JP4581810B2 - Radiation-sensitive resin composition for forming interlayer insulating film and radiation-sensitive composition for forming microlens - Google Patents

Description

The present invention particularly relates to a radiation-sensitive resin composition used 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.
In recent years, TFT-type liquid crystal display elements have been developed to have larger screens, higher brightness, higher definition, faster response, thinner thickness, etc., and the radiation-sensitive resin composition used for forming the interlayer insulating film. Therefore, the interlayer insulating film to be formed is required to have higher performance than the conventional one in terms of low dielectric constant and high light transmittance.

On the other hand, as an optical system material for on-chip color filters such as facsimiles, electronic copiers, solid-state image sensors, etc., or as an optical system material for optical fiber connectors, microlenses having a lens diameter of about 3 to 100 μm and regularly arranged A microlens array is used.
As a method for forming a microlens, a resist pattern corresponding to the lens is formed and then heat-treated and melt-flowed to be used as a lens as it is, or the melt-flowed lens pattern is used as a mask and dried. A method of transferring a lens shape to a base by etching is known, and a radiation sensitive resin composition is widely used for forming such a lens pattern (for example, Patent Document 3 and Patent Document 4). reference.).
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 the microlens obtained in this way, the developing solution penetrates between the pattern and the substrate if the development time is slightly longer than the optimum time in the development process when forming them. In order to avoid such a phenomenon, it is necessary to strictly control the development time, and there has been a problem in terms of product yield and productivity.
Furthermore, proposals to improve heat resistance and surface hardness by adding antimony fluorides as heat-sensitive acid generators to radiation-sensitive resin compositions used to form interlayer insulation films and microlenses (for example, patents) (Refer to Document 5.) However, in the case of this radiation-sensitive resin composition, a problem of toxicity due to antimony compounds 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 on the basis of 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, etc. even beyond the optimum developing time noted to have good development margin that can form a good pattern profile, good solvent resistance, heat resistance, light transmittance, an interlayer insulating film having combined adhesion formative Another object of the present invention is to provide a radiation-sensitive resin composition capable of forming a microlens having a good melt shape, which has excellent solvent resistance, heat resistance, light transmittance, adhesion and the like.
The second object of the present invention is to provide a method capable of forming an interlayer insulating film and a microlens having the above-mentioned excellent characteristics by a simple process.
Still other problems and advantages of the present invention will become apparent from the following description.

According to the present invention, the problem is firstly
[A] (a1) an unsaturated carboxylic acid and / or an unsaturated carboxylic acid anhydride, (a2) a compound represented by the following general formula (1) and / or a compound represented by the following general formula (2)

[In General Formula (1) and General Formula (2), each R independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and each R ¹ independently represents a hydrogen atom or 1 to carbon atoms. Each R ² , each R ³ , each R ⁴ and each R ⁵ are independently of each other a hydrogen atom, a fluorine atom, an alkyl group having 1 to 4 carbon atoms, a phenyl group or 1 to 4 carbon atoms. And each n is an integer of 1 to 6 independently of each other. And (a3) an alkali-soluble copolymer obtained by copolymerizing an olefinic unsaturated compound other than (a1) and (a2), [B] 4,4 ′-[1- {4- ( 1- [4-hydroxyphenyl] -1-methylethyl) phenyl} ethylidene] bisphenol-1,2-naphthoquinonediazide-5-sulfonate , and [C] benzyl (4-hydroxyphenyl) (methyl) sulfonium hexafluoro An interlayer insulating film comprising a non-antimony thermosensitive acid generating compound selected from the group consisting of phosphate, triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium tetrafluoroborate and 4-acetoxyphenyldimethylsulfonium hexafluoroarsenate for forming a radiation-sensitive resin set Objects (hereinafter, referred to as "interlayer insulating film-forming composition".)
Is achieved.

According to the present invention, the problem is secondly ,
An interlayer insulating film formed from a composition for forming an interlayer insulating film,
Is achieved.

According to the present invention, the problem is thirdly ,
A method for forming an interlayer insulating film, comprising the following steps in the following order:
(A) forming a coating film of the composition for forming an interlayer insulating film on a substrate;
(B) irradiating at least a part of the coating film with radiation;
(C) developing the coated film after irradiation;
(D) a step of heating the coated film after development;
Is achieved.

〔一般式（１）および一般式（２）において、各Ｒは相互に独立に水素原子または炭素数１〜４のアルキル基を示し、各Ｒ ¹ は相互に独立に水素原子または炭素数１〜４のアルキル基を示し、各Ｒ ² 、各Ｒ ³ 、各Ｒ ⁴ および各Ｒ ⁵ は相互に独立に水素原子、フッ素原子、炭素数１〜４のアルキル基、フェニル基または炭素数１〜４のパーフルオロアルキル基を示し、各ｎは相互に独立に１〜６の整数である。〕と、（ａ３）前記（ａ１）および（ａ２）以外のオレフィン系不飽和化合物とを共重合して得られるアルカリ可溶性共重合体、〔Ｂ〕４，４’−〔１−｛４−（１−［４−ヒドロキシフェニル］−１−メチルエチル）フェニル｝エチリデン〕ビスフェノール−１，２−ナフトキノンジアジド−５−スルホン酸エステル、並びに〔Ｃ〕ベンジル（４−ヒドロキシフェニル）（メチル）スルホニウムヘキサフルオロホスフェート、トリフェニルスルホニウムトリフルオロメタンスルホネート、トリフェニルスルホニウムテトラフルオロボレートおよび４−アセトキシフェニルジメチルスルホニウムヘキサフルオロアルセネートの群から選ばれる非アンチモン系感熱性酸発生化合物を含有することを特徴とするマイクロレンズ形成用感放射線性樹脂組成物（以下、「マイクロレンズ形成用組成物」という。）、
により達成される。 According to the present invention, the problem is, the fourth,
[A] (a1) an unsaturated carboxylic acid and / or an unsaturated carboxylic acid anhydride, (a2) a compound represented by the following general formula (1) and / or a compound represented by the following general formula (2)

[In General Formula (1) and General Formula (2), each R independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and each R ¹ independently represents a hydrogen atom or 1 to carbon atoms. Each R ² , each R ³ , each R ⁴ and each R ⁵ are independently of each other a hydrogen atom, a fluorine atom, an alkyl group having 1 to 4 carbon atoms, a phenyl group or 1 to 4 carbon atoms. And each n is an integer of 1 to 6 independently of each other. And (a3) an alkali-soluble copolymer obtained by copolymerizing an olefinically unsaturated compound other than (a1) and (a2), [B] 4,4 ′-[1- {4- ( 1- [4-hydroxyphenyl] -1-methylethyl) phenyl} ethylidene] bisphenol-1,2-naphthoquinonediazide-5-sulfonate, and [C] benzyl (4-hydroxyphenyl) (methyl) sulfonium hexafluoro Microlens formation comprising a non-antimony thermosensitive acid generating compound selected from the group consisting of phosphate, triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium tetrafluoroborate and 4-acetoxyphenyldimethylsulfonium hexafluoroarsenate use radiation-sensitive resin A composition (hereinafter referred to as “microlens-forming composition”),
Is achieved.

