JP4677871B2 - Radiation sensitive resin composition and formation of interlayer insulating film and microlens - Google Patents

Description

  The present invention particularly 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 from the radiation-sensitive resin composition, and the interlayer insulating film and the microlens. It relates to a forming method.

In an electronic component such as a thin film transistor (hereinafter referred to as “TFT”) type liquid crystal display element, magnetic head element, integrated circuit element, solid-state imaging element, etc., an interlayer insulation is generally used to insulate between wirings arranged in layers. A membrane is provided. As a material for forming the interlayer insulating film, a material having a small number of steps for obtaining a required pattern shape and sufficient flatness is preferable, and therefore, a radiation sensitive resin composition is widely used (for example, , See Patent Document 1 and Patent Document 2.)
Among the electronic components, for example, a TFT type liquid crystal display element is manufactured through a process of forming a transparent electrode film on an interlayer insulating film and further forming a liquid crystal alignment film on the interlayer insulating film. In the process of forming the transparent electrode film, it is exposed to a high temperature condition or exposed to a resist stripping solution used for forming an electrode pattern, and thus sufficient resistance to these is required.
In recent years, TFT-type liquid crystal display elements have been increased in screen size, brightness, definition, speed response, thinning, and so on. The radiation-sensitive resin composition used in the manufacturing process is required to have high sensitivity, and the formed interlayer insulating film requires higher performance than conventional methods in terms of low dielectric constant and high light transmittance. Has been.

On the other hand, as an imaging optical system for on-chip color filters such as facsimiles, electronic copying machines, and solid-state image sensors, or as an optical system material for optical fiber connectors, microlenses having a lens diameter of about 3 to 100 .mu.m and those regularly are used. An arrayed microlens array is used.
As a method of forming a microlens, after forming a patterned thin film corresponding to the lens, it is heat-treated and melt-flowed to use as it is as a lens, or using a melt-flowed lens pattern as a mask, Although a method of transferring a lens shape to a base by dry etching is known, a radiation sensitive resin composition is widely used for forming such a lens pattern (for example, Patent Document 3 and Patent Document). 4).
The radiation-sensitive resin composition used for forming the lens pattern has high sensitivity, and the microlens formed therefrom has a desired radius of curvature, high heat resistance, and high light transmittance. Etc. are required.

  In addition, in order to remove various insulating films on the bonding pad which is a wiring forming portion, the element on which the microlenses as described above are formed is applied with a planarizing film and an etching resist, and a desired photomask is formed. Then, after irradiating and developing, the resist for etching at the bonding pad portion is removed, and then the planarizing film and various insulating films are removed by etching to expose the bonding pad portion. Therefore, the microlens is required to have solvent resistance, heat resistance, and the like in the coating film forming process and the etching process of the planarizing film and the etching resist.

On the other hand, the interlayer insulating film and microlens thus obtained are peeled off when the developing time exceeds the optimum time in the developing process when forming them, and the developer penetrates between the pattern and the substrate. In order to avoid such a phenomenon, it is necessary to strictly control the development time, and there is a problem in terms of product yield and productivity.
Furthermore, in order to improve the heat resistance and surface hardness of the interlayer insulating film and the microlens, a proposal has been made to add antimony fluorides as a heat-sensitive acid generator to the radiation-sensitive resin composition as a raw material (for example, However, in the case of such a radiation sensitive resin composition, the problem of toxicity due to the antimony compound has been pointed out.

As described above, the radiation-sensitive resin composition used for the formation of the interlayer insulating film and the microlens is required to have high sensitivity, and when the development time becomes excessive in a development process beyond a predetermined time. However, it is required that the pattern does not peel off, and the formed interlayer insulating film is required to have high heat resistance, high solvent resistance, low dielectric constant, high light transmittance, etc. In this case, in addition to a good melt shape (desired radius of curvature) as a microlens, high heat resistance, high solvent resistance, high light transmittance, and the like are required. A radiation-sensitive resin composition that can sufficiently satisfy the requirements and has no problem with safety has not been known.
JP 2001-354822 A JP 2001-343743 A JP-A-6-18702 JP-A-6-136239 JP 2001-330953 A

The present invention has been made based on the circumstances as described above, and the first problem of the present invention is that there is no problem in safety, sensitivity, resolution, storage stability as a solution, and the like in the development process. An object of the present invention is to provide a radiation-sensitive resin composition having a good development margin so that a good pattern shape can be formed even when the optimum development time is exceeded.
The second object of the present invention is to provide a method for forming an interlayer insulating film having excellent solvent resistance, heat resistance, light transmittance, adhesion and the like using the above radiation sensitive resin composition. There is to do.
A third object of the present invention is to provide a microlens having a good melt shape by using the above-mentioned radiation-sensitive resin composition and having excellent solvent resistance, heat resistance, light transmittance, adhesion and the like. It is in providing the method of forming.

According to the present invention, the above-mentioned problems of the present invention are as follows.
(A1) at least one selected from unsaturated carboxylic acid and unsaturated carboxylic anhydride, and (a2) the following general formula (1)

(In the general formula (1), R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms independently of one another, R ¹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms independently of one another, R ² , R ³ , R ⁴ and R ⁵ are each independently 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. N is an integer of 1 to 6 independently of each other.)
And a compound represented by the following general formula (2)

(In the general formula (2), R, R ¹ , R ² , R ³ , R ⁴ and R ⁵ and n have the same meaning as in the general formula (1)). At least one copolymer,
[B] 1,2-quinonediazide compound, and [C] N- (trifluoromethanesulfonyloxy) phthalimide, N- (trifluoromethanesulfonyloxy) diphenylmaleimide, N- (trifluoromethanesulfonyloxy) bicyclo [2.2.1] ] Hept-5-ene-2,3-dicarboximide, N- (trifluoromethanesulfonyloxy) -7-oxabicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N -(Trifluoromethanesulfonyloxy) bicyclo [2.2.1] heptane-5,6-oxy-2,3-dicarboximide, N- (trifluoromethanesulfonyloxy) naphthylimide, N- (10-camphorsulfonyloxy) ) Phthalimide, N- (10-camphorsulfonylo) Xyl) diphenylmaleimide, N- (10-camphorsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (10-camphorsulfonyloxy) -7-oxabicyclo [2.2.1] Hept-5-ene-2,3-dicarboximide, N- (10-camphorsulfonyloxy) bicyclo [2.2.1] heptane-5,6-oxy-2,3- Dicarboximide, N- (10-camphorsulfonyloxy) naphthylimide, N- (p-toluenesulfonyloxy) phthalimide, N- (p-toluenesulfonyloxy) diphenylmaleimide, N- (p-toluenesulfonyloxy) bicyclo [ 2.2.1] Hept-5-ene-2,3-dicarboximide, N- (p-toluenesulfoni Oxy) -7-oxabicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (p-toluenesulfonyloxy) bicyclo [2.2.1] heptane-5,6 -Oxy-2,3-dicarboximide, N- (p-toluenesulfonyloxy) naphthylimide, N- (2-trifluoromethylbenzenesulfonyloxy) phthalimide, N- (2-trifluoromethylbenzenesulfonyloxy) diphenyl Maleimide, N- (2-trifluoromethylbenzenesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (2-trifluoromethylbenzenesulfonyloxy) -7 -Oxabicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (2-to Fluoromethylbenzenesulfonyloxy) bicyclo [2.2.1] heptane-5,6-oxy-2,3-dicarboximide, N- (2-trifluoromethylbenzenesulfonyloxy) naphthylimide, N- (4- Trifluoromethylbenzenesulfonyloxy) phthalimide, N- (4-trifluoromethylbenzenesulfonyloxy) diphenylmaleimide, N- (4-trifluoromethylbenzenesulfonyloxy) bicyclo [2.2.1] hept-5-ene- 2,3-dicarboximide, N- (4-trifluoromethylbenzenesulfonyloxy) -7-oxabicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (4 -Trifluoromethylbenzenesulfonyloxy) bicyclo [2.2.1] hept Tan-5,6-oxy-2,3-dicarboximide, N- (4-trifluoromethylbenzenesulfonyloxy) naphthylimide, N- (nonafluoro-n-butanesulfonyloxy) phthalimide, N- (nonafluoro-n -Butanesulfonyloxy) diphenylmaleimide, N- (nonafluoro-n-butanesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (nonafluoro-n-butanesulfonyl) Oxy) -7-oxabicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (nonafluoro-n-butanesulfonyloxy) bicyclo [2.2.1] heptane-5 , 6-oxy-2,3-dicarboximide, N- (nonafluoro-n-butanesulfonyloxy) Naphthylimide, N- (pentafluorobenzenesulfonyloxy) phthalimide, N- (pentafluorobenzenesulfonyloxy) diphenylmaleimide, N- (pentafluorobenzenesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2 , 3-dicarboximide, N- (pentafluorobenzenesulfonyloxy) -7-oxabicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (pentafluorobenzenesulfonyloxy) ) Bicyclo [2.2.1] heptane-5,6-oxy-2,3-dicarboximide, N- (pentafluorobenzenesulfonyloxy) naphthylimide, N- (perfluoro-n-octanesulfonyloxy) phthalimide N- (perfluoro-n-octane Sulfonyloxy) diphenylmaleimide, N- (perfluoro-n-octanesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (perfluoro-n-octanesulfonyloxy) ) -7-oxabicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (perfluoro-n-octanesulfonyloxy) bicyclo [2.2.1] heptane-5 , 6-oxy-2,3-dicarboximide, N- (perfluoro-n-octanesulfonyloxy) naphthylimide, and at least one thermosensitive acid-generating compound selected from sulfone compounds, sulfonate compounds, and diazomethane compounds It achieves by the radiation sensitive resin composition characterized by containing.

Secondly, the above-mentioned object of the present invention is achieved by a method for forming an interlayer insulating film characterized by including the following steps in the following order.
(A) a step of forming a film of the radiation-sensitive composition on a substrate;
(B) irradiating at least part of the coating with radiation;
(C) a step of developing the film after irradiation, and (d) a step of heating the film after development.

Thirdly, the above object of the present invention is achieved by a microlens forming method characterized by including the following steps in the order described below.
(A) a step of forming a film of the radiation-sensitive composition on a substrate;
(B) irradiating at least part of the coating with radiation;
(C) a step of developing the film after irradiation, and (d) a step of heating the film after development.

The radiation-sensitive resin composition of the present invention has excellent sensitivity and resolution, is excellent in storage stability as a composition solution, and can form a good pattern shape even when the optimum development time is exceeded in the development process. It has such a good development margin, and can be used particularly suitably as a microlens such as an interlayer insulating film of various electronic parts and a solid-state imaging device.
In addition, the method for forming an interlayer insulating film and the method for forming a microlens according to the present invention enable the formation of a good pattern even when the development time exceeds the optimum development time. In addition, a microlens can be easily formed.
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.
In addition, the microlens of the present invention has excellent solvent resistance, heat resistance, light transmittance, adhesion, and the like, and has a good melt shape.

Hereinafter, the present invention will be described in detail.
[A] Copolymer The [A] copolymer contained in the radiation sensitive resin composition of the present invention is at least one selected from (a1) an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride (hereinafter referred to as “a”). , “Unsaturated compound (a1)”), and (a2) at least one selected from the compound represented by the general formula (1) and the compound represented by the general formula (2) (hereinafter, "Unsaturated compound (a2)").

Examples of the unsaturated compound (a1) include a monocarboxylic acid compound, a dicarboxylic acid compound, an anhydride of dicarboxylic acid, a mono [(meth) acryloyloxyalkyl] ester of a polyvalent carboxylic acid, and a carboxyl group and a hydroxyl group at both ends. Examples thereof include mono (meth) acrylates of polymers having the same.
Examples of the monocarboxylic acid compound include acrylic acid, methacrylic acid, crotonic acid, 2-acryloyloxyethyl succinic acid, 2-methacryloyloxyethyl succinic acid, 2-acryloyloxyethyl hexahydrophthalic acid, 2-methacryloyloxyethyl hexa Hydrophthalic acid, etc .;
Examples of the dicarboxylic acid compound include maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid and the like;
Examples of the anhydride of the dicarboxylic acid include an anhydride of the above-described dicarboxylic acid compound;
Examples of the mono [(meth) acryloyloxyalkyl] ester of the polyvalent carboxylic acid include succinic acid mono (2-acryloyloxyethyl), succinic acid mono (2-methacryloyloxyethyl), and phthalic acid mono (2-acryloyloxy). Ethyl), mono (2-methacryloyloxyethyl) phthalate, etc .;
Examples of the mono (meth) acrylate of the polymer having a carboxyl group and a hydroxyl group at both ends include ω-carboxypolycaprolactone monoacrylate, ω-carboxypolycaprolactone monomethacrylate, and the like.

Of these unsaturated compounds (a1), acrylic acid, methacrylic acid, maleic anhydride, and the like are preferable from the viewpoints of copolymerization reactivity, solubility in an alkaline aqueous solution, and availability.
The said unsaturated compound (a1) can be used individually, and can mix and use 2 or more types.
[A] In the polymer, the content of the repeating unit derived from the (a1) unsaturated carboxylic acid compound is preferably 10 to 90% by weight, more preferably 30 to 70% by weight. By setting it as the content rate of this range, the solubility with respect to the alkaline developing solution of the composition obtained can be controlled to a more suitable range.

