KR101289163B1 - Radiation Sensitive Resin Composition, and Formation of Interlayer Insulating Film and Microlens - Google Patents

Abstract

The present invention relates to a radiation-sensitive resin composition containing a copolymer of unsaturated carboxylic acid or unsaturated carboxylic anhydride and (meth) acryloyloxyoctacene, 1,2-quinonediazide compound and thermosensitive acid generating compound. It is about.

This composition has no safety problems, has excellent sensitivity, resolution, storage stability as a solution, and the like, and has a good development margin capable of forming a good pattern shape even when the optimum development time is exceeded in the development process. Used to form the lens.

Radiation-sensitive resin composition, interlayer insulating film, microlens

Description

Radiation Sensitive Resin Composition, and Formation of Interlayer Insulating Film and Microlens

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

[Patent Document 1] Japanese Patent Application Laid-Open No. 2001-354822

[Patent Document 2] Japanese Patent Application Laid-Open No. 2001-343743

[Patent Document 3] Japanese Unexamined Patent Publication No. 6-18702

[Patent Document 4] Japanese Unexamined Patent Publication No. 6-136239

[Patent Document 5] Japanese Patent Application Laid-Open No. 2001-330953

The present invention relates to a radiation sensitive resin composition, an interlayer insulating film and microlens formed from the radiation sensitive resin composition, and a method of forming the interlayer insulating film and microlens.

In electronic components such as thin film transistors (hereinafter referred to as "TFT") type liquid crystal display elements, magnetic head elements, integrated circuit elements, and solid-state image pickup elements, an interlayer insulating film for insulating between wirings arranged in layers is generally provided. It is installed. As the material for forming the interlayer insulating film, a radiation-sensitive resin composition is widely used because it is preferable that the number of steps for obtaining the required pattern shape and sufficient flatness is desirable (Japanese Patent Laid-Open No. 2001-354822 and Japan). See Patent Publication No. 2001-343743).

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 the interlayer insulating film and forming a liquid crystal alignment film thereon, so that the interlayer insulating film is exposed to high temperature conditions in the process of forming the transparent electrode film. Or exposure to a stripping solution of the resist used for pattern formation of the electrode, a sufficient resistance to them is required.

In addition, TFT-type liquid crystal display devices have recently undergone large screens, high brightness, high precision, high-speed response, and thinning, and have high sensitivity to radiation-sensitive resin compositions used to form interlayer insulating films due to the request for product yield in the process. The interlayer insulating film to be formed is required to be more high performance than the conventional one in terms of low dielectric constant, high light transmittance, and the like.

On the other hand, microlenses having a lens diameter of about 3 to 100 µm or microlens arrays arranged regularly are used as an imaging optical system for an on-chip color filter such as a facsimile, an electronic copier, a solid-state imaging device, or an optical system material of an optical fiber connector. .

As a method of forming a microlens, after forming a patterned thin film corresponding to a lens, the method is used as a lens by heat treatment and melt flow, or by using a lens pattern subjected to melt flow as a mask by dry etching. Although a method of transferring the sintered metal is known, a radiation-sensitive resin composition is widely used to form such a lens pattern (see Japanese Patent Laid-Open No. 6-18702 and Japanese Patent Laid-Open No. 6-136239). .

In addition, the radiation sensitive resin composition used to form the lens pattern is highly sensitive, and it is required that the microlenses formed therefrom have a desired radius of curvature and have high heat resistance and high light transmittance.

In addition, the device in which the microlenses are formed as described above is coated with a planarization film and an etching resist to remove various insulating films on the bonding pad, which is a wiring forming portion, and irradiated with radiation through a desired photomask, and developed and bonded. After removing the etching resist of the pad portion, the planarizing film or various insulating films are removed by etching to expose the bonding pad portion. For this reason, the microlenses are required to have solvent resistance, heat resistance and the like in the coating film forming step and the etching step of the planarization film and the etching resist.

On the other hand, in the interlayer insulating film and the microlens obtained in this way, if the developing time is too long than the optimum time in the developing step at the time of forming them, the developing solution penetrates easily between the pattern and the substrate, and peeling occurs easily. In order to control the developing time strictly, there was a problem in terms of yield or productivity of the product.

Furthermore, in order to improve the heat resistance and surface hardness of an interlayer insulating film or microlens, proposals were made to add antimony fluoride as a heat sensitive acid generator to a radiation sensitive resin composition as a raw material (Japanese Patent Laid-Open No. 2001-330953). In the case of such a radiation sensitive resin composition, the toxicity problem by the antimony type compound was pointed out.

As described above, the radiation-sensitive resin composition used to form the interlayer insulating film or the microlens is highly sensitive and it is required that no pattern peeling occurs even when the developing time is longer than a predetermined time in the developing step. High heat resistance, high solvent resistance, low dielectric constant, high light transmittance, etc. are required. On the other hand, in the case of forming microlenses, high heat resistance, high solvent resistance, high light transmittance, etc. in addition to the good melt shape (desired curvature radius) as the microlenses Although required, the radiation sensitive resin composition which satisfies these various requirements and does not have a problem also in safety is not known conventionally.

<Start of invention>

The present invention has been made on the basis of the above circumstances, and the first object of the present invention is no problem in safety, and is excellent in sensitivity, resolution, storage stability as a solution, and the like. It is providing the radiation sensitive resin composition which has favorable image development margin which can form a pattern shape.

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

Further, a third object of the present invention is to provide a method for forming a microlens having a good melt shape by using the radiation-sensitive resin composition together with excellent solvent resistance, heat resistance, light transmittance, adhesiveness, and the like. .

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

According to the present invention, said object of the present invention is firstly,

(a1) at least one compound selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic anhydrides,

(a2) a copolymer of at least one compound selected from the group consisting of a compound represented by the following formula (1) and a compound represented by the following formula (2),

[B] 1,2-quinonediazide compound, and

[C] Thermosensitive Acid Generating Compounds

It is achieved by the radiation sensitive resin composition characterized by including the following.

(Wherein R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R ¹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ² , R ³ , R ⁴ and R ⁵ independently of each other are a hydrogen atom) , A fluorine atom, an alkyl group having 1 to 4 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a perfluoroalkyl group having 1 to 4 carbon atoms, and n is an integer of 1 to 6 independently of each other.)

(Wherein R, R ¹ , R ² , R ³ , R ⁴ and R ⁵ , and n have the same meaning as in Formula 1 above.)

The above object of the present invention is secondly achieved by a method for forming an interlayer insulating film, which comprises the following steps in the order described below.

(A) forming a film of the radiation sensitive composition on a substrate;

(B) irradiating at least a portion of the coating with radiation,

(C) developing the film after irradiation, and

(D) A step of heating the film after development.

The above object of the present invention is thirdly achieved by a method for forming a microlens, comprising the following steps in the order described below.

(A) forming a film of the radiation sensitive composition on a substrate;

(B) irradiating at least a portion of the coating with radiation,

(C) developing the film after irradiation, and

(D) A step of heating the film after development.

BEST MODE FOR CARRYING OUT THE INVENTION [

Hereinafter, the present invention will be described in detail.

[A] copolymer

[A] copolymer contained in the radiation sensitive resin composition of this invention is (a1) 1 or more types of compounds chosen from the group which consists of unsaturated carboxylic acid and unsaturated carboxylic anhydride (Hereinafter, "unsaturated compound (a1)" ) And (a2) a copolymer of at least one compound selected from the group consisting of the compound represented by the formula (1) and the compound represented by the formula (2) (hereinafter referred to as "unsaturated compound (a2)"). .

Examples of the unsaturated compound (a1) include monocarboxylic acid compounds, dicarboxylic acid compounds, anhydrides of dicarboxylic acids, mono [(meth) acryloyloxyalkyl] esters of polyhydric carboxylic acids, and both terminals. The mono (meth) acrylate of the polymer which has a carboxyl group and a hydroxyl group etc. are mentioned.

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 hexahydrophthalic acid, etc .;

As said dicarboxylic acid compound, For example, maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, etc .;

As anhydride of the said dicarboxylic acid, For example, anhydride etc. of said dicarboxylic acid compound;

As mono [(meth) acryloyloxyalkyl] ester of the said polyhydric carboxylic acid, for example, succinic acid mono (2-acryloyloxyethyl), succinic acid mono (2-methacryloyloxyethyl), phthalic acid mono (2-acryloyloxyethyl), monophthalate (2-methacryloyloxyethyl), etc .;

As mono (meth) acrylate of the polymer which has a carboxyl group and a hydroxyl group in the said both terminal, ω-carboxypolycaprolactone monoacrylate, the ω-carboxypolycaprolactone monomethacrylate, etc. are mentioned, respectively.

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

The said unsaturated compound (a1) can be used individually, and can also mix and use 2 or more types.

The content of the repeating unit derived from the unsaturated compound (a1) in the polymer [A] is preferably 10 based on the sum of the repeating unit derived from the unsaturated compound (a1) and the repeating unit derived from the unsaturated compound (a2). To 90% by weight, more preferably 30 to 70% by weight. The solubility with respect to the alkaline developing solution of the composition obtained by making it contain in this range can be controlled to a more appropriate range.

An unsaturated compound (a2) is 1 or more types of compounds chosen from the compound represented by following formula (1), and the compound represented by following formula (2).

&Lt; Formula 1 >

(Wherein R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R ¹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ² , R ³ , R ⁴ and R ⁵ independently of each other are a hydrogen atom) , A fluorine atom, an alkyl group having 1 to 4 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a perfluoroalkyl group having 1 to 4 carbon atoms, and n is an integer of 1 to 6 independently of each other.)

<Formula 2>

(Wherein R, R ¹ , R ² , R ³ , R ⁴ and R ⁵ , and n have the same meaning as in Formula 1 above.)

In the above 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 ⁵ are, for example, methyl group, ethyl group, n-propyl group, i-propyl group, n -Butyl group, i-butyl group, sec-butyl group, t-butyl group, etc. are mentioned.

Moreover, as a C6-C20 aryl group of R <^2> , R <^3> , R <^4> and R <^5> , a phenyl group, a toluyl group, etc. are mentioned, for example. Moreover, as a C1-C4 perfluoroalkyl group of R <^2> , R <^3> , R <^4> and R <^{5>, it} is a trifluoromethyl group, pentafluoroethyl group, heptafluoro-n-propyl group, heptafluoro, for example. -i-propyl group, nonafluoro-n-butyl group, nonafluoro-i-butyl group, nonafluoro-sec-butyl group, nonafluoro-t-butyl group, etc. are mentioned.

