TWI383255B - A method for forming a radiation linear resin composition and an interlayer insulating film and a microlens - Google Patents

Description

Radiation-sensitive linear resin composition, interlayer insulating film and microlens forming method

In particular, the present invention relates to a radiation sensitive resin composition useful for forming an interlayer insulating film and a microlens, an interlayer insulating film and a microlens formed of the radiation sensitive resin composition, and an interlayer insulating film and a microlens. Forming method.

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 imaging element is generally provided with interlayer insulation when insulating wirings arranged in layers. membrane. When a material for forming an interlayer insulating film is extremely small in order to obtain a necessary pattern shape, it is required to have sufficient flatness. Therefore, a radiation-sensitive resin composition is widely used (refer to Japanese Laid-Open Patent Publication No. 2001-354822 and JP-A-2001-343743).

In the above electronic component, for example, a TFT-type liquid crystal display device is exposed to a transparent electrode film on an interlayer insulating film, and is formed thereon by a step of forming a liquid crystal alignment film, and the interlayer insulating film is exposed to the transparent electrode film in the forming step. In the peeling liquid of the photoresist used when forming the electrode pattern under high temperature conditions, it is necessary to have sufficient resistance.

In addition, in the TFT type liquid crystal display device, in recent years, large-screen, high-brightness, high-definition, high-speed response, and thinning have been performed, and in order to meet the requirements for product handling property in the step, it is required to form interlayer insulation. The radiation-sensitive resin composition used in the film has high sensitivity, and the formed interlayer insulating film is required to have higher performance than conventional materials in terms of low dielectric constant, high light transmittance, and the like.

Further, as an optical system material of a junction optical system or a fiber contactor of a high-performance wafer filter such as a facsimile machine, an electronic photocopier, or a solid-state imaging device, a microlens having a lens diameter of about 3 to 100 μm in diameter is used. Or a microlens that is regularly arranged.

The method of forming a microlens is to form a pattern-like film of a corresponding lens, and then melt-flow by heat treatment, directly using a method as a lens, or using a melt-flowing lens pattern as a mask, and performing transfer on the bottom layer by dry etching. The method of the lens shape and the like are known. In the formation of the lens pattern, a radiation-sensitive resin composition can be widely used (refer to Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei.

Therefore, the radiation-sensitive resin composition used for forming the lens pattern is required to have high sensitivity, and the microlens formed therefrom is required to have a desired radius of curvature and has high heat resistance, high light transmittance, and the like.

Further, when the elements for forming the microlenses are supplied to various insulating films on the pads for removing the wiring forming portions, the planarizing film and the photoresist for etching are applied, and the radiation is irradiated through the reticle to be applied. After the photoresist for etching of the pad portion is removed, the planarization film or various insulating films are removed by etching to expose the pad portion. Therefore, the microlens must have solvent resistance, heat resistance, and the like in the coating forming step and the etching step of the planarizing film or the photoresist for etching.

In addition, the obtained interlayer insulating film or microlens is immersed in the developing solution between the pattern and the substrate when the developing time is longer than the optimum time in the developing step of forming the film, and the peeling is likely to occur, in order to avoid In the case of this development, the development time must be strictly controlled, and there is a problem in terms of product handling or productivity.

In addition, in order to improve the heat resistance or the surface hardness of the interlayer insulating film or the microlens, it is proposed to add a fluorinated fluorene as a sensible acid generator to the radiation sensitive resin composition of the raw material (see Japanese Patent Publication No. 2001-330953). When it is a radiation-sensitive resin composition, it is pointed out that the lanthanoid compound is toxic.

The radiation sensitive resin composition used in the formation of the interlayer insulating film or the microlens is required to have high sensitivity, and is required to be produced in the developing step even if the development time is longer than the predetermined time. In the case of peeling, and the formed interlayer insulating film is required to have high heat resistance, high solvent resistance, low dielectric constant, high light transmittance, and the like, in addition, when forming a microlens, it is required to have good as a microlens. The melted shape (required radius of curvature) is required to have high heat resistance, high solvent resistance, high light transmittance, etc., but a radiation-sensitive resin composition which can sufficiently satisfy the various requirements and has no safety problem It is unknown to the past.

The present invention has been invented on the basis of the above, and the first object of the present invention is to provide a problem of no safety, sensitivity, resolution, storage stability as a solvent, and the like, and even in the developing step, even if the optimum imaging time is exceeded. A radiation-sensitive resin composition capable of forming a good development tolerance of a good pattern shape.

A second object of the present invention is to provide a method of forming an interlayer insulating film having excellent solvent resistance, heat resistance, light transmittance, adhesion, and the like using the above-described radiation sensitive resin composition.

Further, a third object of the present invention is to provide a radiation-sensitive resin composition as described above, which can form both excellent solvent resistance, heat resistance, light transmittance, adhesion, and the like, and has a good melt shape. The method of microlens.

Another object and advantage of the present invention is as described below.

In view of the above objects and advantages of the present invention, the first object of the present invention is to provide a radiation sensitive resin composition characterized by containing at least one selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic anhydrides [A] (a1). a group of compounds, (a2) at least one compound selected from the group consisting of a compound represented by the following formula (1) and a compound represented by the following formula (2), (In the formula (1), R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ¹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ² , R ³ , R ⁴ and R ⁵ Each of them independently represents a hydrogen atom, a fluorine atom, an alkyl group having 1 to 4 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a perfluoroalkyl group having 1 to 4 carbon atoms, and n is an integer of 1 to 6) (In the formula (2), R, R ¹ , R ² , R ³ , R ⁴ and R ⁵ and n are the same as defined in the formula (1)) and (a3) has at least one member selected from tetrahydrofuran in the molecule. An unsaturated compound having a structure, a furan structure, a tetrahydropyran structure, a pyran structure, and a structure represented by the following formula (3) (In the formula (3), a copolymer in which R ⁶ represents a hydrogen atom or a methyl group, m represents an integer of 2 to 10), and a [B] 1,2-quinonediazide compound is obtained.

The above object and advantages of the present invention are the second method of forming an interlayer insulating film, which comprises the steps of: (1) forming the above-mentioned radiation-sensitive resin composition on a substrate in the following order: The step of coating the film, (2) the step of irradiating the radiation on at least part of the film, (3) the step of developing the film after the irradiation, and (4) the step of heating the film after the development.

The third object of the present invention is to provide a method for forming a microlens, which comprises the steps of: (1) forming a film of the above-mentioned radiation-sensitive resin composition on a substrate in the following order. The step of (2) at least partially irradiating the coated film with radiation, (3) the step of developing the film after the irradiation, and (4) the step of heating the film after the development are achieved.

[Best form for implementing the invention]

The invention will be described in detail below.

[A] copolymer

The [A] copolymer contained in the radiation sensitive resin composition of the present invention is (a1) at least one compound selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic anhydrides (hereinafter referred to as "unsaturated compounds". (a1)"), (a2) at least one compound selected from the group consisting of the compound represented by the above formula (1) and the compound represented by the above formula (2) (hereinafter referred to as "unsaturated compound (a2)" And (a3) an unsaturated compound having at least one structure selected from the group consisting of a tetrahydrofuran structure, a furan structure, a tetrahydropyran structure, a pyran structure, and a structure represented by the above formula (3) in the molecule (hereinafter referred to as It is a copolymer of "unsaturated compound (a3)").

The unsaturated compound (a1) is, for example, a monocarboxylic acid compound, a dicarboxylic acid compound, an acid anhydride of a dicarboxylic acid, a mono[(meth)acryloylhydroxyalkyl]ester of a polyvalent carboxylic acid, and a polymerization of a carboxyl group and a hydroxyl group at both terminals. Mono (meth) acrylate or the like.

The above monocarboxylic acid compound such as acrylic acid, methacrylic acid, crotonic acid, 2-propenylhydrazine hydroxyethyl succinic acid, 2-methylpropenyl hydroxyethyl succinic acid, 2-propenyl hydroxyethyl hexahydrophthalic acid, 2 - methacrylic acid hydroxyethyl hexahydrophthalic acid or the like; the above dicarboxylic acid compound such as maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid or the like; an acid anhydride of the above dicarboxylic acid such as the above An acid anhydride or the like of a dicarboxylic acid compound; a mono[(meth) propylene hydroxyalkyl] ester of the above polycarboxylic acid, such as succinic acid mono(2-propenyl hydroxyethyl ester), succinic acid mono(2-methyl propylene)醯hydroxyethyl ester), citric acid mono(2-propenylhydrazine hydroxyethyl ester), decanoic acid mono(2-methylpropenyl hydroxyethyl ester), etc.; a single polymer having a carboxyl group and a hydroxyl group at both ends Methyl) acrylate, for example, ω-carboxypolycaprolactone monoacrylate, ω-carboxypolycaprolactone monomethacrylate, and the like.

Among these unsaturated compounds (a1), acrylic acid, methacrylic acid, maleic anhydride, and the like are preferred in terms of copolymerization reactivity, solubility in an aqueous alkali solution, and ease of availability.

The above unsaturated compound (a1) may be used singly or in combination of two or more kinds.

In the [A] polymer, the content of the repeating unit derived from the unsaturated compound (a1) is preferably from 5 to 60% by weight, more preferably from 10 to 50% by weight, most preferably from 15 to 40% by weight. By setting the content in this range, the solubility of the obtained composition in the alkali developing solution can be controlled to a more appropriate range.

The unsaturated compound (a2) is at least one compound selected from the group consisting of a compound represented by the following formula (1) and a compound represented by the following formula (2).

(In the formula (1), R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ¹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ² , R ³ , R ⁴ and R ⁵ Each of them independently represents a hydrogen atom, a fluorine atom, an alkyl group having 1 to 4 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a perfluoroalkyl group having 1 to 4 carbon atoms, and n is an integer of 1 to 6) (In the formula (2), R, R ¹ , R ² , R ³ , R ⁴ and R ⁵ and n are the same as defined in the formula (1)) in the above formulas (1) and (2), R And R ¹ , R ² , R ³ , R ⁴ and R ^{5 have} an alkyl group having 1 to 4 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, and 2-butyl, 3-butyl, and the like.

Further, the carbon number of R ² , R ³ , R ⁴ and R ⁵ is 6 to 20, such as a phenyl group or a tolylylene group. Further, R ² , R ³ , R ⁴ and R ⁵ have a perfluoroalkyl group having 1 to 4 carbon atoms, such as trifluoromethyl, pentafluoroethyl, heptafluoro-n-propyl, heptafluoroisopropyl, and nin. Fluoranyl butyl, nonafluoroisobutyl, nonafluoro 2-butyl, nonafluoro-3-butyl and the like.