  The unsaturated compound (a2) is represented by the following general formula (1)

(In the general formula (1), R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms independently of one another, R ¹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms independently of one another, R ² , R ³ , R ⁴ and R ⁵ are each independently 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. N is an integer of 1 to 6 independently of each other.)
And a compound represented by the following general formula (2)

(In the general formula (2), R, R ¹ , R ² , R ³ , R ⁴ and R ⁵ and n have the same meaning as in the general formula (1).)
It is at least 1 sort (s) selected from the compound represented by these.

In the general formulas (1) and (2), examples of the alkyl group having 1 to 4 carbon atoms of R, R ¹ , R ² , R ³ , R ⁴ and R include a methyl group, an ethyl group, and an n-propyl group. , I-propyl group, n-butyl group, i-butyl group, sec-butyl group, t-butyl group and the like.
Also, R, the aryl group having 6 to 20 carbon atoms of R ^2, R ³ and R ^4, may include, for example, a phenyl group, a tolyl group or the like. Further, examples of the perfluoroalkyl group having 1 to ⁴ carbon atoms of R, R ² , R ³ and R ⁴ include trifluoromethyl group, pentafluoroethyl group, heptafluoro-n-propyl group, heptafluoro-i-propyl. Group, nonafluoro-n-butyl group, nonafluoro-i-butyl group, nonafluoro-sec-butyl group, nonafluoro-t-butyl group and the like.

  Examples of the compound represented by the general formula (1) include 3- (acryloyloxymethyl) oxetane, 3- (acryloyloxymethyl) -2-methyloxetane, 3- (acryloyloxymethyl) -3-ethyloxetane, 3- (acryloyloxymethyl) -2-trifluoromethyloxetane, 3- (acryloyloxymethyl) -2-pentafluoroethyloxetane, 3- (acryloyloxymethyl) -2-phenyloxetane, 3- (acryloyloxymethyl) -2,2-difluorooxetane, 3- (acryloyloxymethyl) -2,2,4-trifluorooxetane, 3- (acryloyloxymethyl) -2,2,4,4-tetrafluorooxetane, 3- (2 -Acryloyloxyethyl) oxetane, 3- (2 Acryloyloxyethyl) -2-ethyloxetane, 3- (2-acryloyloxyethyl) -3-ethyloxetane, 3- (2-acryloyloxyethyl) -2-trifluoromethyloxetane, 3- (2-acryloyloxyethyl) ) -2-Pentafluoroethyloxetane, 3- (2-acryloyloxyethyl) -2-phenyloxetane, 3- (2-acryloyloxyethyl) -2,2-difluorooxetane, 3- (2-acryloyloxyethyl) Acrylic esters such as -2,2,4-trifluorooxetane and 3- (2-acryloyloxyethyl) -2,2,4,4-tetrafluorooxetane;

3- (methacryloyloxymethyl) oxetane, 3- (methacryloyloxymethyl) -2-methyloxetane, 3- (methacryloyloxymethyl) -3-ethyloxetane, 3- (methacryloyloxymethyl) -2-trifluoromethyloxetane, 3- (methacryloyloxymethyl) -2-pentafluoroethyloxetane, 3- (methacryloyloxymethyl) -2-phenyloxetane, 3- (methacryloyloxymethyl) -2,2-difluorooxetane, 3- (methacryloyloxymethyl) -2,2,4-trifluorooxetane, 3- (methacryloyloxymethyl) -2,2,4,4-tetrafluorooxetane, 3- (2-methacryloyloxyethyl) oxetane, 3- (2-methacryloyloxyethyl) 2-ethyloxetane, 3- (2-methacryloyloxyethyl) -3-ethyloxetane, 3- (2-methacryloyloxyethyl) -2-tolylolomethyloxetane, 3- (2-methacryloyloxyethyl) -2- Pentafluoroethyloxetane, 3- (2-methacryloyloxyethyl) -2-phenyloxetane, 3- (2-methacryloyloxyethyl) -2,2-difluorooxetane, 3- (2-methacryloyloxyethyl) -2,2 , 4-trifluorooxetane, methacrylic acid esters such as 3- (2-methacryloyloxyethyl) -2,2,4,4-tetrafluorooxetane, and the like.

  Examples of the compound represented by the general formula (2) include 2- (acryloyloxymethyl) oxetane, 2- (acryloyloxymethyl) -2-methyloxetane, 2- (acryloyloxymethyl) -3-methyloxetane, 2- (acryloyloxymethyl) -4-methyloxetane, 2- (acryloyloxymethyl) -2-trifluoromethyloxetane, 2- (acryloyloxymethyl) -3-trifluoromethyloxetane, 2- (acryloyloxymethyl) -4-trifluoromethyloxetane, 2- (acryloyloxymethyl) -2-pentafluoroethyloxetane, 2- (acryloyloxymethyl) -3-pentafluoroethyloxetane, 2- (acryloyloxymethyl) -4-pentafluoro Ethyloki Tan, 2- (acryloyloxymethyl) -2-phenyloxetane, 2- (acryloyloxymethyl) -3-phenyloxetane, 2- (acryloyloxymethyl) -4-phenyloxetane, 2- (acryloyloxymethyl) -2 , 3-Difluorooxetane, 2- (acryloyloxymethyl) -2,4-difluorooxetane, 2- (acryloyloxymethyl) -3,3-difluorooxetane, 2- (acryloyloxymethyl) -3,4-difluorooxetane 2- (acryloyloxymethyl) -4,4-difluorooxetane, 2- (acryloyloxymethyl-3,3,4-trifluorooxetane, 2- (acryloyloxymethyl) -3,4,4-trifluorooxetane , 2- (acryloyloxime Le) 3,3,4,4 tetrafluorooxetane

2- (2-acryloyloxyethyl) oxetane, 2- [2- (2-methyloxetanyl)] ethyl methacrylate, 2- [2- (3-methyloxetanyl)] ethyl methacrylate, 2- (acryloyloxyethyl) -2 -Methyl oxetane, 2- (2-acryloyloxyethyl) -4-methyl oxetane, 2- (2-acryloyloxyethyl) -2-trifluoromethyl oxetane, 2- (2-acryloyloxyethyl) -3-trifluoro Methyloxetane, 2- (2-acryloyloxyethyl) -4-trifluoromethyloxetane, 2- (2-acryloyloxyethyl) -2-pentafluoroethyloxetane, 2- (2-acryloyloxyethyl) -3-penta Fluoroethyl osetan, 2- (2-acryloyl Oxyethyl) -4-pentafluoroethyloxetane, 2- (2-acryloyloxyethyl) -2-phenyloxetane, 2- (2-acryloyloxyethyl) -3-phenyloxetane, 2- (2-acryloyloxyethyl)- 4-phenyloxetane, 2- (2-acryloyloxyethyl) -2,3-difluorooxetane, 2- (2-acryloyloxyethyl) -2,4-difluorooxetane, 2- (2-acryloyloxyethyl) -3 , 3-Difluorooxetane, 2- (2-acryloyloxyethyl) -3,4-difluorooxetane, 2- (2-acryloyloxyethyl) -4,4-difluorooxetane, 2- (2-acryloyloxyethyl)- 3,3,4-trifluorooxetane, 2- (2-a Leroy oxyethyl) 3,4,4-trifluoro-oxetane, 2- (2-acryloyloxyethyl) 3,3,4,4-tetrafluoro Oki acrylic acid esters such as cetane;

2- (methacryloyloxymethyl) oxetane, 2- (methacryloyloxymethyl) -2-methyloxetane, 2- (methacryloyloxymethyl) -3-methyloxetane, 2- (methacryloyloxymethyl) -4-methyloxetane, 2- (Methacryloyloxymethyl) -2-trifluoromethyloxetane, 2- (methacryloyloxymethyl) -3-trifluoromethyloxetane, 2- (methacryloyloxymethyl) -4-trifluoromethyloxetane, 2- (methacryloyloxymethyl) 2-pentafluoroethyloxetane, 2- (methacryloyloxymethyl) -3-pentafluoroethyloxetane, 2- (methacryloyloxymethyl) -4-pentafluoroethyloxetane, 2- (methacryloyl) Xoxymethyl) -2-phenyloxetane, 2- (methacryloyloxymethyl) -3-phenyloxetane, 2- (methacryloyloxymethyl) -4-phenyloxetane, 2- (methacryloyloxymethyl) -2,3-difluorooxetane, 2 -(Methacryloyloxymethyl) -2,4-difluorooxetane, 2- (methacryloyloxymethyl) -3,3-difluorooxetane, 2- (methacryloyloxymethyl) -3,4-difluorooxetane, 2- (methacryloyloxymethyl) ) -4,4-difluorooxetane, 2- (methacryloyloxymethyl) -3,3,4-trifluorooxetane, 2- (methacryloyloxymethyl) -3,4,4-trifluorooxetane, 2- (methacryloyloxy) Methyl 3,3,4,4-tetra-fluoro-oxetane,

2- (2-methacryloyloxyethyl) oxetane, 2- [2- (2-methyloxetanyl)] ethyl methacrylate, 2- [2- (3-methyloxetanyl)] ethyl methacrylate, 2- (2-methacryloyloxyethyl) 2-methyloxetane, 2- (2-methacryloyloxyethyl) -4-methyloxetane, 2- (2-methacryloyloxyethyl) -2-trifluoromethyloxetane, 2- (2-methacryloyloxyethyl) -3- Trifluoromethyloxetane, 2- (2-methacryloyloxyethyl) -4-trifluoromethyloxetane, 2- (2-methacryloyloxyethyl) -2-pentafluoroethyloxetane, 2- (2-methacryloyloxyethyl) -3 -Pentafluoroethyl oxetane 2- (2-methacryloyloxyethyl) -4-pentafluoroethyloxetane, 2- (2-methacryloyloxyethyl) -2-phenyloxetane, 2- (2-methacryloyloxyethyl) -3-phenyloxetane, 2- ( 2-methacryloyloxyethyl) -4-phenyloxetane, 2- (2-methacryloyloxyethyl) -2,3-difluorooxetane, 2- (2-methacryloyloxyethyl) -2,4-difluorooxetane, 2- (2 -Methacryloyloxyethyl) -3,3-difluorooxetane, 2- (2-methacryloyloxyethyl) -3,4-difluorooxetane, 2- (2-methacryloyloxyethyl) -4,4-difluorooxetane, 2- ( 2-methacryloyloxyethyl) -3,3 Methacryl such as 4-trifluorooxetane, 2- (2-methacryloyloxyethyl) -3,4,4-trifluorooxetane, 2- (2-methacryloyloxyethyl) -3,3,4,4-tetrafluorooxetane Acid esters and the like can be mentioned respectively.

Of these unsaturated compounds (a2), 3- (methacryloyloxymethyl) oxetane, 3- (methacryloyloxymethyl) -3-ethyloxetane, 3- (methacryloyloxymethyl) -2-trifluoromethyloxetane, 3- (Methacryloyloxymethyl) -2-phenyloxetane, 2- (methacryloyloxymethyl) oxetane, 2- (methacryloyloxymethyl) -4-trifluoromethyloxetane, etc. have a wide development margin for the resulting radiation-sensitive resin composition. In addition, it is preferable from the viewpoint of improving the chemical resistance of the obtained interlayer insulating film and microlens.
These unsaturated compounds (a2) can be used alone or in combination of two or more.
[A] The content of the structural unit derived from the unsaturated compound (a2) in the copolymer is preferably 10 to 90% by weight, more preferably 30 to 70% by weight. By setting the content in this range, the balance between the storage stability of the composition and the heat resistance of the obtained interlayer insulating film or microlens will be improved.

  [A] The polymer is a copolymer of the unsaturated compounds (a1) and (a2). Optionally, the unsaturated compounds (a1) and (a2) and (a3) the (a1) and It may be a copolymer of an olefinically unsaturated compound other than (a2) (hereinafter referred to as unsaturated compound (a3)). The unsaturated compound (a3) is not particularly limited as long as it can be copolymerized with the above-described unsaturated compounds (a1) and (a2). For example, an acrylic acid alkyl ester, a methacrylic acid alkyl ester, an acrylic acid Cyclic alkyl ester of methacrylic acid, cyclic alkyl ester of methacrylic acid, aryl ester of acrylic acid, aryl ester of methacrylic acid, unsaturated dicarboxylic acid diester, hydroxyalkyl acrylate, hydroxyalkyl methacrylate, bicyclounsaturated compound, unsaturated dicarbonylimide derivative, styrene and Derivatives thereof, as well as other unsaturated compounds can be mentioned.

