JP2008225162A - Radiation-sensitive resin composition, interlayer insulating film and microlens, and production method thereof - Google Patents

Abstract

[PROBLEMS] To provide a cured product having sufficient process margin and good storage stability, and having heat resistance, solvent resistance, transparency, and adhesion to a base necessary for an interlayer insulating film and a microlens. To provide a radiation sensitive resin composition.
Copolymer of unsaturated carboxylic acid and / or unsaturated carboxylic acid anhydride, (meth) acryloyloxyalkyloxetane and other olefinically unsaturated compound, 1,2-quinonediazide compound, and epoxy group-containing The radiation sensitive resin composition containing a compound and / or another oxetanyl group containing compound.
[Selection figure] None

Description

  The present invention relates to a radiation-sensitive resin composition, an interlayer insulating film and a microlens, and methods for producing them.

In an electronic component such as a thin film transistor (hereinafter referred to as “TFT”) type liquid crystal display element, magnetic head element, integrated circuit element, solid-state imaging element, etc., an interlayer insulation is generally used to insulate between wirings arranged in layers. A membrane is provided. As a material for forming an interlayer insulating film, a material having a small number of steps for obtaining a required pattern shape and having sufficient flatness is preferable, and therefore, a radiation-sensitive resin composition is widely used (patent) Reference 1 and Patent Document 2).
Among the electronic components, for example, a TFT type liquid crystal display element is manufactured through a process of forming a transparent electrode film on the interlayer insulating film and further forming a liquid crystal alignment film on the interlayer insulating film. Since the film is exposed to a high temperature condition in the transparent electrode film forming process or exposed to a resist stripping solution used for forming an electrode pattern, sufficient resistance to these is required.
In recent years, TFT-type liquid crystal display elements have been in the trend of larger screens, higher brightness, higher definition, faster response, thinner thickness, etc., and the composition for forming an interlayer insulating film used therefor has high sensitivity. In addition, the interlayer insulating film to be formed is required to have higher performance than ever in terms of low dielectric constant and high transmittance.

On the other hand, a microlens having a lens diameter of about 3 to 100 μm or an optical system material for an on-chip color filter such as a facsimile, an electronic copying machine, or a solid-state image sensor or an optical fiber connector is defined. An array of microlenses is used.
To form a microlens or microlens array, a resist pattern corresponding to the lens is formed and then melt-flowed by heat treatment and used as it is as a lens, or by using the melt-flowed lens pattern as a mask. A method of transferring a lens shape to a base by etching is known. For the formation of the lens pattern, a radiation sensitive resin composition is widely used (see Patent Document 3 and Patent Document 4).

By the way, the element on which the microlens or the microlens array as described above is formed is then applied with a planarizing film and an etching resist film in order to remove various insulating films on the bonding pad which is a wiring forming portion. Exposure and development are performed using a desired mask to remove the etching resist in the bonding pad portion, and then the etching is performed to remove the planarizing film and various insulating films to expose the bonding pad portion. Therefore, the microlens or the microlens array needs to have solvent resistance and heat resistance in the flattening film and etching resist coating forming process and the etching process.
The radiation-sensitive resin composition used to form such a microlens has high sensitivity, and the microlens formed therefrom has a desired radius of curvature, and has high heat resistance and high transmittance. It is required to be a rate.

In addition, the interlayer insulating film and the microlens thus obtained can penetrate between the pattern and the substrate if the development time is slightly longer than the optimum time in the development process when forming them. Therefore, it is necessary to strictly control the development time, and there is a problem in terms of product yield.
As described above, in forming the interlayer insulating film and the microlens from the radiation-sensitive resin composition, the composition is required to have high sensitivity, and the development time in the development process during the formation process is longer than a predetermined time. Even if it is excessive, the pattern does not peel off and shows good adhesion, and the interlayer insulating film formed therefrom is required to have high heat resistance, high solvent resistance, low dielectric constant, high transmittance, etc. On the other hand, in the case of forming a microlens, a good melt shape (expression of desired curvature radius), high heat resistance, high solvent resistance, and high transmittance are required as a microlens. A radiation-sensitive resin composition that satisfies such requirements has not been known.
JP 2001-354822 A JP 2001-343743 A JP-A-6-18702 JP-A-6-136239

  The present invention has been made on the basis of the circumstances as described above, and its purpose is to have a sufficient process margin and good storage stability, and heat resistance necessary as an interlayer insulating film and a microlens. Another object of the present invention is to provide a radiation-sensitive resin composition capable of giving a cured product having solvent resistance, transparency, and adhesion to a base.

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

  Still another object of the present invention is to provide an interlayer insulating film and a microlens formed by the method of the present invention.

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

According to the present invention, the above objects and advantages of the present invention are as follows.
[A] (a1) at least one selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic anhydride (hereinafter also referred to as “compound (a1)”),
(A2) a compound represented by the following formula (I) or the following formula (II) (hereinafter also referred to as “compound (a2)”),

[Wherein R is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R ¹ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ² , R ³ , R ⁴ and R ⁵ are respectively It is independently a hydrogen atom, a fluorine atom, an alkyl group having 1 to 4 carbon atoms, a phenyl group or a perfluoroalkyl group having 1 to 4 carbon atoms, and n is an integer of 1 to 6. ]
And (a3) an olefinically unsaturated compound other than (a1) and (a2) (hereinafter also referred to as “compound (a3)”).
A copolymer obtained by copolymerizing (hereinafter also referred to as “copolymer [A]”),
[B] A radiation-sensitive resin composition comprising at least one selected from the group consisting of 1,2-quinonediazide compounds, [C] epoxy group-containing compounds and oxetanyl group-containing compounds other than [A] Achieved by things.

The above objects and advantages of the present invention are secondly,
This is achieved by a method for forming an interlayer insulating film or a microlens, which includes the following steps in the order described below.
(1) The process of forming the coating film of said radiation sensitive resin composition on a board | substrate,
(2) A step of irradiating at least a part of the coating film with radiation,
(3) Development step, and (4) Heating step.

Further, the above object and advantage of the present invention are as follows.
This is achieved by the interlayer insulating film and the microlens formed by the above method.

  According to the present invention, a patterned thin film having a sufficient process margin and storage stability, and having heat resistance, solvent resistance, transparency, and adhesion to a base necessary for an interlayer insulating film and microlens Can be obtained.

  Hereinafter, the radiation sensitive resin composition of this invention is explained in full detail.

Copolymer [A]
Copolymer [A] can be synthesized by radical polymerization of compound (a1), compound (a2), and compound (a3) in the presence of a polymerization initiator in a solvent.
The copolymer [A] used in the present invention preferably contains 5 to 40% by weight, particularly preferably 10 to 35% by weight, of structural units derived from the compound (a1). Copolymers whose constituent units are less than 5% by weight are difficult to dissolve in an alkaline aqueous solution, whereas copolymers exceeding 40% by weight tend to be too soluble in an alkaline aqueous solution.

Examples of the compound (a1) include monocarboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid;
Dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid; and anhydrides of these dicarboxylic acids;
Mono [(meth) acryloyloxyalkyl] of polyvalent carboxylic acids such as succinic acid mono [2- (meth) acryloyloxyethyl] and phthalic acid mono [2- (meth) acryloyloxyethyl] ester;
Examples thereof include mono (meth) acrylates of polymers having a carboxyl group and a hydroxyl group at both ends, such as ω-carboxypolycaprolactone mono (meth) acrylate. Of these, acrylic acid, methacrylic acid, maleic anhydride and the like are preferably used from the viewpoints of copolymerization reactivity, solubility in an aqueous alkali solution, and availability. These may be used alone or in combination.

  The copolymer [A] used in the present invention preferably contains 5 to 60% by weight, particularly preferably 10 to 50% by weight, of structural units derived from the compound (a2). When this structural unit is less than 5% by weight, the heat resistance of the resulting coating film tends to decrease, whereas when it exceeds 60% by weight, the storage stability of the copolymer tends to decrease.

Examples of the compound (a2) represented by the formula (I) include 3- (methacryloyloxymethyl) oxetane, 3- (methacryloyloxymethyl) -2-ethyloxetane, and 3- (methacryloyloxymethyl) -2-methyloxetane. 3- (methacryloyloxymethyl) -2-trifluoromethyloxetane, 3- (methacryloyloxymethyl) -2-pentafluoroethyloxetane, 3- (methacryloyloxymethyl) -2-phenyloxetane, 3- (methacryloyloxymethyl) ) -2,2-difluorooxetane, 3- (methacryloyloxymethyl) -2,2,4-trifluorooxetane, 3- (methacryloyloxymethyl) -2,2,4,4-tetrafluorooxetane, 3- (Methacryloyloxyethyl) oxetane 3- (methacryloyloxyethyl) -3-ethyloxetane, 2-ethyl-3- (methacryloyloxyethyl) oxetane, 3- (methacryloyloxyethyl) -2-trifluoromethyloxetane, 3- (methacryloyloxyethyl) -2 -Pentafluoroethyl oxetane, 3- (methacryloyloxyethyl) -2-phenyloxetane, 2,2-difluoro-3- (methacryloyloxyethyl) oxetane, 3- (methacryloyloxyethyl) -2,2,4-trifluoro Methacrylate esters such as oxetane and 3- (methacryloyloxyethyl) -2,2,4,4-tetrafluorooxetane;
3- (acryloyloxymethyl) oxetane, 3- (acryloyloxymethyl) -2-ethyloxetane, 3- (acryloyloxymethyl) -2-methyloxetane, 3- (acryloyloxymethyl) -2-trifluoromethyloxetane, 3- (acryloyloxymethyl) -2-pentafluoroethyloxetane, 3- (acryloyloxymethyl) -2-phenyloxetane, 3- (acryloyloxymethyl) -2,2-difluorooxetane, 3- (acryloyloxymethyl) ) -2,2,4-trifluorooxetane, 3- (acryloyloxymethyl) -2,2,4,4-tetrafluorooxetane, 3- (acryloyloxyethyl) oxetane, 3- (acryloyloxyethyl) -3 -Ethyloxetane, 2-ethyl-3 (Acryloyloxyethyl) oxetane, 3- (acryloyloxyethyl) -2-trifluoromethyloxetane, 3- (acryloyloxyethyl) -2-pentafluoroethyloxetane, 3- (acryloyloxyethyl) -2-phenyloxetane, 2,2-difluoro-3- (acryloyloxyethyl) oxetane, 3- (acryloyloxyethyl) -2,2,4-trifluorooxetane, 3- (acryloyloxyethyl) -2,2,4,4-tetra Acrylic esters such as fluorooxetane are mentioned.