According to the present invention, the object is achieved in the fifth,
A microlens formed from a composition for forming a microlens,
Is achieved.

According to the present invention, the problem is, the sixth,
A method for forming a microlens comprising the following steps in the order described below.
(A) forming a coating film of the composition for forming a microlens on a substrate;
(B) irradiating at least a part of the coating film with radiation;
(C) developing the coated film after irradiation;
(D) a step of heating the coated film after development;
Is achieved.

Interlayer insulating film forming composition and microlens forming composition- [A] copolymer-
[A] component in the composition for forming an interlayer insulating film and the composition for forming a microlens is (a1) an unsaturated carboxylic acid and / or an unsaturated carboxylic acid anhydride (hereinafter referred to as “unsaturated compound (a1 And (a2) a compound represented by the general formula (1) (hereinafter referred to as “unsaturated compound (a2-1)”) and / or a compound represented by the general formula (2). (Hereinafter referred to as “unsaturated compound (a2-2)”.) (Hereinafter, unsaturated compound (a2-1) and unsaturated compound (a2-2) are collectively referred to as “unsaturated compound (a2)”. ) And (a3) an olefinic unsaturated compound other than (a1) and (a2) (hereinafter referred to as “unsaturated compound (a3)”). , "[A] copolymer") Ranaru.

Examples of the unsaturated compound (a1) include monocarboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid; dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid, and itaconic acid; and anhydrides of the dicarboxylic acids. Succinic acid mono (2-acryloyloxyethyl), succinic acid mono (2-methacryloyloxyethyl), phthalic acid mono (2-acryloyloxyethyl), phthalic acid mono (2-methacryloyloxyethyl), etc. Mono [(meth) acryloyloxyalkyl] esters of polyvalent carboxylic acids, such as ω-carboxypolycaprolactone monoacrylate, ω-carboxypolycaprolactone monomethacrylate, and the like. ) Examples include acrylates it can.
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 or in mixture of 2 or more types.

  [A] The content of the structural unit derived from the unsaturated compound (a1) in the copolymer is preferably 5 to 40% by weight, particularly preferably 10 to 35% by weight. In this case, when the content of the structural unit is less than 5% by weight, the solubility of the resulting copolymer in an alkaline aqueous solution tends to decrease, whereas when it exceeds 40% by weight, the resulting copolymer is obtained. There exists a tendency for the solubility with respect to the aqueous alkali solution to become large too much.

Next, in the general formula (1) and the general formula (2), R, R ¹ , R ² , R ³ , R ⁴ and the alkyl group having 1 to 4 carbon atoms as R include a methyl group, an ethyl group, n -Propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group, t-butyl group and the like can be mentioned.
Examples of the perfluoroalkyl group having 1 to 4 carbon atoms of R ² , R ³ , R ⁴ and R include a trifluoromethyl group, a pentafluoroethyl group, a heptafluoro-n-propyl group, and a heptafluoro-i-propyl group. Group, nonafluoro-n-butyl group, nonafluoro-i-butyl group, nonafluoro-sec-butyl group, nonafluoro-t-butyl group and the like.

  Among the unsaturated compounds (a2), examples of the unsaturated compound (a2-1) include 3- (acryloyloxymethyl) oxetane, 3- (acryloyloxymethyl) -2-methyloxetane, and 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-tetra Fluoroxetane, 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- Acrylic acid esters such as (2-acryloyloxyethyl) -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-trifluoromethyloxetane, 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.
These unsaturated compounds (a2-1) can be used individually or in mixture of 2 or more types.

  Examples of the unsaturated compound (a2-2) 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-trifluoro Oxetane, 2- (acryloyloxy Chill) 3,3,4,4-tetra-fluoro-oxetane,

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 Fluoroethyloxetane, 2- (2-acrylo Ruoxyethyl) -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- Methacryloyloxyethyl) 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) Xylmethyl) -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 Examples include acid esters.
These unsaturated compounds (a2-2) can be used individually or in mixture of 2 or more types.

  Among the 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 process margin of the resulting radiation-sensitive resin composition, And it is preferable from the point which improves the chemical resistance of the interlayer insulation film and micro lens which are obtained.

  [A] The content of the structural unit derived from the unsaturated compound (a2) in the copolymer is preferably 5 to 60% by weight, particularly preferably 10 to 50% by weight. In this case, if the content of the structural unit is less than 5% by weight, the heat resistance of the resulting coating film tends to be reduced, whereas if it exceeds 60% by weight, the storage stability of the resulting copolymer is low. There is a tendency to decrease.

Next, the unsaturated compound (a3) is not particularly limited as long as it is copolymerizable with the unsaturated compound (a1) and the unsaturated compound (a2). For example, methyl acrylate, ethyl acrylate, n -Acrylic acid alkyl esters such as propyl acrylate, i-propyl acrylate, n-butyl acrylate, sec-butyl acrylate, t-butyl acrylate; methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, i-propyl methacrylate, n-butyl methacrylate, sec- butyl methacrylate, methacrylic acid alkyl esters such as t- butyl methacrylate; cyclohexyl acrylate, 2-methylcyclohexyl acrylate, tricyclo [5.2.1.0 ^{2, 6]} decane -8 Cyclic esters of acrylic acid such as yl acrylate (hereinafter referred to as “dicyclopentanyl acrylate”), 2-dicyclopentanyloxyethyl acrylate, isobornyl acrylate, etc .; 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, isobornyl methacrylate, and the like. Cyclic esters; Acrylic acid aryl esters such as phenyl acrylate and benzyl acrylate; Methacrylic acid aryl esters such as phenyl methacrylate and benzyl methacrylate; Diethyl maleate and diethyl fumarate Unsaturated dicarboxylic acid diester of diethyl itaconate; 2-hydroxyethyl acrylate, 2-hydroxyalkyl acrylates such as hydroxyethyl acrylate; 2-hydroxyethyl methacrylate, hydroxyalkyl methacrylates such as 2-hydroxypropyl methacrylate;