Examples of the acrylic acid alkyl ester include methyl acrylate, ethyl acrylate, n-propyl acrylate, i-propyl acrylate, n-butyl acrylate, sec-butyl acrylate, and t-butyl acrylate;
Examples of the alkyl methacrylate include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, i-propyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate, and t-butyl methacrylate;
Examples of the cyclic alkyl ester of acrylic acid include cyclohexyl acrylate, 2-methylcyclohexyl acrylate, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl acrylate (hereinafter referred to as “dicyclopentanyl acrylate”). ), 2-dicyclopentanyloxyethyl acrylate, isoboronyl acrylate and the like;
Examples of the cyclic alkyl ester of methacrylic acid include cyclohexyl methacrylate, 2-methylcyclohexyl methacrylate, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl methacrylate (hereinafter referred to as “dicyclopentanyl methacrylate”). .), 2-dicyclopentanyloxyethyl methacrylate, isoboronyl methacrylate and the like;

Examples of the methacrylic acid aryl ester include phenyl methacrylate and benzyl methacrylate;
Examples of the unsaturated dicarboxylic acid diester include diethyl maleate, diethyl fumarate, diethyl itaconate and the like;
Examples of the hydroxyalkyl acrylate include hydroxymethyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxyethyl methacrylate, 3-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, diethylene glycol monomethacrylate, 2,3- Dihydroxypropyl methacrylate, 2-methacryloxyethylglycoside, 5- (2′-hydroxyethyl) bicyclo [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-di (2′-hydroxyethyl) bicyclo [2.2.1] hept-2 -Ene, 5-hydroxy-5- Methylbicyclo [2.2.1] hept-2-ene, 5-hydroxy-5-ethylbicyclo [2.2.1] hept-2-ene, 5-hydroxymethyl-5-methylbicyclo [2.2. 1] hept-2-ene and the like;
Examples of the hydroxyalkyl methacrylate include 2-hydroxyethyl methacrylate and 2-hydroxypropyl methacrylate;

Examples of the bicyclo unsaturated compound include bicyclo [2.2.1] hept-2-ene, 5-methylbicyclo [2.2.1] hept-2-ene, 5-ethylbicyclo [2.2.1]. ] Hept-2-ene, 5-hydroxybicyclo [2.2.1] Hept-2-ene, 5-carboxybicyclo [2.2.1] Hept-2-ene, 5-hydroxymethylbicyclo [2.2 .1] Hept-2-ene, 5- (2-hydroxyethyl) bicyclo [2.2.1] Hept-2-ene, 5-methoxybicyclo [2.2.1] Hept-2-ene, 5- Ethoxybicyclo [2.2.1] hept-2-ene,
5,6-dihydroxybicyclo [2.2.1] hept-2-ene, 5,6-dicarboxybicyclo [2.2.1] hept-2-ene, 5,6-di (hydroxymethyl) bicyclo [ 2.2.1] Hept-2-ene, 5,6-di (2-hydroxyethyl) bicyclo [2.2.1] Hept-2-ene, 5,6-dimethoxybicyclo [2.2.1] Hept-2-ene, 5,6-diethoxybicyclo [2.2.1] Hept-2-ene, 5-hydroxy-5-methylbicyclo [2.2.1] Hept-2-ene, 5-hydroxy -5-ethylbicyclo [2.2.1] hept-2-ene, 5-carboxy-5-methylbicyclo [2.2.1] hept-2-ene, 5-carboxy-5-ethylbicyclo [2. 2.1] Hept-2-ene, 5-hydroxymethyl-5-methylbisci Black [2.2.1] Hept-2-ene, 5-carboxy-6-methylbicyclo [2.2.1] Hept-2-ene, 5-carboxy-6-ethylbicyclo [2.2.1] Hept-2-ene, 5,6-dicarboxybicyclo [2.2.1] hept-2-ene anhydride (hymic acid anhydride), 5-t-butoxycarbonylbicyclo [2.2.1] hept- 2-ene, 5-cyclohexyloxycarbonylbicyclo [2.2.1] hept-2-ene, 5-phenoxycarbonylbicyclo [2.2.1] hept-2-ene, 5,6-di (t-butoxy Carbonyl) bicyclo [2.2.1] hept-2-ene, 5,6-di (cyclohexyloxycarbonyl) bicyclo [2.2.1] hept-2-ene and the like;

Examples of the unsaturated dicarbonylimide derivatives include N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimidobenzoate, N-succinimidyl-4-maleimidobutyrate, and N-succinimidyl-6. -Maleimidocaproate, N-succinimidyl-3-maleimidopropionate, N- (9-acridinyl) maleimide and the like;
Examples of the styrene and derivatives thereof include styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, m-vinyltoluene, p-vinyltoluene, p-methoxystyrene, and the like;
Examples of the other unsaturated compounds include acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, vinyl acetate, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, Glycidyl acrylate, glycidyl methacrylate, glycidyl α-ethyl acrylate, glycidyl α-n-propyl acrylate, glycidyl α-n-butyl acrylate, 3,4-epoxybutyl acrylate, 3,4-epoxybutyl methacrylate 3,4-epoxybutyl α-ethyl acrylate, 6,7-epoxyheptyl acrylate, 6,7-epoxyheptyl methacrylate, 6,7-epoxyheptyl α-ethyl acrylate, o-vinylbenzylglycidyl ether, m-Vinylbenzylglyci Examples thereof include dil ether and p-vinylbenzyl glycidyl ether.

Among these unsaturated compounds (a3), t-butyl methacrylate, 2-methylcyclohexyl acrylate, dicyclopentanyl methacrylate, bicyclo [2.2.1] hept-2-ene, N-phenylmaleimide, N-cyclohexyl Maleimide, styrene, p-methoxystyrene, 1,3-butadiene, glycidyl methacrylate, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether and the like can be obtained. A] It is preferable from the viewpoint of solubility of the copolymer in an aqueous alkali solution.
The unsaturated compound (a3) can be used alone or in combination of two or more.
[A] The content of the structural unit derived from the unsaturated compound (a3) in the copolymer is preferably 70% by weight or less, more preferably 5 to 70% by weight, still more preferably 5 to 50% by weight, Preferably it is 10-30 weight%. By setting the content in this range, the storage stability of the resulting composition and the solubility in an alkali developer can be controlled in a more appropriate range.

[A] The copolymer is preferably a copolymer of the unsaturated compounds (a1), (a2) and (a3).
More preferable [A] copolymer in the present invention is, more specifically, at least one unsaturated compound (a1) selected from the group of acrylic acid, methacrylic acid and maleic anhydride,
3- (methacryloyloxymethyl) oxetane, 3- (methacryloyloxymethyl) -3-ethyloxetane, 3- (methacryloyloxymethyl) -2-trifluoromethyloxetane, 3- (methacryloyloxymethyl) -2-phenyloxetane, At least one unsaturated compound (a2) selected from the group of 2- (methacryloyloxymethyl) oxetane and 2- (methacryloyloxymethyl) -4-trifluoromethyloxetane;
t-butyl methacrylate, 2-methylcyclohexyl acrylate, dicyclopentanyl methacrylate, bicyclo [2.2.1] hept-2-ene, N-phenylmaleimide, N-cyclohexylmaleimide, styrene, p-methoxystyrene, 1, Examples include a copolymer with at least one unsaturated compound (a3) selected from the group of 3-butadiene, glycidyl methacrylate, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, and p-vinylbenzyl glycidyl ether. be able to.

[A] The polystyrene-equivalent weight average molecular weight (hereinafter referred to as “Mw”) of the copolymer is preferably 1 × 10 ^{3 to} 5 × 10 ⁵ , more preferably 3 × 10 ^{3 to} 3 × 10 ⁵ , and still more preferably. Is 5 × 10 ³ to 1 × 10 ⁵ .
[A] The molecular weight distribution defined by the ratio (Mw / Mn) of Mw of the copolymer to the polystyrene-equivalent number average molecular weight (hereinafter referred to as “Mn”) is preferably 5.0 or less, more preferably. Is 1.0-3.0.
The radiation-sensitive resin composition containing the [A] copolymer having Mw and Mw / Mn as described above forms a pattern with a predetermined shape very easily without developing residue and film loss during development. be able to.
[A] The copolymer has at least one of a carboxyl group and a carboxylic acid anhydride group and an oxetane ring structure, has a moderate solubility in an alkaline aqueous solution, and has a special curing agent. Even if it is not used together, it can be easily cured by heating. In addition, the radiation sensitive resin composition containing the [A] copolymer can easily form a film with a predetermined pattern without developing residue or film loss during development.
[A] The copolymer can be used alone or in combination of two or more.

The [A] copolymer as described above is, for example, an unsaturated compound (a1), an unsaturated compound (a2), and optionally an unsaturated compound (a3) in an appropriate solvent in the presence of a radical polymerization initiator. Can be synthesized by polymerization.
Examples of the solvent used for the polymerization include alcohol, ether, ethylene glycol ether, ethylene glycol alkyl ether acetate, diethylene glycol ether, propylene glycol ether, propylene glycol alkyl ether acetate, propylene glycol alkyl ether propionate, and aromatic hydrocarbon. , Ketones, esters and the like.

Examples of the alcohol include methanol, ethanol, benzyl alcohol, 2-phenylethanol, 3-phenyl-1-propanol, and the like; ethers such as tetrahydrofuran;
Examples of ethylene glycol ethers include ethylene glycol monomethyl ether and ethylene glycol monoethyl ether;
Examples of the ethylene glycol alkyl ether acetate include ethylene glycol methyl ether acetate, ethylene glycol ethyl ether acetate, ethylene glycol n-propyl ether acetate, and ethylene glycol n-butyl ether acetate;
Examples of diethylene glycol ether include diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, and diethylene glycol ethyl methyl ether;

Examples of the propylene glycol ether include propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether;
Examples of the propylene glycol alkyl ether acetate include propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol n-propyl ether acetate, propylene glycol n-butyl ether acetate and the like;
Examples of the propylene glycol alkyl ether propionate include propylene glycol methyl ether propionate, propylene glycol ethyl ether propionate, propylene glycol n-propyl ether propionate, propylene glycol n-butyl ether propionate and the like;
Examples of aromatic hydrocarbons include toluene and xylene; examples of ketones include methyl ethyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone, and the like;

Examples of the ester include 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-lactic acid Propyl, n-butyl lactate, methyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, n-propyl 3-hydroxypropionate, n-butyl 3-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, Ethyl 2-hydroxy-2-methylpropionate, methyl 2-hydroxy-3-methylbutanoate, methyl methoxyacetate, ethyl methoxyacetate, n-propyl methoxyacetate, n-butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, ethoxy Acetic acid n-p Pill, n-butyl ethoxyacetate, methyl n-propoxyacetate, ethyl n-propoxyacetate, n-propoxyacetate n-propyl, n-propoxyacetate n-butyl, n-butoxyacetate methyl, n-butoxyacetate, n- N-propyl butoxyacetate, n-butyl n-butoxyacetate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, n-propyl 2-methoxypropionate, n-butyl 2-methoxypropionate, 2-ethoxypropion Acid methyl, ethyl 2-ethoxypropionate, n-propyl 2-ethoxypropionate, n-butyl 2-ethoxypropionate, methyl 2-n-propoxypropionate, ethyl 2-n-propoxypropionate, 2-n- N-propyl propoxypropionate, 2-n-propoxy N-butyl lopionate, methyl 2-n-butoxypropionate, ethyl 2-n-butoxypropionate, n-propyl 2-n-butoxypropionate, n-butyl 2-n-butoxypropionate, 3-methoxypropion Acid methyl, ethyl 3-methoxypropionate, n-propyl 3-methoxypropionate, n-butyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, n-propyl 3-ethoxypropionate 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, 3-n-butoxy Examples thereof include ethyl propionate, n-propyl 3-n-butoxypropionate, n-butyl 3-n-butoxypropionate, and the like.

Among these solvents, ethylene glycol alkyl ether acetate, diethylene glycol ether, propylene glycol ether, propylene glycol alkyl ether acetate and the like are preferable, and diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, propylene glycol monomethyl ether and propylene glycol methyl ether acetate are particularly preferable. .
The said solvent can be used individually or in mixture of 2 or more types.
Examples of the radical polymerization initiator used for the polymerization include 2,2′-azobisisobutyronitrile, 2,2′-azobis- (2,4-dimethylvaleronitrile), and 2,2′-. Azo compounds such as azobis- (4-methoxy-2,4-dimethylvaleronitrile); organics such as benzoyl peroxide, lauroyl peroxide, t-butylperoxypivalate, 1,1′-bis- (t-butylperoxy) cyclohexane Peroxide; hydrogen peroxide and the like. When a peroxide is used as the radical polymerization initiator, it may be used as a redox initiator by using it together with a reducing agent.
These radical polymerization initiators can be used alone or in admixture of two or more.

Further, in the polymerization, a molecular weight modifier can be used to adjust the molecular weight of the [A] copolymer.
Specific examples of molecular weight modifiers include halogenated hydrocarbons such as chloroform and carbon tetrabromide; mercaptans such as n-hexyl mercaptan, n-octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan, and thioglycolic acid. And xanthogens such as dimethylxanthogen sulfide and di-i-propylxanthogen disulfide, terpinolene, α-methylstyrene dimer and the like.
These molecular weight modifiers can be used alone or in admixture of two or more.

[B] 1,2-quinonediazide compound [B] 1,2-quinonediazide compound contained in the radiation-sensitive resin composition of the present invention is a 1,2-quinonediazide compound that generates an acid upon irradiation with radiation, Examples include 1,2-benzoquinone diazide sulfonic acid ester, 1,2-naphthoquinone diazide sulfonic acid ester, 1,2-benzoquinone diazide sulfonic acid amide, 1,2-naphthoquinone diazide sulfonic acid amide, and the like.

