seconds, followed by pre-baking on a hot plate at 90 DEG C for 2 minutes, Thereby forming a coating film having a thickness of 3.0 탆.

The resulting coating film was subjected to exposure by varying the exposure time with a PLA-501F exposure apparatus (ultrahigh-pressure mercury lamp) manufactured by Canon Inc. (through a pattern mask having a predetermined pattern), and then exposed to various concentrations of tetramethylammonium hydroxide Rockside aqueous solution at 25 캜 for 80 seconds. Followed by water washing with ultra-pure water for 1 minute, and then drying, thereby forming a pattern on the substrate. At this time, the amount of exposure required to completely dissolve the space pattern of 3.0 μm line-and-space (10: 1) was examined, and this value is shown in Table 2 as sensitivity. When this value is 600 J / m < 2 > or less, the sensitivity is good.

[Evaluation of Developing Margin]

The compositions described in Table 2 were coated on a silicon substrate in Examples 6 to 9 and Comparative Examples 3 to 4 using a spinner and then prebaked on a hot plate at 90 캜 for 2 minutes to form a coating film . For Example 10, the composition described in Table 2 was applied by a slit die coater, and the solvent was removed by depressurization from normal pressure to 0.5 Torr for 15 seconds, followed by prebaking on a hot plate at 90 DEG C for 2 minutes to obtain a film thickness of 3.0 Mu m.

The resulting coating film was subjected to evaluation using the PLA-501F exposure apparatus (ultrahigh pressure mercury lamp) manufactured by Canon Inc. (Evaluation of Sensitivity) through a mask having a 3.0 μm line and space (10 times) pattern Exposure was carried out at an exposure amount corresponding to the value of the measured sensitivity, and development was carried out by a puddle method in a tetramethylammonium hydroxide aqueous solution at the concentration described in Table 2 at 25 캜 and a development time varying. Followed by water washing with ultra-pure water for 1 minute, and then drying, thereby forming a pattern on the substrate. At this time, the development time necessary for the line line width to become 3 占 퐉 is shown in Table 2 as the optimal development time. Further, when the development was further continued from the optimum development time, the time until the line pattern of 3.0 탆 was peeled off was measured and shown in Table 2 as the developing margin. When this value exceeds 30 seconds, the development margin can be said to be good.

[Evaluation of solvent resistance]

The compositions described in Table 2 were coated on a silicon substrate in the same manner as in Examples 6 to 9 and Comparative Examples 3 to 4 using a spinner, and then prebaked on a hot plate at 90 캜 for 2 minutes to form a coating film. For Example 10, the composition described in Table 2 was applied by a slit die coater, and the solvent was removed by reducing pressure from normal pressure to 0.5 Torr for 15 seconds, and then prebaked on a hot plate at 90 캜 for 2 minutes to form a coating film Respectively.

The resulting coating film was exposed to a total irradiation dose of 3,000 J / m 2 with a PLA-501F exposure apparatus (ultra-high pressure mercury lamp) manufactured by Canon Inc., and the silicon substrate was heated in a clean oven at 220 캜 for 1 hour, A cured film having a thickness of 3.0 탆 was obtained. The film thickness (T1) of the obtained cured film was measured. Then, the silicon substrate on which the cured film was formed was immersed in dimethylsulfoxide controlled at a temperature of 70 占 폚 for 20 minutes, and then the film thickness t1 of the cured film was measured, and the film thickness change rate {| t1-T1 | / T1} x 100 [%]. The results are shown in Table 2. When this value is 5% or less, it can be said that the solvent resistance is good.

Further, in the evaluation of the solvent resistance, patterning of the film to be formed is not necessary, so that the irradiation step and the development step are omitted, and only the film forming step, the post-baking step and the heating step are performed for evaluation.

[Evaluation of heat resistance]

The cured films were respectively formed in the same manner as in the evaluation of the solvent resistance, and the film thicknesses (T2) of the obtained cured films were measured. Subsequently, the substrate having the respective cured films was further baked at 240 DEG C for 1 hour in a clean oven, and the film thickness t2 of the cured film was measured. The film thickness change rate {| t2-T2 | / T2} × 100 [%]. The results are shown in Table 2. When this value is 5% or less, it can be said that the heat resistance is good.

[Evaluation of transparency]

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

[Evaluation of relative dielectric constant]

The compositions shown in Table 2 were coated on a polished SUS304 substrate using a spinner for Examples 6 to 9 and Comparative Examples 3 to 4 and then prebaked on a hot plate at 90 DEG C for 2 minutes to obtain a film having a thickness of 3.0 Mu m. For Example 10, the composition described in Table 2 was applied by a slit die coater, and the solvent was removed by depressurization from normal pressure to 0.5 Torr for 15 seconds, followed by prebaking on a hot plate at 90 DEG C for 2 minutes to obtain a film thickness of 3.0 Mu m.