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-methylbicyclo [2.2.1] hept-2-ene,
5-carboxy-6-methylbicyclo [2.2.1] hept-2-ene,
5-carboxy-6-ethylbicyclo [2.2.1] hept-2-ene,
5,6-dicarboxybicyclo [2.2.1] hept-2-ene anhydride (hymic acid anhydride),
5-t-butoxycarbonylbicyclo [2.2.1] hept-2-ene,
5-cyclohexyloxycarbonylbicyclo [2.2.1] hept-2-ene,
5-phenoxycarbonylbicyclo [2.2.1] hept-2-ene,
5,6-di (t-butoxycarbonyl) bicyclo [2.2.1] hept-2-ene,
A bicyclounsaturated compound such as 5,6-di (cyclohexyloxycarbonyl) bicyclo [2.2.1] hept-2-ene;

N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimidobenzoate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidocaproate, N-succinimidyl-3 -Unsaturated dicarbonylimide derivatives such as maleimide propionate, N- (9-acridinyl) maleimide;

Styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, m-vinyltoluene, p-vinyltoluene, p-methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, acetic acid Vinyl, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, glycidyl acrylate, glycidyl methacrylate, glycidyl α-ethyl acrylate, glycidyl α-n-propyl acrylate, α-n- Glycidyl butyl acrylate, 3,4-epoxybutyl acrylate, 3,4-epoxybutyl methacrylate, 3,4-epoxybutyl acrylate, 6,7-epoxyheptyl acrylate, 6,7- methacrylate Epoxy heptyl, α-ethyl acrylate Acid 6,7-epoxy heptyl, o- vinylbenzyl glycidyl ether, m- vinylbenzyl glycidyl 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 admixture of two or more.

  [A] The content of the structural unit derived from the unsaturated compound (a3) in the copolymer is preferably 10 to 80% by weight, particularly preferably 20 to 70% by weight. In this case, when the content of the structural unit is less than 10% by weight, the storage stability of the resulting copolymer tends to be reduced. On the other hand, when the content exceeds 80% by weight, an alkaline aqueous solution of the resulting copolymer is obtained. There is a tendency for the solubility to be reduced.

  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, and 3- (methacryloyloxy). Methyl) oxetane, 3- (methacryloyloxymethyl) -3-ethyloxetane, 3- (methacryloyloxymethyl) -2-trifluoromethyloxetane, 3- (methacryloyloxymethyl) -2-phenyloxetane, 2- (methacryloyloxy) At least one unsaturated compound (a2) selected from the group of methyl) 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, 1,3-butadiene, glycidyl methacrylate, o-vinylbenzyl glycidyl ether, m- Mention may be made of a copolymer with at least one unsaturated compound (a3) selected from the group of vinylbenzyl glycidyl ether and p-vinylbenzyl glycidyl ether.

[A] The polystyrene-equivalent weight average molecular weight (hereinafter referred to as “Mw”) of the copolymer is usually 2 × 10 ^{3 to} 5 × 10 ⁵ , preferably 5 × 10 ³ to 1 × 10 ⁵ . In this case, if the Mw of the [A] copolymer is less than 2 × 10 ³ , there is a tendency that the remaining film ratio during development tends to decrease, while if it exceeds 5 × 10 ⁵ , there is a risk of developing residue during development. There is.
[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 usually 5.0 or less, preferably 3.0 or less. In this case, when Mw / Mn exceeds 5.0, the pattern shape of the obtained interlayer insulating film or microlens tends to be lowered.
The radiation-sensitive resin composition [I] containing the copolymer [A] having Mw and Mw / Mn does not cause development residue or film loss during development, and easily forms a pattern of a predetermined shape. Can be formed.

[A] The copolymer has a carboxyl group and / or a carboxylic anhydride group and an oxetane ring structure, has moderate solubility in an alkaline aqueous solution, and does not use a special curing agent in combination. However, the radiation-sensitive resin composition [I] containing the copolymer [A] does not cause development residue or film loss during development, and can be applied in a predetermined pattern. A film can be easily formed.
In the composition for forming an interlayer insulating film and the composition for forming a microlens , the [A] copolymer can be used alone or in admixture of two or more.

[A] The copolymer is synthesized, for example, by polymerizing the unsaturated compound (a1), the unsaturated compound (a2), and the unsaturated compound (a3) in a suitable solvent in the presence of a radical polymerization initiator. can do.
Examples of the solvent used for the polymerization include alcohols, ethers, ethylene glycol ethers, ethylene glycol alkyl ether acetates, diethylene glycols, propylene glycol ethers, propylene glycol alkyl ether acetates, propylene glycol alkyl ether propio. Examples thereof include nates, aromatic hydrocarbons, ketones, and esters.

  Specific examples of these solvents include alcohols such as methanol, ethanol, benzyl alcohol, 2-phenylethanol, 3-phenyl-1-propanol, etc .; ethers such as tetrahydrofuran; ethylene glycol ethers such as ethylene glycol monomethyl. Ether, ethylene glycol monoethyl ether, etc .; ethylene glycol alkyl ether acetates, ethylene glycol methyl ether acetate, ethylene glycol ethyl ether acetate, ethylene glycol n-propyl ether acetate, ethylene glycol n-butyl ether acetate, etc .; diethylene glycols, diethylene glycol Monomethyl ether, diethylene glycol monoethyl ether, diethylene Glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether;

As propylene glycol ethers, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether, etc .; as propylene glycol alkyl ether acetates, propylene glycol methyl ether acetate, propylene Glycol ethyl ether acetate, propylene glycol n-propyl ether acetate, propylene glycol n-butyl ether acetate, etc .; as propylene glycol alkyl ether propionates, propylene glycol methyl ether propionate, propylene glycol ethyl ether propionate, propylene glycol n -Propyl ether Ropioneto, propylene glycol n- butyl ether propionate; aromatic hydrocarbons, toluene, xylene; as ketones, methyl ethyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone and the like;

Esters 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-propyl lactate N-butyl lactate, methyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, n-propyl 3-hydroxypropionate, n-butyl 3-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, 2 -Ethyl hydroxy-2-methylpropionate, methyl 2-hydroxy-3-methylbutanoate, methyl methoxyacetate, ethyl methoxyacetate, n-propyl methoxyacetate, n-butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, ethoxyacetic acid n-propyl N-butyl ethoxyacetate, methyl n-propoxyacetate, ethyl n-propoxyacetate, n-propyl n-propoxyacetate, n-butyl n-propoxyacetate, methyl n-butoxyacetate, ethyl n-butoxyacetate, n-butoxyacetic acid n-propyl, n-butoxyacetate n-butyl, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, n-propyl 2-methoxypropionate, n-butyl 2-methoxypropionate, methyl 2-ethoxypropionate , Ethyl 2-ethoxypropionate, n-propyl 2-ethoxypropionate, n-butyl 2-ethoxypropionate, methyl 2-n-propoxypropionate, ethyl 2-n-propoxypropionate, 2-n-propoxypropion Acid n-propyl, 2-n-propoxypropi N-butyl acid, 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-butoxypropionate Examples thereof include ethyl onate, n-propyl 3-n-butoxypropionate, n-butyl 3-n-butoxypropionate, and the like.

