KR20040044164A - Radiosensitive Resin Composition, Insulating Interlayer and Microlens, and Process for Preparing the Same - Google Patents

Abstract

PURPOSE: A radiation sensitive resin composition is provided, which is excellent in radiation sensitivity and developing time. And an insulating membrane in terms and a microlens are provided, which are produced by using the radiation sensitive resin composition and are excellent in an adhesive property, a solvent-resistance, and etc. CONSTITUTION: The radiation sensitive resin composition contains: a copolymer of an unsaturated carboxylic acid and/or an unsaturated carboxylic anhydride, an epoxy containing unsaturated compound, and an olefin-based unsaturated compound; a condensate of a specific phenol compound and 1,2-naphthoquinone diazide sulfonic acid halide, wherein the specific phenol compound is at least one selected from 2-methyl-2-(2,4-dihydroxyphenyl)-4-(4-hydroxyphenyl)-7-hydroxychromane, 2-£bis{(5-isopropyl-4-hydroxy-2-methyl)phenyl}methyl|phenol, and etc. And the insulating membrane in terms and the microlens are produced by a process containing the steps of: forming a film of the radiation sensitive resin composition on a substrate; irradiating a radiation on at least one part of the film; developing; heating.

Description

Radiation sensitive resin composition, interlayer insulating film and microlens, and manufacturing method thereof {Radiosensitive Resin Composition, Insulating Interlayer and Microlens, and Process for Preparing the Same}

The present invention relates to a radiation-sensitive resin composition, an interlayer insulating film and a microlens, and a manufacturing method thereof.

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 imaging elements are generally provided with an interlayer insulating film for insulating between wirings arranged in layers. . As the material for forming the interlayer insulating film, the number of steps for obtaining the required pattern shape is small, and since it is preferable to have sufficient flatness, the radiation-sensitive resin composition is widely used (for example, Japanese Patent Laid-Open No. 2001-354822). And Japanese Patent Laid-Open 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 formed in the process of forming a transparent electrode film. Since it is exposed to high temperature conditions or to the stripping solution of the resist used for pattern formation of the electrode, sufficient resistance to these is required.

In recent years, TFT type liquid crystal display devices have trends such as large screen, high brightness, high precision, high speed response, and thinning, and have high sensitivity as an interlayer insulating film forming composition used therein, and have a low dielectric constant in the interlayer insulating film to be formed. In terms of high transmittance, higher performance is required than before.

On the other hand, a microlens having a lens diameter of about 3 to 100 µm as an imaging system of an on-chip color filter such as a facsimile, an electron copy machine, a solid-state imaging device, or an optical system of an optical fiber connector, or a microlens array in which these microlenses are regularly arranged Is being used.

To form a microlens or microlens array, a resist pattern corresponding to a lens is formed, followed by heat treatment to melt flow, and use the lens as it is, or dry-etch the lens pattern as a mask and dry the lens on the base layer. The method of transferring a shape is known. The radiation sensitive resin composition is widely used for formation of the said lens pattern (for example, refer Unexamined-Japanese-Patent No. 6-18702 and Unexamined-Japanese-Patent No. 6-136239).

By the way, the element in which the microlens or the microlens array as described above is formed is then coated with a planarizing film and an etching resist film in order to remove various insulating films on the bonding pads, which are wiring forming portions, and using an objective mask for exposure, It is used in the process of developing and removing the etching resist of a bonding pad part, then removing a planarization film and various insulating films by etching, and exposing a bonding pad part. For this reason, solvent resistance and heat resistance are required for a microlens or a microlens array in the coating film formation process and the etching process of a planarization film and an etching resist.

The radiation-sensitive resin composition used to form such a microlens is highly sensitive, and the microlenses formed therefrom have a desired radius of curvature and are required to have high heat resistance and high transmittance.

In the development step in forming these, the interlayer insulating film and the microlens obtained as described above are developed in such a manner that, if the developing time is excessively more than the optimum time, the developing solution easily penetrates between the pattern and the substrate, so that the developing time is easy to develop. There is a need to control the product tightly and there is a problem in terms of yield of the product.

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 in the developing step in the forming step, the pattern peeling occurs even when the developing time is more than the predetermined time. It does not have good adhesion, and the interlayer insulating film formed therefrom is required to have high heat resistance, high solvent resistance, low dielectric constant, high transmittance, and the like, and in the case of forming a microlens, a good melt shape (purpose curvature) as a microlens is formed. Radius, high heat resistance, high solvent resistance, and high transmittance are required, but a radiation-sensitive resin composition that satisfies such a requirement is not known in the past.