  Examples of the 1,2-naphthoquinone diazide sulfonate ester include 1,2-naphthoquinone diazide sulfonate ester of trihydroxybenzophenone, 1,2-naphthoquinone diazide sulfonate ester of tetrahydroxybenzophenone, and 1,2-pentahydroxybenzophenone 1,2- Specific examples include naphthoquinone diazide sulfonate, 1,2-naphthoquinone diazide sulfonate of hexahydroxybenzophenone, 1,2-naphthoquinone diazide sulfonate of other (polyhydroxyphenyl) alkanes, and the like. 1,2-naphthoquinone diazide sulfonic acid ester of trihydroxybenzophenone, for example, 2,3,4-trihydroxybenzophenone-1,2-naphthoquino Azido-4-sulfonic acid ester, 2,3,4-trihydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonic acid ester, 2,3,4-trihydroxybenzophenone-1,2-naphthoquinonediazide-6 Sulfonic acid ester, 2,3,4-trihydroxybenzophenone-1,2-naphthoquinonediazide-7-sulfonic acid ester, 2,3,4-trihydroxybenzophenone-1,2-naphthoquinonediazide-8-sulfonic acid ester, 2,4,6-trihydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonic acid ester, 2,4,6-trihydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonic acid ester, 2,4,6 6-Trihydroxybenzophenone-1,2-naphtho Nondiazide-6-sulfonic acid ester, 2,4,6-trihydroxybenzophenone-1,2-naphthoquinonediazide-7-sulfonic acid ester, 2,4,6-trihydroxybenzophenone-1,2-naphthoquinonediazide-8- Sulfonate esters, etc .;

Examples of the 1,2-naphthoquinonediazide sulfonic acid ester of tetrahydroxybenzophenone include 2,2 ′, 4,4′-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonic acid ester, 2,2 ′, 4. , 4′-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonic acid ester, 2,2 ′, 4,4′-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-6-sulfonic acid ester, 2, 2 ′, 4,4′-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-7-sulfonic acid ester, 2,2 ′, 4,4′-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-8-sulfonic acid Ester, 2,3,4,3′-tetrahydroxybenzophenone-1,2 Naphthoquinonediazide-4-sulfonic acid ester, 2,3,4,3′-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonic acid ester, 2,3,4,3′-tetrahydroxybenzophenone-1, 2-naphthoquinonediazide-6-sulfonic acid ester, 2,3,4,3′-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-7-sulfonic acid ester, 2,3,4,3′-tetrahydroxybenzophenone- 1,2-naphthoquinonediazide-8-sulfonic acid ester, 2,3,4,4′-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonic acid ester, 2,3,4,4′-tetrahydroxy Benzophenone-1,2-naphthoquinonediazide-5-sulfonic acid ester, 2, 3,4,4′-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-6-sulfonic acid ester, 2,3,4,4′-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-7-sulfonic acid ester, 2,3,4,4′-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-8-sulfonic acid ester,

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-sulfonic acid ester, 2,3,4,2′-tetrahydroxy-4′-methylbenzophenone-1,2-naphthoquinonediazide-6-sulfonic acid ester, 2,3,4,2 '-Tetrahydroxy-4'-methylbenzophenone-1,2-naphthoquinonediazide-7-sulfonic acid ester, 2,3,4,2'-tetrahydroxy-4'-methylbenzophenone-1,2-naphthoquinonediazide-8 -Sulfonic acid ester, 2,3,4,4'-tetrahydroxy-3'-methoxybenzophenone-1,2-naphthoquinonediadi -4-sulfonic acid ester, 2,3,4,4′-tetrahydroxy-3′-methoxybenzophenone-1,2-naphthoquinonediazide-5-sulfonic acid ester, 2,3,4,4′-tetrahydroxy- 3′-methoxybenzophenone-1,2-naphthoquinonediazide-6-sulfonic acid ester, 2,3,4,4′-tetrahydroxy-3′-methoxybenzophenone-1,2-naphthoquinonediazide-7-sulfonic acid ester, Examples include 2,3,4,4′-tetrahydroxy-3′-methoxybenzophenone-1,2-naphthoquinonediazide-8-sulfonic acid ester and the like.

Examples of the 1,2-naphthoquinone diazide sulfonic acid ester of pentahydroxybenzophenone include 2,3,4,2 ′, 6′-pentahydroxybenzophenone-1,2-naphthoquinone diazide-4-sulfonic acid ester, 2,3,4, 4,2 ′, 6′-pentahydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonic acid ester, 2,3,4,2 ′, 6′-pentahydroxybenzophenone-1,2-naphthoquinonediazide-6 Sulfonic acid ester, 2,3,4,2 ′, 6′-pentahydroxybenzophenone-1,2-naphthoquinonediazide-7-sulfonic acid ester, 2,3,4,2 ′, 6′-pentahydroxybenzophenone-1 , 2-naphthoquinonediazide-8-sulfonic acid ester, etc .;

Examples of the 1,2-naphthoquinonediazide sulfonic acid ester of hexahydroxybenzophenone include 2,4,6,3 ′, 4 ′, 5′-hexahydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonic acid ester, 2 , 4,6,3 ′, 4 ′, 5′-hexahydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonic acid ester, 2,4,6,3 ′, 4 ′, 5′-hexahydroxybenzophenone— 1,2-naphthoquinonediazide-6-sulfonic acid ester, 2,4,6,3 ′, 4 ′, 5′-hexahydroxybenzophenone-1,2-naphthoquinonediazide-7-sulfonic acid ester, 2,4,6 , 3 ′, 4 ′, 5′-hexahydroxybenzophenone-1,2-naphthoquinonediazide-8-sulfonic acid ester, 3,4,5 3 ′, 4 ′, 5′-hexahydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonic acid ester, 3,4,5,3 ′, 4 ′, 5′-hexahydroxybenzophenone-1,2-naphtho Quinonediazide-5-sulfonic acid ester, 3,4,5,3 ′, 4 ′, 5′-hexahydroxybenzophenone-1,2-naphthoquinonediazide-6-sulfonic acid ester, 3,4,5,3 ′, 4 ', 5'-Hexahydroxybenzophenone-1,2-naphthoquinonediazide-7-sulfonic acid ester, 3,4,5,3', 4 ', 5'-hexahydroxybenzophenone-1,2-naphthoquinonediazide-8- Sulfonate esters, etc .;

Examples of the 1,2-naphthoquinone diazide sulfonic acid ester of the above other (polyhydroxyphenyl) alkane include, for example, bis (2,4-dihydroxyphenyl) methane-1,2-naphthoquinone diazide-4-sulfonic acid ester, bis (2, 4-dihydroxyphenyl) methane-1,2-naphthoquinonediazide-5-sulfonic acid ester, bis (2,4-dihydroxyphenyl) methane-1,2-naphthoquinonediazide-6-sulfonic acid ester, bis (2,4- Dihydroxyphenyl) methane-1,2-naphthoquinonediazide-7-sulfonic acid ester, bis (2,4-dihydroxyphenyl) methane-1,2-naphthoquinonediazide-8-sulfonic acid ester, bis (4-hydroxyphenyl) methane -1,2-naphthoquinonediazide- -Sulfonic acid ester, bis (4-hydroxyphenyl) methane-1,2-naphthoquinonediazide-5-sulfonic acid ester, bis (4-hydroxyphenyl) methane-1,2-naphthoquinonediazide-6-sulfonic acid ester, bis (4-Hydroxyphenyl) methane-1,2-naphthoquinonediazide-7-sulfonic acid ester, bis (4-hydroxyphenyl) methane-1,2-naphthoquinonediazide-8-sulfonic acid ester, tris (4-hydroxyphenyl) Methane-1,2-naphthoquinonediazide-4-sulfonic acid ester, tris (4-hydroxyphenyl) methane-1,2-naphthoquinonediazide-5-sulfonic acid ester, tris (4-hydroxyphenyl) methane-1,2- Naphthoquinonediazide-6-sulfonic acid Ether, tris (4-hydroxyphenyl) methane-1,2-naphthoquinonediazide-7-sulfonic acid esters, tris (4-hydroxyphenyl) methane-1,2-naphthoquinonediazide-8-sulfonic acid ester,

1,1,1-tris (4-hydroxyphenyl) ethane-1,2-naphthoquinonediazide-4-sulfonic acid ester, 1,1,1-tris (4-hydroxyphenyl) ethane-1,2-naphthoquinonediazide- 5-sulfonic acid ester, 1,1,1-tris (4-hydroxyphenyl) ethane-1,2-naphthoquinonediazide-6-sulfonic acid ester, 1,1,1-tris (4-hydroxyphenyl) ethane-1 , 2-naphthoquinonediazide-7-sulfonic acid ester, 1,1,1-tris (4-hydroxyphenyl) ethane-1,2-naphthoquinonediazide-8-sulfonic acid ester, bis (2,3,4-trihydroxy) Phenyl) methane-1,2-naphthoquinonediazide-4-sulfonic acid ester, bis (2,3,4-trihydroxy) Enyl) methane-1,2-naphthoquinonediazide-5-sulfonic acid ester, bis (2,3,4-trihydroxyphenyl) methane-1,2-naphthoquinonediazide-6-sulfonic acid ester, bis (2,3,3) 4-trihydroxyphenyl) methane-1,2-naphthoquinonediazide-7-sulfonic acid ester, bis (2,3,4-trihydroxyphenyl) methane-1,2-naphthoquinonediazide-8-sulfonic acid ester, 2, 2-bis (2,3,4-trihydroxyphenyl) propane-1,2-naphthoquinonediazide-4-sulfonic acid ester, 2,2-bis (2,3,4-trihydroxyphenyl) propane-1,2 -Naphthoquinonediazide-5-sulfonic acid ester, 2,2-bis (2,3,4-trihydroxyphenyl) pro 1,2-naphthoquinonediazide-6-sulfonic acid ester, 2,2-bis (2,3,4-trihydroxyphenyl) propane-1,2-naphthoquinonediazide-7-sulfonic acid ester, 2,2- Bis (2,3,4-trihydroxyphenyl) propane-1,2-naphthoquinonediazide-8-sulfonic acid ester,

1,1,3-tris (2,5-dimethyl-4-hydroxyphenyl) -3-phenylpupane-1,2-naphthoquinonediazide-4-sulfonic acid ester, 1,1,3-tris (2,5-dimethyl) -4-hydroxyphenyl) -3-phenylpropane-1,2-naphthoquinonediazide-5-sulfonic acid ester, 1,1,3-tris (2,5-dimethyl-4-hydroxyphenyl) -3-phenylpropane- 1,2-naphthoquinonediazide-6-sulfonic acid ester, 1,1,3-tris (2,5-dimethyl-4-hydroxyphenyl) -3-phenylpropane-1,2-naphthoquinonediazide-7-sulfonic acid ester 1,1,3-tris (2,5-dimethyl-4-hydroxyphenyl) -3-phenylpropane-1,2-naphthoquinonedi Dido-8-sulfonic acid ester, 4,4 ′-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol-1,2-naphthoquinonediazide-4-sulfone Acid ester, 4,4 ′-[1- {4- (1- [4-hydroxyphenyl] -1-methylethyl) phenyl} ethylidene] bisphenol-1,2-naphthoquinonediazide-5-sulfonic acid ester, 4, 4 ′-[1- {4- (1- [4-hydroxyphenyl] -1-methylethyl) phenyl} ethylidene] bisphenol-1,2-naphthoquinonediazide-6-sulfonic acid ester, 4,4 ′-[1 -{4- (1- [4-hydroxyphenyl] -1-methylethyl) phenyl} ethylidene] bisphenol-1,2-naphthoquinonediazide- - sulfonic acid ester, 4,4 '- [1- {4- (1- [4-hydroxyphenyl] -1-methylethyl) phenyl} ethylidene] bisphenol-1,2-naphthoquinonediazide-8-sulfonic acid ester,

Bis (2,5-dimethyl-4-hydroxyphenyl) -2-hydroxyphenylmethane-1,2-naphthoquinonediazide-4-sulfonic acid ester, bis (2,5-dimethyl-4-hydroxyphenyl) -2-hydroxy Phenylmethane-1,2-naphthoquinonediazide-5-sulfonic acid ester, bis (2,5-dimethyl-4-hydroxyphenyl) -2-hydroxyphenylmethane-1,2-naphthoquinonediazide-6-sulfonic acid ester, bis (2,5-Dimethyl-4-hydroxyphenyl) -2-hydroxyphenylmethane-1,2-naphthoquinonediazide-7-sulfonic acid ester, bis (2,5-dimethyl-4-hydroxyphenyl) -2-hydroxyphenyl Methane-1,2-naphthoquinonediazide-8-sulfonic acid ester 3,3,3 ′, 3′-tetramethyl-1,1′-spirobiindene-5,6,7,5 ′, 6 ′, 7′-hexanol-1,2-naphthoquinonediazide-4-sulfone Acid ester 3,3,3 ′, 3′-tetramethyl-1,1′-spirobiindene-5,6,7,5 ′, 6 ′, 7′-hexanol-1,2-naphthoquinonediazide-5 -Sulfonate ester, 3,3,3 ', 3'-tetramethyl-1,1'-spirobiindene-5,6,7,5', 6 ', 7'-hexanol-1,2-naphthoquinonediazide -6-sulfonic acid ester, 3,3,3 ', 3'-tetramethyl-1,1'-spirobiindene-5,6,7,5', 6 ', 7'-hexanol-1,2- Naphthoquinonediazide-7-sulfonic acid ester, 3,3,3 ′, 3′-tetramethyl-1,1′-spirobiinde -5,6,7,5 ', 6', 7'-hexanol-1,2-naphthoquinonediazide-8-sulfonic acid ester, 2,2,4-trimethyl-7,2 ', 4'-trihydroxyflavan -1,2-naphthoquinonediazide-4-sulfonic acid ester, 2,2,4-trimethyl-7,2 ′, 4′-trihydroxyflavan-1,2-naphthoquinonediazide-5-sulfonic acid ester, 2,2 , 4-Trimethyl-7,2 ′, 4′-trihydroxyflavan-1,2-naphthoquinonediazide-6-sulfonic acid ester, 2,2,4-trimethyl-7,2 ′, 4′-trihydroxyflavan- 1,2-naphthoquinonediazide-7-sulfonic acid ester, 2,2,4-trimethyl-7,2 ′, 4′-trihydroxyflavan-1,2-naphthoquinonediazide-8-sulfonic acid ester The ether and the like, can be exemplified respectively.