Of these solvents, ethylene glycol alkyl ether acetates, diethylene glycols, propylene glycol ethers, propylene glycol alkyl ether acetates and the like are preferable, and in particular, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, propylene glycol monomethyl ether, propylene glycol methyl ether. Acetate is preferred.
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-
The component [B] in the composition for forming an interlayer insulating film and the composition for forming a microlens is 4,4 ′-[1- {4- (1- [4-hydroxyphenyl] -1-methylethyl) phenyl} ethylidene It consists of bisphenol-1,2-naphthoquinonediazide-5-sulfonic acid ester (hereinafter referred to as “[B] 1,2-quinonediazide compound”) and is a component that generates an acid upon irradiation with radiation.

The use ratio of [B] 1,2-quinonediazide compound in the composition for forming an interlayer insulating film and the composition for forming a microlens is preferably 5 to 100 parts by weight with respect to 100 parts by weight of the [A] copolymer, Particularly preferred is 10 to 50 parts by weight. In this case, if the use ratio of [B] 1,2-quinonediazide compound is less than 5 parts by weight, the difference in solubility between the irradiated part and the unirradiated part in the alkaline aqueous solution becomes small, and pattern formation is difficult. Or the amount of acid generated in the reaction with the copolymer [A] may be reduced, making it difficult to impart sufficient heat resistance and solvent resistance to the resulting interlayer insulating film and microlens. On the other hand, if the amount exceeds 100 parts by weight, the amount of unreacted 1,2-quinonediazide compound is increased by irradiation with radiation for a short time, and the effect of insolubilization in an aqueous alkali solution becomes too high, making development difficult. There is a risk of becoming.

-[C] acid generating compound-
[C] component in the composition for forming an interlayer insulating film and the composition for forming a microlens includes benzyl (4-hydroxyphenyl) (methyl) sulfonium hexafluorophosphate, triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium tetrafluoroborate and It consists of a non-antimony heat-sensitive acid generating compound selected from the group of 4-acetoxyphenyldimethylsulfonium hexafluoroarsenate (hereinafter referred to as “[C] acid generating compound”), and heat resistance of the resulting interlayer insulating film and microlens It is a component having the effect of improving the properties and surface hardness.

  The [C] acid generating compound can be used alone or in admixture of two or more.

The proportion of the [C] acid generating compound used in the interlayer insulating film forming composition and the microlens forming composition is preferably 0.01 to 20 parts by weight, especially 100 parts by weight of the [A] copolymer. Preferably it is 0.1-5 weight part. In this case, when the proportion of the [C] acid-generating compound used is less than 0.01 parts by weight, the curing rate at the time of curing under heating tends to be slow and the resolution tends to decrease, whereas it exceeds 20 parts by weight. Then, a precipitate may be generated, and pattern formation may be difficult.

-Other ingredients-
In addition to the components [A], [B], and [C], the composition for forming an interlayer insulating film and the composition for forming a microlens may have a polymerization having at least one olefinic unsaturated bond as necessary. An organic compound (hereinafter referred to as “olefin-based polymerizable compound”), a thermosetting resin, a surfactant, an adhesion aid and the like can also be blended.

The olefin-based polymerizable compound is a component having a function of further improving the heat resistance, strength, and the like of the obtained interlayer insulating film and microlens. Preferred examples thereof include monofunctional (meth) acrylates, bifunctional (meta ) Acrylates or tri- or higher functional (meth) acrylates.
Examples of the monofunctional (meth) acrylates include 2-hydroxyethyl (meth) acrylate, carbitol (meth) acrylate, isobornyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, and 2- (meth) acryloyl. Oxyethyl (2-hydroxypropyl) phthalate and the like can be mentioned, and as commercially available products, Aronix M-101, M-111, M-114 (above, manufactured by Toagosei Co., Ltd.), KAYARAD TC-110S TC-120S (manufactured by Nippon Kayaku Co., Ltd.), Biscote 158, and 2311 (manufactured by Osaka Organic Chemical Industries, Ltd.).

  Examples of the bifunctional (meth) acrylates include ethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, tetraethylene glycol di ( (Meth) acrylate, polypropylene glycol di (meth) acrylate, bisphenoxyethanol full orange (meth) acrylate, and the like, and commercially available products thereof include Aronix M-210, M-240, M-6200 (above, Toagosei Co., Ltd.), KAYARAD HDDA, HX-220, R-604 (Nippon Kayaku Co., Ltd.), Biscote 260, 312 and 335HP (Osaka Organic Chemical Co., Ltd.) Manufactured).

Examples of the trifunctional or higher functional (meth) acrylates include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, Examples include pentaerythritol hexa (meth) acrylate, tri [2- (meth) acryloyloxyethyl] phosphate, and commercially available products such as Aronix M-309, M-400, M-405, M -450, M-7100, M-8030, M-8060 (Made by Toagosei Co., Ltd.), KAYARAD TMPTA, DPHA, DPCA-20, DPCA-30, DPCA-60, DPCA-120 (Nippon Kayaku Ltd.)), Viscoat 295, the 300, the 360, the GPT, said 3PA, the 400 (or more, can be given by Osaka Organic Chemical Industry Ltd.) and the like.
The olefin polymerizable compounds can be used alone or in admixture of two or more.

  The blending amount of the olefin-based polymerizable compound is preferably 50 parts by weight or less, more preferably 30 parts by weight or less with respect to 100 parts by weight of the [A] copolymer. In this case, if the blending amount of the olefin-based polymerizable compound exceeds 50 parts by weight, the compatibility with the [A] copolymer becomes insufficient, and there is a possibility that film roughening occurs during coating.