As a compound represented by the said Formula (1), for example, 3- (acryloyloxymethyl) oxetane, 3- (acryloyloxymethyl) -2-methyloxetane, 3- (acryloyloxymethyl)- 3-ethyloxetane, 3- (acryloyloxymethyl) -2-trifluoromethyloxetane, 3- (acryloyloxymethyl) -2-pentafluoroethyloxetane, 3- (acryloyl Oxymethyl) -2-phenyloxetane, 3- (acryloyloxymethyl) -2,2-difluorooxetane, 3- (acryloyloxymethyl) -2,2,4-trifluorojade Cetane, 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-pentafluoroethyl oxetane, 3- (2-acryloyloxyethyl) -2-phenyloxetane, 3- (2-acryloyloxyethyl) -2, 2-difluoro Oxetane, 3- (2-acryloyloxyethyl) -2,2,4-trifluorooxetane, 3- (2-acryloyloxyethyl) -2,2,4,4-tetrafluoro Acrylic acid esters such as oxetane;

3- (methacryloyloxymethyl) oxetane, 3- (methacryloyloxymethyl) oxetane, 3- (methacryloyloxymethyl) (Methacryloyloxymethyl) -2-trifluoromethyloxetane, 3- (methacryloyloxymethyl) -2-pentafluoroethyloxetane, 3- (methacryloyloxymethyl) -2- (Methacryloyloxymethyl) -2,2,4-trifluorooxetane, 3- (methacryloyloxymethyl) -2,2-difluorooxetane, 3- (Methacryloyloxyethyl) -2,2,4,4-tetrafluorooxetane, 3- (2-methacryloyloxyethyl) oxetane, 3- (2-methacryloyloxyethyl) 3- (2-methacryloyloxyethyl) -2-trifluoromethyloxetane, 3- (2-methacryloyloxyethyl) (2-methacryloyloxyethyl) -2-pentafluoroethyloxetane, 3- (2-methacryloyloxyethyl) -2-phenyloxetane, 3- ) -2,2-difluorooxetane, 3- (2- Methacrylic acid, such as kryloyloxyethyl) -2,2,4-trifluorooxetane and 3- (2-methacryloyloxyethyl) -2,2,4,4-tetrafluorooxetane Ester etc. are mentioned, respectively.

As a compound represented by the said Formula (2), for example, 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-pentafluoroethyl oxetane, 2- (acryloyloxymethyl) -4-pentafluoroethyl oxetane, 2- (acryloyloxymethyl) -2-phenylox Cetane, 2- (acryloyloxymethyl) -3-phenyloxetane, 2- (acryloyloxymethyl) -4-phenyloxetane, 2- (acryloyloxymethyl) -2,3-difluoro Oxetane, 2- (acryloyloxymethyl) -2,4-difluorooxetane, 2- (acryloyloxymethyl) -3,3-dimple Oroxoxane, 2- (acryloyloxymethyl) -3,4-difluorooxetane, 2- (acryloyloxymethyl) -4,4-difluorooxetane, 2- (acryloyl Oxymethyl-3,3,4-trifluorooxetane, 2- (acryloyloxymethyl) -3,4,4-trifluorooxetane, 2- (acryloyloxymethyl) -3,3 , 4,4-tetrafluorooxetane,

2- (2-acryloyloxyethyl) oxetane, 2- [2- (2-methyloxetanyl)] ethyl methacrylate, 2- [2- (3-methyloxetanyl)] ethyl methacryl Late, 2- (acryloyloxyethyl) -2-methyloxetane, 2- (2-acryloyloxyethyl) -4-methyloxetane, 2- (2-acryloyloxyethyl) -2- Trifluoromethyloxetane, 2- (2-acryloyloxyethyl) -3-trifluoromethyloxetane, 2- (2-acryloyloxyethyl) -4-trifluoromethyloxetane, 2 -(2-acryloyloxyethyl) -2-pentafluoroethyl oxetane, 2- (2-acryloyloxyethyl) -3-pentafluoroethyl oxetane, 2- (2-acryloyloxy Ethyl) -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-acryloyl jade Ethyl) -3,3-difluorooxetane, 2- (2-acryloyloxyethyl) -3,4-difluorooxetane, 2- (2-acryloyloxyethyl) -4,4 -Difluorooxetane, 2- (2-acryloyloxyethyl) -3,3,4-trifluorooxetane, 2- (2-acryloyloxyethyl) -3,4,4-tri Acrylic esters such as fluorooxetane and 2- (2-acryloyloxyethyl) -3,3,4,4-tetrafluorooxetane;

2- (methacryloyloxymethyl) oxetane, 2- (methacryloyloxymethyl) -2-methyloxetane, 2- (methacryloyloxymethyl) -3-methyloxetane, 2- ( Methacryloyloxymethyl) -4-methyloxetane, 2- (methacryloyloxymethyl) -2-trifluoromethyloxetane, 2- (methacryloyloxymethyl) -3-trifluoro Methyl oxetane, 2- (methacryloyloxymethyl) -4-trifluoromethyloxetane, 2- (methacryloyloxymethyl) -2-pentafluoroethyl oxetane, 2- (methacrylo) Yloxymethyl) -3-pentafluoroethyl oxetane, 2- (methacryloyloxymethyl) -4-pentafluoroethyl oxetane, 2- (methacryloyloxymethyl) -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- (methacryloyloxymethyl) -3,3, 4,4-tetrafluorooxetane,

2- (2-methacryloyloxyethyl) oxetane, 2- [2- (2-methyloxetanyl)] ethyl methacrylate, 2- [2- (3-methyloxetanyl)] ethyl meth Acrylate, 2- (2-methacryloyloxyethyl) -2-methyloxetane, 2- (2-methacryloyloxyethyl) -4-methyloxetane, 2- (2-methacryloyl Oxyethyl) -2-trifluoromethyloxetane, 2- (2-methacryloyloxyethyl) -3-trifluoromethyloxetane, 2- (2-methacryloyloxyethyl) -4- Trifluoromethyloxetane, 2- (2-methacryloyloxyethyl) -2-pentafluoroethyl oxetane, 2- (2-methacryloyloxyethyl) -3-pentafluoroethyl oxetane , 2- (2-methacryloyloxyethyl) -4-pentafluoroethyloxetane, 2- (2-methacryloyloxyethyl) -2-phenyloxetane, 2- (2-methacrylo Yloxyethyl) -3-phenyloxetane, 2- (2-methacryloyloxyethyl) -4-phenyloxetane, 2- (2-methacryloyloxyethyl) -2,3-difluoro Oxetane, 2- (2-methacryloyloxyethyl) -2,4-dip Fluorooxetane, 2- (2-methacryloyloxyethyl) -3,3-difluorooxetane, 2- (2-methacryloyloxyethyl) -3,4-difluorooxetane , 2- (2-methacryloyloxyethyl) -4,4-difluorooxetane, 2- (2-methacryloyloxyethyl) -3,3,4-trifluorooxetane, 2 -(2-methacryloyloxyethyl) -3,4,4-trifluorooxetane, 2- (2-methacryloyloxyethyl) -3,3,4,4-tetrafluorooxetane Methacrylic acid ester, such as these, etc. are 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 -The development margin of the radiation sensitive resin composition from which trifluoromethyl oxetane etc. are obtained is preferable at the point which improves chemical resistance of the interlayer insulation film and microlenses obtained.

These unsaturated compounds (a2) can be used independently and can also be used in mixture of 2 or more type.

The content of the structural unit derived from the unsaturated compound (a2) in the copolymer [A] is preferably based on the sum of the repeating units derived from the unsaturated compound (a1) and the repeating units derived from the unsaturated compound (a2). It is 10-90 weight%, More preferably, it is 30-70 weight%. By including in this range, the balance between the storage stability of the composition and the heat resistance of the resulting interlayer insulating film or microlens is excellent.

[A] The polymer is a copolymer of the unsaturated compounds (a1) and (a2), but optionally other than the unsaturated compounds (a1) and (a2) (a3) other olefins different from the unsaturated compounds (a1) and (a2). It may be a copolymer of unsaturated compounds (a1), (a2) and (a3) using a series unsaturated compound (hereinafter referred to as an unsaturated compound (a3)). The unsaturated compound (a3) is not particularly limited as long as the copolymerization with the above-mentioned unsaturated compounds (a1) and (a2) is possible, but examples thereof include alkyl acrylates, alkyl methacrylates, cyclic alkyl esters of acrylic acid, and methacrylic acid. Cyclic alkyl ester, acrylic acid aryl ester, methacrylic acid aryl ester, unsaturated dicarboxylic acid diester, hydroxyalkyl acrylate, hydroxyalkyl methacrylate, bicyclo unsaturated compound, unsaturated dicarbonylimide compound, styrene compound And other unsaturated compounds.

As said alkyl acrylate, For example, methyl acrylate, ethyl acrylate, n-propyl acrylate, i-propyl acrylate, n-butyl acrylate, sec-butyl acrylate, t-butyl acrylate, etc .;

As said methacrylic acid alkyl ester, for example, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, i-propyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate, t Butyl methacrylate and the like;

Examples of the cyclic alkyl esters of acrylic acid include cyclohexyl acrylate, 2-methylcyclohexyl acrylate and tricyclo [5.2.1.0 ^2,6 ] decane-8-yl acrylate (hereinafter referred to as "dicyclopentanyl acrylate". 2-dicyclopentanyloxyethyl acrylate, isoboroyl acrylate and the like;

Examples of the cyclic alkyl ester of methacrylic acid include cyclohexyl methacrylate, 2-methylcyclohexyl methacrylate and tricyclo [5.2.1.0 ^2,6 ] decane-8-yl methacrylate (hereinafter, " Dicyclopentanyl methacrylate ", 2-dicyclopentanyloxyethyl methacrylate, isoboroyl methacrylate, etc .;

As said methacrylic acid aryl ester, For example, phenyl methacrylate, benzyl methacrylate, etc .;

As said unsaturated dicarboxylic acid diester, For example, diethyl maleate, diethyl fumarate, diethyl itaconate;

As said hydroxyalkyl acrylate, for example, hydroxymethyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxyethyl methacrylate, 3-hydroxypropyl methacrylate Latex, 4-hydroxybutyl methacrylate, diethylene glycol monomethacrylate, 2,3-dihydroxypropyl methacrylate, 2-methacryloxyethylglycoside and the like;

As said hydroxyalkyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, etc. are mentioned, for example;

As said bicyclo unsaturated compound, it is bicyclo [2.2.1] hept-2-ene, 5-methylbicyclo [2.2.1] hept-2-ene, 5-ethyl bicyclo [2.2.1] hept, for example. -2-ene, 5-hydroxybicyclo [2.2.1] hept-2-ene, 5-hydroxymethylbicyclo [2.2.1] hept-2-ene, 5- (2-hydroxyethyl) ratio Cyclo [2.2.1] hept-2-ene, 5-methoxybicyclo [2.2.1] hept-2-ene, 5-ethoxybicyclo [2.2.1] hept-2-ene, 5,6-dihydrate Roxybicyclo [2.2.1] hept-2-ene, 5,6-di (hydroxymethyl) bicyclo [2.2.1] hept-2-ene, 5,6-di (2-hydroxyethyl) ratio Cyclo [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-hydroxymethyl-5- Methylbicyclo [2.2.1] hept-2-ene, 5-t-butoxycarbonylbicyclo [2.2.1] hept-2-ene, 5-cyclohexyloxycarbonylbicyclo [2.2.1] hept 2-en, 5- Oxycarbonylbicyclo [2.2.1] hept-2-ene, 5,6-di (t-butoxycarbonyl) bicyclo [2.2.l] hept-2-ene, 5,6-di (cyclohex) Siloxycarbonyl) bicyclo [2.2.1] hept-2-ene and the like;

As said unsaturated dicarbonyl imide compound, N-phenylmaleimide, N-cyclohexyl maleimide, N-benzyl maleimide, N-succinimidyl-3- maleimide benzoate, N-succinimidyl, for example 4-maleimide butyrate, N-succinimidyl-6-maleimide caproate, N-succinimidyl-3-maleimide propionate, N- (9-acridinyl) maleimide and the like;

As said styrene compound, For example, styrene, (alpha) -methylstyrene, m-methylstyrene, p-methylstyrene, p-methoxy styrene;

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, α-ethyl acrylate glycidyl, α-n-propyl acrylate glycidyl, α-n-butyl acrylate glycidyl, acrylic acid 3, 4-epoxybutyl, methacrylic acid 3,4-epoxybutyl, α-ethylacrylic acid 3,4-epoxybutyl, acrylic acid 6,7-epoxyheptyl, methacrylic acid 6,7-epoxyheptyl, α-ethylacrylic acid 6, 7-epoxyheptyl, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether, etc. are mentioned, respectively.