With respect to the obtained coating film, each of the resulting coating films was exposed with a PLA-501F exposure apparatus (ultrahigh pressure mercury lamp) manufactured by Canon Inc. in such a manner that the cumulative irradiation dose was 3,000 J / m 2, and the substrate was fired in a clean oven at 220 캜 for 1 hour to obtain a cured film . A Pt / Pd electrode pattern was formed on each of the cured films by a vapor deposition method to prepare samples for measuring the dielectric constant. With respect to each substrate, relative dielectric constant was measured by the CV method at a frequency of 10 kHz using an HP16451B electrode manufactured by Yokogawa Hewlett-Packard Co., Ltd. (then) and an HP4284A plasma zone LCR meter. The results are shown in Table 2. When this value is less than 3.9, the dielectric constant is said to be good.

Further, in the evaluation of the dielectric constant, patterning of the film to be formed is not necessary. Therefore, the irradiation step and the development step are omitted, and only the film forming step, the post-baking step and the heating step are performed for evaluation.

- Performance evaluation as microlens -

Examples 11 to 14, Comparative Examples 5 and 6

Using the radiation-sensitive resin compositions prepared in Examples 1 to 5 and Comparative Examples 1 and 2, various properties as microlenses were evaluated as follows. The evaluation of the solvent resistance, the evaluation of the heat resistance and the evaluation of the transparency are the results of the performance evaluation as the interlayer insulating film.

[Evaluation of Sensitivity]

The composition described in Table 3 below was applied to each of the silicon substrates using a spinner and then baked on a hot plate at 90 DEG C for 2 minutes to form a coating film having a thickness of 2.0 mu m. The thus-obtained coating film was exposed to light through a pattern mask having a predetermined pattern with an exposure time varying with an NSR1755i7A reduced projection exposure apparatus (NA = 0.50,? = 365 nm) manufactured by Nikon Corporation, and the concentration of tetramethylammonium hydroxide Was developed by a puddle method at 25 ° C for 1 minute in an aqueous solution of a lockside. Then rinsed with water, and then dried to form a pattern on the substrate. The exposure time required for the 0.8 m line-and-space pattern (one-to-one) to have a space line width of 0.8 mu m was measured. These values are shown in Table 3 with sensitivity. When the value is 2,000 J / m < 2 > or less, the sensitivity is good.

[Evaluation of Developing Margin]

Each of the compositions shown in Table 3 was coated on a silicon substrate using a spinner and then prebaked on a hot plate at 90 DEG C for 2 minutes to form a coating film having a thickness of 2.0 mu m. The obtained coating film was exposed to an exposure amount corresponding to the value of the sensitivity measured in the "evaluation of sensitivity" with a NSR1755i7A reduced projection exposure apparatus (NA = 0.50, λ = 365 nm) manufactured by Nikon Corporation through a pattern mask having a predetermined pattern , And developed in a puddle method at 25 DEG C for 1 minute in an aqueous solution of tetramethylammonium hydroxide at the concentrations shown in Table 3. [ Then rinsed with water, and then dried to form a pattern on the wafer. The developing time required for the space line width of 0.8 占 퐉 line-and-space pattern (one-to-one) to be 0.8 占 퐉 is shown in Table 3 as the optimum developing time. Further, when development continued further from the optimum developing time, the time (developing margin) until the pattern with a width of 0.8 탆 was peeled off was measured and shown in Table 3 as a developing margin. When this value exceeds 30 seconds, it can be said that the developing margin is good.

[Formation of microlens]

Each of the compositions shown in Table 3 was coated on a silicon substrate using a spinner and then prebaked on a hot plate at 90 DEG C for 2 minutes to form a coating film having a thickness of 2.0 mu m. The coating film thus obtained was exposed to light with a sensitivity of 50 nm as measured with the NSR1755i7A miniature projection exposure apparatus (NA = 0.50,? = 365 nm) manufactured by Nikon Corporation under the condition of "Evaluation of Sensitivity" through a pattern mask having a space pattern of 4.0 탆 dot and 2.0 탆 space , And developed by a puddle method at 25 DEG C for 1 minute in an aqueous solution of tetramethylammonium hydroxide having the concentration described as the developer concentration in the evaluation of the sensitivity in Table 3. [ Then rinsed with water, and then dried to form a pattern on the wafer. Thereafter, exposure was performed with a PLA-501F exposure apparatus (ultra-high pressure mercury lamp) manufactured by Canon Inc. so that the cumulative irradiation dose was 3,000 J / m 2. Thereafter, the resultant was heated on a hot plate at 160 DEG C for 10 minutes and then heated at 230 DEG C for 10 minutes to melt-flow the pattern to form a microlens.