The thermosetting resin is a component having an effect of further improving the heat resistance, strength, and the like of the obtained interlayer insulating film and microlens. Examples thereof include an interlayer insulating film forming composition and a microlens forming composition. Although there is no limitation as long as there is no problem in compatibility with other components constituting the product , examples thereof include epoxy resins and amino resins.
Examples of the epoxy resin include bisphenol A type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, cycloaliphatic epoxy resin, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, heterocyclic epoxy resin, Examples thereof include resins obtained by (co) polymerization of glycidyl methacrylate, and among these, bisphenol A type epoxy resins, cresol novolac type epoxy resins, glycidyl ester type epoxy resins and the like are preferable.

The compounding amount of the epoxy resin is preferably 30 parts by weight or less with respect to 100 parts by weight of the [A] copolymer. In this case, when the compounding quantity of an epoxy resin exceeds 30 weight part, there exists a possibility that compatibility with [A] copolymer may become inadequate and it may interfere with coating-film formation.
In addition, when an epoxy group-containing compound is used as the unsaturated compound (a3) when the [A] copolymer is synthesized, the [A] copolymer may be referred to as an “epoxy resin”. The polymer is different from an epoxy resin in that it has alkali solubility and has a relatively high molecular weight.
Examples of the amino resin include the following formula (3):

〔式（３）において、Ｒ⁶ は水素原子または炭素数が１〜６、好ましくは１〜４のアルキル基を示す。〕

In [Equation (3), R ⁶ is 1 to 6 hydrogen atoms or carbon atoms, preferably an 1-4 alkyl group. ]

A compound having preferably two or more monovalent organic groups represented by the formula (1) in a molecule, more preferably a compound in which the monovalent organic group is bonded to a nitrogen atom. When two or more monovalent organic groups are present in one molecule, each monovalent organic group may be the same or different.
When the amino resin having a monovalent organic group is blended with the composition for forming an interlayer insulating film and the composition for forming a microlens , the monovalent organic group is a carboxyl group that the [A] copolymer has and Reacts with carboxylic anhydride groups to form a crosslinked structure.
As a preferred amino resin, more specifically, the following formula (4)

〔式（４）において、各Ｒ⁷ 、各Ｒ⁸ および各Ｒ⁹ は相互に独立に炭素数１〜４のアルキル基を示す。〕

[In Formula (4), each R <^7> , each R < ⁸ >, and each R < ⁹ > show a C1-C4 alkyl group mutually independently. ]

An alkoxymethylated melamine such as N, N, N, N, N, N-hexa (alkoxymethyl) melamine represented by the following formula (5):

〔式（５）において、各Ｒ¹⁰、各Ｒ¹¹、各Ｒ¹²および各Ｒ¹³は相互に独立に炭素数１〜４のアルキル基を示す。〕

[In Formula (5), each R < ¹⁰ >, each R <^11> , each R < ¹² > and each R < ¹³ > shows a C1-C4 alkyl group mutually independently. ]

And an alkoxymethylated glycoluril such as N, N, N, N-tetra (alkoxymethyl) glycoluril represented by the formula:

  In addition, urea-formaldehyde resin, thiourea-formaldehyde resin, melamine-formaldehyde resin, guanamine-formaldehyde resin, benzoguanamine-formaldehyde resin, glycoluril-formaldehyde resin, etc. can be used as amino resin. As a thermosetting resin other than the resin, a compound obtained by introducing a monovalent organic group represented by the above formula (3) into polyvinylphenols can be used.

  The compounding amount of the thermosetting 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.

The surfactant is a component having an action of improving applicability.
Examples of such surfactants include fluorine-based and silicone-based surfactants such as BM-1000, BM-1100 (manufactured by BM CHEMIE), MegaFuck F142D, F172, F173, and F183. (Above, Dainippon Ink & Chemicals, Inc.), Florard FC-135, FC-170C, 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 (above, manufactured by Asahi Glass Co., Ltd.), F-Top EF301, 303, 352 (above, made by Shin-Akita Kasei Co., Ltd.), SH-28PA, SH-190, SH -193, SZ-6032, SF-8428, DC-57, DC-190 (above, manufactured by Toray Dow Corning Silicone Co., Ltd.).

  In addition to fluorine or silicone surfactants, for example, polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether; polyoxyethylene n-octylphenyl Polyoxyethylene aryl ethers such as ether and polyoxyethylene n-nonylphenyl ether; nonionic surfactants such as polyoxyethylene dialkyl esters such as polyoxyethylene dilaurate and polyoxyethylene distearate, and commercially available products , Organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth) acrylic acid copolymer polyflow No. 57, no. 95 (manufactured by Kyoeisha Chemical Co., Ltd.).

  The compounding amount of the surfactant is preferably 5 parts by weight or less, more preferably 2 parts by weight or less, with respect to 100 parts by weight of the [A] copolymer. In this case, when the compounding amount of the surfactant exceeds 5 parts by weight, there is a tendency that film filming is likely to occur at the time of application.

The adhesion aid is a component having an action of further improving the adhesion to the substrate. Examples thereof include a functional group having a reactive substituent such as a carboxyl group, a methacryloyl group, a vinyl group, an isocyanate group, and an epoxy group. Silane coupling agent.
Examples of the functional silane coupling agent include trimethoxysilylbenzoic acid, γ-methacryloyloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, and γ-glycid. Examples include xylpropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and the like.

  The blending amount of the adhesion assistant is preferably 20 parts by weight or less, more preferably 10 parts by weight or less, with respect to 100 parts by weight of the [A] copolymer. In this case, if the compounding amount of the adhesion assistant exceeds 20 parts by weight, there is a tendency that a development residue is likely to occur during development.

-Preparation of interlayer insulating film forming composition and microlens forming composition-
The composition for forming an interlayer insulating film and the composition for forming a microlens are prepared by uniformly mixing the components [A], [B] and [C] and the other components optionally added. However, it is preferably used as a composition solution dissolved in a suitable solvent.

As the solvent used for the preparation of the composition solution, a solvent that uniformly dissolves each component constituting the interlayer insulating film forming composition and the microlens forming composition and does not react with each component is used.
As such a solvent, the thing similar to what was illustrated as a solvent used in order to synthesize | combine the [A] copolymer mentioned above can be mentioned.
Among these solvents, for example, alcohols, ethylene glycol ethers, ethylene glycol alkyl ether acetates, diethylene glycols, from the viewpoints of solubility of each component, reactivity with each component, ease of film formation, etc. Esters are preferred, and in particular, benzyl alcohol, 2-phenylethyl alcohol, 3-phenyl-1-propanol, ethylene glycol ethyl ether acetate, ethylene glycol n-butyl ether acetate, diethylene glycol ethyl ether acetate, diethylene glycol diethyl ether, diethylene glycol ethyl methyl Ether, diethylene glycol dimethyl ether, propylene glycol monomethyl ether, propylene glycol methyl ether acetate, methoxy Methyl propionate, ethyl ethoxypropionate are preferred.
The said solvent can be used individually or in mixture of 2 or more types.