a compound represented by the above formula (1), for example, 3-(propylene hydroxymethyl) oxetane, 3-(propylene hydroxymethyl)-2-methyl oxetane, 3-(propylene醯Hydroxymethyl)-3-ethyloxetane, 3-(propylene hydroxymethyl)-2-trifluoromethyl oxetane, 3-(acrylo hydroxymethyl)-2- Pentafluoroethyl oxetane, 3-(propylene hydroxymethyl)-2-phenyl oxetane, 3-(propylene hydroxymethyl)-2,2-difluorooxetane Alkane, 3-(polypropylene hydroxymethyl)-2,2,4-trifluorooxetane, 3-(propylene hydroxymethyl)-2,2,4,4-tetrafluorooxetane Alkane, 3-(2-propenylhydrazine hydroxyethyl)oxetane, 3-(2-propenylhydrazine hydroxyethyl)-2-ethyloxetane, 3-(2-propenylhydrazine) 3-ethyloxetane, 3-(2-propenylhydrazinohydroxyethyl)-2-trifluoromethyloxetane, 3-(2-propenylhydrazine hydroxyethyl)-2 - pentafluoroethyl oxetane, 3-(2-propenyl hydroxyethyl)-2-phenyl oxetane, 3-(2-propenyl hydroxyethyl)-2,2-di Fluorooxane Alkane, 3-(2-propenylhydrazine hydroxyethyl)-2,2,4-trifluorooxetane, 3-(2-propenylhydrazine hydroxyethyl)-2,2,4,4-tetrafluoro Acrylate such as oxetane; 3-(methacryl oxime hydroxymethyl) oxetane, 3-(methacryl oxime hydroxymethyl)-2-methyl oxetane, 3 -(methacrylofluorene hydroxymethyl)-3-ethyloxetane, 3-(methacryl oxime hydroxymethyl) 2-trifluoromethyloxetane, 3-(methacryl醯Hydroxymethyl)-2-pentafluoroethyl oxetane, 3-(methacryl oxime hydroxymethyl)-2-phenyl oxetane, 3-(methacryl oxime hydroxymethyl )-2,2-difluorooxetane, 3-(methacrylofluorene hydroxymethyl)-2,2,4-trifluorooxetane, 3-(methacryl oxime hydroxymethyl) -2,2,4,4-tetrafluorooxetane, 3-(2-methylpropenylhydroxyethyl)oxetane, 3-(2-methylpropene hydroxyethyl) 2-ethyloxetane, 3-(2-methylpropenylhydroxyethyl)-3-ethyloxetane, 3-(2-methylpropenylhydroxyethyl)-2 -trifluoromethyloxane Alkane, 3-(2-methylpropenyl hydroxyethyl)-2-pentafluoroethyl oxetane, 3-(2-methylpropenyl hydroxyethyl)-2-phenyl oxetane Alkane, 3-(2-methylpropenylhydroxyethyl)-2,2-difluorooxetane, 3-(2-methylpropenylhydroxyethyl)-2,2,4-trifluoro A methacrylate or the like such as oxetane or 3-(2-methylpropene hydroxyethyl)-2,2,4,4-tetrafluorooxetane.

a compound represented by the above formula (2), for example, 2-(acryloyloxymethyl)oxetane, 2-(acryloylhydroxymethyl)-2-methyloxetane, 2-( Propylene hydrazine hydroxymethyl)-3-methyloxetane, 2-(propylene hydrazine hydroxymethyl)-4-methyl oxetane, 2-(propylene hydroxymethyl)-2-tri Fluoromethyl oxetane, 2-(propylene hydroxymethyl)-3-trifluoromethyl oxetane, 2-(propylene hydroxymethyl)-4-trifluoromethyl oxane Butane, 2-(acrylofluorene hydroxymethyl)-2-pentafluoroethyl oxetane, 2-(propylene hydroxymethyl)-3-pentafluoroethyl oxetane, 2-( Propylene hydrazine hydroxymethyl)-4-pentafluoroethyl oxetane, 2-(propylene hydroxymethyl)-2-phenyl oxetane, 2-(propylene hydroxymethyl)-3 -phenyloxetane, 2-(propylene hydroxymethyl)-4-phenyloxetane, 2-(propylene hydroxymethyl)-2,3-difluorooxetane , 2-(propylene hydrazine hydroxymethyl)-2,4-difluorooxetane, 2-(propylene hydroxymethyl)-3,3-difluorooxetane, 2 -(Propane hydroxymethyl)-3,4-difluorooxetane, 2-(propylene hydroxymethyl)-4,4-difluorooxetane, 2-(acryloyloxymethyl) -3,3,4-trifluorooxetane, 2-(propylene hydroxymethyl)-3,4,4-trifluorooxetane, 2-(propylene hydroxymethyl) -3,3,4,4-tetrafluorooxetane, 2-(2-propenylhydrazine hydroxyethyl)oxetane, 2-[2-(2-methyloxetane) Ethyl methacrylate, 2-[2-(3-methyloxetane)]ethyl methacrylate, 2-(propylene hydroxyethyl)-2-methyl oxetane Alkane, 2-(2-propenylhydrazine hydroxyethyl)-4-methyloxetane, 2-(2-propenylhydrazine hydroxyethyl)-2-trifluoromethyloxetane, 2- (2-propenylhydrazine hydroxyethyl)-3-trifluoromethyloxetane, 2-(2-propenylhydrazine hydroxyethyl)-4-trifluoromethyloxetane, 2-(2 - propylene hydroxyethyl)-2-pentafluoroethyl oxetane, 2-(2-propenyl hydroxyethyl)-3-pentafluoroethyl oxetane, 2-(2-propene Hydrazine hydroxyethyl)-4-pentafluoroethyl oxalate Cyclobutane, 2-(2-propenylhydrazine hydroxyethyl)-2-phenyloxetane, 2-(2-propenyl hydroxyethyl)-3-phenyl oxetane, 2- (2-propenylhydrazine hydroxyethyl)-4-phenyloxetane, 2-(2-propenylhydrazineethyl)-2,3-difluorooxetane, 2-(2-propene醯Hydroxyethyl)-2,4-difluorooxetane, 2-(2-propenyl hydroxyethyl)-3,3-difluorooxetane, 2-(2-propenylhydrazine Ethyl)-3,4-difluorooxetane, 2-(2-propenylhydrazinohydroxyethyl)-4,4-difluorooxetane, 2-(2-propenylhydrazine hydroxyethyl -3,3,4-trifluorooxetane, 2-(2-propenylhydroxyethyl)-3,4,4-trifluorooxetane, 2-(2-propenylhydrazine Acrylates such as ethyl)-3,3,4,4-tetrafluorooxetane; 2-(methacrylofluorene hydroxymethyl)oxetane, 2-(methacryloquinonehydroxyl) 2-methyloxetane, 2-(methylpropenyl hydroxymethyl)-3-methyloxetane, 2-(methacryloquinone hydroxymethyl)-4-methyl Oxycyclobutane, 2-(methacryloquinone) Methyl)-2-trifluoromethyl oxetane, 2-(methacryl oxime hydroxymethyl)-3-trifluoromethyl oxetane, 2-(methacryl oxime hydroxyl group 4-trifluoromethyloxetane, 2-(methacrylofluorene hydroxymethyl)-2-pentafluoroethyl oxetane, 2-(methacryl oxime hydroxymethyl) -3-pentafluoroethyl oxetane, 2-(methacryl oxime hydroxymethyl)-4-pentafluoroethyl oxetane, 2-(methacryl oxime hydroxymethyl)-2 -phenyloxetane, 2-(methacrylofluorenylhydroxymethyl)-3-phenyloxetane, 2-(methacryloquinonehydroxymethyl)-4-phenyloxyheterocycle Butane, 2-(methacrylofluorene hydroxymethyl)-2,3-difluorooxetane, 2-(methacryl oxime hydroxymethyl)-2,4-difluorooxetane , 2-(methacrylofluorene hydroxymethyl)-3,3-difluorooxetane, 2-(methacryl oxime hydroxymethyl)-3,4-difluorooxetane, 2 -(methacrylofluorene hydroxymethyl)-4,4-difluorooxetane, 2-(methacryl oxime hydroxymethyl)-3,3,4-trifluorooxetane, 2 -(methyl Propylene hydrazine hydroxymethyl)-3,4,4-trifluorooxetane, 2-(methacryl oxime hydroxymethyl)-3,3,4,4-tetrafluoro oxetane, 2-(2-Methylacryloylhydrazine hydroxyethyl)oxetane, 2-[2-(2-methyloxetanyl)]ethyl methacrylate, 2-[2-(3 -methyloxetanyl)]ethyl methacrylate, 2-(2-methylpropenylhydroxyethyl)-2-methyloxetane, 2-(2-methylpropene醯Hydroxyethyl)-4-methyloxetane, 2-(2-methylpropenylhydroxyethyl)-2-trifluoromethyloxetane, 2-(2-methylpropene醯Hydroxyethyl)-3-trifluoromethyloxetane, 2-(2-methylpropenylhydroxyethyl)-4-trifluoromethyloxetane, 2-(2-A Acrylhydrazine hydroxyethyl)-2-pentafluoroethyl oxetane, 2-(2-methylpropenylhydroxyethyl)-3-pentafluoroethyl oxetane, 2-(2 -Methyl propylene hydroxyethyl)-4-pentafluoroethyl oxetane, 2-(2-methylpropenyl hydroxyethyl)-2-phenyl oxetane, 2-(2 -methacryl oxime hydroxyethyl )-3-phenyloxetane, 2-(2-methylpropenylhydroxyethyl)-4-phenyloxetane, 2-(2-methylpropene hydroxyethyl)- 2,3-Difluorooxetane, 2-(2-methylpropenylhydroxyethyl)-2,4-difluorooxetane, 2-(2-methylpropene hydroxyethyl) -3,3-difluorooxetane, 2-(2-methylpropenylhydroxyethyl)-3,4-difluorooxetane, 2-(2-methylpropene oxime Ethyl)-4,4-difluorooxetane, 2-(2-methylpropenylhydroxyethyl)-3,3,4-trifluorooxetane, 2-(2-methyl Acrylhydrazine hydroxyethyl)-3,4,4-trifluorooxetane, 2-(2-methylpropenylhydroxyethyl)-3,3,4,4-tetrafluorooxetane A methacrylate such as an alkane or the like.

In the unsaturated compound (a2), 3-(methyl) is used in view of the wide tolerance of the radiation-sensitive resin composition obtained and the improvement of the chemical resistance of the obtained interlayer insulating film and microlens. Propylene hydrazine hydroxymethyl)oxetane, 3-(methacryl oxime hydroxymethyl)-3-ethyloxetane, 3-(methacryl oxime hydroxymethyl)-2-trifluoro Methyl oxetane, 3-(methacryl oxime hydroxymethyl)-2-phenyl oxetane, 2-(methacryl oxime hydroxymethyl) oxetane, 2-( Methyl propylene hydroxymethyl)-4-trifluoromethyl oxetane or the like is preferred.

These unsaturated compounds (a2) may be used alone or in combination of two or more.

The content ratio of the constituent unit derived from the unsaturated compound (a2) in the copolymer is preferably from 5 to 60% by weight, more preferably from 10 to 50% by weight. By the content of the range, the storage stability of the composition and the balance between the heat resistance of the obtained interlayer insulating film or the microlens can be further improved.

The unsaturated compound (a3) is an unsaturated group having at least one structure selected from the group consisting of a tetrahydrofuran structure, a furan structure, a tetrahydropyran structure, a pyran structure, and a structure represented by the following formula (3) in the molecule. Compound.

(In the formula (3), R ⁶ represents a hydrogen atom or a methyl group, and m represents an integer of 2 to 10).

Specific examples of the unsaturated compound (a3), an unsaturated compound having a tetrahydrofuran structure, such as tetrahydrofuranyl (meth) acrylate, 2-methylpropenyl hydroxy-propionic acid tetrahydrofuran ester, (meth)acrylic acid tetrahydrofuran-3- An ester or the like; an unsaturated compound having a furan structure, such as 2-methyl-5-(3-furyl)-1-penten-3-one, mercapto (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, 2-furan-2-yl-1-methyl-ethyl acrylate, 6-(2-furanyl) -6-methyl-1-hepten-3-one, etc.; an unsaturated compound having a tetrahydropyran structure, such as (tetrahydropyran-2-yl)methyl methacrylate, 2,6-di Methyl-8-(tetrahydropyran-2-ylhydroxy)-oct-1-en-3-one, 2-tetrahydropyran-2-yl methacrylate, 1-(tetrahydropyran-2 -hydroxy)-butyl-3-en-2-one, etc.; Unsaturated compounds such as 4-(1,4-dioxo-5carbonyl-6-heptenyl)-6-methyl-2-pyrrole, 4-(1,5-dioxo-6-carbonyl-7 - octenyl)-6-methyl-2-pyrrole or the like; an unsaturated compound having a structure represented by the above formula (3), each of which is represented by the following formulas (4) to (6).

(In the formulae (4) to (6), R ⁷ each independently represents a hydrogen atom or a methyl group, and a of the formula (4) and the formula (5) each independently represents an integer of 2 to 10, and the formula (6) The a is an integer from 3 to 10.)

Among these, tetrahydroindenyl (meth) acrylate, tetrahydrofuran-3-(meth) acrylate, 1-(tetrahydropyran-2- oxidized)- Butyl-3-en-2-one, mercapto (meth) acrylate, a compound represented by the above formula (4), and the like are preferred. These may be used alone or in combination of two or more.