Among these unsaturated compounds (a3), 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, methacrylate glycidyl, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glyc Cidyl ether and the like are preferred from the viewpoint of copolymerization reactivity and solubility in an aqueous alkali solution of the obtained [A] copolymer.

The said unsaturated compound (a3) can be used individually, and can also mix and use 2 or more types.

The content of the structural unit derived from the unsaturated compound (a3) in the copolymer [A] is preferably based on the sum of the repeating units derived from the unsaturated compound (a1) and the repeating unit derived from the unsaturated compound (a2). 70 weight% or less, More preferably, it is 5 to 70 weight%, More preferably, it is 5 to 50 weight%, Especially preferably, it is 10 to 30 weight%. By containing in this range, the storage stability of the composition obtained and the solubility to alkaline developing solution can be controlled to a more appropriate range.

[A] The copolymer is preferably a copolymer of the above unsaturated compounds (a1), (a2) and (a3).

As the [A] copolymer preferable in this invention, More specifically, 1 or more types of unsaturated compounds (a1) chosen from the group which consists of acrylic acid, methacrylic acid, and maleic anhydride,

3- (methacryloyloxymethyl) oxetane, 3- (methacryloyloxymethyl) -3-ethyloxetane, 3- (methacryloyloxymethyl) -2-trifluoromethyloxetane, With 3- (methacryloyloxymethyl) -2-phenyloxetane, 2- (methacryloyloxymethyl) oxetane and 2- (methacryloyloxymethyl) -4-trifluoromethyloxetane At least one unsaturated compound (a2) selected from the group consisting of:

t-butyl methacrylate, 2-methylcyclohexyl acrylate, dicyclopentanyl methacrylate, bicyclo [2.2.1] hept-2-ene, N-phenylmaleimide, N-cyclohexyl maleimide, styrene, selected from the group consisting of p-methoxystyrene, 1,3-butadiene, glycidyl methacrylate, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether and p-vinylbenzyl glycidyl ether And copolymers with at least one unsaturated compound (a3).

The polystyrene reduced weight average molecular weight (hereinafter referred to as "Mw") of the copolymer (A) is preferably 1 × 10 ³ to 5 × 10 ⁵ , more preferably 3 × 10 ³ to 3 × 10 ⁵ , further preferably Preferably 5 × 10 ³ to 1 × 10 ⁵ .

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

The radiation sensitive resin composition containing the [A] copolymer having such Mw and Mw / Mn does not cause any development residue or film reduction during development, and thus can form a pattern of a predetermined shape very easily.

The copolymer (A) has at least one of a carboxyl group and a carboxylic anhydride group and an oxetane ring structure, has suitable solubility in an aqueous alkali solution, and can be easily cured by heating without using a special curing agent. . In addition, the radiation-sensitive resin composition containing the copolymer [A] can easily form a film having a predetermined pattern without developing residue or film reduction during development.

The copolymer [A] can be used alone or in combination of two or more thereof.

The above-mentioned [A] copolymer can be synthesized, for example, by polymerizing an unsaturated compound (a1) and an unsaturated compound (a2) and optionally an unsaturated compound (a3) in the presence of a radical polymerization initiator in a suitable solvent. .

Examples of the solvent used for the polymerization include alcohols, ethers, ethylene glycol ethers, ethylene glycol alkyl ether acetates, diethylene glycol ethers, propylene glycol ethers, propylene glycol alkyl ether acetates, propylene glycol alkyl ether propionates and aromatic hydrocarbons. , Ketones, esters and the like.

As said alcohol, For example, methanol, ethanol, benzyl alcohol, 2-phenylethanol, 3-phenyl-1-propanol; As ether, tetrahydrofuran and the like;

As ethylene glycol ether, For example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, etc .;

As ethylene glycol alkyl ether acetate, For example, ethylene glycol methyl ether acetate, ethylene glycol ethyl ether acetate, ethylene glycol n-propyl ether acetate, ethylene glycol n-butyl ether acetate, etc .;

As diethylene glycol ether, For example, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, etc .;

As propylene glycol ether, For example, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether, etc .;

As propylene glycol alkyl ether acetate, For example, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol n-propyl ether acetate, propylene glycol n-butyl ether acetate, etc .;

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;

As an aromatic hydrocarbon, For example, toluene, xylene, etc .; Methyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone and the like as the ketone;

Examples of the ester include methyl acetate, ethyl acetate, n-propyl acetate, n-butyl acetate, methyl hydroxyacetate, ethyl hydroxyacetate, hydroxyacetic acid n-propyl, hydroxyacetic acid n-butyl, methyl lactate, Ethyl lactate, n-propyl lactate, n-butyl lactate, methyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, n-propyl 3-hydroxypropionic acid, n-butyl 3-hydroxypropionic acid, 2-hydroxy- Methyl 2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, methyl 2-hydroxy-3-methylbutanoate, methyl methoxyacetate, ethyl methoxyacetate, methoxyacetic acid n-propyl, methoxyacetic acid n -Butyl, methyl ethoxyacetate, ethyl ethoxyacetate, ethoxyacetic acid n-propyl, ethoxyacetic acid n-butyl, n-propoxyacetic acid, n-propoxyacetic acid, n-propoxyacetic acid n-propyl, n-propoxy N-butyl acetate, n-butoxyacetate, n-butoxyacetate, n-butoxyacetate n-propyl, n-butoxyacetate n-butyl, methyl 2-methoxypropionate, ethyl 2-methoxypropionate , 2-methoxypropionic acid n-propyl, 2-methoxypropionic acid n-butyl, 2-ethoxypropionate methyl, 2-ethoxypropionate ethyl, 2-ethoxypropionic acid n-propyl, 2-ethoxypropionic acid n-butyl , 2-n-propoxypropionate, ethyl 2-n-propoxypropionate, n-propyl 2-n-propoxypropionate, n-butyl 2-n-propoxypropionate, methyl 2-n-butoxypropionate, Ethyl 2-n-butoxypropionate, n-propyl 2-n-butoxypropionate, n-butyl 2-n-butoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3-methoxypropionic acid n-propyl, 3-methoxypropionate n-butyl, 3-ethoxypropionate methyl, 3-ethoxypropionate, 3-ethoxypropy Acids n-propyl, 3-ethoxypropionic acid n-butyl, 3-n-propoxypropionate, ethyl 3-n-propoxypropionate, 3-n-propoxypropionic acid n-propyl, 3-n-propoxypropionic acid n-butyl, 3-n-butoxy methyl propionate, ethyl 3-n-butoxy propionate, n-propyl 3-n-butoxypropionic acid, n-butyl 3-n-butoxypropionate, etc. are mentioned, respectively.

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 in particular, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, propylene glycol monomethyl ether and propylene glycol Methyl ether acetate is preferred.

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

Moreover, as a radical polymerization initiator used for the said superposition | polymerization, for example, 2,2'- azobisisobutyronitrile, 2,2'- azobis- (2, 4- dimethylvaleronitrile), 2,2 ' Azo compounds such as -azobis- (4-methoxy-2,4-dimethylvaleronitrile); Organic peroxides such as benzoyl peroxide, lauroyl peroxide, t-butyl peroxy pivalate, and 1,1'-bis- (t-butylperoxy) cyclohexane; Hydrogen peroxide and the like. When using a peroxide as a radical polymerization initiator, it can also be used with a reducing agent as a redox type initiator.

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

In addition, in order to adjust the molecular weight of the [A] copolymer in the said superposition | polymerization, a molecular weight modifier can be used.

Specific examples of the molecular weight modifier 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 thio glycolic acid; Xanthogens, such as dimethyl xanthogen sulfide and di-i-propyl xanthogen disulfide, terpinolene, the (alpha) -methylstyrene dimer, etc. are mentioned.

These molecular weight modifiers can be used individually or in mixture of 2 or more types.

[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 which generates an acid by irradiation with radiation, for example, 1,2-benzo And quinone diazide sulfonic acid ester, 1,2-naphthoquinone diazide sulfonic acid ester, 1,2-benzoquinone diazide sulfonic acid amide, and 1,2-naphthoquinone diazide sulfonic acid amide.