Examples of the compound (a2) represented by the formula (II) include 2- (methacryloyloxymethyl) oxetane, 2-methyl-2- (methacryloyloxymethyl) oxetane, and 3-methyl-2- (methacryloyloxymethyl) oxetane. 4-methyl-2- (methacryloyloxymethyl) oxetane, 2- (methacryloyloxymethyl) -2-trifluoromethyloxetane, 2- (methacryloyloxymethyl) -3-trifluoromethyloxetane, 2- (methacryloyloxymethyl) ) -4-Trifluoromethyloxetane, 2- (methacryloyloxymethyl) -2-pentafluoroethyloxetane, 2- (methacryloyloxymethyl) -3-pentafluoroethyloxetane, 2- (methacryloyloxymethyl) -4-pentaph Roethyloxetane, 2- (methacryloyloxymethyl) -2-phenyloxetane, 2- (methacryloyloxymethyl) -3-phenyloxetane, 2- (methacryloyloxymethyl) -4-phenyloxetane, 2,3-difluoro-2 -(Methacryloyloxymethyl) oxetane, 2,4-difluoro-2- (methacryloyloxymethyl) oxetane, 3,3-difluoro-2- (methacryloyloxymethyl) oxetane, 3,4-difluoro-2- (methacryloyloxymethyl) ) Oxetane, 4,4-difluoro-2- (methacryloyloxymethyl) oxetane, 2- (methacryloyloxymethyl) -3,3,4-trifluorooxetane, 2- (methacryloyloxymethyl) -3,4,4- Trifluorooxetane, 2- Methacryloyloxymethyl) 3,3,4,4-tetrafluoroethane oxetane,
2- (methacryloyloxyethyl) oxetane, 2- (2- (2-methyloxetanyl)) ethyl methacrylate, 2- (2- (3-methyloxetanyl)) ethyl methacrylate, 2- (methacryloyloxyethyl) -2-methyl Oxetane, 2- (methacryloyloxyethyl) -4-methyloxetane, 2- (methacryloyloxyethyl) -2-trifluoromethyloxetane, 2- (methacryloyloxyethyl) -3-trifluoromethyloxetane, 2- (methacryloyloxy) Ethyl) -4-trifluoromethyloxetane, 2- (methacryloyloxyethyl) -2-pentafluoroethyloxetane, 2- (methacryloyloxyethyl) -3-pentafluoroethyloxetane, 2- (methacryloyloxyethyl) -4- N-tafluoroethyloxetane, 2- (methacryloyloxyethyl) -2-phenyloxetane, 2- (methacryloyloxyethyl) -3-phenyloxetane, 2- (methacryloyloxyethyl) -4-phenyloxetane, 2,3-difluoro- 2- (methacryloyloxyethyl) oxetane, 2,4-difluoro-2- (methacryloyloxyethyl) oxetane, 3,3-difluoro-2- (methacryloyloxyethyl) oxetane, 3,4-difluoro-2- (methacryloyloxy) Ethyl) oxetane, 4,4-difluoro-2- (methacryloyloxyethyl) oxetane, 2- (methacryloyloxyethyl) -3,3,4-trifluorooxetane, 2- (methacryloyloxyethyl) -3,4,4 -Trifluorooxeta , 2- (methacryloyloxyethyl) 3,3,4,4 methacrylic esters tetrafluoroethane oxetane, and the like;
2- (acryloyloxymethyl) oxetane, 2-methyl-2- (acryloyloxymethyl) oxetane, 3-methyl-2- (acryloyloxymethyl) oxetane, 4-methyl-2- (acryloyloxymethyl) oxetane, 2- (Acryloyloxymethyl) -2-trifluoromethyloxetane, 2- (acryloyloxymethyl) -3-trifluoromethyloxetane, 2- (acryloyloxymethyl) -4-trifluoromethyloxetane, 2- (acryloyloxymethyl) 2-Pentafluoroethyl oxetane, 2- (acryloyloxymethyl) -3-pentafluoroethyl oxetane, 2- (acryloyloxymethyl) -4-pentafluoroethyl oxetane, 2- (acryloyloxymethyl) -2-phenyloxet 2- (acryloyloxymethyl) -3-phenyloxetane, 2- (acryloyloxymethyl) -4-phenyloxetane, 2,3-difluoro-2- (acryloyloxymethyl) oxetane, 2,4-difluoro-2 -(Acryloyloxymethyl) oxetane, 3,3-difluoro-2- (acryloyloxymethyl) oxetane, 3,4-difluoro-2- (acryloyloxymethyl) oxetane, 4,4-difluoro-2- (acryloyloxymethyl) ) Oxetane, 2- (acryloyloxymethyl) -3,3,4-trifluorooxetane, 2- (acryloyloxymethyl) -3,4,4-trifluorooxetane, 2- (acryloyloxymethyl) -3,3 , 4,4-tetrafluorooxetane,
2- (acryloyloxyethyl) oxetane, 2- (2- (2-methyloxetanyl)) ethyl methacrylate, 2- (2- (3-methyloxetanyl)) ethyl methacrylate, 2- (acryloyloxyethyl) -2-methyl Oxetane, 2- (acryloyloxyethyl) -4-methyloxetane, 2- (acryloyloxyethyl) -2-trifluoromethyloxetane, 2- (acryloyloxyethyl) -3-trifluoromethyloxetane, 2- (acryloyloxy) Ethyl) -4-trifluoromethyloxetane, 2- (acryloyloxyethyl) -2-pentafluoroethyloxetane, 2- (acryloyloxyethyl) -3-pentafluoroethyloxetane, 2- (acryloyloxyethyl) -4- Pentafluoroethyl Xetane, 2- (acryloyloxyethyl) -2-phenyloxetane, 2- (acryloyloxyethyl) -3-phenyloxetane, 2- (acryloyloxyethyl) -4-phenyloxetane, 2,3-difluoro-2- ( Acryloyloxyethyl) oxetane, 2,4-difluoro-2- (acryloyloxyethyl) oxetane, 3,3-difluoro-2- (acryloyloxyethyl) oxetane, 3,4-difluoro-2- (acryloyloxyethyl) oxetane 4,4-Difluoro-2- (acryloyloxyethyl) oxetane, 2- (acryloyloxyethyl) -3,3,4-trifluorooxetane, 2- (acryloyloxyethyl) -3,4,4-trifluoro Oxetane, 2- (acryloyloxyethyl)- , Acrylic acid esters such as 3,4,4-tetrafluoroethane oxetane.

  Of these, 3- (methacryloyloxymethyl) oxetane, 3- (methacryloyloxymethyl) -2-methyloxetane, 3- (methacryloyloxymethyl) -2-ethyloxetane, 3- (methacryloyloxymethyl) -2-tri A photosensitive resin composition from which fluoromethyloxetane, 3- (methacryloyloxymethyl) -2-phenyloxetane, 2- (methacryloyloxymethyl) oxetane, 2- (methacryloyloxymethyl) -4-trifluoromethyloxetane and the like can be obtained. It is preferably used because it has a wide process margin and improves the chemical resistance of the obtained interlayer insulating film and microlens. These may be used alone or in combination.

  The copolymer [A] used in the present invention preferably contains 10 to 80% by weight, particularly preferably 20 to 70% by weight, of structural units derived from the compound (a3). When this structural unit is less than 10% by weight, the storage stability of the copolymer [A] tends to be lowered, whereas when it exceeds 80% by weight, the copolymer [A] is hardly dissolved in an alkaline aqueous solution. Become.

Examples of the compound (a3) include methacrylic acid alkyl esters such as methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate, and t-butyl methacrylate; acrylic acid alkyl esters such as methyl acrylate and isopropyl acrylate; cyclohexyl methacrylate, 2-methylcyclohexyl methacrylate, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl methacrylate (referred to in the art as dicyclopentanyl methacrylate), dicyclopentanyloxyethyl Methacrylic acid cyclic alkyl esters such as methacrylate and isobornyl methacrylate; cyclohexyl acrylate, 2-methylcyclohexyl acrylate, trisyl B [5.2.1.0 ^2,6] decan-8-yl acrylate (in the art are said to dicyclopentanyl acrylate as trivial name), dicyclopentanyl oxyethyl acrylate, isobornyl acrylate Acrylic acid cyclic alkyl esters such as phenyl methacrylate and benzyl methacrylate; acrylic acid aryl esters such as phenyl acrylate and benzyl acrylate; dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate and diethyl itaconate; 2 -Hydroxyalkyl esters such as hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate;
Bicyclo [2.2.1] hept-2-ene,
5-methylbicyclo [2.2.1] hept-2-ene,
5-ethylbicyclo [2.2.1] hept-2-ene,
5-hydroxybicyclo [2.2.1] hept-2-ene,
5-carboxybicyclo [2.2.1] hept-2-ene,
5-hydroxymethylbicyclo [2.2.1] hept-2-ene,
5- (2′-hydroxyethyl) bicyclo [2.2.1] hept-2-ene,
5-methoxybicyclo [2.2.1] hept-2-ene,
5-ethoxybicyclo [2.2.1] hept-2-ene,
5,6-dihydroxybicyclo [2.2.1] hept-2-ene,
5,6-dicarboxybicyclo [2.2.1] hept-2-ene,
5,6-di (hydroxymethyl) bicyclo [2.2.1] hept-2-ene,
5,6-di (2′-hydroxyethyl) bicyclo [2.2.1] hept-2-ene,
5,6-dimethoxybicyclo [2.2.1] hept-2-ene,
5,6-diethoxybicyclo [2.2.1] hept-2-ene,
5-hydroxy-5-methylbicyclo [2.2.1] hept-2-ene,
5-hydroxy-5-ethylbicyclo [2.2.1] hept-2-ene,
5-carboxy-5-methylbicyclo [2.2.1] hept-2-ene,
5-carboxy-5-ethylbicyclo [2.2.1] hept-2-ene,
5-hydroxymethyl-5-methylbicyclo [2.2.1] hept-2-ene,
5-carboxy-6-methylbicyclo [2.2.1] hept-2-ene,
5-carboxy-6-ethylbicyclo [2.2.1] hept-2-ene,
5,6-dicarboxybicyclo [2.2.1] hept-2-ene anhydride (hymic acid anhydride),
5-t-butoxycarbonylbicyclo [2.2.1] hept-2-ene,
5-cyclohexyloxycarbonylbicyclo [2.2.1] hept-2-ene,
5-phenoxycarbonylbicyclo [2.2.1] hept-2-ene,
5,6-di (t-butoxycarbonyl) bicyclo [2.2.1] hept-2-ene,
A bicyclounsaturated compound such as 5,6-di (cyclohexyloxycarbonyl) bicyclo [2.2.1] hept-2-ene;
Phenylmaleimide, cyclohexylmaleimide, benzylmaleimide, N-succinimidyl-3-maleimidobenzoate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidocaproate, N-succinimidyl-3-maleimidopropionate, Dicarbonylimide derivatives such as N- (9-acridinyl) maleimide;
Styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyl toluene, p-methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, vinyl acetate, 1,3-butadiene , Isoprene, 2,3-dimethyl-1,3-butadiene, glycidyl acrylate, glycidyl methacrylate, glycidyl α-ethyl acrylate, glycidyl α-n-propyl acrylate, glycidyl α-n-butyl acrylate, acrylic acid -3,4-epoxybutyl, methacrylic acid-3,4-epoxybutyl, acrylic acid-6,7-epoxyheptyl, methacrylic acid-6,7-epoxyheptyl, α-ethylacrylic acid-6,7-epoxyheptyl O-Vinylbenzylglycidyl Ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether and the like can be mentioned.