The content of the repeating unit derived from the unsaturated compound (a3) in the copolymer is preferably from 3 to 50% by weight, more preferably from 5 to 40% by weight. By the content in this range, the developability of the composition can be further improved.

The [A] polymer may optionally contain, in addition to the above repeating units of the unsaturated compounds (a1), (a2) and (a3), different from the above unsaturated compounds (a1), (a2) and (a3). The repeating unit of the other olefin-based unsaturated compound (a4) (hereinafter referred to as "unsaturated compound (a4)". The unsaturated compound (a4) is limited to the above unsaturated compounds (a1), (a2), (a3). The copolymerizer is not particularly limited, and is, for example, an alkyl acrylate, an alkyl methacrylate, a cyclic alkyl acrylate, a cyclic alkyl methacrylate, an aryl acrylate, an aryl methacrylate, an unsaturated dicarboxylic acid. Acid diesters, hydroxyalkyl acrylates, hydroxyalkyl methacrylates, bicyclic unsaturated compounds, unsaturated dicarbonyl quinone imine derivatives, styrene and its derivatives, and other unsaturated compounds.

The above alkyl acrylates such as methacrylate, ethacrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, 2-butyl acrylate, 3-butyl acrylate, etc. The above alkyl methacrylate such as methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, 2-butyl methacrylate , 3-butyl methacrylate, etc.; a cyclic alkyl ester of the above acrylic acid such as cyclohexyl acrylate, 2-methylcyclohexyl acrylate, tricyclo [5.2.1.0 ^{2 . 6} ] decane-8-yl acrylate Ester (hereinafter referred to as "dicyclopentyl acrylate"), 2-dicyclopentyloxyethyl acrylate, isobornyl acrylate, etc.; a cyclic alkyl ester of methacrylic acid such as cyclohexyl methacrylate 2-methylcyclohexyl methacrylate, tricyclo[5.2.1.0 ^{2 . 6} ]decane-8-yl methacrylate (hereinafter referred to as "dicyclopentyl methacrylate"), 2- Dicyclopentyloxyethyl methacrylate, isobornyl methacrylate, etc.; The aryl acrylates such as phenyl acrylate, phenyl methacrylate, etc.; the above aryl methacrylates such as phenyl methacrylate, benzyl methacrylate, etc.; the above unsaturated dicarboxylic acid diester For example, diethyl maleate, diethyl fumarate, diethyl itaconate, etc.; the above hydroxyalkyl acrylates such as hydroxymethyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl Acrylate 2-hydroxyethyl methacrylate, 3-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, diethylene glycol monomethacrylate, 2,3-dihydroxypropyl a acrylate, a 2-methacryloxyethyl glycoside or the like; the above hydroxyalkyl methacrylate such as 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, etc.; the above bicyclic unsaturated Compounds such as bicyclo[2.2.1]hept-2-ene, 5-methylbicyclo[2.2.1]hept-2-ene, 5-ethylbicyclo[2.2.1]hept-2-ene, 5-hydroxyl Bicyclo[2.2.1]hept-2-ene, 5-carboxybicyclo[2.2.1]hept-2-ene, 5-hydroxymethylbicyclo[2.2.1] 2-ene, 5-(2-hydroxyethyl)bicyclo[2.2.1]hept-2-ene, 5-methoxybicyclo[2.2.1]hept-2-ene, 5-ethoxybicyclo[ 2.2.1] hept-2-ene, 5,6-dihydroxybicyclo[2.2.1]hept-2-ene, 5,6-di(hydroxymethyl)bicyclo[2.2.1]hept-2-ene, 5,6-bis(2-hydroxyethyl)bicyclo[2.2.1]hept-2-ene, 5,6-dimethoxybicyclo[2.2.1]hept-2-ene, 5,6-diethyl Oxybicyclo[2.2.1]hept-2-ene, 5-hydroxy-5-methylbicyclo[2.2.1]hept-2-ene, 5-hydroxy-5-ethylbicyclo[2.2.1]heptane- 2-ene, 5-hydroxymethyl-5-methylbicyclo[2.2.1]hept-2-ene, 5-tert-butoxycarbonylbicyclo[2.2.1]hept-2-ene, 5-ring Hexyloxycarbonylbicyclo[2.2.1]hept-2-ene, 5-phenoxycarbonylbicyclo[2.2.1]hept-2-ene, 5,6-di(3-butoxycarbonyl)bicyclo[ 2.2.1] hept-2-ene, 5,6-di(cyclohexyloxycarbonyl)bicyclo[2.2.1]hept-2-ene, etc.; the above unsaturated dicarbonyl quinone imine derivatives such as N-benzene Kamalyimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-ammonium imine 3-maleimide benzoate, N-succinimide 4-maleimine butyrate, N-succinimide-6-maleimide caproate, N - amber imino-3-maleimide propionate, N-(9-acridinyl)maleimide, etc.; the above styrene and its derivatives such as styrene, α-methyl Styrene, m-methylstyrene, p-methylstyrene, m-vinyltoluene, p-vinyltoluene, p-methoxystyrene, etc.; other unsaturated compounds such as acrylonitrile, methyl Acrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, vinyl acetate, 1,3-butadiene, isoamylene, 2,3-dimethyl-1, 3-butadiene, glycidyl acrylate, glycidyl methacrylate, α-ethyl acrylate propyl acrylate, α-n-propyl propylene acrylate, α-n-butyl acrylate propylene Ester, 3,4-epoxybutyl acrylate, 3,4-epoxybutyl methacrylate, 3,4-epoxybutyl α-ethyl acrylate, acrylate-6,7- Epoxyheptyl ester, methyl -6,7-epoxyheptyl acrylate, α-ethyl acrylate-6,7-epoxyheptyl ester, o-vinyl benzyl epoxypropyl ether, m-vinyl benzyl epoxide Ether, p-vinylbenzyl glycidyl ether and the like.

In the unsaturated compound (a4), the copolymerization reactivity and the solubility of the obtained [A] copolymer in an aqueous alkali solution are, for example, 3-butyl methacrylic acid or 2-methylcyclohexyl acrylate. Dicyclopentyl methacrylate, bicyclo[2.2.1]hept-2-ene, N-phenylmaleimide, N-cyclohexylmaleimide, styrene, p-methoxystyrene , 1,3-butadiene, glycidyl methacrylate, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl epoxy Propyl ether and the like are preferred.

The above unsaturated compound (a4) may be used singly or in combination of two or more kinds.

The content ratio of the constituent unit derived from the unsaturated compound (a4) in the copolymer is preferably 80% by weight or less, more preferably 10 to 80% by weight, still more preferably 20 to 70% by weight. By the content of the range, the storage stability of the obtained composition and the solubility in the alkali developing solution can be controlled to a more appropriate range.

The preferred [A] copolymer in the present invention, more specifically, for example, at least one unsaturated compound (a1) selected from the group consisting of acrylic acid, methacrylic acid and maleic anhydride, and at least one selected from the group consisting of 3-(A) Acrylhydrazine hydroxymethyl)oxetane, 3-(methylpropenyl hydroxymethyl)-3-ethyloxetane, 3-(methacryloquinone hydroxymethyl)-2-tri Fluorinated methyloxetane, 3-(methacrylofluorenylhydroxymethyl)-2-phenyloxetane, 2-(methacryloquinonehydroxymethyl)oxetane and 2 - an unsaturated compound (a2) in groups of (methacrylofluorene hydroxymethyl)-4-trifluoromethyloxetane, and at least one selected from the group consisting of tetrahydroindenyl (meth) acrylate, Methyl)propionic acid tetrahydrofuran-3-ester, 1-(tetrahydropyran-2-oxo)-butyl-3-en-2-one, mercapto (meth) acrylate and the above formula (4) The unsaturated compound (a3) in groups of compounds shown, and at least one selected from the group consisting of 3-butyl methacrylate, 2-methylcyclohexyl acrylate, dicyclopentyl methacrylate, bicyclo [2.2. 1]hept-2-ene, N-phenyl Maleidin, N-cyclohexylmaleimide, styrene, p-methoxystyrene, 1,3-butadiene, glycidyl methacrylate, o-vinylbenzyl a copolymer of an unsaturated compound (a4) in the group consisting of glycidyl ether, m-vinylbenzyl glycidyl ether and p-vinylbenzyl glycidyl ether.

[A] The polystyrene-equivalent weight average molecular weight of the copolymer (hereinafter referred to as "Mw"), preferably 1 x 10 ³ to 5 x ^{10 5} , more preferably 3 x 10 ³ to 3 x 10 ⁵ , and most preferably ⁵ x 10 ³ to 1 x 10 ⁵ .

In addition, the molecular weight distribution defined by the ratio (Mw/Mn) of the Mw of the [A] copolymer to the polystyrene-equivalent number average molecular weight (hereinafter referred to as "Mn") is preferably 5.0 or less, and more preferably 1.0~3.0.

The radiation-sensitive resin composition containing the [A] copolymer having the Mw and Mw/Mn does not cause development residue or film edge reduction during development, and it is extremely easy to form a pattern having a predetermined shape.

[A] The copolymer has at least one carboxyl group and a carboxylic anhydride group, and an oxetane structure, and has an appropriate solubility to an aqueous alkali solution, and can be easily hardened by heating even if a special hardener is not used in combination. . Further, the radiation sensitive linear resin composition containing the [A] copolymer can form a film of a predetermined pattern without causing development residue or film edge reduction during development.

The [A] copolymer may be used singly or in combination of two or more.

As described above, the [A] copolymer can be obtained by using the unsaturated compound (a1), the unsaturated compound (a2), and the unsaturated compound (a3), and the unsaturated compound (a4) as required, in a suitable solvent. The polymerization is carried out in the presence of a medium or a radical polymerization initiator.

The solvent used in the above polymerization, for example, alcohol, ether, glycol ether, ethylene glycol alkyl ether acetate, diethylene glycol ether, propylene glycol ether, propylene glycol alkyl ether acetate, propylene glycol alkyl ether propionate, aromatic Hydrocarbons, ketones, esters, and the like.

The above alcohols are, for example, methanol, ethanol, benzyl alcohol, 2-phenylethanol, 3-phenyl-1-propanol, etc.; ethers such as tetrahydrofuran, etc.; glycol ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, etc. ; ethylene glycol alkyl ether acetate such as ethylene glycol methyl ether acetate, ethylene glycol ether acetate, ethylene glycol n-propyl ether acetate, ethylene glycol n-butyl ether acetate, etc.; diethylene glycol Ethers such as diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, etc.; propylene glycol ether such as propylene glycol monomethyl ether, Propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether, etc.; propylene glycol alkyl ether acetate such as propylene glycol methyl ether acetate, propylene glycol diethyl ether acetate, propylene glycol n-propyl ether acetate, propylene glycol n-butyl ether An ester or the like; a propylene glycol alkyl ether propionate such as propylene glycol methyl ether propionate, propylene glycol diethyl ether propionate, propylene glycol n-propyl ether propionate, propylene glycol n-butyl ether propionate or the like; an aromatic hydrocarbon such as toluene, xylene, etc. Ketones such as methyl ethyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone Ester such as methyl acetate, ethyl acetate, n-propyl acetate, n-butyl acetate, methyl hydroxyacetate, ethyl hydroxyacetate, n-propyl hydroxyacetate, n-butyl hydroxyacetate, methyl lactate, ethyl lactate , n-propyl lactate, n-butyl lactate, methyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, n-propyl 3-hydroxypropionate, n-butyl 3-hydroxypropionate, 2-hydroxy-2 -methyl methacrylate, ethyl 2-hydroxy-2-methylpropionate, methyl 2-hydroxy-3-methylbutanoate, methyl methoxyacetate, ethyl methoxyacetate, methoxy N-propyl acetate, n-butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, n-propyl ethoxyacetate, n-butyl ethoxyacetate, n-propoxyacetate Ester, n-propoxyacetic acid ethyl ester, n-propoxyacetic acid n-propyl ester, n-propoxyacetic acid n-butyl ester, n-butoxyacetic acid methyl ester, n-butoxyacetic acid ethyl ester, n-butoxyacetic acid Propyl ester, n-butoxy n-butyl ester, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, n-propyl 2-methoxypropionate, 2-methoxypropionic acid Butyl ester, 2 -methyl ethoxypropionate, ethyl 2-ethoxypropionate, n-propyl 2-ethoxypropionate, n-butyl 2-ethoxypropionate, 2-n-propoxypropionic acid Ester, ethyl 2-n-propoxypropionate, n-propyl 2-n-propoxypropionate, n-butyl 2-n-propoxypropionate, methyl 2-n-butoxypropionate, 2- Ethyl n-butoxypropionate, n-propyl 2-n-butoxypropionate, n-butyl 2-n-butoxypropionate, methyl 3-methoxypropionate, 3-methoxypropionic acid Ethyl ester, n-propyl 3-methoxypropionate, n-butyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, 3-ethoxyl N-propyl propionate, n-butyl 3-ethoxypropionate, methyl 3-n-propoxypropionate, ethyl 3-n-propoxypropionate, n-propyl 3-n-propoxypropionate , n-butyl 3-n-propoxypropionate, methyl 3-n-butoxypropionate, ethyl 3-n-butoxypropionate, n-propyl 3-n-butoxypropionate, 3-positive N-butyl butoxypropionate and the like.