Examples of the 1,2-benzoquinone diazide sulfonic acid ester include compounds in which 1,2-naphthoquinone in each of the aforementioned 1,2-naphthoquinone diazide sulfonic acid esters is replaced with 1,2-benzoquinone.
Examples of the 1,2-naphthoquinone diazide sulfonic acid amide include compounds in which the sulfonic acid ester in each 1,2-naphthoquinone diazide sulfonic acid ester described above is replaced with a sulfonic acid amide.
As the 1,2-benzoquinone diazide sulfonic acid amide, a compound in which 1,2-naphthoquinone in each of the 1,2-naphthoquinone diazide sulfonic acid esters described above is replaced with 1,2-benzoquinone, and the sulfonic acid ester is replaced with a sulfonic acid amide. Can be mentioned.
Among these 1,2-quinonediazide compounds, 2,2-bis (2,3,4-trihydroxyphenyl) propane-1,2-naphthoquinonediazide-5-sulfonic acid ester, 1,1,3-tris ( 2,5-dimethyl-4-hydroxyphenyl) -3-phenylpropane-1,2-naphthoquinonediazide-4-sulfonic acid ester or bis (2,5-dimethyl-4-hydroxyphenyl) -2-hydroxyphenylmethane- 1,2-naphthoquinonediazide-4-sulfonic acid ester is preferred.
The 1,2-quinonediazide compounds can be used alone or in admixture of two or more.

  The ratio of the [B] 1,2-quinonediazide compound used in the radiation sensitive resin composition of the present invention is preferably 5 to 100 parts by weight, more preferably 10 to 100 parts by weight of the [A] copolymer. 50 parts by weight. By setting the use ratio within this range, the balance between the pattern formability and developability and the heat resistance and solvent resistance of the obtained interlayer insulating film and microlens becomes better.

[C] Heat-sensitive acid generating compound [C] The heat-sensitive acid generating compound used in the present invention is preferably a nonionic heat-sensitive acid generator, such as a sulfone compound, a sulfonic acid ester compound, and a sulfonimide compound. And diazomethane compounds.
Examples of the sulfone compound include β-ketosulfone and β-sulfonylsulfone. Specific examples thereof include β-ketosulfone such as phenacylphenylsulfone, mesitylphenacylsulfone, etc .;
Examples of β-sulfonylsulfone include bis (phenylsulfonyl) methane and 4-trisphenacylsulfone;
Each can be mentioned.

Examples of the sulfonic acid ester compounds include alkyl sulfonic acid esters and aryl sulfonic acid esters. Specific examples of these include alkyl sulfonate esters such as benzoin tosylate, α-methylol benzoin tosylate, α-methylol benzoin n-octane sulfonate, α-methylol benzoin trifluoromethane sulfonate, α-methylol benzoin n-dodecane sulfonate, etc. ;
Examples of aryl sulfonate esters include pyrogallol tris (trifluoromethanesulfonate), pyrogallol tris (nonafluoro-n-butanesulfonate), pyrogallol tris (methanesulfonate), nitrobenzyl-9,10-diethoxyanthracene-2-sulfonate, and the like. Each can be mentioned.

  As the sulfonimide compound, for example, the following general formula (3)

(In the above formula (3), R ⁶ is a divalent organic group, and R ⁷ is a monovalent organic group.)
The compound etc. which are represented by these can be mentioned.
Examples of the divalent organic group represented by R ⁶ include a methylene group, an alkylene group having 2 to 20 carbon atoms, an aralkylene group having 2 to 20 carbon atoms, a cycloalkylene group having 3 to 10 carbon atoms, and an arylene having 6 to 20 carbon atoms. Group, an arylene group having 6 to 20 carbon atoms, and the like. Examples of the cycloalkylene group include a cyclohexylene group and a norbornylene group. In these R ⁶ , some or all of the hydrogen atoms contained therein may be substituted with a halogen atom, an aryl group having 2 to 20 carbon atoms, or an alkoxyl group having 1 to 8 carbon atoms. Examples of the halogen atom include fluorine.

Examples of the monovalent organic group for R ⁷ include an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a hydrocarbon group having a bicyclo ring having 7 to 15 carbon atoms, and 6 to 12 carbon atoms. An aryl group of Examples of the alkyl group having 1 to 10 carbon atoms include methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-octyl group, n-nonyl group, n -Decyl group and the like;
Examples of the cycloalkyl group having 3 to 10 carbon atoms include a cyclohexyl group and a norbornyl group;
Examples of the aryl group having 6 to 12 carbon atoms include a phenyl group, a toluyl group, and a naphthyl group. In these R ⁷ , some or all of the hydrogen atoms contained therein may be substituted with a halogen atom, an aryl group having 2 to 20 carbon atoms, or an alkoxyl group having 1 to 8 carbon atoms. Examples of the halogen atom include fluorine. In addition, when R ⁷ is a cycloalkyl group, part or all of the hydrogen atoms possessed by it are other than the above-described substituents, an alkyl group having 1 to 8 carbon atoms, and an alkoxycarbonyl having 2 to 8 carbon atoms. Group, an alkylalkoxycarbonyl group having 3 to 8 carbon atoms and the like.

Specific examples of such a sulfonimide compound include, for example, N- (trifluoromethanesulfonyloxy) phthalimide, N- (trifluoromethanesulfonyloxy) diphenylmaleimide, N- (trifluoromethanesulfonyloxy) bicyclo [2.2.1]. Hept-5-ene-2,3-dicarboximide, N- (trifluoromethanesulfonyloxy) -7-oxabicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (Trifluoromethanesulfonyloxy) bicyclo [2.2.1] heptane-5,6-oxy-2,3-dicarboximide, N- (trifluoromethanesulfonyloxy) naphthylimide, N- (10-camphorsulfonyloxy) Phthalimide, N- (10-camphorsulfoni Oxy) diphenylmaleimide, N- (10-camphorsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (10-camphorsulfonyloxy) -7-oxabicyclo [2.2.1] Hept-5-ene-2,3-dicarboximide, N- (10-camphorsulfonyloxy) bicyclo [2.2.1] heptane-5,6-oxy-2,3- Dicarboximide, N- (10-camphorsulfonyloxy) naphthylimide

N- (p-toluenesulfonyloxy) phthalimide, N- (p-toluenesulfonyloxy) diphenylmaleimide, N- (p-toluenesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3- Dicarboximide, N- (p-toluenesulfonyloxy) -7-oxabicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (p-toluenesulfonyloxy) bicyclo [ 2.2.1] Heptane-5,6-oxy-2,3-dicarboximide, N- (p-toluenesulfonyloxy) naphthylimide, N- (2-trifluoromethylbenzenesulfonyloxy) phthalimide, N- (2-trifluoromethylbenzenesulfonyloxy) diphenylmaleimide, N- (2-trifluoromethylbenzene) Zensulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (2-trifluoromethylbenzenesulfonyloxy) -7-oxabicyclo [2.2.1] Hept-5-ene-2,3-dicarboximide, N- (2-trifluoromethylbenzenesulfonyloxy) bicyclo [2.2.1] heptane-5,6-oxy-2,3-dicarboximide,

N- (2-trifluoromethylbenzenesulfonyloxy) naphthylimide, N- (4-trifluoromethylbenzenesulfonyloxy) phthalimide, N- (4-trifluoromethylbenzenesulfonyloxy) diphenylmaleimide, N- (4-tri Fluoromethylbenzenesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (4-trifluoromethylbenzenesulfonyloxy) -7-oxabicyclo [2.2. 1] Hept-5-ene-2,3-dicarboximide, N- (4-trifluoromethylbenzenesulfonyloxy) bicyclo [2.2.1] heptane-5,6-oxy-2,3-dicarboxy Imido, N- (4-trifluoromethylbenzenesulfonyloxy) naphthylimi N- (nonafluoro-n-butanesulfonyloxy) phthalimide, N- (nonafluoro-n-butanesulfonyloxy) diphenylmaleimide, N- (nonafluoro-n-butanesulfonyloxy) bicyclo [2.2.1] hept-5 -Ene-2,3-dicarboximide, N- (nonafluoro-n-butanesulfonyloxy) -7-oxabicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (Nonafluoro-n-butanesulfonyloxy) bicyclo [2.2.1] heptane-5,6-oxy-2,3-dicarboximide,

N- (nonafluoro-n-butanesulfonyloxy) naphthylimide, N- (pentafluorobenzenesulfonyloxy) phthalimide, N- (pentafluorobenzenesulfonyloxy) diphenylmaleimide, N- (pentafluorobenzenesulfonyloxy) bicyclo [2. 2.1] Hept-5-ene-2,3-dicarboximide, N- (pentafluorobenzenesulfonyloxy) -7-oxabicyclo [2.2.1] hept-5-ene-2,3-di Carboximide, N- (pentafluorobenzenesulfonyloxy) bicyclo [2.2.1] heptane-5,6-oxy-2,3-dicarboximide, N- (pentafluorobenzenesulfonyloxy) naphthylimide, N- (Perfluoro-n-octanesulfonyloxy) Talimide, N- (perfluoro-n-octanesulfonyloxy) diphenylmaleimide, N- (perfluoro-n-octanesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide N- (perfluoro-n-octanesulfonyloxy) -7-oxabicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (perfluoro-n-octanesulfonyloxy) ) Bicyclo [2.2.1] heptane-5,6-oxy-2,3-dicarboximide, N- (perfluoro-n-octanesulfonyloxy) naphthylimide and the like.

  Examples of the diazomethane compound include the following general formula (4).

(In the above formula (4), each R ⁸ is independently an alkyl group having 1 to 8 carbon atoms or an aryl group having 2 to 20 carbon atoms.)
The compound etc. which are represented by these can be mentioned.
In R ⁸ in formula (4), part or all of the hydrogen atoms contained therein may be substituted with a halogen atom.
Specific examples of such a diazomethane compound include, for example, bis (trifluoromethanesulfonyl) diazomethane, bis (t-butylsulfonyl) diazomethane, bis (cyclohexanesulfonyl) diazomethane, bis (benzenesulfonyl) diazomethane, and bis (p-toluenesulfonyl). Diazomethane, methanesulfonyl-p-toluenesulfonyldiazomethane, cyclohexanesulfonyl-1,1-dimethylethylsulfonyldiazomethane, bis (1,1-dimethylethanesulfonyl) diazomethane, bis (3,3-dimethyl-1,5-dioxaspiro [5 .5] dodecane-8-sulfonyl) diazomethane, bis (1,4-dioxaspiro [4.5] decan-7-sulfonyl) diazomethane, and the like.

Only one kind of the above-mentioned [C] thermosensitive acid-generating compound can be used, or two or more kinds can be mixed and used.
The [C] thermosensitive acid-generating compound used in the present invention is preferably a sulfonimide compound or a diazomethane compound, and particularly N- (trifluoromethanesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2, 3-dicarboximide, N- (10-camphorsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, bis (cyclohexanesulfonyl) diazomethane, bis (t-butylsulfonyl) It is preferable to use at least one compound selected from the group consisting of diazomethane and bis (1,4-dioxaspiro [4.5] -decan-7-sulfonyl) diazomethane.

  The use ratio of the [C] thermosensitive acid-generating compound in the radiation-sensitive resin composition of the present invention is preferably 0.01 to 20 parts by weight, more preferably 0, relative to 100 parts by weight of the [A] copolymer. .1 to 5 parts by weight. By setting the use ratio within this range, the balance between pattern formability and resolution becomes better.

Other Components The radiation-sensitive resin composition of the present invention contains the above-mentioned copolymer [A], [B] 1,2-quinonediazide compound and [C] thermosensitive acid generating compound component as essential components. As required, [D] a polymerizable compound having at least one ethylenically unsaturated double bond, [E] an epoxy resin, [F] a melamine resin, [G] a surfactant, or [H ] An adhesion assistant can be contained.
Examples of the polymerizable compound [D] having at least one ethylenically unsaturated double bond (hereinafter sometimes referred to as “[D] component”) include monofunctional (meth) acrylate and bifunctional (meta) ) Acrylates or trifunctional or higher functional (meth) acrylates may be mentioned.
Examples of the monofunctional (meth) acrylate include 2-hydroxyethyl (meth) acrylate, carbitol (meth) acrylate, isobornyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, and 2- (meth) acryloyloxyethyl. -2-hydroxypropyl phthalate and the like. As these commercial products, for example, Aronix M-101, M-111, M-114 (above, manufactured by Toagosei Co., Ltd.), KAYARAD TC-110S, TC-120S (above, Nippon Kayaku ( Co., Ltd.), Viscoat 158, 2311 (above, manufactured by Osaka Organic Chemical Industry Co., Ltd.), and the like.