Among these, styrene, t-butyl methacrylate, dicyclopentanyl methacrylate, p-methoxystyrene, 2-methylcyclohexyl acrylate, 1,3-butadiene, glycidyl methacrylate, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl Ether, p-vinylbenzylglycidyl ether, phenylmaleimide, cyclohexylmaleimide, bicyclo [2.2.1] hept-2-ene and the like are preferable from the viewpoint of copolymerization reactivity and solubility in an aqueous alkali solution. These may be used alone or in combination.
As described above, the copolymer [A] used in the present invention has a carboxyl group and / or a carboxylic anhydride group and an oxetanyl group, and has appropriate solubility in an aqueous alkali solution. It can be easily cured by heating without using a special curing agent.
The radiation-sensitive resin composition containing the copolymer [A] can easily form a coating film having a predetermined pattern without causing a development residue during film development and without causing film slippage.

  Examples of the solvent used for the production of the copolymer [A] include alcohol, ether, glycol ether, ethylene glycol alkyl ether acetate, diethylene glycol, propylene glycol monoalkyl ether, propylene glycol alkyl ether acetate, propylene glycol alkyl ether propio Nates, aromatic hydrocarbons, ketones, esters and the like.

Specific examples thereof include alcohols such as methanol, ethanol, benzyl alcohol, 2-phenylethyl alcohol, and 3-phenyl-1-propanol;
Ethers such as tetrahydrofuran;
Examples of glycol ethers include ethylene glycol monomethyl ether and ethylene glycol monoethyl ether;
Examples of ethylene glycol alkyl ether acetate include methyl cellosolve acetate, ethyl cellosolve acetate, ethylene glycol monobutyl ether acetate, and ethylene glycol monoethyl ether acetate;
Examples of diethylene glycol include diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, and diethylene glycol ethyl methyl ether.
Examples of propylene glycol monoalkyl ethers include propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether;
As propylene glycol alkyl ether propionate, for example, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, propylene glycol butyl ether acetate and the like;
As propylene glycol alkyl ether acetate, for example, propylene glycol methyl ether propionate, propylene glycol ethyl ether propionate, propylene glycol propyl ether propionate, propylene glycol butyl ether propionate, etc .;
Aromatic hydrocarbons such as toluene, xylene, etc .;
Examples of ketones include methyl ethyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone, and the like;
Examples of esters include methyl acetate, ethyl acetate, propyl acetate, butyl acetate, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, methyl hydroxyacetate, hydroxy Ethyl acetate, hydroxybutyl acetate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, methyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, propyl 3-hydroxypropionate, butyl 3-hydroxypropionate, 2-hydroxy -3-methylbutanoate, methyl methoxyacetate, ethyl methoxyacetate, propyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, propyl ethoxyacetate, butyl ethoxyacetate, propoxy Methyl acetate, ethyl propoxyacetate, propyl propoxyacetate, butyl propoxyacetate, methyl butoxyacetate, ethyl butoxyacetate, propyl butoxyacetate, butylbutoxyacetate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, 2-methoxypropionic acid Propyl, butyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, propyl 2-ethoxypropionate, butyl 2-ethoxypropionate, methyl 2-butoxypropionate, ethyl 2-butoxypropionate Propyl 2-butoxypropionate, butyl 2-butoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, 3-methoxypropyl Butyl pionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, propyl 3-ethoxypropionate, butyl 3-ethoxypropionate, methyl 3-propoxypropionate, ethyl 3-propoxypropionate, 3-propoxypropionate Examples thereof include esters such as propyl acid, butyl 3-propoxypropionate, methyl 3-butoxypropionate, ethyl 3-butoxypropionate, propyl 3-butoxypropionate, and butyl 3-butoxypropionate.

  Of these, ethylene glycol alkyl ether acetate, diethylene glycol, propylene glycol monoalkyl ether, and propylene glycol alkyl ether acetate are preferable, and diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, propylene glycol methyl ether, and propylene glycol methyl ether acetate are particularly preferable. .

  As the polymerization initiator used for the production of the copolymer [A], those generally known as radical polymerization initiators can be used. For example, 2,2′-azobisisobutyronitrile, 2,2 Azo compounds such as' -azobis- (2,4-dimethylvaleronitrile), 2,2'-azobis- (4-methoxy-2,4-dimethylvaleronitrile); benzoyl peroxide, lauroyl peroxide, t-butylperoxypi And organic peroxides such as barate, 1,1′-bis- (t-butylperoxy) cyclohexane; and hydrogen peroxide. When a peroxide is used as the radical polymerization initiator, it may be a redox initiator using the peroxide together with a reducing agent.

  In the production of the copolymer [A], a molecular weight modifier can be used to adjust the molecular weight. Specific examples thereof include halogenated hydrocarbons such as chloroform and carbon tetrabromide; mercaptans such as n-hexyl mercaptan, n-octyl mercaptan, n-dodecyl mercaptan, tert-dodecyl mercaptan and thioglycolic acid; dimethylxanthogen sulfide And xanthogens such as diisopropylxanthogen disulfide; terpinolene, α-methylstyrene dimer and the like.

The copolymer [A] used in the present invention has a polystyrene-equivalent weight average molecular weight (hereinafter referred to as “Mw”), preferably 2 × 10 ^{3 to} 5 × 10 ⁵ , more preferably 5 × 10 ³ to 1 ×. 10 ⁵ is desirable. If the Mw is less than 2 × 10 ³ , the residual film ratio after development tends to be low, whereas if it exceeds 5 × 10 ⁵ , there may be a residual development.

1,2-quinonediazide compound [B]
Examples of the 1,2-quinonediazide compound [B] used in the present invention include 1,2-benzoquinonediazidesulfonic acid ester, 1,2-naphthoquinonediazidesulfonic acid ester, 1,2-benzoquinonediazidesulfonic acid amide, Examples include 2-naphthoquinonediazide sulfonic acid amide.

Specific examples thereof include 2,3,4-trihydroxybenzophenone-1,2-naphthoquinone azide-4-sulfonic acid ester, 2,3,4-trihydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfone. Acid ester, 2,3,4-trihydroxybenzophenone-1,2-naphthoquinonediazide-6-sulfonic acid ester, 2,3,4-trihydroxybenzophenone-1,2-naphthoquinonediazide-7-sulfonic acid ester, 2 , 3,4-Trihydroxybenzophenone-1,2-naphthoquinonediazide-8-sulfonic acid ester, 2,4,6-trihydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonic acid ester, 2,4,6 -Trihydroxybenzophenone-1,2-naphthoquinone diazi -5-sulfonic acid ester, 2,4,6-trihydroxybenzophenone-1,2-naphthoquinonediazide-6-sulfonic acid ester, 2,4,6-trihydroxybenzophenone-1,2-naphthoquinonediazide-7-sulfone 1,2-naphthoquinone diazide sulfonic acid esters of trihydroxybenzophenone such as acid esters, 2,4,6-trihydroxybenzophenone-1,2-naphthoquinone diazide-8-sulfonic acid esters;
2,2 ′, 4,4′-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonic acid ester, 2,2 ′, 4,4′-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-5 Sulfonic acid ester, 2,2 ′, 4,4′-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-6-sulfonic acid ester, 2,2 ′, 4,4′-tetrahydroxybenzophenone-1,2-naphtho Quinonediazide-7-sulfonic acid ester, 2,2 ′, 4,4′-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-8-sulfonic acid ester, 2,3,4,3′-tetrahydroxybenzophenone-1, 2-naphthoquinonediazide-4-sulfonic acid ester, 2,3,4,3′-tetrahydroxybenzophenone 1,2-naphthoquinonediazide-5-sulfonic acid ester, 2,3,4,3′-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-6-sulfonic acid ester, 2,3,4,3′-tetrahydroxy Benzophenone-1,2-naphthoquinonediazide-7-sulfonic acid ester, 2,3,4,3′-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-8-sulfonic acid ester, 2,3,4,4′- Tetrahydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonic acid ester, 2,3,4,4′-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonic acid ester, 2,3,4,4 '-Tetrahydroxybenzophenone-1,2-naphthoquinonediazide-6-sulfonic acid ester 2,3,4,4′-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-7-sulfonic acid ester, 2,3,4,4′-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-8- Sulfonic acid ester, 2,3,4,2′-tetrahydroxy-4′-methylbenzophenone-1,2-naphthoquinonediazide-4-sulfonic acid ester, 2,3,4,2′-tetrahydroxy-4′- Methylbenzophenone-1,2-naphthoquinonediazide-5-sulfonic acid ester, 2,3,4,2′-tetrahydroxy-4′-methylbenzophenone-1,2-naphthoquinonediazide-6-sulfonic acid ester, 2,3 , 4,2′-Tetrahydroxy-4′-methylbenzophenone-1,2-naphthoquinonediazide-7-sulfonic acid ester 2,3,4,2′-tetrahydroxy-4′-methylbenzophenone-1,2-naphthoquinonediazide-8-sulfonic acid ester, 2,3,4,4′-tetrahydroxy-3′-methoxybenzophenone -1,2-naphthoquinonediazide-4-sulfonic acid ester, 2,3,4,4′-tetrahydroxy-3′-methoxybenzophenone-1,2-naphthoquinonediazide-5-sulfonic acid ester, 2,3,4 , 4′-Tetrahydroxy-3′-methoxybenzophenone-1,2-naphthoquinonediazide-6-sulfonic acid ester, 2,3,4,4′-tetrahydroxy-3′-methoxybenzophenone-1,2-naphthoquinonediazide -7-sulfonic acid ester, 2,3,4,4′-tetrahydroxy-3′-methoxybenzophenone-1,2-naphtho 1,2-naphthoquinone diazide sulfonic acid ester of tetrahydroxybenzophenone such as quinone diazide-8-sulfonic acid ester;