Among these solvents, ethylene glycol alkyl ether acetate, diethylene glycol ether, propylene glycol ether, propylene glycol alkyl ether acetate, etc. are preferred, especially diethylene glycol dimethyl ether, diethylene glycol. Ethyl methyl ether, propylene glycol monomethyl ether, and propylene glycol methyl ether acetate are preferred.

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

Further, a radical polymerization initiator used in the above polymerization, for example, 2,2'-azobisisobutyronitrile, 2,2'-azobis(2.4-dimethylvaleronitrile), 2,2'- An azo compound such as azobis(4-methoxy-2,4-dimethylvaleronitrile); benzhydryl peroxide, lauryl peroxide, butyl 3-peroxy valeric acid An organic peroxide such as an ester or 1,1'-bis(3-butylperoxy)cyclohexane; hydrogen peroxide or the like. When a peroxide is used as the radical polymerization initiator, the substance may be used together with a reducing agent as a redox type initiator.

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

Further, at the time of the above polymerization, a molecular weight modifier may be used in order to adjust the molecular weight of the [A] copolymer.

Specific examples of the molecular weight modifier include halogenated hydrocarbons such as chloroform and carbon tetrabromide; n-hexyl mercaptan, n-octyl mercaptan, n-dodecyl mercaptan, tert-dodecyl mercaptan, thioglycol, etc. a thiol; dimethyl ketone sulphate, di-isopropyl isopropyl sulphate or the like; or lignin, α-methyl styrene dimer, and the like.

These molecular weight modifiers may be used alone or in combination of two or more.

[B] 1,2-quinonediazide

The [B] 1,2-quinonediazide compound contained in the radiation sensitive resin composition of the present invention is a 1,2-quinonediazide compound which generates an acid by radiation irradiation, for example, 1,2- Benzoquinonediazide sulfonate, 1,2-naphthoquinonediazide sulfonate, 1,2-benzoquinonediazidesulfonium decylamine, 1,2-naphthoquinonediazidesulfonate decylamine, etc. .

1,2-naphthoquinonediazide sulfonate such as 1,2-naphthoquinonediazide sulfonate of trihydroxybenzophenone, 1,2-naphthoquinone quinone of tetrahydroxybenzophenone 1,5-naphthoquinonediazide sulfonate of sulfamate, pentahydroxybenzophenone, 1,2-naphthoquinonediazide sulfonate of hexahydroxybenzophenone, other (polyhydroxyl) 1,2-naphthoquinonediazide sulfonate of phenyl)alkane, and the like. Moreover, it is specifically, for example, a 1,2-naphthoquinonediazide sulfonate of trihydroxybenzophenone (e.g., 2,3,4-trihydroxybenzophenone-1,2-naphthoquinonediazide-4) -sulfonate, 2,3,4-trihydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonate, 2,3,4-trihydroxybenzophenone-1,2 -naphthoquinonediazide-6-sulfonate, 2,3,4-trihydroxybenzophenone-1,2-naphthoquinonediazide-7-sulfonate, 2,3,4-trihydroxyl Benzophenone-1,2-naphthoquinonediazide-8-sulfonate, 2,4,6-trihydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonate, 2,4,6-trihydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonate, 2,4,6-trihydroxybenzophenone-1,2-naphthoquinone Nitro-6-sulfonate, 2,4,6-trihydroxybenzophenone-1,2-naphthoquinonediazide-7-sulfonate, 2,4,6-trihydroxybenzophenone- 1,2-naphthoquinonediazide-8-sulfonate, etc.; 1,2-naphthoquinonediazide sulfonate of tetrahydroxybenzophenone, such as 2,2',4,4'-tetrahydroxyl Benzophenone-1,2-naphthoquinonediazide-4-sulfonate, 2,2',4,4'-tetrahydroxybenzophenone-1,2-naphthoquinone Diazide-5-sulfonate, 2,2',4,4'-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-6-sulfonate, 2,2',4, 4'-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-7-sulfonate, 2,2',4,4'-tetrahydroxybenzophenone-1,2-naphthoquinone Azide-8-sulfonate, 2,3,4,3'-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonate, 2,3,4,3'- Tetrahydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonate, 2,3,4,3'-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-6 -sulfonate, 2,3,4,3'-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-7-sulfonate, 2,3,4,3'-tetrahydroxydiphenyl Ketone-1,2-naphthoquinonediazide-8-sulfonate, 2,3,4,4'-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonate , 2,3,4,4'-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonate, 2,3,4,4'-tetrahydroxybenzophenone-1 , 2-naphthoquinonediazide-6-sulfonate, 2,3,4,4'-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-7-sulfonate, 2,3 , 4,4'-tetrahydroxybenzophenone-1, 2-naphthoquinonediazide-8-sulfonate, 2,3,4,2'-tetrahydroxy-4'-methylbenzophenone-1,2-naphthoquinonediazide-4-sulfonic acid Ester, 2,3,4,2'-tetrahydroxy-4'-methylbenzophenone-1,2-naphthoquinonediazide-5-sulfonate, 2,3,4,2'-tetra Hydroxy-4'-methylbenzophenone-1,2-naphthoquinonediazide-6-sulfonate, 2,3,4,2'-tetrahydroxy-4'-methylbenzophenone- 1,2-naphthoquinonediazide-7-sulfonate, 2,3,4,2'-tetrahydroxy-4'-methylbenzophenone-1,2-naphthoquinonediazide-8- Sulfonate, 2,3,4,4'-tetrahydroxy-3'-methoxybenzophenone-1,2-naphthoquinonediazide-4-sulfonate, 2,3,4,4 '-Tetrahydroxy-3'-methoxybenzophenone-1,2-naphthoquinonediazide-5-sulfonate, 2,3,4,4'-tetrahydroxy-3'-methoxy Benzophenone-1,2-naphthoquinonediazide-6-sulfonate, 2,3,4,4'-tetrahydroxy-3'-methoxybenzophenone-1,2-naphthoquinone Diazide-7-sulfonate, 2,3,4,4'-tetrahydroxy-3'-methoxybenzophenone-1,2-naphthoquinonediazide-8-sulfonate, and the like.

1,2-naphthoquinonediazide sulfonate of the above-mentioned pentahydroxybenzophenone, for example, 2,3,4,2',6'-pentahydroxybenzophenone-1,2-naphthoquinonediazide 4-sulfonate, 2,3,4,2',6'-pentahydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonate, 2,3,4,2' ,6'-pentahydroxybenzophenone-1,2-naphthoquinonediazide-6-sulfonate, 2,3,4,2',6'-pentahydroxybenzophenone-1,2- Naphthoquinonediazide-7-sulfonate, 2,3,4,2',6'-pentahydroxybenzophenone-1,2-naphthoquinonediazide-8-sulfonate, etc.; 1,2-naphthoquinonediazide sulfonate of hydroxybenzophenone, such as 2,4,6,3',4',5'-hexahydroxybenzophenone-1,2-naphthoquinone Nitro-4-sulfonate, 2,4,6,3',4',5'-hexahydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonate, 2,4, 6,3',4',5'-hexahydroxybenzophenone-1,2-naphthoquinonediazide-6-sulfonate, 2,4,6,3',4',5'-six Hydroxybenzophenone-1,2-naphthoquinonediazide-7-sulfonate, 2,4,6,3',4',5'-hexahydroxybenzophenone-1,2-naphthoquinone Diazide-8-sulfonate, 3,4,5,3',4 , 5'-hexahydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonate, 3,4,5,3',4',5'-hexahydroxybenzophenone-1 , 2-naphthoquinonediazide-5-sulfonate, 3,4,5,3',4',5'-hexahydroxybenzophenone-1,2-naphthoquinonediazide-6-sulfonate Acid ester, 3,4,5,3',4',5'-hexahydroxybenzophenone-1,2-naphthoquinonediazide-7-sulfonate, 3,4,5,3', 4',5'-hexahydroxybenzophenone-1,2-naphthoquinonediazide-8-sulfonate, etc.; 1,2-naphthoquinone quinone of the above other (polyhydroxyphenyl)alkane A sulfonate such as bis(2,4-dihydroxyphenyl)methane-1,2-naphthoquinonediazide-4-sulfonate, bis(2,4-dihydroxyphenyl)methane-1, 2-naphthoquinonediazide-5-sulfonate, bis(2,4-dihydroxyphenyl)methane-1,2-naphthoquinonediazide-6-sulfonate, bis(2,4-di Hydroxyphenyl)methane-1,2-naphthoquinonediazide-7-sulfonate, bis(2,4-dihydroxyphenyl)methane-1,2-naphthoquinonediazide-8-sulfonate , bis(4-hydroxyphenyl)methane-1,2-naphthoquinonediazide-4-sulfonate, bis(4-hydroxyphenyl)methane-1,2-naphthoquinonediazide -5-sulfonate, bis(4-hydroxyphenyl)methane-1,2-naphthoquinonediazide-6-sulfonate, bis(4-hydroxyphenyl)methane-1,2-naphthoquinone Azide-7-sulfonate, bis(4-hydroxyphenyl)methane-1,2-naphthoquinonediazide-8-sulfonate, ginseng(4-dihydroxyphenyl)methane-1,2- Naphthoquinonediazide-4-sulfonate, ginseng (4-dihydroxyphenyl)methane-1,2-naphthoquinonediazide-5-sulfonate, ginseng (4-dihydroxyphenyl)methane- 1,2-naphthoquinonediazide-6-sulfonate, ginseng (4-dihydroxyphenyl)methane-1,2-naphthoquinonediazide-7-sulfonate, ginseng (4-dihydroxybenzene) Methane-1,2-naphthoquinonediazide-8-sulfonate, 1,1,1-cis (4-dihydroxyphenyl)ethane-1,2-naphthoquinonediazide-4- Sulfonate, 1,1,1-gin(4-dihydroxyphenyl)ethane-1,2-naphthoquinonediazide-5-sulfonate, 1,1,1-cis (4-dihydroxyl) Phenyl)ethane-1,2-naphthoquinonediazide 6-sulfonate, 1,1,1-cis (4-dihydroxyphenyl)ethane-1,2-naphthoquinonediazide-7 -sulfonate, 1,1,1-cis (4-dihydroxyphenyl)ethane-1,2-naphthoquinonediazide-8-sulfonate, double ( 2,3,4-trihydroxyphenyl)methane-1,2-naphthoquinonediazide-4-sulfonate, bis(2,3,4-trihydroxyphenyl)methane-1,2-naphthoquinone Diazide-5-sulfonate, bis(2,3,4-trihydroxyphenyl)methane-1,2-naphthoquinonediazide-6-sulfonate, bis(2,3,4-tri) Hydroxyphenyl)methane-1,2-naphthoquinonediazide-7-sulfonate, bis(2,3,4-trihydroxyphenyl)methane-1,2-naphthoquinonediazide-8-sulfonate Acid ester, 2,2-bis(2,3,4-trihydroxyphenyl)propane-1,2-naphthoquinonediazide-4-sulfonate, 2,2-bis(2,3,4- Trihydroxyphenyl)propane-1,2-naphthoquinonediazide-5-sulfonate, 2,2-bis(2,3,4-trihydroxyphenyl)propane-1,2-naphthoquinone Nitro-6-sulfonate, 2,2-bis(2,3,4-trihydroxyphenyl)propane-1,2-naphthoquinonediazide-7-sulfonate, 2,2-dual (2 , 3,4-trihydroxyphenyl)propane-1,2-naphthoquinonediazide-8-sulfonate, 1,1,3-glycol (2,5-dimethyl-4-hydroxyphenyl) -3-phenylpropane-1,2-naphthoquinonediazide-4-sulfonate, 1,1,3-gin(2,5-dimethyl-4-hydroxyphenyl)-3-phenyl Propane-1,2-naphthoquinonediazide 5-sulfonate, 1,1,3-glycol (2,5-dimethyl-4-hydroxyphenyl)-3-phenylpropane-1,2-naphthoquinonediazide-6-sulfonate 1,1,3-glycol (2,5-dimethyl-4-hydroxyphenyl)-3-phenylpropane-1,2-naphthoquinonediazide-7-sulfonate, 1,1, 3-paraxyl (2,5-dimethyl-4-hydroxyphenyl)-3-phenylpropane-1,2-naphthoquinonediazide-8-sulfonate, 4,4'-[1-[ 4-[1-[4-Hydroxyphenyl]-1-methylethyl]phenyl]ethenyl]bisphenol-1,2-naphthoquinonediazide-4-sulfonate, 4,4' -[1-[4-[1-[4-hydroxyphenyl]-1-methylethyl]phenyl]ethenyl]bisphenol-1,2-naphthoquinonediazide-5-sulfonate 4,4'-[1-[4-[1-[4-Hydroxyphenyl]-1-methylethyl]phenyl]ethylidene]bisphenol-1,2-naphthoquinonediazide- 6-sulfonate, 4,4'-[1-[4-[1-[4-hydroxyphenyl]-1-methylethyl]phenyl]ethylidene]bisphenol-1,2-naphthalene Bismuth azide-7-sulfonate, 4,4'-[1-[4-[1-[4-hydroxyphenyl]-1-methylethyl]phenyl]ethylidene]bisphenol- 1,2-naphthoquinonediazide-8-sulfonate, bis(2,5-di 4-hydroxyphenyl)-2-hydroxyphenylmethane-1,2-naphthoquinonediazide-4-sulfonate, bis(2,5-dimethyl-4-hydroxyphenyl)-2 -hydroxyphenylmethane-1,2-naphthoquinonediazide-5-sulfonate, bis(2,5-dimethyl-4-hydroxyphenyl)-2-hydroxyphenylmethane-1,2- Naphthoquinonediazide-6-sulfonate, bis(2,5-dimethyl-4-hydroxyphenyl)-2-hydroxyphenylmethane-1,2naphthoquinonediazide-7-sulfonate , bis(2,5-dimethyl-4-hydroxyphenyl)-2-hydroxyphenylmethane-1,2-naphthoquinonediazide-8-sulfonate, 3,3,3',3' -tetramethyl-1,1'-rotating diterpene-5,6,7,5',6',7'-hexanol-1,2-naphthoquinonediazide-4-sulfonate, 3, 3,3',3'-tetramethyl-1,1'-rotating diterpene-5,6,7,5',6',7'-hexanol-1,2-naphthoquinonediazide-5 -sulfonate, 3,3,3',3'-tetramethyl-1,1'-rotating diterpene-5,6,7,5',6',7'-hexanol-1,2- Naphthoquinonediazide-6-sulfonate, 3,3,3',3'-tetramethyl-1,1'-rotating diterpene-5,6,7,5',6',7'- Hexanol-1,2-naphthoquinonediazide-7 Sulfonate, 3,3,3',3'-tetramethyl-1,1'-rotating diterpene-5,6,7,5',6',7'-hexanol-1,2-naphthalene Bismuth azide-8-sulfonate, 2,2,4-trimethyl-7,2',4'-trihydroxy xanthogen-1,2-naphthoquinonediazide-4-sulfonate, 2,2,4-trimethyl-7,2',4'-trihydroxy xanthine-1,2-naphthoquinonediazide-5-sulfonate, 2,2,4-trimethyl-7 , 2',4'-trihydroxy xanthine-1,2-naphthoquinonediazide-6-sulfonate, 2,2,4-trimethyl-7,2',4'-trihydroxy xanthogen -1,2-naphthoquinonediazide-7-sulfonate, 2,2,4-trimethyl-7,2',4'-trihydroxy xanthogen-1,2-naphthoquinonediazide- 8-sulfonate and the like.