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 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 high boiling solvents, N, N-dimethylacetamide, N-methylpyrrolidone, γ-butyrolactone and the like are preferable.
The high boiling point solvents can be used alone or in admixture of two or more.

  When a high boiling point solvent is used in combination as a solvent for the composition solution, the amount used is preferably 50% by weight or less, more preferably 40% by weight or less, and particularly preferably 30% by weight or less based on the total amount of the solvent. . In this case, when the amount of the high-boiling solvent used exceeds 50% by weight, the sensitivity, the film thickness uniformity of the coating film and the remaining film rate may be lowered.

The total solid content of the composition solution can be arbitrarily set according to the purpose of use, desired film thickness and the like, and is usually 5 to 50% by weight, preferably 10 to 40% by weight, more preferably 15 to 35%. % By weight.
In addition, the composition solution thus prepared can be used after being filtered using a Millipore filter having a pore diameter of about 0.2 μm.

Interlayer Insulating Film and Microlens The interlayer insulating film of the present invention is formed from an interlayer insulating film forming composition, and the microlens of the present invention is formed from a microlens forming composition .
The interlayer insulating film of the present invention can be used very suitably for electronic parts such as TFT type liquid crystal display elements, magnetic head elements, integrated circuit elements, solid-state imaging elements, and the like. The microlens array arranged in the above can be used very suitably 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.

Method for Forming Interlayer Insulating Film and Microlens The method for forming an interlayer insulating film and the method for forming a microlens according to the present invention include the following steps in the order described below.
(A) forming a coating film of the composition for forming an interlayer insulating film or the composition for forming a microlens on a substrate;
(B) a step of irradiating at least a part of the coating film with radiation (hereinafter referred to as “exposure”); (c) a step of developing the coating film after exposure;
(D) A step of heating the coated film after development.

Hereinafter, these steps will be sequentially described.
-(I) Process-
In this step, the composition for forming an interlayer insulating film or the composition for forming a microlens is preferably applied as a composition solution to the substrate surface, and then pre-baked to remove the solvent to form a coating film.
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.
As prebaking conditions, although it changes with the kind of each component, a using ratio, etc., it can be set as about 30 seconds-15 minutes at 60-110 degreeC, for example.
The film thickness of the coating film to be formed is about 3 to 6 μm, for example, when the interlayer insulating film is formed as a value after pre-baking, and is about 0.5 to about 3 to 6 μm when the microlens is formed. About 3 μm is preferable.

-(B) Process-
In this step, at least a part of the formed coating film is exposed. When only a part of the coating film is exposed, it is usually exposed 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) Process-
In this step, a predetermined pattern is formed by developing the exposed coating film and removing the exposed portion.
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 can also 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 the conventionally known radiation-sensitive resin composition, if the development time exceeds about 20 to 25 seconds from the optimum value, peeling occurs in the formed pattern, so it was necessary to strictly control the development time. In the case of the composition for forming an interlayer insulating film and the composition for forming a microlens of the present invention, good pattern formation is possible even when the excess time from the optimum development time is 30 seconds or more, and the product yield or productivity is high. This is advantageous.

-(D) Process-
In this step, the coating film on which the predetermined pattern is formed is preferably washed with running water, and more preferably exposed to radiation (post-exposure) such as a high-pressure mercury lamp over the entire surface. After the decomposition treatment of the 1,2-quinonediadito compound remaining in the coating film, the coating film is cured by heat treatment (post-baking) with a heating device such as a hot plate or oven. 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, and the shape of the microlens of the present invention is as shown in FIG. Good semi-convex lens shape.

The composition for forming an interlayer insulating film and the composition for forming a microlens of the present invention have excellent sensitivity and resolution, excellent storage stability as a composition solution, and even when the optimum development time is exceeded in the development process. In addition, it has a good development margin that can form a good pattern shape, 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.
Further, 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.
In addition, the method for forming an interlayer insulating film and the method for forming a microlens according to the present invention can form a good pattern even when the development time exceeds the optimum development time, and the interlayer insulating film having the above-described excellent characteristics. In addition, a microlens can be easily formed.

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 methyl ether acetate. Subsequently, 22 parts by weight of methacrylic acid, 38 parts by weight of dicyclopentanyl methacrylate, 40 parts by weight of 3- (methacryloyloxymethyl) -2-phenyloxetane and 1.5 parts of α-methylstyrene dimer were charged, and then nitrogen substitution was performed. By gently stirring, the temperature of the solution is raised to 70 ° C., and this temperature is maintained for 4 hours for polymerization to obtain a solution of [A] copolymer (solid content concentration 31.8% by weight). It was.
Mw of the obtained [A] copolymer was 17,900, and Mw / Mn was 1.8. In addition, Mw and Mn are polystyrene conversion average molecular weights measured using GPC (gel permeation chromatography) (HLC-8020 manufactured by Tosoh Corporation). This [A] copolymer is referred to as “copolymer (A-1)”.

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 methyl 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, and 5 parts by weight of styrene were charged, and then gently stirred while replacing with nitrogen. Was raised to 70 ° C. and polymerization was carried out while maintaining this temperature for 4 hours to obtain a solution of [A] copolymer (solid content concentration 31.9% by weight).
Mw of the obtained [A] copolymer was 20,200 and Mw / Mn was 1.9. This [A] copolymer is referred to as “copolymer (A-2)”.

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 methyl ether acetate. Subsequently, 20 parts by weight of styrene, 25 parts by weight of methacrylic acid, 20 parts by weight of N-cyclohexylmaleimide, 35 parts by weight of 3- (methacryloyloxymethyl) -2-trifluoromethyloxetane, and 1.5 parts by weight of α-methylstyrene dimer were added. After charging, the mixture was gradually stirred while purging with nitrogen, the temperature of the solution was raised to 70 ° C., and this temperature was maintained for 4 hours to polymerize to obtain a solution of [A] copolymer (solid content concentration). 38.7% by weight).
Mw of the obtained [A] copolymer was 21,500 and Mw / Mn was 2.2. This [A] copolymer is referred to as “copolymer (A-3)”.

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 methyl ether acetate. Subsequently, 20 parts by weight of styrene, 30 parts by weight of methacrylic acid, 50 parts by weight of 2- (methacryloyloxymethyl) -4-trifluoromethyl oxetane, and 2.0 parts by weight of α-methylstyrene dimer were charged, and then gradually replaced with nitrogen. Then, the temperature of the solution was raised to 70 ° C., and this temperature was maintained for 5 hours for polymerization to obtain a solution of [A] copolymer (solid content concentration 31.0% by weight). .
Mw of the obtained [A] copolymer was 19,000 and Mw / Mn was 1.7. This [A] copolymer is referred to as “copolymer (A-4)”.