2,3,4,2 ′, 6′-pentahydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonic acid ester, 2,3,4,2 ′, 6′-pentahydroxybenzophenone-1,2-naphtho Quinonediazide-5-sulfonic acid ester, 2,3,4,2 ′, 6′-pentahydroxybenzophenone-1,2-naphthoquinonediazide-6-sulfonic acid ester, 2,3,4,2 ′, 6′-penta Of pentahydroxybenzophenone such as hydroxybenzophenone-1,2-naphthoquinonediazide-7-sulfonic acid ester, 2,3,4,2 ′, 6′-pentahydroxybenzophenone-1,2-naphthoquinonediazide-8-sulfonic acid ester, etc. 1,2-naphthoquinonediazide sulfonic acid ester;
2,4,6,3 ′, 4 ′, 5′-hexahydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonic acid ester, 2,4,6,3 ′, 4 ′, 5′-hexahydroxybenzophenone -1,2-naphthoquinonediazide-5-sulfonic acid ester, 2,4,6,3 ′, 4 ′, 5′-hexahydroxybenzophenone-1,2-naphthoquinonediazide-6-sulfonic acid ester, 2,4, 6,3 ′, 4 ′, 5′-hexahydroxybenzophenone-1,2-naphthoquinonediazide-7-sulfonic acid ester, 2,4,6,3 ′, 4 ′, 5′-hexahydroxybenzophenone-1,2 -Naphthoquinonediazide-8-sulfonic acid ester, 3,4,5,3 ', 4', 5'-hexahydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonic acid ester 3,4,5,3 ′, 4 ′, 5′-hexahydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonic acid ester, 3,4,5,3 ′, 4 ′, 5′-hexa Hydroxybenzophenone-1,2-naphthoquinonediazide-6-sulfonic acid ester, 3,4,5,3 ′, 4 ′, 5′-hexahydroxybenzophenone-1,2-naphthoquinonediazide-7-sulfonic acid ester, 3, 1,2-naphthoquinone diazide sulfonic acid ester of hexahydroxybenzophenone such as 4,5,3 ′, 4 ′, 5′-hexahydroxybenzophenone-1,2-naphthoquinone diazide-8-sulfonic acid ester;
Bis (2,4-dihydroxyphenyl) methane-1,2-naphthoquinonediazide-4-sulfonic acid ester, bis (2,4-dihydroxyphenyl) methane-1,2-naphthoquinonediazide-5-sulfonic acid ester, bis ( 2,4-dihydroxyphenyl) methane-1,2-naphthoquinonediazide-6-sulfonic acid ester, bis (2,4-dihydroxyphenyl) methane-1,2-naphthoquinonediazide-7-sulfonic acid ester, bis (2, 4-dihydroxyphenyl) methane-1,2-naphthoquinonediazide-8-sulfonic acid ester, bis (p-hydroxyphenyl) methane-1,2-naphthoquinonediazide-4-sulfonic acid ester, bis (p-hydroxyphenyl) methane -1,2-naphthoquinonediazide-5-sulfonic acid Tellurium, bis (p-hydroxyphenyl) methane-1,2-naphthoquinonediazide-6-sulfonic acid ester, bis (p-hydroxyphenyl) methane-1,2-naphthoquinonediazide-7-sulfonic acid ester, bis (p- Hydroxyphenyl) methane-1,2-naphthoquinonediazide-8-sulfonic acid ester, tri (p-hydroxyphenyl) methane-1,2-naphthoquinonediazide-4-sulfonic acid ester, tri (p-hydroxyphenyl) methane-1 , 2-Naphthoquinonediazide-5-sulfonic acid ester, tri (p-hydroxyphenyl) methane-1,2-naphthoquinonediazide-6-sulfonic acid ester, tri (p-hydroxyphenyl) methane-1,2-naphthoquinonediazide- 7-sulfonic acid ester, tri (p-hydride Kishifeniru) methane-1,2-naphthoquinonediazide-8-sulfonic acid ester,
1,1,1-tri (p-hydroxyphenyl) ethane-1,2-naphthoquinonediazide-4-sulfonic acid ester, 1,1,1-tri (p-hydroxyphenyl) ethane-1,2-naphthoquinonediazide- 5-sulfonic acid ester, 1,1,1-tri (p-hydroxyphenyl) ethane-1,2-naphthoquinonediazide-6-sulfonic acid ester, 1,1,1-tri (p-hydroxyphenyl) ethane-1 , 2-Naphthoquinonediazide-7-sulfonic acid ester, 1,1,1-tri (p-hydroxyphenyl) ethane-1,2-naphthoquinonediazide-8-sulfonic acid ester, bis (2,3,4-trihydroxy) Phenyl) methane-1,2-naphthoquinonediazide-4-sulfonic acid ester, bis (2,3,4-trihydroxyphenyl) Tan-1,2-naphthoquinonediazide-5-sulfonic acid ester, bis (2,3,4-trihydroxyphenyl) methane-1,2-naphthoquinonediazide-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-sulfonic acid ester, 2,2- Bis (2,3,4-trihydroxyphenyl) propane-1,2-naphthoquinonediazide-4-sulfonic acid ester, 2,2-bis (2,3,4-trihydroxyphenyl) propane-1,2-naphtho Quinonediazide-5-sulfonic acid ester, 2,2-bis (2,3,4-trihydroxyphenyl) propane-1, -Naphthoquinonediazide-6-sulfonic acid ester, 2,2-bis (2,3,4-trihydroxyphenyl) propane-1,2-naphthoquinonediazide-7-sulfonic acid ester, 2,2-bis (2,3 , 4-trihydroxyphenyl) propane-1,2-naphthoquinonediazide-8-sulfonic acid ester,

1,1,3-tris (2,5-dimethyl-4-hydroxyphenyl) -3-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-hydroxyphenyl) -3-phenylpropane -1,2-naphthoquinonediazide-6-sulfonic acid ester, 1,1,3-tris (2,5-dimethyl-4-hydroxyphenyl) -3-phenylpropane-1,2-naphthoquinonediazide-7-sulfonic acid Ester, 1,1,3-tris (2,5-dimethyl-4-hydroxyphenyl) -3-phenylpropane-1,2-naphthoquinone Azido-8-sulfonic acid ester, 4,4 ′-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol-1,2-naphthoquinonediazide-4-sulfone Acid ester, 4,4 ′-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol-1,2-naphthoquinonediazide-5-sulfonic acid ester, 4, 4 ′-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol-1,2-naphthoquinonediazide-6-sulfonic acid ester, 4,4 ′-[1 -[4- [1- [4-Hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol-1,2-naphthoquinonediazide 7-sulfonic acid ester, 4,4 ′-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol-1,2-naphthoquinonediazide-8-sulfonic acid ester ,
Bis (2,5-dimethyl-4-hydroxyphenyl) -2-hydroxyphenylmethane-1,2-naphthoquinonediazide-4-sulfonic acid ester, bis (2,5-dimethyl-4-hydroxyphenyl) -2-hydroxy Phenylmethane-1,2-naphthoquinonediazide-5-sulfonic acid ester, bis (2,5-dimethyl-4-hydroxyphenyl) -2-hydroxyphenylmethane-1,2-naphthoquinonediazide-6-sulfonic acid ester, bis (2,5-Dimethyl-4-hydroxyphenyl) -2-hydroxyphenylmethane-1,2-naphthoquinonediazide-7-sulfonic acid ester, bis (2,5-dimethyl-4-hydroxyphenyl) -2-hydroxyphenyl Methane-1,2-naphthoquinonediazide-8-sulfonic acid ester 3,3,3 ′, 3′-tetramethyl-1,1′-spirobiindene-5,6,7,5 ′, 6 ′, 7′-hexanol-1,2-naphthoquinonediazide-4-sulfone Acid ester 3,3,3 ′, 3′-tetramethyl-1,1′-spirobiindene-5,6,7,5 ′, 6 ′, 7′-hexanol-1,2-naphthoquinonediazide-5 -Sulfonate ester, 3,3,3 ', 3'-tetramethyl-1,1'-spirobiindene-5,6,7,5', 6 ', 7'-hexanol-1,2-naphthoquinonediazide -6-sulfonic acid ester, 3,3,3 ', 3'-tetramethyl-1,1'-spirobiindene-5,6,7,5', 6 ', 7'-hexanol-1,2- Naphthoquinonediazide-7-sulfonic acid ester, 3,3,3 ′, 3′-tetramethyl-1,1′-spirobiinde -5,6,7,5 ', 6', 7'-hexanol-1,2-naphthoquinonediazide-8-sulfonic acid ester, 2,2,4-trimethyl-7,2 ', 4'-trihydroxyflavan -1,2-naphthoquinonediazide-4-sulfonic acid ester, 2,2,4-trimethyl-7,2 ′, 4′-trihydroxyflavan-1,2-naphthoquinonediazide-5-sulfonic acid, 2,2, 4-trimethyl-7,2 ′, 4′-trihydroxyflavan-1,2-naphthoquinonediazide-6-sulfonic acid ester, 2,2,4-trimethyl-7,2 ′, 4′-trihydroxyflavan-1 2,2-naphthoquinonediazide-7-sulfonic acid, 2,2,4-trimethyl-7,2 ′, 4′-trihydroxyflavan-1,2-naphthoquinonediazide-8-sulfonic acid, etc. Phenyl) include 1,2-naphthoquinonediazide sulfonic acid esters of alkanoic.