The above-mentioned 1,2-benzoquinonediazidesulfonate is, for example, a compound in which 1,2-naphthoquinone of each of the above 1,2-naphthoquinonediazidesulfonate is substituted with 1,2-benzoquinone.

The above-mentioned 1,2-naphthoquinonediazidesulfonium sulfonate is, for example, a compound obtained by substituting a sulfonate of each of the above 1,2-naphthoquinonediazidesulfonate with a sulfonate decylamine.

The above-mentioned 1,2-benzoquinonediazidesulfonylamine, for example, substituted 1,2-naphthoquinone of each of the above 1,2-naphthoquinonediazide sulfonates with 1,2-benzoquinone, and The sulfonate is a compound substituted with decylamine sulfonate.

Among these 1,2-naphthoquinonediazide compounds, 2,2-bis(2,3,4-trihydroxyphenyl)propane-1,2-naphthoquinonediazide-5-sulfonate 1,1,3-glycol (2,5-dimethyl-4-hydroxyphenyl)-3-phenylpropane-1,2-naphthoquinonediazide-4-sulfonate or double (2, 5-Dimethyl-4-hydroxyphenyl)-2-hydroxyphenylmethane 1,2-naphthoquinonediazide-4-sulfonate is preferred.

The above-mentioned 1,2-quinonediazide compound may be used singly or in combination of two or more kinds.

The use ratio of the 1,2-quinonediazide compound in the radiation sensitive resin composition of the present invention is preferably 5 to 100 parts by weight, more preferably 10 to 50 parts by weight, per 100 parts by weight of the [A] copolymer. good. By using the ratio of the range, the pattern formation property, the development property, and the balance between the heat resistance and solvent resistance of the obtained interlayer insulating film or microlens can be improved.

Other ingredients

The radiation sensitive resin composition of the present invention contains the above-mentioned copolymers [A] and [B] as essential components, and other materials may contain [C] sensible acid generating compound, and [D] may have at least one ethylene. A polymerizable compound of an unsaturated double bond, [E] epoxy resin, [F] surfactant or [G] adhesion aid.

The above [C] sensible acid generating compound is used to improve the heat resistance or hardness of the formed interlayer insulating film or microlens. Specific examples thereof include sulfonium salts of sulfonium salts, benzothiazolium salts, ammonium salts, phosphonium salts and the like.

[C] A thermosensitive acid generating compound, among which a sulfonium salt and a benzothiazolium salt are preferably used.

Specific examples of the above sulfonium salt include an alkyl phosphonium salt, a benzyl hydrazine salt, a diphenylmethyl phosphonium salt, a substituted benzyl hydrazine salt, and the like, and a specific example of an alkyl phosphonium salt such as an alkyl sulfonium salt Bismuth phenyl dimethyl hexafluoroantimonate, bismuth 4-ethyl hydroxy phenyl dimethyl hexafluoro arsenate, bismuth dimethyl-4-(benzyloxycarbonyl hydroxy) phenyl hexafluoroantimonate Salt, dimethyl 4-(benzylidene hydroxy)phenyl hexafluoroantimonate strontium salt, dimethyl-4-(benzylidene hydroxy)phenyl hexafluoroarsenate bismuth salt, dimethyl-3- Chloro-4-ethenylhydroxyphenyl hexafluoroantimonate ruthenium salt; benzyl sulfonium salt such as benzyl-4-hydroxyphenylmethyl hexafluoroantimonate cesium salt, benzyl-4-hydroxyphenyl Bismuth methyl hexafluorophosphate, bismuth 4-ethyl hydroxyphenylbenzylmethyl hexafluoroantimonate, benzyl benzyl-4-methoxyphenylmethyl hexafluoroantimonate, benzyl -2--methyl 4-hydroxyphenylmethyl hexafluoroantimonate, benzyl-3-chloro-4-hydroxyphenylmethyl hexafluoroarsenate, 4-methoxybenzyl 4-hydroxyphenylmethyl hexafluorophosphate strontium salt; etc.; diphenylmethyl phosphonium salt such as diphenylmethyl-4 Hydroxyphenyl hexafluoroantimonate cerium salt, benzhydryl-4-hydroxyphenyl hexafluorophosphate cerium salt, 4-ethyl hydroxyphenyl diphenylmethyl hexafluoroantimonate cerium salt, diphenylmethyl-4 -Methoxyphenyl hexafluoroantimonate bismuth salt, benzhydryl-3-chloro-4-hydroxyphenyl hexafluoroarsenate bismuth salt, benzhydryl-3-methyl-4-hydroxy-5- Tertiary 3-butylphenyl hexafluoroantimonate, benzyl 4-methoxybenzyl-4-hydroxyphenyl hexafluorophosphate, and the like; substituted benzyl sulfonium salts such as p-chlorophenyl Base 4-hydroxyphenylmethyl hexafluoroantimonate, p-nitrobenzyl-4-hydroxyphenylmethyl hexafluoroantimonate, p-chlorobenzyl-4-hydroxyphenylmethyl Bismuth hexafluorophosphate, p-nitrobenzyl-3-methyl-4-hydroxyphenylmethyl hexafluoroantimonate, 3,5-dichlorobenzyl-4-hydroxyphenylmethyl Bismuth fluoroantimonate, o-chlorobenzyl-3-chloro-4-hydroxyphenylmethylhexafluoroantimonate, and the like.

Among the [C] sensitizing acid-forming compounds used herein, 4-ethyl hydroxyphenyl dimethyl hexafluoroarsenate cerium salt, benzyl-4-hydroxyphenylmethyl hexafluoroantimonate cerium salt is used. , 4-ethylhydrazine hydroxyphenylbenzylmethyl hexafluoroantimonate cerium salt, diphenylmethyl-4-hydroxyphenyl hexafluoroantimonate cerium salt, 4-ethyl hydroxyphenyl benzyl hexafluoroantimony The acid sulfonium salt and 3-benzyl benzothiazole hexafluoroantimonate are preferred.

Such commercially available products include, for example, Sainton SI-L85, the same SI-L110, the same SI-L145, the same SI-L150, and the same SI-L160 (Sanshin Chemical Industry Co., Ltd.).

The ratio of use of the heat-sensitive acid generating compound is preferably 20 parts by weight or less per 100 parts by weight of the [A] copolymer, more preferably 0.01 to 20 parts by weight, still more preferably 0.1 to 5 parts by weight. By using the amount in this range, the film formation property of the composition is not impaired, and the heat resistance and hardness of the formed interlayer insulating film and microlens can be further improved.

The above [D] is a polymerizable compound having at least one ethylenically unsaturated double bond (hereinafter referred to as "D" component), for example, a monofunctional (meth) acrylate, a bifunctional (meth) acrylate or a trifunctional or higher functional group. (Meth) acrylate.

The above monofunctional (meth) acrylates, such as 2-hydroxyethyl (meth) acrylate, carbitol (meth) acrylate, isobornyl (meth) acrylate, 3-methoxy butyl (Meth) acrylate, 2-(meth) propylene hydroxyethyl 2-hydroxypropyl phthalate, and the like. Such commercial products are, for example, Jalonigus M-101, M-111, M-114 (above is East Asia Synthetic Co., Ltd.), KAYARAD TC-110S, and TC-120S (above) It is made up of Nippon Kayaku Co., Ltd., Bisketon 158, and Twenty-three (the above is Osaka Organic Chemical Industry Co., Ltd.).