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 ethyl methyl ether. Subsequently, 23 parts by weight of methacrylic acid, 47 parts by weight of dicyclopentanyl methacrylate, 20 parts by weight of glycidyl methacrylate, and 2.0 parts by weight of α-methylstyrene dimer were charged. The temperature was raised to 70 ° C., and this temperature was maintained for 5 hours for polymerization to obtain a copolymer solution (solid content concentration: 32.8% by weight).
Mw of the obtained copolymer was 24,000 and Mw / Mn was 2.3. This copolymer is referred to as “copolymer (a-1)”.

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 ethyl methyl ether. Subsequently, 25 parts by weight of methacrylic acid, 35 parts by weight of dicyclopentanyl methacrylate, 40 parts by weight of 2-hydroxyethyl methacrylate, and 2.0 parts by weight of α-methylstyrene dimer were charged. The temperature of the solution was raised to 70 ° C., and this temperature was maintained for 5 hours for polymerization to obtain a copolymer solution (solid content concentration: 32.8% by weight).
Mw of the obtained copolymer was 25,000 and Mw / Mn was 2.4. This copolymer is referred to as “copolymer (a-2)”.

Preparation and evaluation of composition solutions Example 1
As component [A], the solution of copolymer (A-1) obtained in Synthesis Example 1 is 100 parts by weight (solid content) as copolymer (A-1), and 4,4 ′ as component [B]. -[1- {4- (1- [4-hydroxyphenyl] -1-methylethyl) phenyl} ethylidene] bisphenol-1,2-naphthoquinonediazide-5-sulfonic acid ester 30 parts by weight, [C] component, After mixing 1 part by weight of triphenylsulfonium trifluoromethanesulfonate and 5 parts by weight of γ-methacryloyloxypropyltrimethoxysilane as the other components, after dissolving in propylene glycol methyl ether acetate so that the solid content concentration becomes 30% by weight. The solution was filtered through a Millipore filter having a pore size of 0.5 μm to prepare a composition solution (S-1).

Evaluation of Storage Stability The composition solution (S-1) was heated in an oven at 40 ° C. for 1 week, and evaluated by the rate of change in viscosity before and after heating. At this time, when the viscosity change rate is less than 5%, the storage stability is good, and when it is 5% or more, the storage stability is poor. The evaluation results are shown in Table 1.

Evaluation as interlayer insulation film- Formation of patterned thin film-
The composition solution (S-1) was applied onto a glass substrate using a spinner and then pre-baked on an 80 ° C. hot plate for 3 minutes to form a coating film.
Next, the obtained coating film was exposed to ultraviolet rays having an intensity at a wavelength of 365 nm of 100 W / m ² 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 is exposed to ultraviolet rays having an intensity of 100 W / m ² at a wavelength of 365 nm for 30 seconds, and then cured by heating for 60 minutes in an oven at 220 ° C., thereby forming a patterned thin film having a thickness of 3 μm. Got. Also, 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 pattern-like thin film was evaluated as “◯” when a blank pattern (5 μm × 5 μm hole) was resolved, and “x” when it was not resolved. The evaluation results are shown in Table 2.

-Evaluation of heat-resistant dimensional stability-
The patterned thin film formed at a pre-baking temperature of 80 ° C. was heated in an oven at 220 ° C. for 60 minutes, and the rate of change in film thickness before and after heating was measured and evaluated. At this time, the heat-resistant dimensional stability is good when the film thickness change rate is within 5%, and the heat-resistant dimensional stability is poor when it exceeds 5%. The evaluation results are shown in Table 2.

-Evaluation of transparency-
The transmittance at a wavelength of 400 nm of the patterned thin film formed at a prebake temperature of 80 ° C. was measured and evaluated using a spectrophotometer (150-20 type double beam (manufactured by Hitachi, Ltd.)). At this time, it can be said that the transparency is good when the transmittance is 90% or more, and the transparency is poor when it is less than 90%. The evaluation results are shown in Table 2.

-Evaluation of heat discoloration-
A substrate having a patterned thin film formed at a pre-baking temperature of 80 ° C. is heated in an oven at 250 ° C. for 1 hour, and the transmittance of the patterned thin film before and after heating at a wavelength of 400 nm is referred to as “transparency evaluation”. It measured similarly and evaluated by the change rate of the transmittance | permeability before and behind a heating. At this time, when the rate of change in transmittance is less than 5%, the heat discoloration is good, and when it exceeds 5%, the heat discoloration is poor. The evaluation results are shown in Table 2.

-Evaluation of adhesion-
The adhesion of the patterned thin film formed at a pre-baking temperature of 80 ° C. to the substrate was evaluated by a cross-cut peel test after a pressure cooker test (120 ° C., humidity 100%, 4 hours). Table 2 shows the number of grids remaining in 100 grids at this time.

Evaluation as a microlens-Formation of microlenses-
The composition solution (S-1) was applied to a 6-inch silicon substrate using a spinner so that the film thickness after drying was 2.5 μm, and then pre-baked on a hot plate at 70 ° C. for 3 minutes. A film was formed.
Next, the obtained coating film was exposed to ultraviolet rays having an intensity of 100 W / m ^{2 at} a wavelength of 436 nm through a photomask having a predetermined pattern while changing the exposure amount. Thereafter, development was carried out with a 2.38 wt% tetramethylammonium hydroxide aqueous solution at 25 ° C. for 1 minute, followed by washing with pure water for 1 minute, whereby unnecessary portions were removed to obtain a patterned thin film.
Next, the obtained patterned thin film was post-exposed for 30 seconds with ultraviolet light having an intensity of 100 W / m ² at a wavelength of 436 nm, then heated in an oven at 160 ° C. for 60 minutes, and further heated in an oven at 230 ° C. for 10 minutes. And the pattern was melt-flowed to form a microlens.

-Evaluation of sensitivity-
The obtained microlens was evaluated based on the minimum exposure amount capable of resolving the space line width (0.08 μm) of the line line width 0.8 μm line and space pattern (10 to 1). The sensitivity is good when this value is 1,000 J / m ² or less, and the sensitivity is poor when it exceeds 1,000 J / m ² . The evaluation results are shown in Table 3.