These 1,2-quinonediazide compounds can be used alone or in combination of two or more.
[B] The usage-amount of a component becomes like this. Preferably it is 5-100 weight part with respect to 100 weight part of copolymers [A], More preferably, it is 10-50 weight part.
When this ratio is less than 5 parts by weight, the amount of acid generated by irradiation with radiation is small, so the difference in solubility in an alkaline aqueous solution that is a developer between the irradiated part and the unirradiated part is small, and patterning is difficult. Tend to be. In addition, since the amount of acid involved in the reaction with the copolymer [A] decreases, sufficient heat resistance and solvent resistance may not be obtained. On the other hand, if this ratio exceeds 100 parts by weight, a large amount of unreacted [B] component remains after irradiation for a short time, so that the effect of insolubilization in the alkaline aqueous solution is too high and development is performed. Tend to be difficult.

Epoxy group-containing compound and oxetanyl group-containing compound other than [A] [C]
-Epoxy group-containing compound-
The epoxy group-containing compound used in the present invention is not limited as long as the compatibility is not affected. Preferably, bisphenol A type epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, cyclic aliphatic epoxy resin, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, heterocyclic epoxy resin, glycidyl methacrylate ) Polymerized resin and the like. Examples of the commercially available products include Epicoat 807, 828, 834, 1001, 1004, 1007, 1009, 152, 154, 180, and 157 (Japan Epoxy Resin Co., Ltd.). be able to.
Among these, bisphenol A type epoxy resin, cresol novolac type epoxy resin, glycidyl ester type epoxy resin and the like are preferable.

-Oxetanyl group-containing compound-
The oxetanyl group-containing compound used in the present invention is not limited as long as the compatibility is not affected. Preferably bisphenol A type oxetane resin, phenol novolak type oxetane resin, cresol novolac type oxetane resin, cycloaliphatic oxetane resin, biphenyl type oxetane resin, glycidyl ester type oxetane resin, glycidylamine type oxetane resin, heterocyclic oxetane resin, glycidyl Examples thereof include a resin obtained by (co) polymerizing methacrylate. Examples of the commercially available products include Aron Oxetane OXE-121, OXE-221, PNOX-1009 (manufactured by Toa Gosei Co., Ltd.), ETERNACOLL OXEP (manufactured by Ube Industries, Ltd.), and the like.
Among these, bisphenol A type oxetane resin, phenol novolac type oxetane resin, biphenyl type oxetane resin, glycidyl ester type oxetane resin and the like are preferable.

The proportion of the component [C] used is preferably 30 parts by weight or less with respect to 100 parts by weight of the copolymer [A].
By containing the component [C] at such a ratio, the heat resistance, strength, and the like of the patterned coating film obtained from the radiation-sensitive resin composition of the present invention can be further improved.
When this ratio exceeds 30 parts by weight, the compatibility with the alkali-soluble resin becomes insufficient, and sufficient coating film forming ability cannot be obtained.
The copolymer [A] can also be referred to as an “oxetanyl group-containing resin”, but the copolymer [A] is [C] because it has alkali solubility and is required to have a relatively high molecular weight. It differs from the component oxetane resin. The oxetanyl group-containing compound of component [C] is insoluble in alkali.

In the radiation sensitive resin composition of the other components present invention, the [A], [B], in addition to the component [C], if necessary, the heat-sensitive acid generator [D], at least one ethylenically The polymerizable compound [E] having a polymerizable unsaturated double bond, the melamine resin [F], the surfactant [G], and the adhesion assistant [H] can be contained.
Examples of the thermal acid generator as the component [D] include sulfonium salts (excluding the triarylsulfonium salts), benzothiazonium salts, ammonium salts, phosphonium salts (provided that the diarylphosphonium salts are used). And sulfonimide compounds, and among them, sulfonium salts, benzothiazonium salts, and sulfonimide compounds are particularly preferable.

Among the thermal acid generators, as the sulfonium salt, for example,
4-acetophenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium hexafluoroarsenate, dimethyl-4- (benzyloxycarbonyloxy) phenylsulfonium hexafluoroantimonate, dimethyl-4- (benzoyloxy) phenylsulfonium hexamonate Alkylsulfonium salts such as fluoroantimonate, dimethyl-4- (benzoyloxy) phenylsulfonium hexafluoroarsenate, dimethyl-3-chloro-4-acetoxyphenylsulfonium hexafluoroantimonate;
Benzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, benzyl-4-hydroxyphenylmethylsulfonium hexafluorophosphate, 4-acetoxyphenylbenzylmethylsulfonium hexafluoroantimonate, benzyl-4-methoxyphenylmethylsulfonium hexafluoroantimonate, Benzyl-2-methyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, benzyl-3-chloro-4-hydroxyphenylmethylsulfonium hexafluoroarsenate, 4-methoxybenzyl-4-hydroxyphenylmethylsulfonium hexafluorophosphate, etc. Benzylsulfonium salt;
Dibenzyl-4-hydroxyphenylsulfonium hexafluoroantimonate, dibenzyl-4-hydroxyphenylsulfonium hexafluorophosphate, dibenzyl-4-acetoxyphenylsulfonium hexafluoroantimonate, dibenzyl-4-methoxyphenylsulfonium hexafluoroantimonate, dibenzyl-3 -Chloro-4-hydroxyphenylsulfonium hexafluoroarsenate, dibenzyl-3-methyl-4-hydroxy-5-t-butylphenylsulfonium hexafluoroantimonate, benzyl-4-methoxybenzyl-4-hydroxyphenylsulfonium hexafluorophosphate Dibenzylsulfonium salts such as;
4-chlorobenzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, 4-nitrobenzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, 4-chlorobenzyl-4-hydroxyphenylmethylsulfonium hexafluorophosphate, 4-nitro Benzyl-3-methyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, 3,5-dichlorobenzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, 2-chlorobenzyl-3-chloro-4-hydroxyphenylmethylsulfonium Examples thereof include substituted benzylsulfonium salts such as hexafluoroantimonate.

  Among these sulfonium salts, 4-acetoxyphenyldimethylsulfonium hexafluoroarsenate, benzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, 4-acetoxyphenylbenzylmethylsulfonium hexafluoroantimonate, dibenzyl-4-hydroxyphenylsulfonium Hexafluoroantimonate, dibenzyl-4-acetoxyphenylsulfonium hexafluoroantimonate, and the like are preferable.

  Examples of the benzothiazonium salt include 3-benzylbenzothiazonium hexafluoroantimonate, 3-benzylbenzothiazonium hexafluorophosphate, 3-benzylbenzothiazonium tetrafluoroborate, 3- ( Benzylbenzothia such as 4-methoxybenzyl) benzothiazonium hexafluoroantimonate, 3-benzyl-2-methylthiobenzothiazonium hexafluoroantimonate, 3-benzyl-5-chlorobenzothiazonium hexafluoroantimonate Zonium salts and the like can be mentioned. Of these benzothiazonium salts, 3-benzylbenzothiazonium hexafluoroantimonate is particularly preferable.

Among the commercially available products of thermal acid generators, examples of the alkylsulfonium salt include Adeka Opton CP-66, Adeka Opton CP-77 (manufactured by Asahi Denka Kogyo Co., Ltd.), and the like.
Examples of the benzylsulfonium salt include SI-60, SI-80, SI-100, SI-110, SI-145, SI-150, SI-80L, SI-100L, SI-110L (above, Sanshin). Chemical Industry Co., Ltd.).
Among these commercially available products, SI-80, SI-100, SI-110 and the like are preferable in that the obtained protective film has high surface hardness.
The said heat-sensitive acid generator can be used individually or in mixture of 2 or more types.

Among the thermal acid generators, as the sulfonimide, for example,
N- (trifluoromethanesulfonyloxy) succinimide, N- (trifluoromethanesulfonyloxy) phthalimide, N- (trifluoromethanesulfonyloxy) diphenylmaleimide, N- (trifluoromethanesulfonyloxy) bicyclo [2.2.1] hept-5 -Ene-2,3-dicarboximide, N- (trifluoromethanesulfonyloxy) -7-oxabicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (trifluoromethane Sulfonyloxy) bicyclo [2.2.1] heptane-5,6-oxy-2,3-dicarboximide, N- (trifluoromethanesulfonyloxy) naphthylimide, N- (10-camphorsulfonyloxy) succinimide, N -(10-Camphors Phonyloxy) phthalimide, N- (10-camphorsulfonyloxy) diphenylmaleimide, N- (10-camphorsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- ( 10-camphorsulfonyloxy) -7-oxabicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (10-camphorsulfonyloxy) bicyclo [2.2.1] heptane -5,6-oxy-2,3-dicarboximide, N- (10-camphorsulfonyloxy) naphthylimide, N- (p-toluenesulfonyloxy) succinimide, N- (p-toluenesulfonyloxy) phthalimide, N -(P-toluenesulfonyloxy) diphenylmaleimide, N- (p-tolu Sulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (p-toluenesulfonyloxy) -7-oxabicyclo [2.2.1] hept-5. -Ene-2,3-dicarboximide, N- (p-toluenesulfonyloxy) bicyclo [2.2.1] heptane-5,6-oxy-2,3-dicarboximide, N- (p-toluene) Sulfonyloxy) naphthylimide, N- (2-trifluoromethylbenzenesulfonyloxy) succinimide, N- (2-trifluoromethylbenzenesulfonyloxy) phthalimide, N- (2-trifluoromethylbenzenesulfonyloxy) diphenylmaleimide, N -(2-trifluoromethylbenzenesulfonyloxy) bicyclo [2.2.1] hept- 5-ene-2,3-dicarboximide, N- (2-trifluoromethylbenzenesulfonyloxy) -7-oxabicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (2-trifluoromethylbenzenesulfonyloxy) bicyclo [2.2.1] heptane-5,6-oxy-2,3-dicarboximide, N- (2-trifluoromethylbenzenesulfonyloxy) naphthylimide N- (4-trifluoromethylbenzenesulfonyloxy) succinimide, N- (4-trifluoromethylbenzenesulfonyloxy) phthalimide, N- (4-trifluoromethylbenzenesulfonyloxy) diphenylmaleimide, N- (4-tri Fluoromethylbenzenesulfonyloxy) bicyclo [2.2.1] hept -5-ene-2,3-dicarboximide, N- (4-trifluoromethylbenzenesulfonyloxy) -7-oxabicyclo [2.2.1] hept-5-ene-2,3-dicarboximide N- (4-trifluoromethylbenzenesulfonyloxy) bicyclo [2.2.1] heptane-5,6-oxy-2,3-dicarboximide, N- (4-trifluoromethylbenzenesulfonyloxy) naphthyl Imido, N- (nonafluoro-n-butanesulfonyloxy) succinimide, N- (nonafluoro-n-butanesulfonyloxy) phthalimide, N- (nonafluoro-n-butanesulfonyloxy) diphenylmaleimide, N- (nonafluoro-n-butane Sulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3 Dicarboximide, N- (nonafluoro-n-butanesulfonyloxy) -7-oxabicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (nonafluoro-n-butanesulfonyl) Oxy) bicyclo [2.2.1] heptane-5,6-oxy-2,3-dicarboximide, 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 -Dicarboximide, N- (pentafluorobenze Sulfonyloxy) -7-oxabicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (pentafluorobenzenesulfonyloxy) bicyclo [2.2.1] heptane-5 , 6-oxy-2,3-dicarboximide, N- (pentafluorobenzenesulfonyloxy) naphthylimide, N- (perfluoro-n-octanesulfonyloxy) succinimide, N- (perfluoro-n-octanesulfonyloxy) ) Phthalimide, N- (perfluoro-n-octanesulfonyloxy) diphenylmaleimide, N- (perfluoro-n-octanesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboxy Imido, N- (perfluoro-n-octanesulfonyloxy) -7-oxa Cyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (perfluoro-n-octanesulfonyloxy) bicyclo [2.2.1] heptane-5,6-oxy- 2,3-dicarboximide, N- (perfluoro-n-octanesulfonyloxy) naphthylimide, N-{(5-methyl-5-carboxymethanebicyclo [2.2.1] hept-2-yl) sulfonyl One or two or more of oxy} succinimide and the like can be mixed and used.