  Examples of the bifunctional (meth) acrylate include ethylene glycol (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, polypropylene glycol di (meth) acrylate, Examples include tetraethylene glycol di (meth) acrylate, bisphenoxyethanol full orange acrylate, and bisphenoxyethanol full orange acrylate. As these commercial products, for example, Aronix M-210, M-240, M-6200 (above, manufactured by Toagosei Co., Ltd.), KAYARAD HDDA, HX-220, R-604 (above, Nippon Kayaku) Medicine Co., Ltd.), Biscoat 260, 312 and 335HP (Osaka Organic Chemical Co., Ltd.).

  Examples of the trifunctional or higher functional (meth) acrylate include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, tri ((meth) acryloyloxyethyl) phosphate, and pentaerythritol tetra (meth) acrylate. , Dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate and the like, and as commercially available products thereof, for example, Aronix M-309, M-400, M-405, M-450, M-7100, M-8030, M-8060 (above, manufactured by Toagosei Co., Ltd.), KAYARAD TMPTA, DPHA, DPCA-20, DPCA-30, DPCA-60, DPCA-120 (Nippon Kayaku Co., Ltd.) Viscoat 295, the 300, the 360, the GPT, said 3PA, the 400 (or more, manufactured by Osaka Organic Chemical Industry Co., Ltd.).

Of these, a tri- or higher functional (meth) acrylate is preferably used, and among them, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, and dipentaerythritol hexa (meth) acrylate are particularly preferable.
These monofunctional, bifunctional, or trifunctional or higher (meth) acrylates can be used alone or in combination of two or more. The proportion of component [D] used is preferably 50 parts by weight or less, more preferably 30 parts by weight or less, based on 100 parts by weight of [A] copolymer.
By including the component [D] at such a ratio, the heat resistance and surface hardness of the obtained interlayer insulating film or microlens can be further improved without affecting the film forming property of the composition.

The [E] epoxy resin is not limited as long as the compatibility is not affected, but preferably a bisphenol A type epoxy resin, a phenol novolac type epoxy resin, a cresol novolac type epoxy resin, a cyclic aliphatic epoxy resin, Examples thereof include glycidyl ester type epoxy resins, glycidyl amine type epoxy resins, heterocyclic epoxy resins, and resins obtained by (co) polymerization of glycidyl methacrylate. Among these, bisphenol A type epoxy resin, cresol novolac type epoxy resin, glycidyl ester type epoxy resin and the like can be mentioned.
[E] The use ratio of the epoxy resin is preferably 30 parts by weight or less with respect to 100 parts by weight of the [A] copolymer. By containing the component [E] in such a ratio, the heat resistance and surface hardness of the obtained interlayer insulating film or microlens can be reduced without impairing the film forming property of the composition, particularly the uniformity of the film thickness. Further improvement can be achieved.
In addition, when an epoxy group-containing monomer is used as a copolymerization monomer of the [A] copolymer, the [A] copolymer can also be referred to as an “epoxy resin”, but it has an alkali solubility [E]. Different from epoxy resin.

  The [F] melamine resin can be used to further improve the heat resistance and strength of the interlayer insulating film or microlens to be formed. [F] As the melamine resin, for example, the following formula (5)

(In the above formula (5), R ¹¹ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms (preferably 1 to 4 carbon atoms).)
Is a compound having one or more groups represented by The [F] melamine resin is preferably a compound having two or more groups represented by the above formula (5), more preferably a compound in which these groups are bonded to a nitrogen atom. [F] When the melamine resin is a compound having two or more groups represented by the above formula (5) in the molecule, the plurality of R ⁶ may be the same or different from each other.
As such [F] melamine resin, for example, the following formula (6)

(In the above formula (6), each R ¹² is independently an alkyl group having 1 to 4 carbon atoms.)
A compound represented by the following formula (7):

(In the above formula (7), each R ¹³ is independently an alkyl group having 1 to 4 carbon atoms.)
Represented by the above formula (5) and urea-formaldehyde resins, thiourea-formaldehyde resins, melamine-formaldehyde resins, guanamine-formaldehyde resins, benzoguanamine-formaldehyde resins, glycoluril-formaldehyde resins and polyvinylphenols. And a resin having a group bonded thereto.
[F] The use ratio of the melamine resin is preferably 10 parts by weight or less, more preferably 7 parts by weight or less with respect to 100 parts by weight of the [A] copolymer.

As said [G] surfactant, a fluorochemical surfactant, a silicone type surfactant, and a nonionic surfactant can be used conveniently.
Specific examples of the fluorosurfactant include, for example, 1,1,2,2-tetrafluorooctyl (1,1,2,2-tetrafluoropropyl) ether, 1,1,2,2-tetrafluorooctylhexyl. Ether, octaethylene glycol di (1,1,2,2-tetrafluorobutyl) ether, hexaethylene glycol (1,1,2,2,3,3-hexafluoropentyl) ether, octapropylene glycol di (1, 1,2,2-tetrafluorobutyl) ether, hexapropylene glycol di (1,1,2,2,3,3-hexafluoropentyl) ether, sodium perfluorododecylsulfonate, 1,1,2,2, In addition to 8,8,9,9,10,10-decafluorododecane, 1,1,2,2,3,3-hexafluorodecane, etc., fluoroalkyl Fluoroalkyloxyethylene ethers; Fluoroalkylammonium iodides, Fluoroalkylpolyoxyethylene ethers, Perfluoroalkylpolyoxyethanols; Perfluoroalkylalkoxylates; Fluoroalkyl esters, etc. Can be mentioned.
These commercial products include BM-1000, BM-1100 (manufactured by BM Chemie), MegaFuck F142D, F172, F173, F183, F178, F191, F191 (and above, Dainippon Ink). Chemical Industries, Ltd.), Fluorad FC-170C, FC-171, FC-430, FC-431 (above, manufactured by Sumitomo 3M), Surflon S-112, S-113, S-131, S-141, S-145, S-382, SC-101, SC-102, SC-103, SC-104, SC-105, SC-106 (manufactured by Asahi Glass Co., Ltd.) ), F-top EF301, 303, and 352 (manufactured by Shin-Akita Kasei Co., Ltd.).

Examples of the silicone surfactant include DC3PA, DC7PA, FS-1265, SF-8428, SH11PA, SH21PA, SH28PA, SH29PA, SH30PA, SH-190, SH-193, SZ-6032 (above, Toray Dow Corning) -Silicone Co., Ltd.), TSF-4440, TSF-4300, TSF-4445, TSF-4446, TSF-4460, TSF-4442 (above, GE Toshiba Silicone Co., Ltd.) are commercially available. You can list what you have.
Examples of the nonionic surfactant include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, and polyoxyethylene oleyl ether; polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether Polyoxyethylene aryl ethers such as polyoxyethylene dilaurate, polyoxyethylene dialkyl esters such as polyoxyethylene distearate, etc .; (meth) acrylic acid copolymer polyflow Nos. 57 and 95 (Kyoeisha Chemical Co., Ltd.) ))) Can be used.
These surfactants can be used alone or in combination of two or more.
These [G] surfactants are preferably used in an amount of 5 parts by weight or less, more preferably 2 parts by weight or less based on 100 parts by weight of the [A] copolymer.

  As the [H] adhesion aid, for example, a functional silane coupling agent is preferably used, and in particular, a silane coupling agent having a reactive substituent such as a carboxyl group, a methacryloyl group, an isocyanate group, and an epoxy group can be mentioned. Specifically, trimethoxysilylbenzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane and the like. Such [H] adhesion assistant is preferably used in an amount of 20 parts by weight or less, more preferably 10 parts by weight or less, based on 100 parts by weight of the [A] copolymer.

Radiation Sensitive Resin Composition The radiation sensitive resin composition of the present invention comprises the above [A] copolymer, [B] 1,2-quinonediazide compound and [C] thermosensitive acid generating compound, and optionally It is prepared by mixing uniformly the other components that can be added. The radiation-sensitive resin composition of the present invention is preferably used in a solution state after being dissolved in an appropriate solvent. For example, [A] copolymer, [B] 1,2-quinonediazide compound and [C] thermosensitive acid generating compound and other optional components are mixed in a suitable solvent at a predetermined ratio. Thus, a radiation-sensitive resin composition in a solution state can be prepared.
Solvents used for the preparation of the radiation sensitive resin composition of the present invention include [A] copolymer, [B] 1,2-quinonediazide compound and [C] thermosensitive acid generating compound, and optionally mixed. The other components are dissolved uniformly and do not react with each component.

As such a solvent, the thing similar to what was illustrated as a solvent which can be used in the case of the superposition | polymerization for manufacturing the above-mentioned [A] copolymer can be mentioned.
Among such solvents, alcohol, glycol ether, ethylene glycol alkyl ether acetate, ester and diethylene glycol are preferably used from the viewpoints of solubility of each component, reactivity with each component, ease of film formation, and the like. Among these, benzyl alcohol, 2-phenylethyl alcohol, 3-phenyl-1-propanol, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol dimethyl ether, propylene glycol monomethyl ether, Purpylene glycol monomethyl ether acetate, methyl methoxypropionate, and ethyl ethoxypropionate can be particularly preferably used.

Furthermore, in order to improve the in-plane uniformity of the film thickness together with the solvent, a high boiling point solvent can be used in combination. Examples of the high boiling point solvent that can be used in combination include N-methylformamide, N, N-dimethylformamide, N-methylformanilide, N-methylacetamide, N, N-dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, and benzylethyl ether. , Dihexyl ether, acetonyl acetone, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, phenyl Examples include cellosolve acetate. Of these, N-methylpyrrolidone, γ-butyrolactone, and N, N-dimethylacetamide are preferable.
When a high boiling point solvent is used in combination as the solvent of the radiation sensitive resin composition of the present invention, the amount used is 50% by weight or less, preferably 40% by weight or less, more preferably 30% by weight or less, based on the total amount of the solvent. can do. By setting the use amount in this range, the film thickness uniformity (in-plane uniformity) of the coating can be further improved without impairing the sensitivity and remaining film ratio of the composition.

When preparing the radiation-sensitive resin composition of the present invention in a solution state, components other than the solvent in the solution (ie, [A] copolymer and [B] 1,2-quinonediazide compound and optionally added) The ratio of the total amount of the other components can be arbitrarily set according to the purpose of use and the value of the desired film thickness, but is preferably 5 to 50% by weight, more preferably 10 to 40% by weight, More preferably, it is 15 to 35% by weight.
The composition solution thus prepared can be used after being filtered using a Millipore filter having a pore size of about 0.2 to 0.5 μm.
Especially the radiation sensitive resin composition of this invention can be used very suitably for formation of an interlayer insulation film and a micro lens.

Method for Forming Interlayer Insulating Film and Microlens The method for forming an interlayer insulating film and the method for forming a microlens of the present invention include the following steps in the following order.
(B) A step of forming a film of the radiation sensitive resin composition on the substrate (b) A step of irradiating at least a part of the film (c) A step of developing the film after exposure (d) After development Step of heating the coating Hereinafter, each of these steps will be described.

(A) Step of forming a coating film of a radiation sensitive resin composition on a substrate In this step, the radiation sensitive resin composition of the present invention is coated or transferred onto the substrate surface to thereby form a radiation sensitive resin composition. This is a step of forming a film. When the radiation-sensitive resin composition of the present invention contains a solvent, a film can be formed by applying or transferring the solution-like composition to the substrate surface and then pre-baking to remove the solvent.
Examples of the substrate that can be used include a glass substrate, a silicon wafer, and a substrate on which various metal films are formed.
The coating method is not particularly limited, and for example, an appropriate method such as a spray method, a roll coating method, a spin coating method (spin coating method), a slit die coating method, a bar coating method, or an ink jet coating method is adopted. In particular, a spin coating method and a slit die coating method are preferable.

An example of the transfer method is a dry film method.
When the dry film method is adopted when forming the coating film of the radiation sensitive resin composition on the substrate, the dry film is formed on a base film, preferably a flexible base film, on the radiation sensitive resin of the present invention. It is formed by laminating a radiation-sensitive layer made of a composition (hereinafter referred to as “radiation-sensitive dry film”).
The radiation-sensitive dry film can be formed by laminating a radiation-sensitive layer by applying the radiation-sensitive resin composition of the present invention on a base film, preferably as a liquid composition, and then drying.
As the base film of the radiation-sensitive dry film, for example, a synthetic resin film such as polyethylene terephthalate (PET) film, polyethylene, polypropylene, polycarbonate, polyvinyl chloride or the like can be used. The thickness of the base film is suitably in the range of 15 to 125 μm.
The application method when laminating the radiation sensitive layer on the base film is not particularly limited, but for example, an appropriate method such as an applicator coating method, a bar coating method, a roll coating method, or a curtain flow coating method is adopted. can do.

The pre-baking conditions vary depending on the type of each component, the use ratio, and the like, but can be, for example, 60 to 110 ° C. for 30 seconds to 15 minutes.
The film thickness to be formed is preferably about 3 to 6 μm, for example, when forming an interlayer insulating film, and about 0.5 to 3 μm, for example, when forming a microlens. In addition, this film thickness should be understood as a value after solvent removal, when the radiation sensitive resin composition of this invention contains a solvent.