Table 3 shows the dimensions (diameter) and the cross-sectional shape of the bottom portion of the formed microlens (surface contacting the substrate). It can be said that the dimension of the bottom of the micro lens is good when it is more than 4.0 mu m and less than 5.0 mu m. When the dimension is 5.0 m or more, adjacent lenses are in contact with each other, which is not preferable. The cross-sectional shape is good when it is a semi-convex lens shape as shown in (a) of FIG. 1, and is bad when it has a roughly trapezoidal shape as shown in (b).

1 is a schematic view of a cross-sectional shape of a microlens.

Claims (10)

[A] (a1) an unsaturated compound having a carboxyl group represented by the following formula (1) (a2) an unsaturated compound having an alicyclic epoxy skeleton selected from the following formulas (2-1) to (2-3), and (a3) methacrylic acid alkyl ester; Alkyl acrylate esters; Methacrylic acid cyclic alkyl esters; Methacrylic esters having a hydroxyl group; Acrylic acid cyclic alkyl esters; Methacrylic acid aryl esters; Acrylic acid aryl esters; Unsaturated dicarboxylic acid diesters; Bicyclo unsaturated compounds; Maleimide compounds; Unsaturated aromatic compounds; Conjugated dienes; At least one member selected from the group consisting of a tetrahydrofuran skeleton, a furan skeleton, a tetrahydropyran skeleton, a pyran skeleton, a glycidyl skeleton, or an unsaturated compound having a skeleton represented by Formula 3 below; A phenolic hydroxyl group-containing unsaturated compound represented by the following formula (4); At least one unsaturated compound selected from the group consisting of acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide and vinyl acetate ≪ / RTI > [B] a radiation-sensitive resin composition comprising a 1,2-quinonediazide compound. ≪ Formula 1 >

(Wherein R represents hydrogen or a methyl group, and X represents a methylene group, an alkylene group having 2 to 6 carbon atoms, or a bivalent group represented by any one of the following formulas (1-1) to (1-6)

(Wherein X ¹ is each independently a methylene group or an alkylene group having 2 to 6 carbon atoms, and the number of bonds on the right side of the formulas (1-1) to (1-6) is bonded to a carboxyl group)

(3)

(Wherein R ³ is a hydrogen atom or a methyl group, and n is a repeating number of 2 to 10) ≪ Formula 4 >

(Wherein R ⁴ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, a plurality of R ⁵ are each independently a hydrogen atom, a hydroxyl group or an alkyl group having 1 to 4 carbon atoms, X ² is a single bond, -COO- or -CONH- and m is an integer of 0 to 3, provided that at least one of R < ⁵ > is a hydroxyl group) The positive resist composition according to claim 1, wherein the copolymer [A] is a copolymer comprising a repeating unit derived from the compound (a1), a repeating unit derived from the compound (a2), and a repeating unit derived from the compound (a3) 10 to 80% by weight and 5 to 80% by weight, respectively, based on the total of the repeating units derived from the compound (a2) and the compound (a3). The radiation sensitive resin composition according to claim 2, wherein the content of the [B] 1,2-quinonediazide compound is from 5 to 100 parts by weight per 100 parts by weight of the [A] copolymer. The radiation sensitive resin composition according to claim 1, wherein the content of the [B] 1,2-quinonediazide compound is from 5 to 100 parts by weight based on 100 parts by weight of the [A] copolymer. The radiation sensitive resin composition according to any one of claims 1 to 4, which is used for forming an interlayer insulating film. A method for forming an interlayer insulating film, comprising the steps of: (1) A step of forming a coating film of the radiation sensitive resin composition according to claim 5 on a substrate (2) a step of irradiating at least a part of the coating film with radiation (3) Development process (4) Heating process An interlayer insulating film formed by the method of claim 6. The radiation sensitive resin composition according to any one of claims 1 to 4, which is used for forming a microlens. A method for forming a microlens, comprising the steps of: (1) A step of forming a coating film of the radiation sensitive resin composition according to claim 8 on a substrate (2) a step of irradiating at least a part of the coating film with radiation (3) Development process (4) Heating process A microlens formed by the method of claim 9.

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