The present invention has been made on the basis of the above circumstances, and its object is to have a high radiation sensitivity, a development margin capable of forming a good pattern shape even when the optimum development time is exceeded in the development process, and excellent adhesion. It is possible to easily form a patterned thin film, and furthermore, to form an interlayer insulating film, and to form an interlayer insulating film of high transmittance and low dielectric constant, and to use a microlens to form a high transmittance and good melt shape. It is providing the radiation sensitive resin composition which can form the microlens which has the following.

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

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

According to the present invention, the above objects and advantages of the present invention firstly,

(A) (a1) unsaturated carboxylic acid and / or unsaturated carboxylic anhydride (hereinafter also referred to as "compound (a1)"),

(a2) epoxy group-containing unsaturated compounds (hereinafter also referred to as "compound (a2)"), and

(a3) copolymers of olefinically unsaturated compounds other than (a1) and (a2) (hereinafter also referred to as "compound (a3)") (hereinafter also referred to as "copolymer [A]"), and

[B] 2-methyl-2- (2,4-dihydroxyphenyl) -4- (4-hydroxyphenyl) -7-hydroxychroman, 2- [bis {(5-isopropyl-4- Hydroxy-2-methyl) phenyl} methyl] phenol, 1- [1- (3- {1- (4-hydroxyphenyl) -1-methylethyl} -4,6-dihydroxyphenyl) -1- Methylethyl] -3- (1- (3- {1- (4-hydroxyphenyl) -1-methylethyl} -4,6-dihydroxyphenyl) -1-methylethyl) benzene, and 4,6 A condensate of at least one selected from -bis {1- (4-hydroxyphenyl) -1-methylethyl} -1,3-dihydroxybenzene with 1,2-naphthoquinonediazidesulfonic acid halide (hereinafter , "Also referred to as" [B] component "), is achieved by the radiation-sensitive resin composition characterized by the above-mentioned.

The object and advantages of the present invention is second,

It is achieved by a method for forming an interlayer insulating film or microlens, which comprises at least the following steps.

(1) forming a coating film of the radiation-sensitive composition on the substrate;

(2) irradiating at least a part of the coating film with radiation;

(3) developing process, and

(4) heating step.

In addition, the third object and advantage of the present invention,

It is achieved by an interlayer insulating film or microlens formed by the above method.

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

Copolymer [A]

Copolymer [A] can be produced 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 is preferably a structural unit derived from the compound (a1) based on the sum of the repeating units derived from the compound (a1), (a2) and (a3). 5 to 40% by weight, particularly preferably 10 to 30% by weight. When this copolymer of the structural unit is less than 5 weight%, it will become difficult to melt | dissolve in aqueous alkali solution at the time of a developing process, and the copolymer exceeding 40 weight% tends to become too high in aqueous alkali solution.

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

Specific examples thereof include acrylic acid, methacrylic acid, crotonic acid and the like as monocarboxylic acids;

Examples of the dicarboxylic acids include maleic acid, fumaric acid, citraconic acid, mesaconic acid and itaconic acid;

Anhydrides of compounds exemplified as the above dicarboxylic acids as anhydrides of dicarboxylic acids;

Mono [(meth) acryloyloxyalkyl] esters of polyhydric carboxylic acids, such as mono succinate mono [2- (meth) acryloyloxyethyl] and mono phthalate [2- (meth) acryloyloxyethyl];

Ω-carboxypolycaprolactone mono (meth) acrylate and the like as mono (meth) acrylates of polymers having a carboxyl group and a hydroxyl group at both terminals;

Polycyclic compounds having a carboxyl group and anhydrides thereof as 5-carboxybicyclo [2.2.1] hept-2-ene, 5,6-dicarboxybicyclo [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-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, and the like. have.

Among them, monocarboxylic acids and anhydrides of dicarboxylic acids are preferably used, and acrylic acid, methacrylic acid and maleic anhydride are particularly preferably used in view of copolymerization reactivity, solubility in aqueous alkali solution and easy availability. These are used alone or in combination.