-Evaluation of transparency-
A microlens was formed in the same manner as in the “formation of microlens” except that a glass substrate was used instead of the silicon substrate.
Subsequently, about the glass substrate which has a microlens, the transmittance | permeability in wavelength 400nm was measured and evaluated using the spectrophotometer (150-20 type double beam (made by Hitachi, Ltd.)). At this time, it can be said that the transparency is good when the transmittance is 90% or more, and the transparency is poor when it is less than 90%. The evaluation results are shown in Table 3.

-Evaluation of heat discoloration-
A patterned thin film was obtained in the same manner as in “Formation of microlenses” except that a glass substrate was used instead of the silicon substrate.
Subsequently, the glass substrate having the patterned thin film was heated in an oven at 250 ° C. for 1 hour, and evaluated by the change rate of transmittance at a wavelength of 400 nm before and after heating. At this time, when the rate of change in transmittance is less than 5%, the heat discoloration is good, and when it exceeds 5%, the heat discoloration is poor. The evaluation results are shown in Table 3.

-Evaluation of adhesion-
A patterned thin film was obtained in the same manner as in “Formation of microlenses”.
Next, for the silicon substrate having the patterned thin film, the adhesion of the patterned thin film to the substrate was evaluated by a cross-cut peel test after a pressure cooker test (120 ° C., humidity 100%, 4 hours). Table 3 shows the number of grids remaining in 100 grids at this time.

-Evaluation of solvent resistance-
A patterned thin film was obtained in the same manner as in “Formation of microlenses” except that a glass substrate was used instead of the silicon substrate.
Subsequently, the glass substrate which has a patterned thin film was immersed in i-propanol of 50 degreeC for 10 minutes, and the film thickness change rate before and behind immersion was measured and evaluated. At this time, the solvent resistance is good when the film thickness change rate is 5% or less, and the solvent resistance is poor when it exceeds 5% or when the thin film is dissolved and the film thickness is reduced. The evaluation results are shown in Table 3.

Example 2
A composition solution was prepared and evaluated in the same manner as in Example 1 except that the solution of copolymer (A-2) was used instead of the solution of copolymer (A-1). The evaluation results are shown in Tables 1-3.

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

Example 4
A composition solution was prepared and evaluated in the same manner as in Example 1 except that the solution of copolymer (A-4) was used instead of the solution of copolymer (A-1). The evaluation results are shown in Tables 1-3.

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

Comparative Example 2
The copolymer (a-2) solution obtained in Comparative Synthesis Example 2 was used as the copolymer (a-2) as 100 parts by weight (solid content), and as the component (B), 4,4 ′-[1- { 4- (1- [4-Hydroxyphenyl] -1-methylethyl) phenyl} ethylidene] bisphenol-1,2-naphthoquinonediazide-5-sulfonic acid ester, 30 parts by weight, as other components, γ-methacryloyloxypropyltri 5 parts by weight of methoxysilane was mixed, dissolved in propylene glycol methyl ether acetate so that the solid content concentration was 30% by weight, and then filtered through a Millipore filter having a pore size of 0.5 μm to prepare a composition solution.
Next, evaluation was performed in the same manner as in Example 1 except that the composition solution was used instead of the composition solution (S-1). The evaluation results are shown in Tables 1-3.

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

Claims (6)

[A] (a1) an unsaturated carboxylic acid and / or an unsaturated carboxylic acid anhydride, (a2) a compound represented by the following general formula (1) and / or a compound represented by the following general formula (2)

[In General Formula (1) and General Formula (2), each R independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and each R ¹ independently represents a hydrogen atom or 1 to carbon atoms. Each R ² , each R ³ , each R ⁴ and each R ⁵ are independently of each other a hydrogen atom, a fluorine atom, an alkyl group having 1 to 4 carbon atoms, a phenyl group or 1 to 4 carbon atoms. And each n is an integer of 1 to 6 independently of each other. And (a3) an alkali-soluble copolymer obtained by copolymerizing an olefinic unsaturated compound other than (a1) and (a2), [B] 4,4 ′-[1- {4- ( 1- [4-hydroxyphenyl] -1-methylethyl) phenyl} ethylidene] bisphenol-1,2-naphthoquinonediazide-5-sulfonate , and [C] benzyl (4-hydroxyphenyl) (methyl) sulfonium hexafluoro An interlayer insulating film comprising a non-antimony thermosensitive acid generating compound selected from the group consisting of phosphate, triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium tetrafluoroborate and 4-acetoxyphenyldimethylsulfonium hexafluoroarsenate for forming a radiation-sensitive resin set Thing. An interlayer insulating film formed from the radiation-sensitive resin composition for forming an interlayer insulating film according to claim 1 . A method for forming an interlayer insulating film, comprising the following steps in the order described below.
(A) forming a coating film of the radiation-sensitive resin composition for forming an interlayer insulating film according to claim 1 on a substrate;
(B) irradiating at least a part of the coating film with radiation;
(C) developing the coated film after irradiation;
(D) A step of heating the coated film after development. [A] (a1) an unsaturated carboxylic acid and / or an unsaturated carboxylic acid anhydride, (a2) a compound represented by the following general formula (1) and / or a compound represented by the following general formula (2)

[In General Formula (1) and General Formula (2), each R independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and each R ¹ independently represents a hydrogen atom or 1 to carbon atoms. Each R ² , each R ³ , each R ⁴ and each R ⁵ are independently of each other a hydrogen atom, a fluorine atom, an alkyl group having 1 to 4 carbon atoms, a phenyl group or 1 to 4 carbon atoms. And each n is an integer of 1 to 6 independently of each other. And (a3) an alkali-soluble copolymer obtained by copolymerizing an olefinically unsaturated compound other than (a1) and (a2), [B] 4,4 ′-[1- {4- ( 1- [4-hydroxyphenyl] -1-methylethyl) phenyl} ethylidene] bisphenol-1,2-naphthoquinonediazide-5-sulfonate, and [C] benzyl (4-hydroxyphenyl) (methyl) sulfonium hexafluoro A microlens formation comprising a non-antimony thermosensitive acid generating compound selected from the group consisting of phosphate, triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium tetrafluoroborate and 4-acetoxyphenyldimethylsulfonium hexafluoroarsenate use radiation-sensitive resin Composition. A microlens formed from the radiation-sensitive resin composition for forming a microlens according to claim 4 . A method for forming a microlens comprising the following steps in the order described below.
(A) forming a coating film of the radiation-sensitive resin composition for microlens formation according to claim 4 on a substrate;
(B) irradiating at least a part of the coating film with radiation;
(C) developing the coated film after irradiation;
(D) A step of heating the coated film after development.

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