(B) Step of irradiating at least a part of the film with radiation (hereinafter referred to as “exposure”) In this step, at least a part of the formed film is exposed. When exposing only a part of the film, the exposure is usually performed through a photomask having a predetermined pattern.
Examples of radiation used for exposure include ultraviolet rays such as g-ray (wavelength 436 nm) and i-ray (wavelength 365 nm), far ultraviolet rays such as KrF excimer laser, X-rays such as synchrotron radiation, and charged particle beams such as electron beams. Among these, ultraviolet rays are preferable, and radiation containing g-line and / or i-line is particularly preferable.
Energy of exposure, in the case of forming an interlayer insulating film, for example 50~1,500J / m ² approximately, in the case of forming a microlens, for example, about 50~2,000J / m ² is preferable.

(C) Step of developing the film after exposure In this step, the film after exposure is developed and the exposed portion is removed to form a predetermined pattern.
Examples of the developer used for development include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, ammonia, ethylamine, n-propylamine, diethylamine, diethylaminoethanol, di-n-propylamine. , Triethylamine, methyldiethylamine, dimethylethanolamine, triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, pyrrole, piperidine, 1,8-diazabicyclo [5,4,0] -7-undecene, 1,5- An aqueous solution of an alkali (basic compound) such as diazabicyclo [4,3,0] -5-nonene is preferable, but various organic solvents capable of dissolving the coating film of the radiation-sensitive resin composition can be used in some cases. .
In addition, an appropriate amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant can be added to the alkali aqueous solution.
As a developing method, an appropriate method such as a liquid piling method, a dipping method, a rocking dipping method, a shower method or the like can be employed.
The development time varies depending on the type of each component, the use ratio, and the like, but can be, for example, about 30 to 120 seconds.
In addition, in the conventionally known radiation-sensitive resin composition, if the development time exceeds about 20 to 25 seconds from the optimum time, the formed pattern is peeled off, so that it is necessary to strictly control the development time. However, in the case of the radiation-sensitive resin composition of the present invention, even when the excess time from the optimum development time is 30 seconds or more, a good pattern can be formed, which is extremely advantageous in terms of product yield or productivity. is there.

(D) Step of heating the film after development In this step, the film on which the predetermined pattern is formed is preferably washed with running water, for example, and more preferably irradiated with radiation such as a high-pressure mercury lamp over the entire surface. After decomposing the 1,2-quinonediazite compound remaining in the coating film by exposure (post-exposure), the coating film is heated (post-baked) with a heating device such as a hot plate or oven. To cure. When forming a microlens, the formed pattern is melt-flowed by post-baking to obtain a predetermined shape.
Exposure amount in the post-exposure is preferably 2,000~5,000J / m ² approximately.
Moreover, the heating temperature in a post-bake is about 120-250 degreeC, for example. Although heating time changes with kinds of heating apparatus, it can be set to about 5 to 30 minutes, for example on a hot plate, and can be set to about 30 to 90 minutes in an oven, for example. At this time, a step baking method or the like in which heat treatment is performed twice or more may be employed.
In this way, a patterned thin film corresponding to the target interlayer insulating film or microlens can be formed on the substrate surface.

Interlayer Insulating Film and Microlens Each of the interlayer insulating film and the microlens of the present invention is preferably formed from the radiation sensitive resin composition of the present invention as described above.
The interlayer insulating film of the present invention can be used very suitably for electronic components such as TFT liquid crystal display elements, magnetic head elements, integrated circuit elements, solid-state imaging elements and the like.
Further, the microlens of the present invention has a semi-convex lens shape with a good shape. The microlens of the present invention and the microlens array in which the microlenses are regularly arranged are extremely suitable as an imaging optical system for an on-chip color filter such as a facsimile, an electronic copying machine, a solid-state imaging device, or an optical system material for an optical fiber connector. Can be used.

EXAMPLES The present invention will be described more specifically with reference to the following examples and comparative examples. However, the present invention is not limited to the following examples.
Synthesis of copolymer Synthesis example 1
A flask equipped with a condenser and a stirrer was charged with 7 parts by weight of 2,2′-azobis (2,4-dimethylvaleronitrile) and 220 parts by weight of propylene glycol monomethyl ether acetate. Subsequently, 22 parts by weight of methacrylic acid, 38 parts of dicyclopentanyl methacrylate, 40 parts by weight of 3- (methacryloyloxymethyl) -2-phenyloxetane and 1.5 parts by weight of α-methylstyrene dimer were charged and gently stirred while replacing with nitrogen. Started. The temperature of the solution was raised to 70 ° C. and heated at this temperature for 4 hours to obtain a polymer solution containing the copolymer (A-1). The obtained polymer solution had a solid content concentration of 31.8%, a weight average molecular weight of 17,900, and a molecular weight distribution (Mw / Mn) of 1.8. In addition, a weight average molecular weight and a number average molecular weight are polystyrene conversion average molecular weights measured using GPC (Gel permeation chromatography (Tosoh Co., Ltd. product HLC-8020)).

Synthesis example 2
A flask equipped with a condenser and a stirrer was charged with 7 parts by weight of 2,2′-azobis (2,4-dimethylvaleronitrile) and 220 parts by weight of propylene glycol monomethyl ether acetate. Subsequently, 5 parts by weight of styrene, 22 parts by weight of methacrylic acid, 45 parts by weight of 3- (methacryloyloxymethyl) -3-ethyloxetane, 5 parts by weight of styrene, and 1.5 parts by weight of α-methylstyrene dimer were charged and gradually replaced with nitrogen. Stirring was started. The temperature of the solution was raised to 70 ° C. and heated at this temperature for 4 hours to obtain a polymer solution containing the copolymer (A-2). The resulting polymer solution had a solid content concentration of 31.9%, a weight average molecular weight of 20,200, and a molecular weight distribution of 1.9.

Synthesis example 3
A flask equipped with a condenser and a stirrer was charged with 7 parts by weight of 2,2′-azobis (2,4-dimethylvaleronitrile) and 150 parts by weight of propylene glycol monomethyl ether acetate. Subsequently, 20 parts by weight of styrene, 25 parts by weight of methacrylic acid, 20 parts of cyclohexylmaleimide, 35 parts by weight of 3- (methacryloyloxymethyl) -2-trifluoromethyloxetane and 1.5 parts by weight of α-methylstyrene dimer were charged and replaced with nitrogen. While stirring, it started gently. The temperature of the solution was raised to 70 ° C. and heated at this temperature for 4 hours to obtain a polymer solution containing the copolymer (A-3). The obtained polymer solution had a solid content of 38.7%, the polymer had a weight average molecular weight of 21,500 and a molecular weight distribution of 2.2.

Synthesis example 4
A flask equipped with a condenser and a stirrer was charged with 7 parts by weight of 2,2′-azobis (2,4-dimethylvaleronitrile) and 220 parts by weight of propylene glycol monomethyl ether acetate. Subsequently, 20 parts by weight of styrene, 30 parts by weight of methacrylic acid, 50 parts by weight of 2- (methacryloyloxymethyl) -4-trifluoromethyloxetane and 2.0 parts by weight of α-methylstyrene dimer were charged and gently stirred while replacing with nitrogen. I started. The temperature of the solution was raised to 70 ° C. and heated at this temperature for 5 hours to obtain a polymer solution containing the copolymer (A-4). The obtained polymer solution had a solid content concentration of 31.0%, a weight average molecular weight of 19000, and a molecular weight distribution of 1.7.

Comparative Synthesis Example 1
A flask equipped with a condenser and a stirrer was charged with 7 parts by weight of 2,2′-azobis (2,4-dimethylvaleronitrile) and 220 parts by weight of diethylene glycol methyl ethyl ether. Subsequently, 23 parts by weight of methacrylic acid, 47 parts of dicyclopentanyl methacrylate, 20 parts by weight of glycidyl methacrylate and 2.0 parts by weight of α-methylstyrene dimer were charged, and gentle stirring was started while replacing with nitrogen. The temperature of the solution was raised to 70 ° C., and this temperature was maintained for 5 hours to obtain a polymer solution containing the copolymer (a-1). The obtained polymer solution had a solid content concentration of 32.8%, a weight average molecular weight of 24,000, and a molecular weight distribution of 2.3.

Comparative Synthesis Example 2
A flask equipped with a condenser and a stirrer was charged with 7 parts by weight of 2,2′-azobis (2,4-dimethylvaleronitrile) and 220 parts by weight of diethylene glycol methyl ethyl ether. Subsequently, 25 parts by weight of methacrylic acid, 35 parts of dicyclopentanyl methacrylate, 40 parts by weight of 2-hydroxyethyl methacrylate and 2.0 parts by weight of α-methylstyrene dimer were charged, and gentle stirring was started while replacing with nitrogen. The temperature of the solution was raised to 70 ° C., and this temperature was maintained for 5 hours to obtain a polymer solution containing the copolymer (a-2). The obtained polymer solution had a solid content concentration of 32.8%, a weight average molecular weight of 25,000, and a molecular weight distribution of 2.4.

Preparation and evaluation of the composition Example 1
Preparation of Radiation Sensitive Resin Composition An amount corresponding to 100 parts by weight of the polymer solution containing the copolymer [A-1] obtained in Synthesis Example 1 in terms of the copolymer (A-1), [B] 4,4 ′-[1- [4- [1- [4-Hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol (1 mol) and 1,2-quinonediazide compound Condensation product with naphthoquinonediazide-5-sulfonic acid chloride (2 mol) (4,4 ′-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol-1 , 2-naphthoquinonediazide-5-sulfonic acid ester) 30 parts by weight, [H] 5 parts by weight of γ-methacryloxypropyltrimethoxysilane as an adhesion aid, and [C] N- (trifluoro) as a thermosensitive acid-generating compound. 1 part by weight of methanesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide is mixed, and the solid content concentration (the total amount of the components excluding the solvent in the total amount of the composition) The solution (S-1) of the radiation sensitive resin composition was prepared by diluting with propylene glycol monomethyl ether acetate so that the ratio was 30% by weight, followed by filtration through a Millipore filter having a pore size of 0.2 μm.

Evaluation of Storage Stability A part of the composition (S-1) prepared above was taken, sealed in a glass screw tube, heated in an oven at 40 ° C. for 1 week, and the rate of change in viscosity before and after heating. Was measured. The results are shown in Table 1. Here, it can be said that the storage stability is good when the viscosity change rate is 0 to + 5%.

Evaluation of Development Margin Each composition (S-1) was applied onto a plurality of silicon substrates using a spinner, and then pre-baked on a hot plate at 90 ° C. for 2 minutes to form a film. Using a PLA-501F exposure machine (extra high pressure mercury lamp) manufactured by Canon Inc. through a mask having a 3.0 μm line and space (10 to 1) pattern on the obtained film, at a wavelength of 365 nm After irradiating with 80 W / m ² of ultraviolet light for 40 seconds, developing with a puddle method using a tetramethylammonium hydroxide aqueous solution having a concentration of 0.4% by weight as a developing solution at 25 ° C., changing the developing time for each substrate. did. Subsequently, the substrate was washed with ultrapure water for 1 minute and dried to form a pattern having a thickness of 3.0 μm on the wafer. At this time, the minimum development time required for the line line width to be 3.0 μm is shown in Table 1 as the optimum development time. Further, when the development was further continued from the optimum development time, the time until the 3.0 μm line pattern was peeled was measured and shown in Table 1 as a development margin. When this value is 30 seconds or more, it can be said that the development margin is good.

I. Evaluation as Interlayer Insulating Film (1) Resolution Evaluation-Formation of Patterned Thin Film-
The composition (S-1) was applied onto a glass substrate using a spinner, and then prebaked on an 80 ° C. hot plate for 3 minutes to form a coating.
Next, the obtained film was irradiated with ultraviolet rays having an intensity of 100 W / m ^{2 at} a wavelength of 365 nm for 15 seconds through a photomask having a predetermined pattern. Thereafter, development was performed with a 0.5 wt% tetramethylammonium hydroxide aqueous solution at 25 ° C. for 1 minute, followed by washing with pure water for 1 minute to remove unnecessary portions and form a pattern.
Next, the formed pattern was irradiated with ultraviolet rays having an intensity of 100 W / m ² at a wavelength of 365 nm for 30 seconds, and then heated (post-baked) in an oven at 220 ° C. for 60 minutes, whereby a film thickness of 3.0 μm was obtained. A patterned thin film was obtained. Further, except that the pre-baking temperature was set to 90 ° C. or 100 ° C., the same operation as described above was performed to obtain a total of three types of patterned thin films having different pre-baking temperatures.
-Evaluation of resolution-
The obtained patterned thin film was evaluated as “◯” when the blank pattern (5 μm × 5 μm hole) was resolved, and “x” when it was not resolved. The results are shown in Table 2.

(2) Evaluation of heat-resistant dimensional stability In the above-mentioned “(1) Resolution evaluation” — “Formation of patterned thin film—”, a pattern formed at a pre-baking temperature of 80 ° C. is post-baked in an oven at 220 ° C. for 60 minutes. The film thickness before and after the measurement was measured. The results are shown in Table 2. here,. When the rate of change in film thickness is within ± 5%, it can be said that the heat-resistant dimensional stability is good.
(3) Evaluation of transparency After coating the composition (S-1) on a glass substrate using a spinner, it was pre-baked on a hot plate at 80 ° C for 3 minutes to form a film.
Subsequently, the entire surface of the obtained film was irradiated with ultraviolet rays having an intensity of 100 W / m ^{2 at} a wavelength of 365 nm for 30 seconds. Subsequently, it heated for 60 minutes in 220 degreeC oven (post-baking), and the film | membrane with a film thickness of 3.0 micrometers was obtained.
Using the spectrophotometer (150-20 type double beam (manufactured by Hitachi, Ltd.)), the same kind of glass substrate as that used for the substrate on the reference side is used for the light transmittance at a wavelength of 400 nm of the film obtained above. Was measured. The results are shown in Table 2. Here, it can be said that the transparency is good when the transmittance is 90% or more.