As said 1, 2- naphthoquinone diazide sulfonic acid ester, the 1, 2- naphthoquinone diazide sulfonic acid ester of trihydroxy benzophenone, and 1, 2- naphthoquinone diazide of tetrahydroxy benzophenone, for example Sulfonate, 1,2-naphthoquinone diazide sulfonate of pentahydroxybenzophenone, 1,2-naphthoquinone diazide sulfonic acid ester of hexahydroxybenzophenone, and other (polyhydroxyphenyl) alkanes 1 And 2-naphthoquinone diazide sulfonic acid ester and the like, and specific examples thereof include 1,2-naphthoquinone diazide sulfonic acid ester of trihydroxy benzophenone, for example, 2,3,4-trihydroxy. Benzophenone-1,2-naphthoquinoneazide-4-sulfonic acid ester, 2,3,4-trihydroxybenzophenone-1,2-naphthoquinone diazide-5-sulfonic acid ester, 2,3,4- Trihydroxybenzophenone-1,2-naphthoquinone diazide-6-sulfonic acid ester, 2,3,4-t Hydroxybenzophenone-1,2-naphthoquinonediazide-7-sulfonic acid ester, 2,3,4-trihydroxybenzophenone-1,2-naphthoquinonediazide-8-sulfonic acid ester, 2,4 , 6-trihydroxybenzophenone-1,2-naphthoquinone diazide-4-sulfonic acid ester, 2,4,6-trihydroxybenzophenone-1,2-naphthoquinone diazide-5-sulfonic acid ester , 2,4,6-trihydroxybenzophenone-1,2-naphthoquinone diazide-6-sulfonic acid ester, 2,4,6-trihydroxybenzophenone-1,2-naphthoquinone diazide- 7-sulfonic acid ester, 2,4,6-trihydroxybenzophenone-1,2-naphthoquinone diazide-8-sulfonic acid ester, etc .;

As 1,2-naphthoquinone diazide sulfonic acid ester of tetrahydroxy benzophenone, it is 2,2 ', 4,4'- tetrahydroxy benzophenone-1,2-naphthoquinone diazide-4-, for example. Sulfonic acid ester, 2,2 ', 4,4'-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonic acid ester, 2,2', 4,4'-tetrahydroxybenzophenone- 1,2-naphthoquinone diazide-6-sulfonic acid ester, 2,2 ', 4,4'-tetrahydroxybenzophenone-1,2-naphthoquinone diazide-7-sulfonic acid ester, 2,2' , 4,4'-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-8-sulfonic acid ester, 2,3,4,3'-tetrahydroxybenzophenone-1,2-naphthoquinonedia Zide-4-sulfonic acid ester, 2,3,4,3'- tetrahydroxy benzophenone-1,2-naphthoquinone diazide-5-sulfonic acid ester, 2,3,4,3'- tetrahydroxy benzo Phenone-1,2-naphthoquinonediazide-6-sulfonic acid ester, 2,3,4,3'-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-7-sul Phonic acid ester, 2,3,4,3'-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-8-sulfonic acid ester, 2,3,4,4'-tetrahydroxybenzophenone-1, 2-naphthoquinone diazide-4-sulfonic acid ester, 2,3,4,4'-tetrahydroxybenzophenone-1,2-naphthoquinone diazide-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-naphthoquinone diazide-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-naphthoquinone diazide-7-sulfonic acid ester, 2,3,4,2'-tetra Hydroxy-4'-methylbenzophenone-1,2-naphthoquinonediazide-8-sulfonic acid ester, 2,3,4,4'-tetrahydroxy-3'-methoxybenzophenone-1,2- Naphthoquinone diazide-4-sulfonic acid ester, 2,3,4,4'-tetrahydroxy-3'-methoxybenzophenone-1,2-naphthoquinone diazide-5-sulfonic acid ester, 2,3 , 4,4'-tetrahydroxy-3'-methoxybenzophenone-1,2-naphthoquinonediazide-6-sulfonic acid ester, 2,3,4,4'-tetrahydroxy-3'-meth Toxybenzophenone-1,2-naphthoquinone diazide-7-sulfonic acid ester And 2,3,4,4'-tetrahydroxy-3'-methoxybenzophenone-1,2-naphthoquinone diazide-8-sulfonic acid ester and the like.

As 1,2-naphthoquinone diazide sulfonic acid ester of the said pentahydroxy benzophenone, for example, 2,3,4,2 ', 6'-pentahydroxy benzophenone-1,2-naphthoquinone diazide 4-sulfonic acid ester, 2,3,4,2 ', 6'-pentahydroxybenzophenone-1,2-naphthoquinone diazide-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-naphthoquinone diazide-8-sulfonic acid ester, etc .;

As 1,2-naphthoquinone diazide sulfonic acid ester of the said hexahydroxy benzophenone, it is 2,4,6,3 ', 4', 5'-hexahydroxy benzophenone-1,2-naphtho, for example. Quinonediazide-4-sulfonic acid ester, 2,4,6,3 ', 4', 5'-hexahydroxybenzophenone-1,2-naphthoquinone diazide-5-sulfonic acid ester, 2,4,6 , 3 ', 4', 5'-hexahydroxybenzophenone-1,2-naphthoquinonediazide-6-sulfonic acid ester, 2,4,6,3 ', 4', 5'-hexahydroxybenzo Phenone-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-naphthoquinone diazide-4-sulfonic acid ester, 3,4,5,3 ', 4' , 5'-hexahydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonic acid ester, 3,4,5,3 ', 4', 5'-hexahydroxybenzophenone-1,2- Naphthoquinone diazide-6-sulfonic acid ester, 3,4,5,3 ', 4', 5'-hexahydroxybenzophenone-1,2-naphtho And the like non-diazide-7-sulfonic acid ester, 3,4,5,3 ', 4', 5'-hexa-hydroxy benzophenone-1, 2-naphthoquinonediazide-8-sulfonic acid ester;

As 1,2-naphthoquinone diazide sulfonic acid ester of the said other (polyhydroxyphenyl) alkane, it is bis (2, 4- dihydroxy phenyl) methane- 1, 2- naphthoquinone diazide-, for example. 4-sulfonic acid ester, bis (2,4-dihydroxyphenyl) methane-1,2-naphthoquinonediazide-5-sulfonic acid ester, bis (2,4-dihydroxyphenyl) methane-1,2- Naphthoquinone diazide-6-sulfonic acid ester, bis (2,4-dihydroxyphenyl) methane-1,2-naphthoquinone diazide-7-sulfonic acid ester, bis (2,4-dihydroxyphenyl) Methane-1,2-naphthoquinone diazide-8-sulfonic acid ester, bis (4-hydroxyphenyl) methane-1,2-naphthoquinone diazide-4-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-hydride Ciphenyl) methane-1,2-naphthoquinonediazide-8-sulfonic acid ester, tris (4-hydroxyphenyl) methane-1,2-naphthoquinonediazide-4-sulfonic acid ester, tris (4-hydride) Hydroxyphenyl) methane-1,2-naphthoquinonediazide-5-sulfonic acid ester, tris (4-hydroxyphenyl) methane-1,2-naphthoquinonediazide-6-sulfonic acid ester, tris (4-hydride Hydroxyphenyl) methane-1,2-naphthoquinonediazide-7-sulfonic acid ester, 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 Naphthoquinone diazide-5-sulfonic acid ester, 1,1,1-tris (4-hydroxyphenyl) ethane-1,2-naphthoquinone diazide-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-trihydroxyphenyl) methane-1,2-naphthoquinone diazide-4-sulfonic acid ester, bis (2,3,4-trihydroxyphenyl) methane- 1,2-naphthoquinone diazide-5-sulfonic acid ester, bis (2,3,4-trihydroxyphenyl) methane-1,2-naphthoquinone diazide-6-sulfonic acid ester, bis (2,3 , 4-trihydroxyphenyl) methane-1,2-naphthoquinonediazide-7-sulfonic acid ester, bis (2,3,4-trihydroxyphenyl) methane-1,2-naphthoquinonediazide- 8-sulfone Ester, 2,2-bis (2,3,4-trihydroxyphenyl) propane-1,2-naphthoquinone diazide-4-sulfonic acid ester, 2,2-bis (2,3,4-trihydrate Oxyphenyl) propane-1,2-naphthoquinonediazide-5-sulfonic acid ester, 2,2-bis (2,3,4-trihydroxyphenyl) propane-1,2-naphthoquinonediazide-6 Sulfonic acid esters, 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-phenylpropane-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-hydroxy Phenyl) -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-naphthoquinonediazide- 8-sulfonic acid ester, 4,4 '-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol-1,2-naphthoquinonediazide-4 Sulfonic 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] bispe Nol-1,2-naphthoquinonediazide-6-sulfonic acid ester, 4,4 '-[1- {4- (1- [4-hydroxyphenyl] -1-methylethyl) phenyl} ethylidene] bisphenol -1,2-naphthoquinonediazide-7-sulfonic acid ester, 4,4 '-[1- {4- (1- [4-hydroxyphenyl] -1-methylethyl) phenyl} ethylidene] bisphenol- 1,2-naphthoquinone diazide-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-hydroxyphenylmethane-1,2-naphthoquinonediazide-5-sulfonic acid ester, bis (2,5-dimethyl-4-hydroxyphenyl) -2-hydroxyphenylmethane-1,2 Naphthoquinone diazide-6-sulfonic acid ester, bis (2,5-dimethyl-4-hydroxyphenyl) -2-hydroxyphenylmethane-1,2-naphthoquinone diazide-7-sulfonic acid ester, bis (2,5-dimethyl-4-hydroxyphenyl) -2-hydroxyphenylmethane-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-sulfonic acid ester, 3,3,3 ', 3' -Tetramethyl-1,1'-spirobiindene-5,6,7,5 ', 6', 7'-hexanol-1,2-naphthoquinonediazide-5-sulfonic acid ester, 3,3, 3 ', 3'-tetramethyl-1,1'-spirobiindene-5,6,7,5', 6 ', 7'-hexanol-1,2-naphthoquinonedia Zide-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'-spirobiindene-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-naphthoquinone diazide-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-naphthoquinone diazide-7-sulfonic acid ester, 2,2,4-trimethyl-7,2 ', 4'-trihydroxyflavan-1,2-naphthoquinone diazide-8- And sulfonic acid esters.

As said 1, 2- benzoquinone diazide sulfonic acid ester, the compound which replaced the 1, 2- naphthoquinone of each said 1, 2- naphthoquinone diazide sulfonic acid ester with 1, 2- benzoquinone is mentioned.

As said 1,2-naphthoquinone diazide sulfonic acid amide, the compound which replaced the sulfonic acid ester of each said 1, 2- naphthoquinone diazide sulfonic acid ester with sulfonic acid amide is mentioned.

As said 1, 2- benzoquinone diazide sulfonic acid amide, 1, 2- naphthoquinone of said 1, 2- naphthoquinone diazide sulfonic acid ester is mentioned as 1, 2- benzoquinone, and sulfonate is used as sulfonate amide The compound which replaced with is 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-naphthoquinone diazide-4-sulfonic acid ester or bis (2,5-dimethyl-4-hydroxyphenyl)- 2-hydroxyphenylmethane-1,2-naphthoquinone diazide-4-sulfonic acid ester is preferable.

The 1,2-quinonediazide compounds may be used alone or in combination of two or more thereof.

The use ratio of the [B] 1,2-quinonediazide compound in the radiation sensitive resin composition of the present invention is preferably 5 to 100 parts by weight, more preferably 10 to 10 parts by weight of the [A] copolymer. 50 parts by weight. By using it in the ratio of this range, the balance of pattern formation property, developability, and the heat resistance and solvent resistance of the obtained interlayer insulation film and microlenses becomes more favorable.

[C] Thermosensitive Acid Generating Compounds

[C] The thermosensitive acid generating compound used in the present invention is preferably a nonionic thermosensitive acid generator, and examples thereof include a sulfone compound, a sulfonic acid ester compound, a sulfone imide compound, and a diazomethane compound. .

As said sulfone compound, (beta) -keto sulfone, (beta) -sulfonyl sulfone, etc. are mentioned, for example. Specific examples thereof include, for example, phenacylphenyl sulfone, mesityl phenacyl sulfone, and the like as β-keto sulfone; As (beta) -sulfonyl sulfone, bis (phenylsulfonyl) methane, 4-trisphenacyl sulfone, etc. are mentioned, respectively.