The ratio of the component [D] used is preferably 0.01 to 20 parts by weight, more preferably 0.1 to 5 parts by weight with respect to 100 parts by weight of the copolymer [A].
When this proportion exceeds 20 parts by weight, precipitates are generated and patterning tends to be difficult. On the other hand, when this proportion is less than 0.01 part by weight, the curing rate during thermosetting tends to be slow and the resolution tends to decrease.
As the polymerizable compound having at least one ethylenically unsaturated double bond as the component [E], monofunctional (meth) acrylate, bifunctional (meth) acrylate, or trifunctional or higher (meth) acrylate is preferable. Can be used.

  Examples of the monofunctional (meth) acrylate include 2-hydroxyethyl (meth) acrylate, carbitol (meth) acrylate, isobornyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, and 2- (meth) acryloyloxyethyl. -Hydroxypropyl phthalate and the like are listed, and examples of commercially available products thereof include Aronix M-101, M-111, M-114 (manufactured by Toagosei Co., Ltd.), KAYARAD TC-110S, and TC-120S. (Nippon Kayaku Co., Ltd.), Biscote 158, 2311 (Osaka Organic Chemical Co., Ltd.).

  Examples of the bifunctional (meth) acrylate include ethylene glycol (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, polypropylene glycol di (meth) acrylate, Tetraethylene glycol di (meth) acrylate, bisphenoxyethanol full orange acrylate, bisphenoxyethanol full orange acrylate, and the like are listed. Examples of commercially available products include Aronix M-210, M-240, and M-6200 (Toagosei ( KAYARAD HDDA, HX-220, R-604 (manufactured by Nippon Kayaku Co., Ltd.), Biscoat 260, 312 and 335HP (manufactured by Osaka Organic Chemical Industries, Ltd.).

  Examples of the trifunctional or higher functional (meth) acrylate include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, tri ((meth) acryloyloxyethyl) phosphate, and pentaerythritol tetra (meth) acrylate. , Dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate and the like, and as commercially available products thereof, for example, Aronix M-309, M-400, M-405, M-450, M-7100, M-8030, M-8060 (manufactured by Toagosei Co., Ltd.), KAYARAD TMPTA, DPHA, DPCA-20, DPCA-30, DPCA-60, DPCA-120 (Japan) Kayaku Co., Ltd.), Biscoat 95, the 300, the 360, the GPT, said 3PA, the 400 (manufactured by Osaka Organic Chemical Industry Ltd.) and the like.

These monofunctional, bifunctional, or trifunctional or higher (meth) acrylates can be used alone or in combination.
The proportion of the component [E] used is preferably 50 parts by weight or less, particularly preferably 30 parts by weight or less, based on 100 parts by weight of the copolymer [A].
By containing the [E] component at such a ratio, the heat resistance, strength, and the like of the patterned thin film obtained from the radiation-sensitive resin composition can be improved. If this proportion exceeds 50 parts by weight, the compatibility with the copolymer [A] becomes insufficient, and film roughening may occur during coating.
As the melamine resin which is the [F] component, the following formula (III),

[Wherein, R ⁶ represents an alkyl group having 1 to 6, preferably 1 to 4 carbon atoms or a hydrogen atom. ]
A compound having preferably 2 or more monovalent organic groups in a molecule is preferable, and more preferably a compound in which the monovalent organic group is bonded to a nitrogen atom, that is, an N-methylol group and / or an N-alkoxymethyl group. The compound containing is mentioned. When two or more organic groups of the above formula (III) are present in one molecule, R ^{6 of} these groups may be the same or different.

When the component [F] is used in the radiation-sensitive resin composition of the present invention, the organic group represented by the above formula (III) reacts with the carboxyl group of the copolymer of the component [A] to form a crosslinked structure. Form.
Examples of the component [F] include, for example, the following formula (IV)

[Wherein, each R ⁷ is the same or different and is an alkyl group having 1 to 4 carbon atoms. ]
An alkoxymethylated melamine such as N, N, N ′, N ′, N ″, N ″-(hexaalkoxymethyl) melamine represented by the formula (V)

[Wherein, each R ⁸ is the same or different and is an alkyl group having 1 to 4 carbon atoms. ]
And alkoxymethylated glycolurils such as N, N ′, N ″, N ′ ″-(tetraalkoxymethyl) glycoluril represented by the formula:

[F] component includes urea-formaldehyde resin, thiourea-formaldehyde resin, melamine-formaldehyde resin, guanamine-formaldehyde resin, benzoguanamine-formaldehyde resin, glycoluril-formaldehyde resin, and polyvinylphenols in the above formula (III The compound which introduce | transduced group shown by this can also be used.
The proportion of the component [F] used is preferably 10 parts by weight or less, more preferably 7 parts by weight or less with respect to 100 parts by weight of the copolymer [A].
By containing the component [F] at such a ratio, the heat resistance, strength, and the like of the patterned coating film obtained from the radiation-sensitive resin composition of the present invention can be further improved.

  In the radiation-sensitive resin composition of the present invention, a surfactant as the [G] component can be used in order to improve applicability. Examples of commercially available products include BM-1000, BM-1100 (manufactured by BM CHEMIE), MegaFuck F142D, F172, F173, F183 (manufactured by Dainippon Ink & Chemicals, Inc.), Florard FC-135, FC-170C, FC-430, FC-431 (above, manufactured by Sumitomo 3M), Surflon S-112, S-113, S-131, S-141, S-145, S-382, SC-101, SC-102, SC-103, SC-104, SC-105, SC-105, SC-106 (above, manufactured by Asahi Glass Co., Ltd.), Ftop EF301, 303, 352 (manufactured by Shin-Akita Kasei Co., Ltd.), SH-28PA, SH-190, SH-193, SZ-6032, SF-8428, DC-57, D -190 (manufactured by Dow Corning Toray Silicone Co.) and the fluorine-based and silicone-based surfactants, such as.

Other polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether;
Polyoxyethylene aryl ethers such as polyoxyethylene octyl phenyl ether and polyoxyethylene nonyl phenyl ether;
Nonionic surfactants such as polyoxyethylene dialkyl esters such as polyoxyethylene dilaurate and polyoxyethylene distearate;
Organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth) acrylic acid copolymer polyflow No. 57, 95 (manufactured by Kyoeisha Chemical Co., Ltd.).

These surfactants [G] 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 copolymer [A]. When the amount of the surfactant [G] is more than 5 parts by weight, there is a tendency that film defects occur during application.
In order to improve the adhesion to the substrate, an adhesion aid can be used as the [H] component. As such an adhesion assistant, a functional silane coupling agent is preferably used, and examples thereof include a silane coupling agent having a reactive substituent such as a carboxyl group, a methacryloyl group, an isocyanate group, and an epoxy group. Specifically, trimethoxysilylbenzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane and the like.
Such an adhesion assistant is preferably used in an amount of 20 parts by weight or less, more preferably 10 parts by weight or less, based on 100 parts by weight of the copolymer [A]. When the amount of the adhesion assistant exceeds 20 parts by weight, a development residue tends to occur.

Radiation-sensitive resin composition The radiation-sensitive resin composition of the present invention is a uniform mixture of the above-mentioned copolymers [A], [B], [C] and other components optionally added as described above. To be prepared. The radiation-sensitive resin composition of the present invention is preferably used in a solution state after being dissolved in an appropriate solvent. For example, a radiation-sensitive resin composition in a solution state is prepared by mixing the copolymer [A] and [B], [C] component and other optionally added components in a predetermined ratio. Can do.
As a solvent used for preparation of the radiation sensitive resin composition of the present invention, each component of the copolymer [A] and [B], [C] component and other components optionally blended is uniformly dissolved. And what does not react with each component is used.
As such a solvent, the thing similar to what was illustrated as a solvent which can be used in order to manufacture copolymer [A] mentioned above can be mentioned.