(4) Evaluation of heat-resistant discoloration After the substrate having the coating film measured in the above “(3) Evaluation of transparency” was heated in an oven at 250 ° C. for 1 hour, the same as “(3) Evaluation of transparency” Then, the light transmittance at a wavelength of 400 nm was measured. The change rate of the transmittance before and after heating is shown in Table 2. Here, it can be said that the heat discoloration is good when the transmittance change rate is less than 5%.
(5) Evaluation of Adhesion A film having a thickness of 3.0 μm was obtained in the same manner as in the previous part of “(3) Evaluation of transparency”. The substrate having this film was placed in a pressure cooker at a temperature of 120 ° C. and a humidity of 100% for 4 hours, and then a cross-cut peel test was performed in accordance with JIS-K5400. Table 2 shows the number of remaining grids out of 100 grids at this time.

II. Evaluation as a microlens (1) Evaluation of sensitivity After applying the composition (S-1) on a plurality of silicon substrates using a spinner so that the film thickness after removal of the solvent is 2.5 μm, respectively. A plurality of substrates having a coating were formed by pre-baking on a hot plate at 70 ° C. for 3 minutes.
Next, the obtained film was exposed with a different exposure amount for each substrate through a mask having a line width of 0.8 μm line and space pattern (10 to 1), and then 2.38 weight. A patterned thin film was obtained by developing with 25% tetramethylammonium hydroxide aqueous solution at 25 ° C. for 1 minute and washing with pure water for 1 minute.
The plurality of substrates described above were observed with a microscope, and the minimum exposure amount capable of resolving the space line width (0.08 μm) was examined. The results are shown in Table 3. It can be said that the sensitivity is good when this value is 1,000 J / m ² or less.

(2) Evaluation of transparency After coating the composition (S-1) on a glass substrate using a spinner, it was pre-baked on a hot plate at 70 ° C for 3 minutes to form a film.
Subsequently, the entire surface of the obtained film was irradiated with ultraviolet rays having an intensity of 100 W / m ^{2 at} a wavelength of 365 nm for 30 seconds. Subsequently, it heated for 60 minutes in 160 degreeC oven (post-baking), and the film | membrane with a film thickness of 2.5 micrometers was obtained.
Using the spectrophotometer (150-20 type double beam (manufactured by Hitachi, Ltd.)), the same kind of glass substrate as that used for the substrate on the reference side is used for the light transmittance at a wavelength of 400 nm of the film obtained above. Was measured. The results are shown in Table 3. Here, it can be said that the transparency is good when the transmittance is 90% or more.
(3) Evaluation of heat-resistant discoloration After the substrate having the film measured in the above “(2) Evaluation of transparency” was heated in an oven at 250 ° C. for 1 hour, the same as “(2) Evaluation of transparency” Then, the light transmittance at a wavelength of 400 nm was measured. Table 3 shows the rate of change in transmittance before and after heating. Here, it can be said that the heat discoloration is good when the transmittance change rate is less than 5%.

(5) Evaluation of solvent resistance A film having a film thickness of 2.5 μm was obtained in the same manner as in the preceding part of “(3) Evaluation of transparency”. The board | substrate which has this film | membrane was immersed in 50 degreeC isopropanol for 10 minutes, and the film thickness change rate before and behind immersion was measured. The results are shown in Table 3. If this value is 0 to + 5%, the solvent resistance is good.
(6) Evaluation of adhesion A film having a film thickness of 2.5 μm was obtained in the same manner as in the previous part of “(3) Evaluation of transparency” except that a silicon substrate was used instead of the glass substrate. The substrate having this film was placed in a pressure cooker at a temperature of 120 ° C. and a humidity of 100% for 4 hours, and then a cross-cut peel test was performed in accordance with JIS-K5400. Table 3 shows the number of remaining grids out of 100 grids at this time.

(7) Evaluation of microlens shape After applying the composition (S-1) on a plurality of silicon substrates using a spinner so that the film thickness after removal of the solvent becomes 2.5 μm, hot at 70 ° C. Pre-baked on the plate for 3 minutes to form a substrate with a coating.
Next, the NSR1755i7A reduction projection exposure machine (NA = 0.50, λ = 365 nm) manufactured by Nikon Corporation was passed through a pattern mask having 4.0 μm dots and 2.0 μm space pattern on the obtained film. Then, exposure was performed at an exposure amount of 3000 J / m ^{2, and} development was performed by a puddle method at 25 ° C. for 1 minute in an aqueous solution of 1.1% by weight of tetramethylammonium hydroxide. Next, after washing with water, it was dried to form a pattern on the wafer. Then, it exposed so that an integrated irradiation amount might be set to 3,000 J / m < ² > with the PLA-501F exposure machine (extra-high pressure mercury lamp) by Canon. Thereafter, the pattern was melt-flowed by heating at 160 ° C. for 10 minutes on a hot plate and further at 230 ° C. for 10 minutes to form a microlens.
Table 3 shows the size (diameter) and cross-sectional shape of the bottom (surface contacting the substrate) of the formed microlens. It can be said that the microlens bottom portion is good when it is larger than 4.0 μm and smaller than 5.0 μm. In addition, when this dimension is 5.0 μm or more, the adjacent lenses are in contact with each other, which is not preferable. Further, the cross-sectional shape is good when it is a semi-convex lens shape as shown in (a) in the schematic diagram shown in FIG. 1, and it is bad when it is on a substantially trapezoidal shape as shown in (b).

Examples 2 to 4 and Comparative Example 1
In the said Example 1, instead of the solution containing a copolymer (A-1), the solution containing the copolymer of Table 1 was used, respectively, and [C] N- as a thermosensitive acid production | generation compound (Trifluoromethanesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide was used in the same manner as in Example 1 except that each of the compounds shown in Table 1 was used. A composition was prepared and evaluated. The results are shown in Tables 1 to 3.

Comparative Example 2
The solution containing the copolymer (a-2) obtained in Comparative Synthesis Example 2 was converted into the copolymer (a-2) in an amount corresponding to 100 parts by weight, and the component (B) was 4, 4 '-[1- {4- (1- [4-Hydroxyphenyl] -1-methylethyl) phenyl} ethylidene] bisphenol-1,2-naphthoquinonediazide-5-sulfonate, 30 parts by weight, as other components Then, 5 parts by weight of γ-methacryloyloxypropyltrimethoxysilane is mixed, dissolved in propylene glycol methyl ether acetate so that the solid content concentration becomes 30% by weight, and then filtered through a Millipore filter having a pore size of 0.5 μm. A product was prepared.
Evaluation was performed in the same manner as in Example 1 except that the above composition was used instead of the composition (S-1). The evaluation results are shown in Tables 1 to 3. In Comparative Example 2, since the adjacent lenses were in contact with each other when the microlenses were formed, the cross-sectional shape of the microlenses could not be evaluated.

Comparative Example 3
In Example 1 above, [C] N- (trifluoromethanesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide was not used as the thermosensitive acid generating compound. Others were prepared and evaluated in the same manner as in Example 1. The results are shown in Tables 1 to 3.

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

Claims (8)

[A] (a1) at least one selected from unsaturated carboxylic acid and unsaturated carboxylic anhydride, and (a2) the following general formula (1)

(In General Formula (1), R independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R ¹ independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ² , R ³ , R ⁴ and R ⁵ are each independently 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. N is an integer of 1 to 6 independently of each other.)
And a compound represented by the following general formula (2)

(In the general formula ^{(2), R, R 1} , R 2, R 3, R 4 and ^{R 5} and n are the same meaning as in the general formula (1).)
At least one copolymer selected from the compounds represented by:
[B] 1,2-quinonediazide compound, and [C] N- (trifluoromethanesulfonyloxy) phthalimide, N- (trifluoromethanesulfonyloxy) diphenylmaleimide, N- (trifluoromethanesulfonyloxy) bicyclo [2.2.1] ] Hept-5-ene-2,3-dicarboximide, N- (trifluoromethanesulfonyloxy) -7-oxabicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N -(Trifluoromethanesulfonyloxy) bicyclo [2.2.1] heptane-5,6-oxy-2,3-dicarboximide, N- (trifluoromethanesulfonyloxy) naphthylimide, N- (10-camphorsulfonyloxy) ) Phthalimide, N- (10-camphorsulfonylo) Xyl) diphenylmaleimide, N- (10-camphorsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (10-camphorsulfonyloxy) -7-oxabicyclo [2.2.1] Hept-5-ene-2,3-dicarboximide, N- (10-camphorsulfonyloxy) bicyclo [2.2.1] heptane-5,6-oxy-2,3- Dicarboximide, N- (10-camphorsulfonyloxy) naphthylimide, N- (p-toluenesulfonyloxy) phthalimide, N- (p-toluenesulfonyloxy) diphenylmaleimide, N- (p-toluenesulfonyloxy) bicyclo [ 2.2.1] Hept-5-ene-2,3-dicarboximide, N- (p-toluenesulfoni Oxy) -7-oxabicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (p-toluenesulfonyloxy) bicyclo [2.2.1] heptane-5,6 -Oxy-2,3-dicarboximide, N- (p-toluenesulfonyloxy) naphthylimide, N- (2-trifluoromethylbenzenesulfonyloxy) phthalimide, N- (2-trifluoromethylbenzenesulfonyloxy) diphenyl Maleimide, N- (2-trifluoromethylbenzenesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (2-trifluoromethylbenzenesulfonyloxy) -7 -Oxabicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (2-to Fluoromethylbenzenesulfonyloxy) bicyclo [2.2.1] heptane-5,6-oxy-2,3-dicarboximide, N- (2-trifluoromethylbenzenesulfonyloxy) naphthylimide, N- (4- Trifluoromethylbenzenesulfonyloxy) phthalimide, N- (4-trifluoromethylbenzenesulfonyloxy) diphenylmaleimide, N- (4-trifluoromethylbenzenesulfonyloxy) bicyclo [2.2.1] hept-5-ene- 2,3-dicarboximide, N- (4-trifluoromethylbenzenesulfonyloxy) -7-oxabicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (4 -Trifluoromethylbenzenesulfonyloxy) bicyclo [2.2.1] hept Tan-5,6-oxy-2,3-dicarboximide, N- (4-trifluoromethylbenzenesulfonyloxy) naphthylimide, N- (nonafluoro-n-butanesulfonyloxy) phthalimide, N- (nonafluoro-n -Butanesulfonyloxy) diphenylmaleimide, N- (nonafluoro-n-butanesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (nonafluoro-n-butanesulfonyl) Oxy) -7-oxabicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (nonafluoro-n-butanesulfonyloxy) bicyclo [2.2.1] heptane-5 , 6-oxy-2,3-dicarboximide, N- (nonafluoro-n-butanesulfonyloxy) Naphthylimide, N- (pentafluorobenzenesulfonyloxy) phthalimide, N- (pentafluorobenzenesulfonyloxy) diphenylmaleimide, N- (pentafluorobenzenesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2 , 3-dicarboximide, N- (pentafluorobenzenesulfonyloxy) -7-oxabicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (pentafluorobenzenesulfonyloxy) ) Bicyclo [2.2.1] heptane-5,6-oxy-2,3-dicarboximide, N- (pentafluorobenzenesulfonyloxy) naphthylimide, N- (perfluoro-n-octanesulfonyloxy) phthalimide N- (perfluoro-n-octane Sulfonyloxy) diphenylmaleimide, N- (perfluoro-n-octanesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (perfluoro-n-octanesulfonyloxy) ) -7-oxabicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (perfluoro-n-octanesulfonyloxy) bicyclo [2.2.1] heptane-5 , 6-oxy-2,3-dicarboximide, N- (perfluoro-n-octanesulfonyloxy) naphthylimide, and at least one heat-sensitive acid-generating compound selected from sulfone compounds, sulfonate compounds, and diazomethane compounds Radiation sensitive resin composition characterized by containing. [A] The radiation-sensitive composition according to claim 1, wherein the copolymer is a copolymer of (a1) and (a2) and (a3) an olefinically unsaturated compound other than (a1) and (a2). Resin composition. The radiation-sensitive resin composition according to claim 1, which is used for forming an interlayer insulating film. A method for forming an interlayer insulating film, comprising the following steps in the order described below.
(A) forming a film of the radiation-sensitive composition according to claim 3 on a substrate;
(B) irradiating at least a part of the coating with radiation;
(C) a step of developing the film after irradiation, and (d) a step of heating the film after development. The interlayer insulation film formed from the radiation sensitive resin composition of Claim 3. The radiation-sensitive resin composition according to claim 1, which is used for forming a microlens. A method for forming a microlens comprising the following steps in the order described below.
(A) forming a film of the radiation-sensitive composition according to claim 6 on a substrate;
(B) irradiating at least a part of the coating with radiation;
(C) a step of developing the film after irradiation, and (d) a step of heating the film after development. A microlens formed from the radiation-sensitive resin composition according to claim 6.

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