The copolymer [A] used in the present invention is preferably 10 based on the sum of the repeating units derived from the compounds (a1), (a2) and (a3) of the structural units derived from the compound (a2). To 70% by weight, particularly preferably 20 to 60% by weight. When this structural unit is less than 10 weight%, there exists a tendency for the heat resistance and surface hardness of the obtained interlayer insulation film and microlens to fall, and when the quantity of this structural unit exceeds 70 weight%, it preserve | saves a radiation sensitive resin composition There exists a tendency for stability to fall.

Examples of the compound (a2) include glycidyl acrylate, glycidyl methacrylate, glycidyl alpha -ethyl acrylate, glycidyl alpha -n-propyl acrylate, glycidyl alpha -n-butyl acrylate, and 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-vinylbenzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether, and the like. Among these, glycidyl methacrylate and methacrylic acid-6,7 Epoxyheptyl, o-vinylbenzylglycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, etc. are copolymerized and the heat resistance and surface hardness of the resulting interlayer insulating film or microlens are improved. It is preferably used. These are used alone or in combination.

The copolymer [A] used in the present invention preferably has a structural unit derived from the compound (a3) based on the sum of the repeating units derived from the compound (a1), (a2) and (a3). To 70% by weight, particularly preferably 15 to 50% by weight. When this structural unit is less than 10 weight%, the storage stability of a radiation sensitive resin composition tends to fall, and when it exceeds 70 weight%, it will melt | dissolve in aqueous alkali solution in the image development process in formation of an interlayer insulation film or a microlens. It is difficult.

Examples of the compound (a3) include methacrylic acid alkyl esters, methacrylic acid cyclic alkyl esters, methacrylic acid cyclic alkyl esters, methacrylic acid esters having a hydroxyl group, acrylic acid cyclic alkyl esters, and methacrylic acid. Acid aryl esters, acrylic aryl esters, unsaturated dicarboxylic acid diesters, bicyclo unsaturated compounds, maleimide compounds, unsaturated aromatic compounds, conjugated dienes, and other unsaturated compounds are mentioned.

Specific examples thereof include, for example, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate, t-butyl methacrylate, 2- as alkyl methacrylates. Ethylhexyl methacrylate, isodecyl methacrylate, n-lauryl methacrylate, tridecyl methacrylate, n-stearyl methacrylate and the like;

Methacrylic acid cyclic alkyl esters such as methyl acrylate and isopropyl acrylate;

As methacrylic acid cyclic alkyl esters, cyclohexyl methacrylate, 2-methylcyclohexyl methacrylate, tricyclo [5.2.1.O ^2,6 ] decane-8-yl methacrylate, tricyclo [5.2.1 .0 ^2,6 ] decane-8- ^yloxyethyl methacrylate, isoboroyl methacrylate, and the like;

As methacrylic acid ester having a hydroxyl group, hydroxymethyl methacrylate, 2-hydroxyethyl methacrylate, 3-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, diethylene glycol monomethacrylate , 2,3-dihydroxypropyl methacrylate, 2-methacryloxyethyl glycoside, 4-hydroxyphenyl methacrylate, and the like;

Acrylic acid cyclic alkyl esters such as cyclohexyl acrylate, 2-methylcyclohexyl acrylate, tricyclo [5.2.1.O ^2,6] decan-8-yl acrylate, tricyclo [5.2.1.O ^2,6 ] Decane-8-yloxyethyl acrylate, isoboroyl acrylate and the like;

Methacrylic acid aryl esters such as phenyl methacrylate and benzyl methacrylate;

As acrylic acid aryl ester, Phenyl acrylate, Benzyl acrylate, etc .;

Examples of the unsaturated dicarboxylic acid diesters include diethyl maleate, diethyl fumarate, diethyl itaconate, and the like;

As the bicyclo unsaturated compounds, bicyclo [2.2.1] hept-2-ene, 5-methylbicyclo [2.2.1] hept-2-ene, 5-ethylbicyclo [2.2.1] hept-2-ene , 5-methoxybicyclo [2.2.1] hept-2-ene, 5-ethoxybicyclo [2.2.1] hept-2-ene, 5,6-dimethoxybicyclo [2.2.1] hept-2- N, 5,6-diethoxybicyclo [2.2.1] hept-2-ene, 5-t-butoxycarbonylbicyclo [2.2.1] hept-2-ene, 5-cyclohexyloxycarbonyl ratio Cyclo [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, 5,6-di (cyclohexyloxycarbonyl) bicyclo [2.2.1] hept-2-ene, 5- (2'-hydroxyethyl) bicyclo [2.2.1] hept -2-ene, 5,6-dihydroxybicyclo [2.2.1] hept-2-ene, 5,6-di (hydroxymethyl) bicyclo [2.2.1] hept-2-ene, 5, 6-di (2'-hydroxyethyl) bicyclo [2.2.1] hept-2-ene, 5-hydroxy-5-methylbicyclo [2.2.1] hept-2-ene, 5-hydroxy- 5-ethylbicyclo [2.2.1] Bit-2-ene, 5-hydroxy-5-methyl [2.2.1] hept-2-ene and the like;