As said sulfonic acid ester compound, an alkyl sulfonic acid ester, an aryl sulfonic acid ester, etc. are mentioned, for example. As these specific examples, as alkyl sulfonic acid ester, benzointosylate, (alpha) -methylol benzo intosylate, (alpha)-methylol benzoin n-octane sulfonate, (alpha)-methylol benzoin trifluoromethanesulfonate, for example , α-methylolbenzoin n-dodecanesulfonate and the like;

As the aryl sulfonic acid ester, for example, pyrogallol tris (trifluoromethanesulfonate), pyrogallol tris (nonafluoro-n-butanesulfonate), pyrogallol tris (methanesulfonate), nitrobenzyl-9,10 -Diethoxy anthracene-2-sulfonate, etc. are mentioned, respectively.

As said sulfonimide compound, the compound etc. which are represented by following formula (3) are mentioned, for example.

(Wherein, R ⁶ is a divalent organic group, R ⁷ is a monovalent organic group.)

As a divalent organic group of R <^6> , a methylene group, a C2-C20 alkylene group, a C7-C20 aralkylene group, a C3-C10 cycloalkylene group, a C6-C20 allylene group, C1-C20, for example 6-20 arylene groups etc. are mentioned. As said cycloalkylene group, a cyclohexylene group, a norbornylene group, etc. are mentioned, for example. Some or all of these hydrogen atoms in R ⁶ may be substituted with a halogen atom, an aryl group having 2 to 20 carbon atoms, and an alkoxyl group having 1 to 8 carbon atoms. As said halogen atom, fluorine is mentioned, for example.

Examples of the monovalent organic group of 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, an aryl group having 6 to 12 carbon atoms, and the like. As said C1-C10 alkyl group, a methyl group, an ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-octyl group, n-nonyl group, n-decyl group, for example My back;

As a C3-C10 cycloalkyl group, For example, cyclohexyl group, norbornyl group, etc .;

As a C6-C12 aryl group, a phenyl group, toluyl group, a naphthyl group, etc. are mentioned, respectively. Some or all of these hydrogen atoms in R ⁷ may be substituted with a halogen atom, an aryl group having 6 to 20 carbon atoms, and an alkoxyl group having 1 to 8 carbon atoms. As said halogen atom, fluorine is mentioned, for example. In addition, when R <^7> is a cycloalkyl group, some or all of the hydrogen atoms which it has may be substituted by the other C1-C8 alkyl group, the C2-C8 alkoxycarbonyl group, etc. among the above-mentioned substituents.

Specific examples of such sulfonimide compounds include, for example, N- (trifluoromethanesulfonyloxy) succinimide, N- (trifluoromethanesulfonyloxy) phthalimide, and N- (trifluoromethanesulphate). Ponyloxy) diphenylmaleimide, N- (trifluoromethanesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide, N- (trifluoromethanesulfonyloxy ) -7-oxabicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide, N- (trifluoromethanesulfonyloxy) bicyclo [2.2.1] heptane-5,6- Oxy-2,3-dicarboxyimide, N- (trifluoromethanesulfonyloxy) naphthylimide, N- (10-camphorsulfonyloxy) succinimide, N- (10-camphorsulfonyloxy) Phthalimide, N- (10-camphorsulfonyloxy) diphenylmaleimide, N- (10-camphorsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide, N- (10-camphorsulfonyloxy) -7-oxabicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide, N- (10- Camphorsulfonyloxy) bicyclo [2.2.1] heptan-5,6-oxy-2,3-dicarboxyimide, N- (10-camphorsulfonyloxy) naphthylimide,

N- (p-toluenesulfonyloxy) succinimide, N- (p-toluenesulfonyloxy) phthalimide, N- (p-toluenesulfonyloxy) diphenylmaleimide, N- (p-toluenesul Ponyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide, N- (p-toluenesulfonyloxy) -7-oxabicyclo [2.2.1] hept-5-ene -2,3-dicarboxyimide, N- (p-toluenesulfonyloxy) bicyclo [2.2.1] heptan-5,6-oxy-2,3-dicarboxyimide, N- (p-toluenesulfonyl Oxy) naphthylimide, N- (2-trifluoromethylbenzenesulfonyloxy) succinimide, N- (2-trifluoromethylbenzenesulfonyloxy) phthalimide, N- (2-trifluoro Chloromethylbenzenesulfonyloxy) diphenylmaleimide, N- (2-trifluoromethylbenzenesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide, N- ( 2-trifluoromethylbenzenesulfonyloxy) -7-oxabicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide, N- (2-trifluoromethylbenzenesulfonyloxy) Vehicle [2.2.1] heptane-5,6-oxy-2,3-dicarboxyimide,

N- (2-trifluoromethylbenzenesulfonyloxy) naphthylimide, N- (4-trifluoromethylbenzenesulfonyloxy) succinimide, N- (4-trifluoromethylbenzenesulfonyloxy ) Phthalimide, N- (4-trifluoromethylbenzenesulfonyloxy) diphenylmaleimide, N- (4-trifluoromethylbenzenesulfonyloxy) bicyclo [2.2.1] hept-5-ene -2,3-dicarboxyimide, N- (4-trifluoromethylbenzenesulfonyloxy) -7-oxabicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide, N- (4-trifluoromethylbenzenesulfonyloxy) bicyclo [2.2.1] heptan-5,6-oxy-2,3-dicarboxyimide, N- (4-trifluoromethylbenzenesulfonyloxy) nap Thylimide, N- (nonafluoro-n-butanesulfonyloxy) succinimide, N- (nonafluoro-n-butanesulfonyloxy) phthalimide, N- (nonafluoro-n-butane Sulfonyloxy) diphenylmaleimide, N- (nonafluoro-n-butanesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicar Siimide, N- (nonafluoro-n-butanesulfonyloxy) -7-oxabicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide, N- (nonafluoro-n -Butanesulfonyloxy) bicyclo [2.2.1] heptan-5,6-oxy-2,3-dicarboxyimide,

N- (nonafluoro-n-butanesulfonyloxy) naphthylimide, N- (pentafluorobenzenesulfonyloxy) succinimide, N- (pentafluorobenzenesulfonyloxy) phthalimide, N -(Pentafluorobenzenesulfonyloxy) diphenylmaleimide, N- (pentafluorobenzenesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide, N- ( Pentafluorobenzenesulfonyloxy) -7-oxabicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide, N- (pentafluorobenzenesulfonyloxy) bicyclo [2.2.1 ] Heptan-5,6-oxy-2,3-dicarboxyimide, N- (pentafluorobenzenesulfonyloxy) naphthylimide, N- (perfluoro-n-octanesulfonyloxy) succinimide , N- (perfluoro-n-octanesulfonyloxy) phthalimide, N- (perfluoro-n-octanesulfonyloxy) diphenylmaleimide, N- (perfluoro-n-octanesulfonyl Oxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide, N- (perfluoro-n-octanesulfonyloxy) -7-oxabisi Rho [2.2.1] hept-5-ene-2,3-dicarboxyimide, N- (perfluoro-n-octanesulfonyloxy) bicyclo [2.2.1] heptane-5,6-oxy-2 , 3-dicarboxyimide, N- (perfluoro-n-octanesulfonyloxy) naphthylimide, N-{(5-methyl-5-carboxy methanebicyclo [2.2.1] hepta-2-yl ) Sulfonyloxy} succinimide and the like.

As said diazomethane compound, the compound etc. which are represented by following formula (4) are mentioned, for example.

(In formula, R <^8> is respectively independently a C1-C8 alkyl group or a C2-C20 aryl group.)

In Formula 4, R ⁸ may be substituted with a halogen atom in part or in all of its hydrogen atoms.

Specific examples of such diazomethane compounds include bis (trifluoromethanesulfonyl) diazomethane, bis (t-butylsulfonyl) diazomethane, bis (cyclohexanesulfonyl) diazomethane and bis ( Benzenesulfonyl) diazomethane, 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, etc. are mentioned.

Only one kind may be used for the above-mentioned [C] thermosensitive acid generating compound, and two or more kinds thereof may be mixed and used.

As the [C] thermosensitive acid generating compound used in the present invention, a sulfonimide compound or a diazomethane compound is preferable, and in particular, N- (trifluoromethanesulfonyloxy) succinimide, N- (trifluoromethane Sulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide, N- (10-camphorsulfonyloxy) succinimide, N- (10-camphorsulfonyloxy) ratio Cyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide and N-{(5-methyl-5-carboxymethanebicyclo [2.2.1] hepta-2-yl) sulfonyloxy} succinate With imide, bis (cyclohexanesulfonyl) diazomethane, bis (t-butylsulfonyl) diazomethane, bis (1,4-dioxaspiro [4.5] -decane-7-sulfonyl) diazomethane It is preferable to use at least one compound selected from the group consisting of.

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 0.1 to 5 parts by weight based on 100 parts by weight of the [A] copolymer. to be. By using it in the ratio of this range, the balance of pattern formation property and resolution will become more favorable.

Other components

Although the radiation sensitive resin composition of this invention contains the said copolymer [A], a 1, 2- quinonediazide compound [B], and a thermosensitive acid generating compound [C], one [D] is further needed as needed. The polymeric compound which has the above ethylenically unsaturated double bond, [E] epoxy resin, [F] melamine resin, [G] surfactant, or [H] adhesion | attachment adjuvant can be contained.

Examples of the polymerizable compound having one or more ethylenically unsaturated double bonds [D] (hereinafter also referred to as "[D] component") include monofunctional (meth) acrylate, bifunctional (meth) acrylate, or the like. Trifunctional or more than (meth) acrylate is mentioned.

As said monofunctional (meth) acrylate, 2-hydroxyethyl (meth) acrylate, carbitol (meth) acrylate, isoboroyl (meth) acrylate, 3-methoxybutyl (meth), for example Acrylate, 2- (meth) acryloyloxyethyl-2-hydroxypropyl phthalate, etc. are mentioned. As these commercial items, for example, Alonics M-101, M-111, M-114 (above, manufactured by Toagosei Co., Ltd.), KAYARAD TC-110S, and TC-120S (above, Nippon Kayaku Co., Ltd.) ), Biscot 158, East 2311 (above, Osaka Yugaku Kagaku Kogyo Co., Ltd. make), etc. are mentioned.

As said bifunctional (meth) acrylate, for example, ethylene glycol (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, polypropylene glycol Di (meth) acrylate, tetraethylene glycol di (meth) acrylate, bisphenoxy ethanol fluorene diacrylate, bisphenoxy ethanol fluorene diacrylate, etc. are mentioned. As these commercial items, for example, Alonics M-210, M-240, M-6200 (above, Toagosei Co., Ltd.), KAYARAD HDDA, HX-220, R-604 (above, Nippon Kaya) Cub Co., Ltd., Biscot 260, 312, 335 HP (above, Osaka Yuki Kagaku Kogyo Co., Ltd.), etc. are mentioned.