The above bifunctional (meth) acrylate such as ethylene glycol (meth) acrylate, 1,6-hexane diol di(meth) acrylate, 1,9-nonanediol di(meth) acrylate, Polypropylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, bisphenoxyethanol oxime diacrylate, bisphenoxyethanol oxime diacrylate, and the like. Such commercial products are, for example, Jalonigus M-210, M-240, M-6200 (above is East Asia Synthetic Co., Ltd.), KAYARAD HDDA, HX-220, and R-604 (above). It is manufactured by Nippon Chemical Co., Ltd., Bisketon 260, 312, and 335HP (above is Osaka Organic Chemical Industry Co., Ltd.).

The above-mentioned trifunctional or higher (meth) acrylate, for example, trimethylolpropane tri(meth) acrylate, pentaerythritol tri(meth) acrylate, tris((meth) propylene hydroxyethyl) phosphate, Pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, etc., and commercial products such as Jalonigus M-309, same M-400, same M-405, the same M-7100, the same M-8030, the same M-8060 (the above is East Asia Synthetic (stock) system), KAYARAD TMPTA, the same DPHA, the same DPCA-20, the same DPCA-30, the same DPCA-60, It is the same as DPCA-120 (the above is manufactured by Nippon Kayaku Co., Ltd.), Bisketon 295, the same 300, the same 360, the same GPT, the same 3PA, and the same 400 (the above is the Osaka Organic Chemical Industry Co., Ltd.).

Among these, it is preferred to use a trifunctional or higher (meth) acrylate, wherein trimethylolpropane tri(meth) acrylate, pentaerythritol tetra(meth) acrylate, dipentaerythritol hexa(a) Base) acrylate is preferred.

These monofunctional, bifunctional or trifunctional or higher functional (meth) acrylates may be used singly or in combination of two or more.

The ratio of use of the component [D] is preferably 50 parts by weight or less per 100 parts by weight of the [A] copolymer, more preferably 30 parts by weight or less.

By including the component [D] in this ratio, the film formation property of the composition is not affected, and the heat resistance, surface hardness, and the like of the obtained interlayer insulating film or microlens can be further improved.

The above [E] epoxy resin is not particularly limited as long as it does not affect the compatibility, and is preferably a bisphenol A type epoxy resin, a phenol novolac type epoxy resin, or a cresol novolak type ring. Oxygen resin, cyclic aliphatic epoxy resin, glycidyl ester epoxy resin, epoxy propylamine epoxy resin, heterocyclic epoxy resin, epoxypropyl methacrylate (co)polymerized resin, etc. Among these, a bisphenol A type epoxy resin, a cresol novolac type epoxy resin, a glycidyl ester type epoxy resin, and the like are used.

The use ratio of the [E] epoxy resin is preferably 30 parts by weight or less per 100 parts by weight of the [A] copolymer. By containing the component [E] in this ratio, the film formation property of the composition, particularly the film thickness uniformity, is not impaired, and the heat resistance and surface hardness of the obtained interlayer insulating film or microlens can be further improved.

Further, when an epoxy group-containing monomer is used as the copolymerizable monomer of the [A] copolymer, the [A] copolymer may also be referred to as "epoxy resin", but in terms of alkali solubility, [A] copolymer and The alkali-insoluble [E] epoxy resin is different.

As the above [F] surfactant, a fluorine-based surfactant, a polyoxyalkylene-based surfactant, and a nonionic surfactant can be used.

Specific examples of the fluorine-based surfactant are 1,1,2,2-tetrafluorooctyl (1,1,2,2-tetrafluoropropyl)ether, 1,1,2,2-tetrafluorooctyl hexyl ether. , octaethylene glycol di(1,1,2,2-tetrafluorobutyl)ether, hexaethylene glycol (1,1,2,2,3,3-hexafluoropentyl)ether, octapropylene glycol II ( 1,1,2,2-tetrafluorobutyl)ether, hexapropylene glycol bis(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, etc., and fluorinated alkylbenzenesulfonic acid Sodium; fluorinated alkyl oxyethylene ether; fluorinated alkyl ammonium iodide; fluorinated alkyl polyoxyethylene ether, perfluoroalkyl polyhydroxyethanol; perfluoroalkyl alkylate; fluoroalkyl ester.

Such commercial products such as BM-1000, BM-1100 (above BM Chemie), Mekafa Valley (transliteration) F142D, same as F172, same F173, same F183, same F178, same F191, same F471 ( The above is the Dainippon Ink Chemical Industry Co., Ltd., Floraton FC-170C, FC-171, FC-430, FC-431 (above Sumitomo 3M), Safir Long (transliteration) S-112, the same S-113, the same S-131, the same S-141, the same S-145, the same S-382, the same SC-101, the same SC-102, the same SC-103, the same SC -104, the same as SC-105, the same SC-106 (Asahi Glass Co., Ltd.), Yevtton (transliteration) EF301, the same 303, the same 352 (new Akita Chemical Co., Ltd.).

The polyoxyalkylene-based surfactants are, for example, commercially available DC3PA, DC7PA, FS-1265, SF-8428, SH11PA, SH21PA, SH28PA, SH29PA, SH30PA, SH-190, SH-193, and SZ-6032 (above Ray Taknin Valley (transliteration). Polyoxyalkylene (manufactured by the company), TSF-4440, TSF-4300, TSF-4445, TSF-4446, TSF-4460, TSF-4452 (above is GE Toshiba Poly The name of the product such as oxyalkylene (stock).

The above-mentioned nonionic surfactant such as polyoxyethylene alkyl ether such as polyoxyethylene lauryl ether, polyethylene oxide stearyl ether or polyethylene oxide oleyl ether; polyoxyethylene octylphenyl ether, poly(decidyl vinyl phenyl ether) Polyoxyethylene aryl ether; polyoxyethylene dialkyl ester such as polyoxyethylene dilaurate, polyoxyethylene distearate, etc.; (meth)acrylic copolymer polyfron (transliteration) No. 57, 95 (Kongrongsha Chemical Co., Ltd.) and so on.

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

The [F] surfactant is preferably 5 parts by weight or less, more preferably 2 parts by weight or less, per 100 parts by weight of the [A] copolymer.

The above [G] binder is preferably a functional decane coupling agent, for example, a decane coupling agent having a reactive substituent such as a carboxyl group, a methacryl group, an isocyanate group or an epoxy group. Specifically, for example, trimethoxymethane alkyl benzoic acid, γ-methyl propylene hydroxypropyl trimethoxy decane, vinyl triethylene hydroxy decane, vinyl trimethoxy decane, γ-isocyanate propyl triethyl Oxydecane, γ-glycidoxypropyltrimethoxydecane, β-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, and the like. The [G] binder is preferably 20 parts by weight or less, more preferably 10 parts by weight or less, per 100 parts by weight of the [A] copolymer.

Radiation-sensitive resin composition

The radiation sensitive resin composition of the present invention can be prepared by uniformly mixing the above [A] copolymer and [B] 1,2-quinonediazide compound and the above-mentioned optional components which can be arbitrarily added. The radiation sensitive resin composition of the present invention is preferably in a solution state dissolved in a suitable solvent. For example, the composition of the radiation-sensitive resin can be prepared by mixing the [A] copolymer and the [B] 1,2-quinonediazide compound and other components which can be arbitrarily added in a suitable ratio in a predetermined ratio. Things.

The solvent used in the preparation of the radiation sensitive resin composition of the present invention is such that the [A] copolymer and the [B] 1,2-quinonediazide compound and other components which can be arbitrarily added are uniformly dissolved, and Do not react with each component.

This solvent is, for example, the same as those exemplified for the solvent used in the polymerization when the above-mentioned [A] copolymer is produced.

In the solvent, alcohol, ethanol ether, ethylene glycol alkyl ether acetate, ester, and diethylene glycol are used in terms of solubility of each component, reactivity with each component, easiness of formation of a film, and the like. Preferably. Among these, benzyl alcohol, 2-phenylethanol, 3-phenyl-1-propanol, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, and diethylene glycol are used. Alcohol diethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol dimethyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, methyl methoxypropionate, ethyl ethoxy propionate good.

Further, in order to improve the in-plane uniformity of the solvent and the film thickness, a high boiling point solvent may be used in combination. High-boiling solvents which can be used in combination such as N-methylformamide, N,N-dimethylformamide, N-methyltoluidine, N-methylacetamide, N,N-dimethylacetamidine Amine, N-methylpyrrolidone, dimethyl hydrazine, benzyl ether, dihexyl ether, acetonitrile acetone, isophorone, hexanoic acid, heptanoic acid, 1-octanol, 1-nonanol, benzyl acetate Ester, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, phenyl cellosolve acetate, and the like. Among these, N-methylpyrrolidone, γ-butyrolactone, and N,N-dimethylacetamide are preferred.

When the solvent of the radiation sensitive resin composition of the present invention is used in a high boiling point solvent, the amount thereof is 50% by weight or less, preferably 40% by weight or less, and more preferably 30% by weight or less based on the total solvent. By using the amount in this range, the sensitivity of the composition and the residual film ratio are not impaired, and the film thickness uniformity (in-plane uniformity) of the film can be further improved.

When the radiation sensitive resin composition of the present invention is prepared into a solution state, components other than the solvent occupied by the solution (ie, [A] copolymer and [B] 1,2-quinonediazide compound and optionally added The ratio of the total amount of the other components may be arbitrarily set depending on the purpose of use or the desired film thickness value, and is preferably from 5 to 80% by weight. More preferably, the solid content concentration differs depending on the method of forming the film. The solid content concentration at the time of coating the film formation is preferably 15 to 35% by weight, and preferably 50 to 70% by weight when the film is formed by the ruthenium film method.

The prepared composition solution can be used after being filtered using a micropore filter having a pore diameter of about 0.2 to 0.5 μm.

The radiation sensitive resin composition of the present invention is particularly suitably used for the formation of an interlayer insulating film and a microlens.

Interlayer insulating film and method for forming microlens

The method for forming the interlayer insulating film of the present invention and the method for forming the microlens are the following steps including the procedure described below.

(1) a step of forming a film of a radiation-sensitive resin composition on a substrate, (2) a step of irradiating at least a part of the film with radiation, (3) a step of developing a film after the irradiation, and (4) The step of heating the film after development.

In the following, the steps related to these are explained.

(1) Step of forming a film of a radiation-sensitive resin composition on a substrate

This step is a step of forming a film of the radiation-sensitive resin composition by coating or transferring the radiation-sensitive resin composition of the present invention onto the surface of the substrate. When the radiation sensitive resin composition of the present invention contains a solvent, the solution composition can be coated or transferred onto the surface of the substrate, and then pre-baked to remove the solvent to form a film.

A substrate that can be used, such as a glass substrate, a germanium wafer, or a substrate on which various metal films are formed on the surface.

The coating method is not particularly limited, and for example, a suitable method such as a spray method, a roll coating method, a rotary coating method (spin coating method), a slit molding method, a rod coating method, an inkjet coating method, or the like is employed. In particular, it is more preferably a spin coating method or a slit mold coating method.

A transfer method such as a ruthenium film method.

When a ruthenium film is used to form a film of a radiation sensitive resin composition on a substrate, the ruthenium film is formed on a base film (preferably a flexible substrate film), and the radiation sensitive resin of the present invention is laminated. A radiation-sensitive layer formed by a composition (hereinafter referred to as a "radiosensitive linear film").

The radiation sensitive resin composition can be formed by applying a radiation sensitive resin composition of the present invention (preferably a liquid composition) to a base film, followed by drying, and laminating a radiation layer.

As the base film of the radiation-sensitive bismuth film, for example, a polyethylene terephthalate (PET) film, a synthetic resin film of polyethylene, polypropylene, polycarbonate, polyvinyl chloride or the like can be used. The thickness of the base film is preferably in the range of 15 to 125 μm.

The coating method for laminating the radiation sensitive layer on the base film is not particularly limited, and for example, a suitable method such as a thin layer coating method, a bar coating method, a roll coating method, a curtain flow coating method, or the like can be employed.

The prebaking conditions vary depending on the type of each component, the ratio of use, and the like, and are, for example, about 60 to 110 ° C for about 30 seconds to 15 minutes.