As maleimide compounds, phenylmaleimide, cyclohexyl maleimide, benzyl maleimide, N-succinimidyl-3-maleimide benzoate, N-succinimidyl-4-maleimide butyrate, N-succinimidyl- 6-maleimide caproate, N-succinimidyl-3-maleimide propionate, N- (9-acridinyl) maleimide and the like;

As unsaturated aromatic compounds, styrene, (alpha) -methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, p-methoxy styrene, etc .;

Examples of the conjugated dienes include 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, and the like;

As other unsaturated compounds, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, and vinyl acetate are mentioned, respectively.

Among these, methacrylic acid alkyl esters, methacrylic acid cyclic alkyl esters, bicyclo unsaturated compounds, unsaturated aromatic compounds and conjugated dienes are preferably used, and in particular, styrene, t-butyl methacrylate and tricyclo [ 5.2.1.O ^2,6 ] decane-8-ylmethacrylate, p-methoxystyrene, 2-methylcyclohexylacrylate, 1,3-butadiene, bicyclo [2.2.1] hept-2-ene This is preferable in view of copolymerization reactivity and solubility in aqueous alkali solution. These are used alone or in combination.

As a preferred embodiment of the copolymer [A] used in the present invention, for example, methacrylic acid / styrene / tricyclo [5.2.1.O ^2,6 ] decane-8-yl methacrylate / methacrylic acid Glycidyl copolymer, methacrylic acid / styrene / tricyclo [5.2.1.O ^2,6 ] decane-8-yl methacrylate / glycidyl methacrylate / p-vinylbenzyl glycidyl ether copolymer , Methacrylic acid / styrene / tricyclo [5.2.1.O ^2,6 ] decane-8-yl methacrylate / glycidyl methacrylate / 2-hydroxyethyl methacrylate copolymer, methacrylic acid / Styrene / tricyclo [5.2.1.O ^2,6 ] decane-8-ylmethacrylate / glycidyl methacrylate / n-lauryl methacrylate copolymer.

The copolymer [A] used in the present invention has a polystyrene reduced weight average molecular weight (hereinafter referred to as "Mw") of usually 2 × 10 ³ to 1 × 10 ⁵ , preferably 5 × 10 ³ to 5 × 10 ⁴ . It is preferable. If Mw is less than 2 × 10 ^{3, the} development margin may not be sufficient, and the remaining film ratio of the resulting film may be lowered, or the pattern shape, heat resistance, etc. of the resulting interlayer insulating film or microlens may be inferior. When x10 <^5> is exceeded, a sensitivity may fall or a pattern shape may be inferior. The radiation sensitive resin composition containing said copolymer [A] can form a predetermined pattern shape easily, without developing residue when developing.

Examples of the solvent used in the preparation of the copolymer [A] include alcohols, ethers, glycol ethers, ethylene glycol alkyl ether acetates, diethylene glycol, propylene glycol monoalkyl ethers, and propylene glycol alkyl ethers. Acetates, propylene glycol alkyl ether propionates, aromatic hydrocarbons, ketones, esters and the like.

As these specific examples, For example, alcohol, methanol, ethanol, etc .;

Tetrahydrofuran etc. as ethers;

Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, etc. as glycol ethers;

As ethylene glycol alkyl ether acetates, methyl cellosolve acetate, ethyl cellosolve acetate, etc .;

Diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, etc. as diethylene glycol;

Propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether and the like as propylene glycol monoalkyl ethers;

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 acetates;

As propylene glycol alkyl ether propionates, propylene glycol methyl ether propionate, propylene glycol ethyl ether propionate, propylene glycol propyl ether propionate, propylene glycol butyl ether propionate, etc .;

Toluene, xylene and the like as the aromatic hydrocarbons;

Methyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone, etc. as ketones;