As said trifunctional or more than (meth) acrylate, for example, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, tri ((meth) acryloyloxyethyl) phosphate, pentaerythritol Tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and the like. Examples thereof include, for example, Alonics M-309 and Copper M-. 400, copper M-405, copper M-450, copper M-7100, copper M-8030, copper M-8060 (above, manufactured by Toagosei Co., Ltd.), KAYARAD TMPTA, copper DPHA, copper DPCA-20, copper DPCA -30, East DPCA-60, East DPCA-120 (above, manufactured by Nippon Kayaku Co., Ltd.), Biscot 295, East 300, East 360, East GPT, East 3PA, East 400 (above, Osaka Yuki Kagaku High School) Co., Ltd.) etc. are mentioned.

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

These monofunctional, bifunctional or trifunctional or more (meth) acrylates can be used independently, and can also be used in combination of 2 or more type.

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

By containing [D] component in such a ratio, the heat resistance, surface hardness, etc. of an interlayer insulation film or microlens obtained without affecting the film formation property of a composition can be improved more.

The epoxy resin [E] is not limited as long as it does not affect compatibility, but preferably bisphenol A epoxy resin, phenol novolac epoxy resin, cresol novolac epoxy resin, cyclic aliphatic epoxy resin, and glycidyl Ester type epoxy resin, glycidyl amine type epoxy resin, heterocyclic epoxy resin, resin which co-polymerized glycidyl methacrylate, etc. are mentioned. Among these, bisphenol A epoxy resin, cresol novolak-type epoxy resin, glycidyl ester type epoxy resin, etc. are mentioned.

The use ratio of the epoxy resin (E) is preferably 30 parts by weight or less based on 100 parts by weight of the [A] copolymer. By containing [E] component in such a ratio, the heat resistance, surface hardness, etc. of an interlayer insulation film or microlens obtained, without impairing the film formation property of a composition, especially the uniformity of a film thickness, can be improved further.

In addition, when an epoxy group containing monomer is used as a copolymerization monomer of [A] copolymer, although [A] copolymer can also be called "epoxy resin," [A] copolymer is alkali-insoluble in that it is alkali-soluble, [E] ] It is 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 formed. [F] Melamine resin is a compound which has 1 or more of groups represented by following formula (5) in 1 molecule, for example.

(In formula, R <^11> is a hydrogen atom or a C1-C6 alkyl group, Preferably it is a C1-C4 alkyl group.)

[F] The melamine resin is preferably a compound having two or more groups represented by the above formula (5), and more preferably a compound in which these groups are bonded to a nitrogen atom. When the [F] melamine resin is a compound having two or more groups represented by the above formula (5) in the molecule, a plurality of R ¹¹ may be the same or different from each other.

As such [F] melamine resin, for example, the compound represented by the following formula (6), the compound represented by the following formula (7), and urea-formaldehyde resin, thiourea-formaldehyde resin, melamine-formaldehyde resin, guanamine- And a formaldehyde resin, a benzoguanamine-formaldehyde resin, a glycoluril-formaldehyde resin, and a polyvinylphenol group in which the group represented by the formula (5) is bonded.

(In formula, R <^12> is respectively independently a C1-C4 alkyl group.)

(In formula, R <^13> is respectively independently a C1-C4 alkyl group.)

The use ratio of the [F] melamine resin is preferably 10 parts by weight or less, more preferably 7 parts by weight or less based on 100 parts by weight of the [A] copolymer.

As said [G] surfactant, a fluorine-type surfactant, a silicone type surfactant, and a nonionic surfactant can be used preferably.

As a specific example of a fluorine-type surfactant, For example, 1,1,2,2- tetrafluoro octyl (1,1,2,2- tetrafluoro propyl) ether, 1,1,2,2- tetrafluoro octyl Hexyl 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 perfluorododecylsulfonic acid, 1, Sodium fluoroalkylbenzenesulfonate, in addition to 1,2,2,8,8,9,9,10,10-decafluorododecane, 1,1,2,2,3,3-hexafluorodecane and the like; Fluoroalkyloxyethylene ethers; Fluoroalkylammonium iodide, fluoroalkylpolyoxyethylene ether, perfluoroalkylpolyoxyethanol; Perfluoroalkyl alkoxylates; Fluorine-based alkyl esters and the like.

As these commercial items, BM-1000, copper-1100 (above, manufactured by BM Chemie Co., Ltd.), Megapack F142D, Copper F172, Copper F173, Copper F183, Copper F178, Copper F191, Copper F471 (or more, Dai Nippon Ink Chemical Industries, Ltd.) Co., Ltd.), Florard FC-170C, Copper FC-171, Copper FC-430, Copper FC-431 (above, Sumitomo 3M Co., Ltd.), Suplon S-112, Copper S-113, Copper S-131, S-141, S-145, S-382, SC-101, SC-102, SC-103, SC-104, SC-105, SC-106 And Asahi Glass Co., Ltd., F-Top EF301, EF303, EF352 (above, manufactured by Kasei Co., Ltd.), and the like.

As said silicone type surfactant, For example, DC3PA, DC7PA, FS-1265, SF-8428, SH11PA, SH21PA, SH28PA, SH29PA, SH30PA, SH-190, SH-193, SZ-6032 (above, Toray Dow Corning What is marketed under brand names, such as a silicone company make, TSF-4440, TSF-4300, TSF-4445, TSF-4446, TSF-4460, TSF-4452 (above, GE Toshiba Silicone Co., Ltd. product) are mentioned. have.

Examples of the nonionic surfactant include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether and polyoxyethylene oleyl ether; Polyoxyethylene aryl ethers such as polyoxyethylene octylphenyl ether and polyoxyethylene nonylphenyl ether; Polyoxyethylene dialkyl esters such as polyoxyethylene dilaurate and polyoxyethylene distearate; (Meth) acrylic acid copolymer polyflow N0. 57, 95 (above, Kyoesha Chemical Co., Ltd. product) etc. can be used.

These surfactant can be used individually or in combination of 2 or more types.

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 said [H] adhesion | attachment adjuvant, a functional silane coupling agent is used preferably, for example, Especially the silane coupling agent which has reactive substituents, such as a carboxyl group, a methacryloyl group, an isocyanate group, an epoxy group, is mentioned. Specific examples include trimethoxysilylbenzoic acid,? -Methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane,? -Isocyanatepropyltriethoxysilane,? -Glycidoxypropyltrimethoxy Silane,? - (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and the like. Such [H] adhesion aid 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 uniformly contains the above-mentioned [A] copolymer, [B] 1,2-quinonediazide compound and [C] thermosensitive acid generating compound, and the other optional component that can be optionally added. It is prepared by mixing. The radiation sensitive resin composition of the present invention is preferably dissolved in a suitable solvent and used in a solution state. For example, the [A] copolymer, the [B] 1,2-quinonediazide compound, the [C] thermosensitive acid generating compound, and the other components optionally added may be mixed in a suitable solvent in a predetermined ratio so as to be in a solution state. A radiation sensitive resin composition can be manufactured.

As a solvent used for manufacture of the radiation sensitive resin composition of this invention, a [A] copolymer, a [B] 1,2-quinone diazide compound, and a [C] thermosensitive acid generating compound, and the other component mix | blended arbitrarily It is used to dissolve each component uniformly and not to react with each component.

As such a solvent, the same thing as what was illustrated as a solvent which can be used for superposition | polymerization for manufacturing the above-mentioned [A] copolymer is mentioned.

Among these solvents, alcohols, glycol ethers, ethylene glycol alkyl ether acetates, esters and diethylene glycol are preferably used in view of solubility of each component, reactivity with each component, ease of film formation, and the like. Among them, 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, fulpyrene glycol monomethyl ether acetate, methyl methoxy propionate and ethyl ethoxypropionate can be particularly preferably used.

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

When using a high boiling point solvent together as a solvent of the radiation sensitive resin composition of this invention, the usage-amount can be 50 weight% or less with respect to solvent whole quantity, Preferably it is 40 weight% or less, More preferably, it is 30 weight% or less. . By using it in the quantity of this range, the film thickness uniformity (in-plane uniformity) of a film can be improved more, without impairing the sensitivity and residual film rate of a composition.

When manufacturing the radiation sensitive resin composition of this invention as a solution state, components other than the solvent which occupy in a solution (namely, [A] copolymer and [B] 1,2-quinonediazide compound, and the other optionally added) Although the ratio of the total amount of components) can be arbitrarily set according to a purpose of use, a desired film thickness value, etc., Preferably it is 5-50 weight%, More preferably, it is 10-40 weight%, More preferably, it is 15-35 weight%. .

The composition solution thus prepared may be used for use after being filtered using a Millipore filter having a pore size of about 0.2 to 0.5 µm.

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

Method of forming interlayer insulating film and microlens

The method for forming the interlayer insulating film and the method for forming the microlens of the present invention include the following steps in the order described below.

(A) forming a film of radiation-sensitive resin composition on a substrate,

(B) irradiating at least a portion of the coating with radiation,

(C) developing the film after exposure;

(D) a step of heating the film after development.

Each of these steps will be described below.

(A) Process of forming the film of radiation sensitive resin composition on a board | substrate

This process is a process of forming the film of a radiation sensitive resin composition by apply | coating or transferring the radiation sensitive resin composition of this invention to the board | substrate surface. When the radiation sensitive resin composition of this invention contains a solvent, a film can be formed by prebaking and removing a solvent, after apply | coating or transferring a solution composition to the surface of a board | substrate.

As a board | substrate which can be used, a glass substrate, a silicon wafer, the board | substrate which provided various metal films on these surfaces, etc. are mentioned, for example.

It does not specifically limit as a coating method, For example, the appropriate method, such as the spraying method, the roll coating method, the spin coating method (spin coating method), the slit die coating method, the bar coating method, the inkjet coating method, can be employ | adopted, Especially, Spin coating and slit die coating are preferred.

As a transfer method, the dry film method is mentioned, for example.

When the dry film method is employed when forming a film of the radiation sensitive resin composition on a substrate, the dry film is a radiation film made of the radiation sensitive resin composition of the present invention on a base film, preferably a flexible base film. It is what laminates a layer (henceforth "a radiation sensitive dry film").

The radiation-sensitive dry film may be formed by laminating a radiation-sensitive layer by applying the radiation-sensitive resin composition of the present invention as a liquid composition, preferably on a base film, and then drying.

As a base film of a radiation sensitive dry film, synthetic resin films, such as a polyethylene terephthalate (PET) film, polyethylene, a polypropylene, polycarbonate, polyvinyl chloride, can be used, for example. The thickness of the base film is suitably in the range of 15 to 125 占 퐉.

Although it does not specifically limit as a coating method at the time of laminating | stacking a radiation sensitive layer on a base film, For example, the appropriate method, such as an applicator coating method, a bar coating method, a roll coating method, a curtain flow coating method, can be employ | adopted.

Although the conditions of the said prebaking differ according to the kind, usage ratio, etc. of each component, it can be made into about 30 second-15 minutes at 60-110 degreeC, for example.