  Of these solvents, alcohols, glycol ethers, ethylene glycol alkyl ether acetates, esters and diethylene glycol are preferably used from the viewpoints of solubility of each component, reactivity with each component, ease of film formation, and the like. It is done. Among these, for example, 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 Propylene glycol monomethyl ether acetate, methyl methoxypropionate, and ethyl ethoxypropionate can be particularly preferably used.

  Furthermore, in order to improve the in-plane uniformity of the film thickness together with the solvent, a high boiling point solvent can be used in combination. Examples of the high boiling point solvent that can be used in combination include N-methylformamide, N, N-dimethylformamide, N-methylformanilide, N-methylacetamide, N, N-dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, and benzylethyl ether. , Dihexyl ether, acetonyl acetone, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, phenyl Examples include cellosolve acetate. Of these, N-methylpyrrolidone, γ-butyrolactone, and N, N-dimethylacetamide are preferable.

  When a high boiling point solvent is used in combination as the solvent of the radiation sensitive resin composition of the present invention, the amount used is preferably 50% by weight or less, more preferably 40% by weight or less, still more preferably 30%, based on the total amount of the solvent. It can be made into weight% or less. If the amount of the high-boiling solvent used exceeds this amount, the coating film thickness uniformity, sensitivity, and residual film rate may decrease.

When the radiation-sensitive resin composition of the present invention is prepared in a solution state, components other than the solvent in the solution, that is, the copolymers [A] and [B], [C] components and other optionally added The ratio of the total amount of the components can be arbitrarily set according to the purpose of use and the value of the desired film thickness, for example, 5 to 50% by weight, preferably 10 to 40% by weight, more preferably 15 to 35% by weight.
The composition solution thus prepared can be used after being filtered using a Millipore filter having a pore diameter of about 0.2 μm.

Formation of Interlayer Insulating Film and Microlens Next, a method for forming the interlayer insulating film and microlens of the present invention using the radiation sensitive resin composition of the present invention will be described. The method for forming each of the interlayer insulating film and the microlens of the present invention can include the following steps in the order described below.
(1) The process of forming the coating film of the radiation sensitive resin composition of this invention on a board | substrate,
(2) A step of irradiating at least a part of the coating film with radiation,
(3) Development step, and (4) Heating step.

(1) Step of forming a coating film of the radiation sensitive resin composition of the present invention on a substrate In the step of (1) above, the composition solution of the present invention is applied to the substrate surface, preferably prebaked. To remove the solvent and form a coating film of the radiation-sensitive resin composition.
Examples of the types of substrates that can be used include glass substrates, silicon wafers, and substrates on which various metals are formed.
The coating method of the composition solution is not particularly limited, and for example, an appropriate method such as a spray method, a roll coating method, a spin coating method (spin coating method), a slit die coating method, a bar coating method, an ink jet coating method, etc. is adopted In particular, spin coating and slit die coating are preferred. The pre-baking conditions vary depending on the type of each component, the use ratio, and the like. For example, it can be set at 60 to 110 ° C. for about 30 seconds to 15 minutes.
The thickness of the coating film to be formed is, for example, 3 to 6 μm when the interlayer insulating film is formed, and 0.5 to 3 μm, for example, when the microlens is formed, as the value after pre-baking. preferable.

(2) Step of irradiating at least a part of the coating film In the step (2), the formed coating film is irradiated with radiation through a mask having a predetermined pattern. Thereafter, in the next step (3), patterning is performed by developing with a developer to remove the irradiated portion. Examples of the radiation used at this time include ultraviolet rays, far ultraviolet rays, X-rays, and charged particle beams.
Examples of the ultraviolet rays include g-line (wavelength 436 nm), i-line (wavelength 365 nm), and the like. Examples of the far ultraviolet rays include KrF excimer laser. Examples of X-rays include synchrotron radiation. Examples of the charged particle beam include an electron beam.
Among these, ultraviolet rays are preferable, and radiation including g-line and / or i-line is particularly preferable.
Energy of exposure, in the case of forming an interlayer insulating film, for example 50~1,500J / ^{m 2,} in a case of forming a micro-lens, for example, be a 50~2,000J / ^{m 2} Is preferred.

(3) Development process Examples of the developer used in the development process include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, ammonia, ethylamine, n-propylamine, diethylamine, diethylaminoethanol, di-acid. N-propylamine, triethylamine, methyldiethylamine, dimethylethanolamine, triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, pyrrole, piperidine, 1,8-diazabicyclo [5,4,0] -7-undecene An aqueous solution of an alkali (basic compound) such as 1,5-diazabicyclo [4,3,0] -5-nonane can be used. In addition, an aqueous solution obtained by adding an appropriate amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant to the above aqueous alkali solution, or various organic solvents that dissolve the composition of the present invention can be used as a developing solution. Furthermore, as a developing method, an appropriate method such as a liquid piling method, a dipping method, a rocking dipping method, a shower method, or the like can be used. The development time at this time varies depending on the composition of the composition, but can be, for example, 30 to 120 seconds.
In addition, the conventionally known radiation-sensitive resin composition has been required to strictly control the development time because the formed pattern peels when the development time exceeds about 20 to 25 seconds from the optimum value. In the case of the radiation-sensitive resin composition of the invention, good pattern formation is possible even when the excess time from the optimum development time is 30 seconds or more, and there is an advantage in product yield.

(4) Heating step (3) Performed as described above (3) After the development step, the patterned thin film is preferably rinsed, for example, by washing with running water, and more preferably irradiated with radiation from a high-pressure mercury lamp or the like. (After post-exposure), the 1,2-quinonediadito compound remaining in the thin film is decomposed, and then the thin film is heated (post-baked) with a heating device such as a hot plate or an oven. Then, the thin film is cured. The exposure amount in the post-exposure step is preferably about 2,000 to 5,000 J / m ² . Moreover, the heating temperature in this hardening process is 120-250 degreeC, for example. The heating time varies depending on the type of heating device. For example, when heat treatment is performed on a hot plate, the heating time is, for example, 5 to 30 minutes. When heat treatment is performed in an oven, the heating time is, for example, 30 to 90 minutes. Can do. At this time, a step baking method or the like in which a heating process is performed twice or more can also be used.
In this way, a patterned thin film corresponding to the target interlayer insulating film or microlens can be formed on the surface of the substrate.
The interlayer insulating film and the microlens formed as described above are excellent in adhesion, heat resistance, solvent resistance, transparency, and the like, as will be apparent from examples described later.

Interlayer Insulating Film The interlayer insulating film of the present invention formed as described above has good adhesion to the substrate, excellent solvent resistance and heat resistance, high transmittance, and low dielectric constant. Therefore, it can be suitably used as an interlayer insulating film of electronic parts.

The microlens of the present invention formed as described above has good adhesion to the substrate, excellent solvent resistance and heat resistance, and has high transmittance and a good melt shape. It can be suitably used as a microlens for a solid-state imaging device.
The shape of the microlens of the present invention is a semi-convex lens shape as shown in FIG.

  Synthesis Examples, Examples and Comparative Examples are shown below to describe the present invention more specifically. However, the present invention is not limited to the following examples.

Synthesis example 1
A flask equipped with a condenser and a stirrer was charged with 7 parts by weight of 2,2′-azobis (2,4-dimethylvaleronitrile) and 220 parts by weight of propylene glycol monomethyl ether acetate. Subsequently, 22 parts by weight of methacrylic acid, 38 parts by weight of dicyclopentanyl methacrylate, 40 parts by weight of 3- (methacryloyloxymethyl) -2-ethyloxetane, and 1.5 parts by weight of α-methylstyrene dimer were charged and gradually replaced with nitrogen. Stirring started. The temperature of the solution was raised to 70 ° C. and heated at this temperature for 4 hours to obtain a polymer solution containing the copolymer [A-1]. The obtained polymer solution had a solid content concentration of 31.8% by weight, a polymer weight average molecular weight of 17,900, and a molecular weight distribution (ratio of weight average molecular weight / number average molecular weight) of 1.8. In addition, a weight average molecular weight and a number average molecular weight are polystyrene conversion average molecular weights measured using GPC (Gel permeation chromatography (HLC-8020 manufactured by Tosoh Corporation)).

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

Example 1
Preparation of radiation sensitive resin composition Polymer solution containing copolymer [A-1] obtained in Synthesis Example 1 (corresponding to 100 parts by weight (solid content) of copolymer [A-1]),
As component [B], 4,4 ′-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol (1 mol) and 1,2-naphthoquinonediazide-5 Condensation product with sulfonic acid chloride (2 mol) (4,4 ′-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol-1,2-naphthoquinonediazide -5-sulfonic acid ester) 30 parts by weight, bisphenol A type epoxy resin (Japan Epoxy Resin Co., Ltd. Epicoat 807) 5 parts by weight, and γ-methacryloxypropyltrimethoxysilane 5 parts by weight are mixed. After dissolving in propylene glycol monomethyl ether acetate so as to be 30% by weight, Millipore The solution (S-1) of the radiation sensitive resin composition was prepared by filtering with a filter.

Evaluation of interlayer insulation film
(I) Formation of Patterned Thin Film After applying the composition solution (S-1) on a glass substrate using a spinner, the coating film was formed by prebaking on a hot plate at 80 ° C. for 3 minutes.
The coating film obtained above was irradiated with ultraviolet rays having an intensity at 365 nm of 10 mW / cm ² for 15 seconds using a predetermined pattern mask. Subsequently, after developing with a 0.5% by weight aqueous solution of tetramethylammonium hydroxide at 25 ° C. for 1 minute, it was rinsed with pure water for 1 minute. By these operations, unnecessary portions were removed.
The pattern formed above was irradiated with ultraviolet rays having an intensity at 365 nm of 10 mW / cm ² for 30 seconds, and then heated and cured in an oven at 220 ° C. for 60 minutes to obtain a patterned thin film having a thickness of 3 μm.
Further, except that the prebaking temperature was set to 90 ° C. and 100 ° C., the same operation as described above was performed to form three types of patterned thin films having different prebaking temperatures.

(II) Evaluation of resolution In the pattern-like thin film obtained in (I) above, the case where the extraction pattern (5 μm × 5 μm hole) was resolved was evaluated as ◯, and the case where the pattern was not resolved was evaluated as ×. The results are shown in Table 1.