The film thickness of the formed film is, for example, about 3 to 6 μm when the interlayer insulating film is formed, and is preferably about 0.5 to 3 μm when the microlens is formed. Further, when the film thickness of the radiation sensitive resin composition of the present invention is a solvent-containing material, the value after solvent removal can be used.

(2) a step of irradiating radiation on at least part of the film (hereinafter referred to as "exposure")

In this step, exposure is performed on at least a portion of the formed film. When only a part of the film is exposed, it is usually exposed through a photomask having a predetermined pattern.

Radiation to be used for exposure, for example, ultraviolet rays such as g-line (wavelength: 436 nm), i-line (wavelength: 365 nm), far ultraviolet rays such as KrF excimer laser, X-rays such as synchrotron radiation, and charged particle lines such as electron beams. Among these, ultraviolet rays are preferred, and particularly radiation containing g-line and/or i-line is more preferable.

The exposure amount is, for example, about 50 to 3,000 J/m ² when the interlayer insulating film is formed, and is preferably about 50 to 5,000 J/m ² when the microlens is formed.

(3) Step of developing the film after irradiation

In this step, by exposing the film after exposure, the exposed portion is removed to form a predetermined pattern.

a developing solution used for development, such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium citrate, sodium methyl citrate, ammonium, ethylamine, n-propylamine, diethylamine, diethylamine ethanol, N-propylamine, triethylamine, methyldiethylamine, dimethylethanolamine, triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, pyrrole, piperidine, 1,8-diazabicyclo[5.4 .0] an aqueous solution of a base such as 7-undecene or 1,5-diazabicyclo[4.3.0]-5-decene (basic compound) is preferred, and may be used as needed. A variety of organic solvents in which the film of the radiation-linear resin composition is dissolved.

Further, an appropriate amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant may be added to the aqueous alkali solution.

The developing method may be a suitable method such as a liquid immersion method, a dipping method, a shaking dipping method, a rinsing method, or the like.

The development time varies depending on the type of each component or the ratio of use, and may be, for example, about 30 to 120 seconds.

Moreover, when the conventional radiation-sensitive resin composition exhibits a peeling condition in the formed pattern when the development time exceeds the optimum time by about 20 to 25 seconds, the development time must be strictly controlled, but the feeling of the present invention is When the linear resin composition is irradiated, a good pattern can be formed even when the optimum development time exceeds the optimum development time by about 30 seconds, which is extremely advantageous in terms of handleability or productivity of the radiation-sensitive resin composition.

(4) Step of heating the film after development

In this step, it is preferable that the film forming the predetermined pattern is subjected to a washing treatment by running water, for example, by subjecting the radiation of a high-pressure mercury lamp or the like to full exposure (post exposure), and remaining in the coating film. After the 1,2-quinonediazide compound is subjected to decomposition treatment, the coating film is subjected to heat treatment (post-baking) by a heating device such as a hot plate or an oven to be cured. Further, when the microlens is formed, the formed pattern is melted and flowed by post-baking to form a predetermined shape.

The exposure amount of the post exposure is preferably about 2,000 to 5,000 J/m ² .

Further, the heating temperature of the post-baking is, for example, about 120 to 250 °C. The heating time varies depending on the type of the heating machine, for example, about 5 to 30 minutes on a hot plate and about 30 to 90 minutes in an oven, for example. In this case, a segmented baking method or the like which performs heat treatment twice or more may be employed.

Thus, a pattern-like film of an interlayer insulating film or a microlens corresponding to the purpose can be formed on the surface of the substrate.

Interlayer insulating film and microlens

The interlayer insulating film and the microlens of the present invention are each preferably formed of the radiation sensitive resin composition of the present invention.

The interlayer insulating film of the present invention is extremely suitable for use in an electronic component of a TFT type liquid crystal display element, a magnetic head element, an integrated circuit element, and a solid-state imaging element.

Further, the shape of the microlens of the present invention is a good semi-convex lens shape. The microlens of the present invention and the microlens which are regularly arranged are suitably used as an optical system material for a junction optical system or a fiber optic contactor of a high performance wafer filter such as a facsimile machine, an electronic photocopier, or a solid-state imaging device.

As described above, the radiation sensitive resin composition of the present invention has excellent sensitivity and resolution, and has excellent storage stability as a composition solution, and can be formed even better than an optimum development time in the developing step. The good development tolerance of the pattern shape is particularly suitable for use as a microlens such as an interlayer insulating film and a solid-state imaging element of various electronic components.

Further, in the method for forming an interlayer insulating film of the present invention and the method for forming a microlens, even if the development time exceeds the optimum development time, a good pattern can be formed, and an interlayer insulating film having the above-described excellent characteristics can be easily formed. Microlens.

The interlayer insulating film of the present invention has excellent solvent resistance, heat resistance, light transmittance, adhesion, and the like, and has a low dielectric constant.

Further, the microlens of the present invention has excellent solvent resistance, heat resistance, light transmittance, adhesion, and the like, and has a good melt shape.

In the following, the present invention will be more specifically illustrated by the examples and comparative examples, but the present invention is not limited by the following examples.

Synthesis of copolymer Synthesis Example 1

In a flask equipped with a cooling tube and a stirrer, 7 parts by weight of 2,2'-azobis(2,4-dimethylvaleronitrile) and 220 parts by weight of propylene glycol methyl ether acetate were added. Then, 22 parts by weight of methacrylic acid, 28 parts by weight of dicyclopentyl methacrylate, 40 parts by weight of 3-(methacryl hydroxymethyl)-2-phenyloxetane, and 10 parts by weight are added. After tetrahydrofurfuryl methacrylate and 1.5 parts by weight of α-methylstyrene dimer, the mixture was replaced with nitrogen and stirring was started slowly, the temperature of the solution was raised to 70 ° C, and the temperature was maintained for 4 hours to be polymerized. A solution of the [A] copolymer (solid concentration: 33.8 wt%) was obtained.

The obtained [A] copolymer had Mw of 14,000 and Mw/Mn of 2.1. Further, Mw and Mn are polystyrene-converted average molecular weights measured by GPC (gel permeation chromatography) (HLC-8020, manufactured by Tosoh Corporation). The [A] copolymer is "copolymer (A-1)".

Synthesis Example 2

In a flask equipped with a cooling tube and a stirrer, 7 parts by weight of 2,2'-azobis(2,4-dimethylvaleronitrile) and 220 parts by weight of propylene glycol methyl ether acetate were added. Then, 5 parts by weight of styrene, 11 parts by weight of methacrylic acid, 45 parts by weight of 3-(methacrylic acid hydroxymethyl)-3-ethyloxetane, 5 parts by weight of styrene, and 10 parts by weight are added. After tetrahydrofurfuryl methacrylate and 1.5 parts by weight of α-methylstyrene dimer, the mixture was replaced with nitrogen and stirring was started slowly, the temperature of the solution was raised to 70 ° C, and the temperature was maintained for 4 hours to be polymerized. A solution of [A] copolymer (solid content concentration: 32.8 wt%) was obtained.

The obtained [A] copolymer had Mw of 22,000 and Mw/Mn of 2.1. The [A] copolymer is "copolymer (A-2)".

Synthesis Example 3

In a flask equipped with a cooling tube and a stirrer, 7 parts by weight of 2,2'-azobis(2,4-dimethylvaleronitrile) and 150 parts by weight of propylene glycol methyl ether acetate were added. Then, 5 parts by weight of styrene, 25 parts by weight of methacrylic acid, 20 parts by weight of N-cyclohexylmaleimide, and 35 parts by weight of 3-(methacryloquinone hydroxymethyl)-2-trifluoromethyl are added. Oxetane, 15 parts by weight of the compound represented by the above formula (4) (the average value of a in the formula is 2.2) and 1.5 parts by weight of the α-methylstyrene dimer, then replaced with nitrogen and slowly Stirring was started, the temperature of the solution was raised to 70 ° C, and the temperature was maintained for 4 hours to carry out polymerization to obtain a solution of the [A] copolymer (solid content concentration: 32.7 wt%).

The obtained [A] copolymer had Mw of 18,500 and Mw/Mn of 2.2. The [A] copolymer is "copolymer (A-3)".

Synthesis Example 4

In a flask equipped with a cooling tube and a stirrer, 7 parts by weight of 2,2'-azobis(2,4-dimethylvaleronitrile) and 220 parts by weight of propylene glycol methyl ether acetate were added. Then, 20 parts by weight of styrene, 10 parts by weight of methacrylic acid, 50 parts by weight of 2-(methylpropenyl hydroxymethyl)-4-trifluoromethyloxetane, and 20 parts by weight of tetrahydroindenyl group were added. After methacrylate and 2.0 parts by weight of α-methylstyrene dimer, the mixture was replaced with nitrogen and slowly stirred, the temperature of the solution was raised to 70 ° C, and the temperature was maintained for 5 hours to be polymerized. [A] A solution of a copolymer (solid content concentration: 32.0% by weight).

The obtained [A] copolymer had Mw of 16,500 and Mw/Mn of 1.7. The [A] copolymer is "copolymer (A-4)".

Comparative Synthesis Example 1

In a flask equipped with a cooling tube and a stirrer, 7 parts by weight of 2,2'-azobis(2,4-dimethylvaleronitrile) and 220 parts by weight of diethylene glycol ethyl methyl ether were added. Then, after adding 23 parts by weight of methacrylic acid, 47 parts by weight of dicyclopentyl methacrylate, 20 parts by weight of glycidyl methacrylate, and 2.0 parts by weight of α-methylstyrene dimer, it was replaced with nitrogen. Stirring was started slowly, the temperature of the solution was raised to 70 ° C, and the temperature was maintained for 5 hours to carry out polymerization to obtain a solution of the [A] copolymer (solid content concentration: 32.8 wt%).

The obtained [A] copolymer had Mw of 24,000 and Mw/Mn of 2.3. This copolymer is "copolymer (a-1)".

Comparative Synthesis Example 2

In a flask equipped with a cooling tube and a stirrer, 7 parts by weight of 2,2'-azobis(2,4-dimethylvaleronitrile) and 220 parts by weight of propylene glycol methyl ether acetate were added. Then, 22 parts by weight of methacrylic acid, 28 parts by weight of dicyclopentyl methacrylate, 40 parts by weight of 3-(methacryl hydroxymethyl)-2-phenyloxetane, and 10 parts by weight are added. After styrene and 1.5 parts by weight of α-methylstyrene dimer, the mixture was replaced with nitrogen and stirring was started slowly, the temperature of the solution was raised to 70 ° C, and the temperature was maintained for 4 hours to be polymerized to obtain [A]. A solution of the copolymer (solid content concentration: 31.8% by weight).

The obtained [A] copolymer had Mw of 18,000 and Mw/Mn of 2.01. This copolymer is "copolymer (a-2)".

Modulation and evaluation of radiation sensitive linear resin composition Example 1

The solution containing the copolymer (A-1) obtained in Synthesis Example 1 as the component [A] is converted into a copolymer (A-1) in an amount corresponding to 100 parts by weight, and 30 parts by weight is mixed as the component [B]. 4,4'-[1-(4-(1-[4-Hydroxyphenyl]-1-methylethyl)phenyl)ethylidene]bisphenol-1,2-naphthoquinonediazide-5 - sulfonate, 1 part by weight of triphenylsulfonium trifluoromethanesulfonate as the component [C], and 5 parts by weight of γ-methylpropenyl hydroxypropyltrimethoxydecane as other component, in solid concentration After dissolving in propylene glycol methyl ether acetate at 30% by weight, the mixture was filtered through a micropore filter having a pore size of 0.2 μm to prepare a composition (S-1).

Evaluation of preservation stability

The composition (S-1) partially prepared as described above was sealed in a glass spiral tube, and heated in an oven at 40 ° C for one week, and then the viscosity change rate before and after heating was measured. The results are shown in Table 1. Here, when the viscosity change rate is 0 to +5%, the storage stability is good.