The film thickness of the formed film is, for example, about 3 to 6 µm 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 removing a solvent, when the radiation sensitive resin composition of this invention contains a solvent.

(B) A step of irradiating at least a part of the film with radiation (hereinafter referred to as "exposure")

In this step, at least part of the formed film is exposed. When exposing only a part of the said film, it exposes normally through the photomask which has a predetermined pattern.

Examples of the radiation used for exposure include ultraviolet rays such as g-ray (wavelength 436 nm) and i-rays (365 nm), far-ultraviolet rays such as KrF excimer laser, X-rays such as synchrotron radiation, and charged particle beams such as electron beams. Etc. can be mentioned. Among these, ultraviolet rays are preferable, and radiation including g rays and / or i rays is particularly preferable.

As the exposure amount, in the case of forming an interlayer insulating film, for example, the case of forming a 50 to 1,500 J / m ² or so, a microlens, for example, is preferably 50 to 2,000 J / m ² or so.

(C) Process of developing the film after exposure

In this process, a predetermined pattern is formed by developing the film after exposure and removing an exposure part.

As a developing solution used for image development, for example, 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, Alkali (basic compound) aqueous solutions, such as 0] -7-undecene and 1,5-diazabicyclo [4,3,0] -5-nonene, are preferable. In some cases, various organic solvents capable of dissolving the film of the radiation-sensitive resin composition may be used.

Moreover, an appropriate amount of water-soluble organic solvents and surfactants, such as methanol and ethanol, can also be added to the said aqueous alkali solution.

As a developing method, appropriate methods, such as a puddle method, the dipping method, the oscillation dipping method, the shower method, can be employ | adopted.

Although developing time changes with kinds, usage ratios, etc. of each component, it can be made into about 30 to 120 second, for example.

In addition, in the radiation-sensitive resin composition known in the art, since the peeling occurs in the formed pattern when the developing time exceeds the optimum time of about 20 to 25 seconds, the developing time needs to be strictly controlled, but the radiation of the present invention In the case of the resin composition, even if the optimum developing time exceeds 30 seconds or more, good pattern formation is possible, which is very advantageous in terms of product yield to productivity.

(D) step of heating the film after development

In this step, the film on which the predetermined pattern is formed is preferably washed, for example, by running water, and, preferably, remains in the coating film by exposing (post-exposure) radiation, such as a high pressure mercury lamp, to the entire surface. After decomposing the 1,2-quinonediazide compound, the coating film is cured by heat treatment (post-baking) with a heating apparatus such as a hot plate or an oven. In addition, when forming a microlens, the formed pattern is melt-flowed by postbaking, and it is made into a predetermined shape.

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

In addition, the heating temperature in postbake is about 120-250 degreeC, for example. Although heating time changes with kinds of heating apparatus, it can be made into about 5 to 30 minutes on a hotplate, for example about 30 to 90 minutes in an oven. At this time, the step baking method which performs 2 or more times of heat processings, etc. can also be employ | adopted.

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

Interlayer Insulator and Micro Lens

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

The interlayer insulating film of this invention can be used very favorably for electronic components, such as a TFT type liquid crystal display element, a magnetic head element, an integrated circuit element, and a solid-state image sensor.

In addition, the shape of the microlens of the present invention is a good semiconvex lens shape. The microlenses of the present invention and microlens arrays regularly arranged thereon, facsimile, electron duplicators, solid-state imaging devices, and the like can be used as an optical material of an imaging optical system or an optical fiber connector of an on-chip color filter.

As mentioned above, the radiation sensitive resin composition of this invention has the outstanding sensitivity and resolution, is excellent in the storage stability as a composition solution, and is favorable development which can form a favorable pattern shape even if it exceeds the optimal developing time in a developing process. It has a margin and can use very preferably especially as microlenses, such as an interlayer insulation film and a solid-state image sensor of various electronic components.

In addition, the method of forming the interlayer insulating film and the method of forming the microlens according to the present invention can form a good pattern even when the developing time exceeds the optimum developing time, thereby easily forming the interlayer insulating film and the microlens with the above excellent characteristics.

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

In addition, the microlenses of the present invention have excellent solvent resistance, heat resistance, light transmittance, adhesiveness, and the like, and have a good melt shape.

Example

Although an Example and a comparative example are given to the following and this invention is demonstrated to it further more concretely, this invention is not limited to a following example.

Synthesis of Copolymer

Synthesis Example 1

7 parts by weight of 2,2'-azobis (2,4-dimethylvaleronitrile) and 220 parts by weight of propylene glycol monomethyl ether acetate were added to a flask equipped with a cooling tube and a stirrer. 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 by weight of α-methylstyrene dimer were added thereto. Agitation was started slowly with nitrogen substitution. 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). Solid content concentration of the obtained polymer solution was 31.8 weight%, the weight average molecular weight of the polymer was 17,900, and molecular weight distribution (Mw / Mn) was 1.8. In addition, a weight average molecular weight and a number average molecular weight are the polystyrene conversion average molecular weights measured using GPC (gel permeation chromatography (Tosoh Co., Ltd. product HLC-8020).

Synthesis Example 2

7 parts by weight of 2,2'-azobis (2,4-dimethylvaleronitrile) and 220 parts by weight of propylene glycol monomethyl ether acetate were added to a flask equipped with a cooling tube and a stirrer. 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 are added thereto. Agitation was started slowly with nitrogen substitution. 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). Solid content concentration of the obtained polymer solution was 31.9 weight%, the weight average molecular weight of the polymer was 20,200, and molecular weight distribution was 1.9.

Synthesis Example 3

7 parts by weight of 2,2'-azobis (2,4-dimethylvaleronitrile) and 150 parts by weight of propylene glycol monomethyl ether acetate were added to a flask equipped with a cooling tube and a stirrer. Next, 20 parts by weight of styrene, 25 parts by weight of methacrylic acid, 20 parts by weight of cyclohexylmaleimide, 35 parts by weight of 3- (methacryloyloxymethyl) -2-trifluoromethyloxetane and 2 parts of? -Methylstyrene 1.5 parts by weight of the sieve was added and stirring was started slowly with nitrogen substitution. 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). Solid content concentration of the obtained polymer solution was 38.7 weight%, the weight average molecular weight of the polymer was 21,500, and molecular weight distribution was 2.2.

Synthesis Example 4

7 parts by weight of 2,2'-azobis (2,4-dimethylvaleronitrile) and 220 parts by weight of propylene glycol monomethyl ether acetate were added to a flask equipped with a cooling tube and a stirrer. Subsequently, 20 weight part of styrene, 30 weight part of methacrylic acid, 50 weight part of 2- (methacryloyloxymethyl) -4-trifluoromethyl oxetane, and 2.0 weight part of (alpha) -methylstyrene dimers are put, and nitrogen substitution is carried out. Stirring began slowly. 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). Solid content concentration of the obtained polymer solution was 31.0 weight%, the weight average molecular weight of the polymer was 19,000, and molecular weight distribution was 1.7.

Comparative Synthesis Example 1

7 parts by weight of 2,2'-azobis (2,4-dimethylvaleronitrile) and 220 parts by weight of diethylene glycol methylethyl ether were added to a flask equipped with a cooling tube and a stirrer. 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 added thereto, and the mixture was slowly stirred with nitrogen substitution. The temperature of the solution was raised to 70 ° C. to maintain this temperature for 5 hours to obtain a polymer solution containing the copolymer (a-1). Solid content concentration of the obtained polymer solution was 32.8 weight%, the weight average molecular weight of the polymer was 24,000, and molecular weight distribution was 2.3.

Comparative Synthesis Example 2

7 parts by weight of 2,2'-azobis (2,4-dimethylvaleronitrile) and 220 parts by weight of diethylene glycol methylethyl ether were added to a flask equipped with a cooling tube and a stirrer. Subsequently, 25 weight part of methacrylic acid, 35 weight part of dicyclopentanyl methacrylate, 40 weight part of 2-hydroxyethyl methacrylates, and 2.0 weight part of (alpha) -methylstyrene dimers were added, and it stirred slowly, nitrogen-substituting. . The temperature of the solution was raised to 70 ° C. to maintain this temperature for 5 hours to obtain a polymer solution containing the copolymer (a-2). Solid content concentration of the obtained polymer solution was 32.8 weight%, the weight average molecular weight of the polymer was 25,000, and molecular weight distribution was 2.4.

Preparation and Evaluation of the Composition

Example 1

Preparation of radiation-sensitive resin composition

An amount equivalent to 100 parts by weight of the polymer solution containing the copolymer [A-1] obtained in Synthesis Example 1 as a copolymer (A-1), 4, as a [B] 1,2-quinonediazide compound; 4 '-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol (1 mol) and 1,2-naphthoquinone diazide-5-sulfonic acid chloride 4,4 '-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol-1,2-naphthoquinonedia as a condensate with (2 moles) 30 parts by weight of the zide-5-sulfonic acid ester, 5 parts by weight of γ-methacryloxypropyltrimethoxysilane as the [H] adhesion aid, and N- (trifluoromethanesulfonyloxy) as the [C] thermosensitive acid generating compound. 1 part by weight of bicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide was mixed, and propylene glycol monomethyl was obtained so that the solid content concentration (the ratio of the total amount of the component except the solvent in the total amount of the composition) was 30% by weight. 0 after dilution with ether acetate A solution (S-1) of the radiation sensitive resin composition was prepared by filtration with a .2 μm millipore filter.

Evaluation of Preservation Stability

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

Evaluation of developing margin

After apply | coating composition (S-1) each using the spinner on the some silicon substrate, it prebaked at 90 degreeC for 2 minutes on the hotplate, and formed the film. The intensity | strength in wavelength 365nm was 80W / using the Canon-made PLA-501F exposure machine (ultra-high pressure mercury lamp) through the mask which has a pattern of a line and space (10 to 1) of 3.0 micrometers in the obtained film. After irradiating m ² ultraviolet rays for 40 seconds, it developed by the puddle method by changing the developing time for every board | substrate at 25 degreeC using the aqueous solution of tetramethylammonium hydroxide of concentration 0.4weight% as a developing solution. Subsequently, flowing water was washed with ultrapure water for 1 minute and dried to form a pattern having a thickness of 3.0 mu m on the wafer. At this time, the minimum developing time required for the line line width to be 3.0 mu m is shown in Table 1 as the optimum developing time. In addition, when developing was continued from the optimum developing time, the time taken until the 3.0 µm line / pattern was peeled off was measured, and this is shown in Table 1 as the developing margin. When this value is 30 seconds or more, the development margin can be said to be good.

I. Evaluation as an interlayer insulating film

(1) evaluation of resolution

Formation of patterned thin film

After apply | coating composition (S-1) on a glass substrate using a spinner, it prebaked for 3 minutes on the 80 degreeC hotplate, and formed the film.