(III) Evaluation of heat-resistant dimensional stability In the above (I), the thin film pattern formed at a pre-baking temperature of 80 ° C. was heated in an oven at 220 ° C. for 60 minutes. Table 2 shows the rate of change in film thickness before and after heating. When the dimensional change rate at this time is within 5% before and after heating, the heat resistant dimensional stability is good, and when the dimensional change rate exceeds 5%, it can be said to be defective.

(IV) Evaluation of Transparency In (I) above, the transmittance of 400 nm of the patterned thin film formed at a pre-bake temperature of 80 ° C. was measured using a spectrophotometer (150-20 type double beam (manufactured by Hitachi, Ltd.)). And measured for transparency. The results are shown in Table 2. At this time, when the transmittance is 90% or more, the transparency is good, and when the transmittance is less than 90%, the transparency is poor.

(V) Evaluation of heat-resistant discoloration In (I) above, a substrate having a patterned thin film formed at a pre-baking temperature of 80 ° C. is heated in an oven at 250 ° C. for 1 hour, and the change in transmittance of the patterned thin film before and after heating. Was used to evaluate heat discoloration. The evaluation results at this time are shown in Table 2. When the rate of change is less than 5%, the heat discoloration is good, and when it exceeds 5%, it can be said that the color change is poor. The transmittance was determined in the same manner as (VI) transparency evaluation.

(VI) Evaluation of adhesion In (I) above, the adhesion of the patterned thin film formed at a pre-baking temperature of 80 ° C. was evaluated by a cross-cut peel test after a pressure cooker test (120 ° C., humidity 100%, 4 hours). did. The evaluation results at this time are shown in Table 2. The evaluation result was represented by the number of remaining grids out of 100 grids.

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

Evaluation of microlenses
(I) Formation of microlens A 6-inch silicon substrate was spin-coated with the above composition solution (S-1) so as to have a film thickness of 2.5 μm, and pre-baked on a hot plate at 70 ° C. for 3 minutes to form a coating film. Formed.
The coating film obtained above was irradiated with ultraviolet rays having an intensity at 436 nm of 10 mW / cm ² using a predetermined pattern mask. Next, the film was developed with a 2.38 wt% aqueous solution of tetramethylammonium hydroxide at 25 ° C. for 1 minute, and then rinsed with pure water for 1 minute. By these operations, unnecessary portions were removed and a pattern was formed.
The pattern formed above was irradiated with 200 mJ / cm ^{2 of} ultraviolet light having an intensity of 10 mW / cm ² at 436 nm, then heated at 160 ° C. for 10 minutes, and further heated at 230 ° C. for 10 minutes to melt-flow the pattern. A lens was formed.

(II) Evaluation of Sensitivity Minimum irradiation capable of resolving the space line width of 0.8 μm line and space pattern (10 to 1) of the microlens pattern after melt flow obtained in (I) above. The amount is shown in Table 3. When this value is 100 mJ / cm ² or less, it can be said that the resolution is good and when the sensitivity exceeds 100 mJ / cm ² , the resolution is poor.

(III) Evaluation of transparency A patterned thin film was formed on a glass substrate in the same manner as (I) above.
About the glass substrate in which the microlens pattern after the melt flow was formed, the transmittance at 400 nm was measured using a spectrophotometer (150-20 type double beam (manufactured by Hitachi, Ltd.)), and the transparency was evaluated. It was. The transmittance at 400 nm at this time is shown in Table 3. When the transmittance is 90 to 100%, the transmittance is good, and when it is less than 90%, the transmittance is poor.

(IV) Evaluation of heat-resistant discoloration The glass substrate having the patterned thin film formed in (III) above is heated in an oven at 250 ° C. for 1 hour, and heat-resistant due to the change in transmittance of the patterned thin film before and after heating. The discoloration was evaluated. Table 3 shows the change rate of the transmittance at this time. When the rate of change is less than 5%, the heat discoloration is good, and when it exceeds 5%, it can be said to be defective. The transmittance was determined in the same manner as (III) transparency evaluation.

(V) Evaluation of adhesion The adhesion of the patterned thin film formed in the above (I) was evaluated by a cross-cut peel test after a pressure cooker test (120 ° C., humidity 100%, 4 hours). The evaluation results at this time are shown in Table 3. The evaluation result was represented by the number of remaining grids out of 100 grids.

(VII) Evaluation of solvent resistance A glass substrate having a patterned thin film formed in the same manner as in the above (III) was immersed in isopropyl alcohol at 50 ° C. for 10 minutes, and the change in film thickness was evaluated. Table 3 shows the rate of change at this time. When the rate of change is 0 to 5%, the solvent resistance is good, and when it exceeds 5% and when the film thickness is reduced by dissolution, the solvent resistance can be said to be poor.

Example 2
In Example 1, a solution containing a cresol novolac type epoxy resin (Epicoat 180 manufactured by Japan Epoxy Resin Co., Ltd.) was used instead of a solution containing bisphenol A type epoxy resin (Epicoat 807 manufactured by Japan Epoxy Resin Co., Ltd.). Prepared and evaluated the composition solution (S-2) in the same manner as in Example 1. The results are shown in Tables 1-3.

Example 3
In Example 1, instead of a solution containing bisphenol A type epoxy resin (Epicoat 807 manufactured by Japan Epoxy Resin Co., Ltd.), a solution containing phenol novolac type oxetane resin (Aron Oxetane 121 manufactured by Toagosei Co., Ltd.) was used. Prepared and evaluated the composition solution (S-3) in the same manner as in Example 1. The results are shown in Tables 1-3.

Example 4
In Example 1, instead of using a solution containing a bisphenol A type epoxy resin (Epicoat 807 manufactured by Japan Epoxy Resin Co., Ltd.) and a solution containing a biphenyl type oxetane resin (ETERNACOLL OXEP manufactured by Ube Industries, Ltd.), A composition solution (S-4) was prepared and evaluated in the same manner as in Example 1. The results are shown in Tables 1-3.

Example 5
A polymer solution containing the copolymer [A-1] obtained in Synthesis Example 1 (corresponding to 100 parts by weight (solid content) of the copolymer [A-1]);
As component [B], 4,4 ′-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol (1 mol) and 1,2-naphthoquinonediazide-5 Condensation product with sulfonic acid chloride (2 mol) (4,4 ′-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol-1,2-naphthoquinonediazide -5-sulfonic acid ester) 30 parts by weight and bisphenol A type epoxy resin (Japan Epoxy Resin Co., Ltd. Epicoat 807) 5 parts by weight, γ-methacryloxypropyltrimethoxysilane 5 parts by weight, triphenylsulfonium trifluoromethanesulfonate ( Sanshin Chemical Co., Ltd. SI-300) 1 part by weight is mixed, and the solid content concentration becomes 30% by weight. It was dissolved in propylene glycol monomethyl ether acetate as to prepare a solution (S-5) of the radiation-sensitive resin composition was filtered through a Millipore filter having a pore size 0.5 [mu] m.

Comparative Example 1
A polymer solution containing the copolymer [A-1] obtained in Synthesis Example 1 (corresponding to 100 parts by weight (solid content) of the copolymer [A-1]);
As component [B], 4,4 ′-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol (1 mol) and 1,2-naphthoquinonediazide-5 Condensation product with sulfonic acid chloride (2 mol) (4,4 ′-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol-1,2-naphthoquinonediazide -5-sulfonic acid ester) 30 parts by weight and 5 parts by weight of γ-methacryloxypropyltrimethoxysilane were mixed and dissolved in propylene glycol monomethyl ether acetate so that the solid content concentration would be 30% by weight. A solution (S-1R) of a radiation sensitive resin composition was prepared by filtration through a 5 μm Millipore filter. In Example 1, the above (S-1R) was used instead of the resin composition solution (S-1) to form an interlayer insulating film, and evaluation was performed. The results are shown in Tables 1-3.

Comparative Example 2
A polymer solution containing the copolymer [A-1R] obtained in Comparative Example 1 (corresponding to 100 parts by weight (solid content) of the copolymer [A-1R]),
As component [B], 4,4 ′-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol (1 mol) and 1,2-naphthoquinonediazide-5 Condensation product with sulfonic acid chloride (2 mol) (4,4 ′-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol-1,2-naphthoquinonediazide -5-sulfonic acid ester) 30 parts by weight, bisphenol A type epoxy resin (Japan Epoxy Resin Co., Ltd. Epicoat 807) 5 parts by weight, and γ-methacryloxypropyltrimethoxysilane 5 parts by weight are mixed. After dissolving in propylene glycol monomethyl ether acetate so as to be 30% by weight, Millipore The solution (S-2R) of the radiation sensitive resin composition was prepared by filtering with a filter. In Example 1, the above (S-2R) was used instead of the resin composition solution (S-1) to form an interlayer insulating film, and evaluation was performed. The results are shown in Tables 1-3.

The schematic diagram which shows the shape of a micro lens.

Claims (7)

[A] (a1) at least one selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic anhydride,
(A2) a compound represented by the following formula (I) or the following formula (II),

[Wherein R is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R ¹ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ² , R ³ , R ⁴ and R ⁵ are respectively It is independently a hydrogen atom, a fluorine atom, an alkyl group having 1 to 4 carbon atoms, a phenyl group or a perfluoroalkyl group having 1 to 4 carbon atoms, and n is an integer of 1 to 6. ]
And (a3) a copolymer obtained by copolymerizing an olefinically unsaturated compound other than (a1) and (a2),
[B] A radiation-sensitive resin composition comprising at least one selected from the group consisting of 1,2-quinonediazide compounds, [C] epoxy group-containing compounds, and oxetanyl group-containing compounds other than [A] object. The radiation-sensitive resin composition according to claim 1, which is used for forming an interlayer insulating film. A method for forming an interlayer insulating film, comprising the following steps in the order described below.
(1) The process of forming the coating film of the radiation sensitive resin composition of Claim 1 on a board | substrate,
(2) A step of irradiating at least a part of the coating film with radiation,
(3) Development step, and (4) Heating step. An interlayer insulating film formed by the method according to claim 3. The radiation-sensitive resin composition according to claim 1, which is used for forming a microlens. A method for forming a microlens comprising the following steps in the order described below.
(1) The process of forming the coating film of the radiation sensitive composition of Claim 1 on a board | substrate,
(2) A step of irradiating at least a part of the coating film with radiation,
(3) Development step, and (4) Heating step. A microlens formed by the method of claim 6.

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