Evaluation of imaging tolerance

Each of the compositions (S-1) was coated on a plurality of ruthenium substrates using a rotator, and then pre-baked at 90 ° C for 2 minutes on a hot plate to form a film. On the obtained film, a mask having a pattern of a line and a gap (10 to 1) of 3.0 μm was used, and a PLA-501F exposure machine (ultra-high pressure mercury lamp) manufactured by Kennon was used, and the intensity of the irradiation wavelength of 365 nm was 80 W/ After ultraviolet light of m ² for 40 seconds, an aqueous solution of tetramethylammonium hydroxide having a concentration of 0.4% by weight was developed as a developing solution, and the development time was changed on the same substrate at 25 ° C to develop the image by liquid immersion. Then, it was washed with ultrapure water for 1 minute, dried, and a pattern having a thickness of 3.0 μm was formed on the wafer. At this time, the minimum development time necessary when the line width is 3.0 μm is taken as the optimum development time, as shown in Table 1. Further, the time from the development of the optimum development time to the line of 3.0 μm and the peeling of the pattern was measured as the image tolerance, as shown in Table 1. When the value is 30 seconds or longer, the development tolerance is good.

I. Evaluation of interlayer insulating film

(1) Evaluation of resolution

- Formation of Patterned Film - The composition (S-1) was coated on a glass substrate using a spinner, and then prebaked on a hot plate at 80 ° C for 3 minutes to form a film.

Then, on the obtained film, ultraviolet rays having a intensity of 100 W/m ² having a wavelength of 365 nm were irradiated for 15 seconds through a mask of a predetermined pattern. Next, after developing for 1 minute at 25 ° C by an aqueous solution of 0.5% by weight of tetramethylammonium hydroxide, it was washed with pure water for 1 minute to remove unnecessary portions, and a pattern was formed.

Next, ultraviolet rays having a intensity of 100 W/m ² having a wavelength of 365 nm were applied to the formed pattern for 30 seconds, and then heated in an oven at 220 ° C for 60 minutes (post-baking) to obtain a pattern film having a film thickness of 3.0 μm. Further, the same operation as above was carried out except that the prebaking temperature was 90 ° C or 100 ° C, and a total of three kinds of pattern-like films having different pre-baking temperatures were obtained.

- Evaluation of resolution - Regarding the obtained pattern-like film, the evaluation removal pattern (5 μm x 5 μm hole) was "○" when the image was resolved, and "×" when the image was not resolved. The results are shown in Table 2.

(2) Evaluation of heat-resistant dimensional stability In the above-mentioned "(1) Evaluation of resolution" - "Formation of patterned film -", a pattern formed at a prebaking temperature of 80 ° C in an oven at 220 ° C The film thickness before and after baking after 60 minutes was measured. The results are shown in Table 2. Among them, when the rate of change in film thickness is within ±5%, the heat resistance dimensional stability is good.

(3) Evaluation of transparency After the composition (S-1) was coated on a glass substrate with a spinner, it was prebaked on a hot plate at 80 ° C for 3 minutes to form a film.

Then, ultraviolet rays having a wavelength of 365 nm and an intensity of 100 W/m ² were irradiated for 30 seconds on the entire film to be obtained. Then, it was heated in an oven at 220 ° C for 60 minutes (post-baking) to obtain a pattern film having a film thickness of 3.0 μm.

The light transmittance of the film obtained above was measured at a wavelength of 400 nm using a spectrophotometer (manufactured by Hitachi, Ltd., Model No. 150-20), and the same glass substrate as that used for the substrate was placed on the reference side. The results are shown in Table 2. Among them, when the transmittance is 90% or more, the permeability is good.

(4) Evaluation of heat-resistant discoloration The substrate having the film measured in the above "(3) Evaluation of transparency" was heated in an oven at 250 ° C for 1 hour, and was the same as "(3) Evaluation of transparency" The light transmittance at a wavelength of 400 nm was measured. The rate of change of the transmittance before and after heating is shown in Table 2. Here, when the rate of change of the transmittance is less than 5%, the heat discoloration resistance is good.

(5) Evaluation of Adhesiveness A film having a film thickness of 3.0 μm was obtained in the same manner as in the previous section of "(3) Evaluation of transparency". The substrate having the film was allowed to stand in a pressure cooker at a temperature of 120 ° C and a humidity of 100% for 4 hours, and then a checkerboard peeling test was performed based on JIS-K5400. In the 100 checkerboard grids at this time, the number of remaining checkerboards is as shown in Table 2.

II. Evaluation of microlenses

(1) Evaluation of Sensitivity The composition (S-1) was coated on a plurality of tantalum substrates with a film thickness of 2.5 μm after being removed by a solvent, and then pre-baked on a hot plate at 70 ° C. In minutes, a plurality of substrates having a film are formed.

Next, on the resulting film, a line width of 0.8 μm is passed. versus. The mask of the gap pattern (10 to 1) was exposed to the substrate by changing the exposure amount, and then exposed to pure water for 1 minute by using a 2.38 wt% aqueous solution of tetramethylammonium hydroxide for 1 minute at 25 ° C. , a patterned film was produced.

The above-mentioned several substrates were observed under a microscope, and the minimum exposure amount which made the gap line width (0.08 μm) solvable was observed. The results are shown in Table 3. When the value is 1,000 J/m ² or less, the sensitivity is good.

(2) Evaluation of transparency The composition (S-1) was coated on a glass substrate with a spinner, and then prebaked on a hot plate at 70 ° C for 3 minutes to form a film.

Then, ultraviolet rays having a wavelength of 365 nm and an intensity of 100 W/m ² were irradiated for 30 seconds on the entire film to be obtained. Then, it was heated in an oven at 160 ° C for 60 minutes (post-baking) to obtain a pattern film having a film thickness of 2.5 μm.

The light transmittance of the film obtained above was measured at a wavelength of 400 nm using a spectrophotometer (manufactured by Hitachi, Ltd., Model No. 150-20), and the same glass substrate as that used for the substrate was placed on the reference side. The results are shown in Table 3. Among them, when the transmittance is 90% or more, the transparency is good.

(3) Evaluation of heat-resistant discoloration The substrate having the film measured in the above "(2) Evaluation of transparency" was heated in an oven at 250 ° C for 1 hour, and was the same as "(2) Evaluation of transparency" The light transmittance at a wavelength of 400 nm was measured. The rate of change in transmittance before and after heating is shown in Table 3. Here, when the rate of change of the transmittance is less than 5%, the heat discoloration resistance is good.

(5) Evaluation of Solvent Resistance As in the previous section of "(3) Evaluation of Transparency", a film having a film thickness of 2.5 μm was obtained. The substrate having the film was immersed in isopropyl alcohol at a temperature of 50 ° C for 10 minutes, and the film thickness change rate before and after immersion was measured. The results are shown in Table 3. When the value is 0 to +5%, the solvent resistance is good.

(6) Evaluation of Adhesiveness A film having a film thickness of 2.5 μm was produced in the same manner as in the previous section of "(3) Evaluation of transparency", except that a ruthenium substrate was used instead of the glass substrate. The substrate having the film was allowed to stand in a pressure cooker at a temperature of 120 ° C and a humidity of 100% for 4 hours, and then a checkerboard peeling test was performed based on JIS-K5400. In the 100 checkerboard grids at this time, the remaining number of checkerboards is shown in Table 3.

(7) Evaluation of Microlens Shapes The composition (S-1) was coated on a plurality of tantalum substrates with a film thickness of 2.5 μm after being removed by a solvent, and then pre-baked on a hot plate at 70 ° C. Bake for 3 minutes to form a number of substrates with a film.

Secondly, via the 4.0 μm point on the resulting film. A 2.0 μm gap pattern mask was exposed using a NSR1755i7A NUS1755i7A reduction projection exposure machine (NA=0.50, λ=365 nm), and exposure was performed at an exposure amount of 3,000 J/m ² at a concentration of 1.1% by weight. The aqueous solution of methylammonium hydroxide was developed at 25 ° C for 1 minute by liquid ablation. Then, after washing with water, it is dried to form a pattern on the wafer. Next, exposure was performed at a total exposure amount of 3,000 J/m ² by a PLA-501F exposure machine (ultra-high pressure mercury lamp) manufactured by Kennon Co., Ltd. Thereafter, the film was heated on a hot plate at 160 ° C for 10 minutes, and further heated at 230 ° C for 10 minutes to melt the pattern to form a microlens.

The dimensions (diameter) and cross-sectional shape of the bottom of the formed microlens (the surface of the connection substrate) are shown in Table 3. When the size of the bottom of the microlens is larger than 4.0 μm and less than 5.0 μm, it is preferable. Further, when the size is 5.0 μm or more, the adjacent microlenses are in a contact state, which is not desirable. Further, the cross-sectional shape is preferably as shown in Fig. 1 in the case of the semi-convex lens shape as in (a), and is not preferable in the case of (b).

Examples 2 to 4, Comparative Example 1

The composition was prepared and evaluated in the same manner as in Example 1 except that the solution containing the copolymer described in Table 1 was used instead of the solution containing the copolymer (A-1). The results are shown in Tables 1-3.

Comparative example 2

The solution containing the copolymer (a-2) obtained in Comparative Synthesis Example 2 was converted into a copolymer (a-2) in an amount corresponding to 100 parts by weight, and 30 parts by weight was mixed as 4, 4' of the [B] component. -[1-(4-(1-[4-hydroxyphenyl]-1-methylethyl)phenyl)ethylidene]bisphenol-1,2-naphthoquinonediazide-5-sulfonate 5 parts by weight of γ-methylpropenyl hydroxypropyltrimethoxydecane as another component, dissolved in propylene glycol methyl ether acetate at a solid concentration of 30% by weight, and a micropore filter having a pore diameter of 0.5 μm Filter and modulate the composition.

The evaluation was carried out in the same manner as in Example 1 except that the above composition was substituted for the composition (S-1). The evaluation results are not shown in Tables 1~3. Further, when the microlens was formed in Comparative Example 2, since the adjacent microlenses were in a contact state, the cross-sectional shape of the microlens could not be evaluated.

Fig. 1 is a typical view showing the cross-sectional shape of a microlens.

Claims (8)

A radiation sensitive resin composition characterized by containing [A] (a1) at least one compound selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic anhydrides, and at least one selected from the group consisting of the following formula (1) a compound and a compound grouped by a compound represented by the following formula (2), (In the formula (1), R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ¹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ² , R ³ , R ⁴ and R ⁵ Each of them independently represents a hydrogen atom, a fluorine atom, an alkyl group having 1 to 4 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a perfluoroalkyl group having 1 to 4 carbon atoms, and n is an integer of 1 to 6) (In the formula (2), R, R ¹ , R ² , R ³ , R ⁴ and R ⁵ and n are the same as defined in the formula (1)) and (a3) has at least one member selected from tetrahydrofuran in the molecule. An unsaturated compound having a structure, a furan structure, a tetrahydropyran structure, a pyran structure, and a structure represented by the following formula (3) (In the formula (3), R ⁶ represents a hydrogen atom or a methyl group, m represents a copolymer of an integer of 2 to 10), and [B] 1,2-quinonediazide compound. The radiation sensitive resin composition of claim 1, wherein the [A] copolymer is a copolymer of the components (a1), (a2) and (a3) and (a4), and the (a4) is Other olefin-based unsaturated compounds having different components (a1), (a2) and (a3). A radiation sensitive resin composition according to claim 1 or 2, which is used for forming an interlayer insulating film. A method for forming an interlayer insulating film, comprising the steps of: (1) forming a film of a radiation-sensitive resin composition according to claim 1 of the patent application, in the following order, (2) a step of irradiating radiation on at least a portion of the film, (3) a step of developing a film after the irradiation, and (4) a step of heating the film after development. An interlayer insulating film formed of the radiation sensitive resin composition as in the first aspect of the patent application. The radiation sensitive resin composition of claim 1 or 2, which is formed by microlens formation. A method of forming a microlens, comprising the steps of: (1) forming a film of a radiation sensitive resin composition according to claim 1 of the patent application form, and (2) at least in the following order; a step of irradiating a part of the film to be irradiated with radiation, (3) a step of developing a film after irradiation, and (4) a step of heating the film after development. A microlens formed of a radiation sensitive resin composition as in the first aspect of the patent application.