Subsequently, the obtained film was irradiated with the ultraviolet-ray whose intensity | strength is 100 W / m <^2> at wavelength 365nm for 15 second through the photomask of a predetermined pattern. Thereafter, the solution was developed at 25 ° C. for 1 minute using a 0.5 wt% tetramethylammonium hydroxide aqueous solution, and then washed with pure water for 1 minute to remove unnecessary portions to form a pattern.

Subsequently, 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 (postbaked) in an oven at 220 ° C. for 60 minutes to obtain a patterned thin film having a thickness of 3.0 μm. Moreover, except having made prebaking temperature into 90 degreeC or 100 degreeC, the same operation as the above was performed, and three types of patterned thin films from which the prebaking temperature differs were obtained.

Resolution evaluation

"(Circle)" and the case where it was not resolved were evaluated as "x" when the pattern (5 micrometer x 5 micrometer hole) which was missing from the obtained patterned thin film was resolved. The results are shown in Table 2.

(2) Evaluation of heat resistance dimensional stability

The film thickness before and after postbaking for 60 minutes in an oven at 220 degreeC was measured about the pattern formed by the prebaking temperature of 80 degreeC in "the formation of a patterned thin film" of the said "(1) resolution evaluation". The results are shown in Table 2. Here, when the rate of change of the film thickness is within ± 5%, it can be said that the heat-resistant dimensional stability is good.

(3) evaluation of transparency

After apply | coating composition (S-1) on a glass substrate using a spinner, it prebaked for 3 minutes on the 80 degreeC hotplate, and formed the film.

Subsequently, ultraviolet rays having an intensity of 100 W / m ² at a wavelength of 365 nm were irradiated to the entire surface of the obtained film for 30 seconds. Subsequently, the film | membrane whose film thickness is 3.0 micrometers was obtained by heating (postbaking) for 60 minutes in 220 degreeC oven.

A glass substrate of the same kind as that used for the substrate on the reference side using a spectrophotometer (150-20 type double beam (manufactured by Hitachi Seisakusho Co., Ltd.)) for a light transmittance having a wavelength of 400 nm of the film obtained above. It measured and installed.The result is shown in Table 2. Here, when a transmittance | permeability is 90% or more, it can be said that transparency is favorable.

(4) evaluation of heat discoloration resistance

After heating the board | substrate which has the film measured by said "(3) transparency evaluation" in 250 degreeC oven for 1 hour, the light transmittance of wavelength 400nm was measured similarly to "(3) transparency evaluation". . The transmittance change rate before and after heating is shown in Table 2. Here, it can be said that heat discoloration resistance is favorable when the transmittance change rate is less than 5%.

(5) Evaluation of adhesion

The film | membrane whose film thickness is 3.0 micrometers was obtained like the shear part of said "(3) transparency evaluation". After placing the board | substrate which has this film | membrane in the pressure cooker of 120 degreeC of temperature, and 100% of humidity for 4 hours, the board | substrate eye peeling test was done according to JIS-K5400. Table 2 shows the number of remaining checkerboard eyes among the 100 checkerboard eyes at this time.

II. Evaluation as a microlens

(1) Evaluation of sensitivity

The composition (S-1) was applied onto a plurality of silicon substrates using a spinner so that the film thickness after removing the solvent was 2.5 µm, respectively, and then prebaked on a hot plate at 70 ° C. for 3 minutes to form a substrate having a film. A plurality was formed.

Subsequently, after changing the exposure amount for every board | substrate through the mask which has a line-and-space pattern (10 to 1) of 0.8 micrometers of line | wire line widths, the obtained film | membrane was exposed and it used 25 using the 2.38 weight% tetramethylammonium hydroxide aqueous solution. It developed at 1 degreeC for 1 minute, and wash | cleaned for 1 minute with pure water, and obtained the patterned thin film.

The said several board | substrate was observed under the microscope, and the minimum exposure amount which can resolve the space line width (0.08 micrometer) was investigated. The results are shown in Table 3. When this value is 1,000 J / m <^2> or less, it can be said that a sensitivity is favorable.

(2) Evaluation of transparency

After apply | coating composition (S-1) on a glass substrate using a spinner, it prebaked for 3 minutes on the 70 degreeC hotplate, and formed the film.

Subsequently, ultraviolet rays having an intensity of 100 W / m ² at a wavelength of 365 nm were irradiated to the entire surface of the obtained film for 30 seconds. Subsequently, the film | membrane of 2.5 micrometers in thickness was obtained by heating (post-baking) for 60 minutes in 160 degreeC oven.

The light transmittance of the wavelength of 400 nm of the film | membrane obtained above is measured using the spectrophotometer (150-20 type double beam (made by Hitachi Seisakusho Co., Ltd.), and installing the glass substrate of the same kind as what was used for the board | substrate to the reference side. The results are shown in Table 3. Here, the transparency can be said to be good when the transmittance is 90% or more.

(3) Evaluation of heat discoloration resistance

After heating the board | substrate with the film measured by said "(2) transparency evaluation" in 250 degreeC oven for 1 hour, the light transmittance of wavelength 400nm was measured similarly to "(2) transparency evaluation". . Table 3 shows the change in transmittance before and after heating. Here, it can be said that heat discoloration resistance is favorable when the transmittance change rate is less than 5%.

(5) Evaluation of solvent resistance

The film | membrane whose film thickness is 2.5 micrometers was obtained like the shear part of said "(3) transparency evaluation". The board | substrate which has this film 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. Solvent resistance is favorable for this value being 0 to +5%.

(6) Evaluation of adhesiveness

A film having a film thickness of 2.5 µm was obtained in the same manner as the front end of the above-mentioned "(3) transparency evaluation" except that a silicon substrate was used instead of the glass substrate. After placing the board | substrate which has this film | membrane in the pressure cooker of 120 degreeC of temperature, and 100% of humidity for 4 hours, the board | substrate eye peeling test was done according to JIS-K5400. Table 3 shows the number of checkerboard eyes remaining among the checkerboard eyes at this time.

(7) Evaluation of microlens shape

After apply | coating composition (S-1) on several silicon substrate using the spinner so that the film thickness after removing a solvent might be set to 2.5 micrometers, it pre-baked on a 70 degreeC hotplate for 3 minutes, and several board | substrates which have a film Formed.

Subsequently, the obtained film was exposed to an exposure dose of 3000 J / m ² using a Nikon Corporation NSR1755i7A reduced projection exposure machine (NA = 0.50, lambda = 365 nm) through a pattern mask having a 4.0 μm dot 2.0 μm space pattern. It developed using the puddle method at 25 degreeC for 1 minute using the tetramethylammonium hydroxide aqueous solution of 1.1 weight% of concentration. Subsequently, after washing with water, it was dried to form a pattern on the wafer. Then, it exposed by the Canon Co., Ltd. product PLA-501F exposure machine (super high pressure mercury lamp) so that accumulated irradiation amount might be 3,000 J / m <^2> . Thereafter, the plate was heated at 160 ° C. for 10 minutes and further heated at 230 ° C. for 10 minutes to melt the pattern to form a microlens.

Table 3 shows the dimensions (diameter) and the cross-sectional shape of the bottom portion (surface in contact with the substrate) of the formed microlenses. The dimension of the microlens bottom portion can be said to be good when it is more than 4.0 micrometers and less than 5.0 micrometers. Moreover, when this dimension becomes 5.0 micrometers or more, it will be in the state which the adjacent lens contacted, and is unpreferable. In addition, 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.

Examples 2 to 4, Comparative Example 1

In Example 1, instead of the solution containing the copolymer (A-1), a solution containing the copolymer shown in Table 1 was used, respectively, and N- (trifluoromethane as the [C] thermosensitive acid generating compound. The composition was prepared and evaluated in the same manner as in Example 1 except that the compounds shown in Table 1 were used instead of sulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide, respectively. The results are shown in Tables 1 to 3.

Comparative Example 2

`The amount equivalent to 100 parts by weight of the solution containing the copolymer (a-2) obtained in Comparative Synthesis Example 2 as the copolymer (a-2), 4,4 '[1- 30 parts by weight of {4- (1- [4-hydroxyphenyl] -1-methylethyl) phenyl} ethylidene] bisphenol-1,2-naphthoquinone diazide-5-sulfonic acid ester, γ- as other components 5 parts by weight of methacryloyloxypropyltrimethoxysilane was mixed and dissolved in propylene glycol methyl ether acetate so that the solid content concentration was 30% by weight, followed by filtration with a Millipore filter having a pore size of 0.5 mu m.

It evaluated like Example 1 except having used the said composition instead of the composition (S-1). The evaluation results are shown in Tables 1-3. In Comparative Example 2, when the microlenses were formed, the adjacent lenses were in contact with each other, so that the cross-sectional shape of the microlenses could not be evaluated.

Comparative Example 3

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

The radiation-sensitive resin composition of the present invention has no problem in stability, is excellent in sensitivity, resolution, storage stability as a solution, and has a good developing margin capable of forming a good pattern shape even when the optimum developing time is exceeded in the developing step. . Accordingly, the radiation-sensitive resin composition of the present invention can be very usefully used for forming the interlayer insulating film and the microlens.

Claims (8)

(A) (a1) at least one compound selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic anhydrides, (a2) a copolymer of at least one compound selected from the group consisting of a compound represented by the following formula (1) and a compound represented by the following formula (2), [B] 1,2-quinonediazide compound, and [C] at least one nonionic thermosensitive acid generator selected from sulfone compounds, sulfonic acid ester compounds, sulfonimide compounds and diazomethane compounds A radiation-sensitive resin composition comprising a. &Lt; Formula 1 >

(Wherein R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R ¹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ² , R ³ , R ⁴ and R ⁵ independently of each other are a hydrogen atom) , A fluorine atom, an alkyl group having 1 to 4 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a perfluoroalkyl group having 1 to 4 carbon atoms, and n is an integer of 1 to 6 independently of each other.) <Formula 2>

(Wherein R, R ¹ , R ² , R ³ , R ⁴ and R ⁵ , and n have the same meaning as in Formula 1 above.) The component (a) is a copolymer of the component (a3) according to claim 1, wherein the copolymer (A) is a component (a1), a component (a2) and another olefinically unsaturated compound different from the components (a1) and (a2). Radiation-sensitive resin composition. The radiation sensitive resin composition according to claim 1 or 2, which is used for forming an interlayer insulating film. (A) a step of forming a coating film of the radiation sensitive resin composition according to claim 1 on a substrate, (B) irradiating at least a portion of the coating with radiation, (C) developing the film after irradiation, and (D) step of heating the film after development The method of forming an interlayer insulating film comprising the above in the order described above. The interlayer insulation film formed from the radiation sensitive resin composition of Claim 1. The radiation sensitive resin composition according to claim 1, which is used for forming a microlens. (A) a step of forming a coating film of the radiation sensitive resin composition according to claim 1 on a substrate, (B) irradiating at least a portion of the coating with radiation, (C) developing the film after irradiation, and (D) step of heating the film after development Method for forming a microlens, characterized in that it comprises in the order described above. The microlens formed from the radiation sensitive resin composition of Claim 1.

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