As esters, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, methyl hydroxyacetate, and hydroxy Ethyl hydroxy acetate, butyl hydroxy acetate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, methyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, 3-hydroxypropionate, butyl 3-hydroxypropionate, 2 Methyl hydroxy-3-methyl butyrate, methyl methoxy acetate, ethyl methoxy acetate, methoxy acetate propyl, butyl butyl acetate, ethoxy acetate, ethoxy acetate, ethoxy acetate, ethoxy acetate Methyl propoxy acetate, ethyl propoxy acetate, propyl propoxy acetate, butyl propoxy acetate, methyl butoxy acetate, butoxy Ethyl acetate, propyl butoxy acetate, butyl butoxy acetate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, butyl 2-methoxypropionate, methyl 2-ethoxypropionate, 2 Ethyl ethoxypropionate, propyl 2-ethoxypropionate, butyl 2-ethoxypropionate, methyl 2-butoxypropionate, ethyl 2-butoxypropionate, propyl 2-butoxypropionate, butyl 2-butoxypropionate, 3- Methyl methoxypropionate, 3-methoxy ethylpropionate, 3-methoxy propylpropionate, 3-methoxy propylpropionate, 3-ethoxypropionate methyl, 3-ethoxypropionate, 3-ethoxypropionate, 3-e Butyl oxypropionate, 3-propoxy methyl propionate, 3-propoxy propionate, 3-propoxy propionate, 3-butyl propoxypropionate, 3-butoxy methyl propionate, 3-butoxy ethyl propionate, 3-part When acid profile, may be mentioned esters such as butyl-3-butoxy-propionic acid, respectively.

Among these, ethylene glycol alkyl ether acetates, diethylene glycols, propylene glycol monoalkyl ethers and propylene glycol alkyl ether acetates are preferable, and in particular, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, propylene glycol methyl ether, Propylene glycol methyl ether acetate is preferred.

As a polymerization initiator used for manufacture of copolymer [A], what is generally known as a radical polymerization initiator can be used, For example, 2,2'- azobisisobutyronitrile, 2,2'- azobis- Azo compounds such as (2,4-dimethylvaleronitrile) and 2,2'-azobis- (4-methoxy-2,4-dimethylvaleronitrile); Organic peroxides such as benzoyl peroxide, lauroyl peroxide, t-butylperoxy pivalate, 1,1'-bis- (t-butylperoxy) cyclohexane; And hydrogen peroxide. When using a peroxide as a radical polymerization initiator, you may use it as a redox initiator by using a peroxide together with a reducing agent.

In manufacture of copolymer [A], in order to adjust molecular weight, a molecular weight modifier can be used. 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; Xanthogens such as dimethyl xanthogen sulfide and diisopropyl xanthogen disulfide; Tapinene, (alpha) -methylstyrene dimer, etc. are mentioned.

[B] component

The component [B] used in the present invention is 2-methyl-2- (2,4-dihydroxyphenyl) -4- (4-hydroxyphenyl) -7-hydroxychrome, 2- [bis { (5-isopropyl-4-hydroxy-2-methyl) phenyl} methyl] phenol, 1- [1- (3- {1- (4-hydroxyphenyl) -1-methylethyl} -4,6- Dihydroxyphenyl) -1-methylethyl] -3- (1- (3- {1- (4-hydroxyphenyl) -1-methylethyl} -4,6-dihydroxyphenyl) -1-methyl Ethyl) benzene, and at least one selected from 4,6-bis {1- (4-hydroxyphenyl) -1-methylethyl} -1,3-dihydroxybenzene (hereinafter also referred to as "specific phenolic compound" ) And 1,2-naphthoquinonediazidesulfonic acid halide. As the 1,2-naphthoquinone diazide sulfonic acid halide, 1,2-naphthoquinone diazide sulfonic acid chloride is preferable.

Such a component [B] can be obtained by dropping a specific phenol compound and 1,2-naphthoquinonediazidesulfonic acid halide, usually by dropping a catalyst and condensation reaction in the presence of a solvent. The usage-amount of the specific phenol compound and 1,2-naphthoquinone diazide sulfonic-acid halide at this time changes with kinds of the specific phenolic compound to be used. The amount of 1,2-naphthoquinone diazide sulfonic acid halide to 1 mol of specific phenol compounds is

When the specific phenolic compound is 2-methyl-2- (2,4-dihydroxyphenyl) -4- (4-hydroxyphenyl) -7-hydroxychroman, preferably 1.0 to 4.0 moles, more preferably Preferably from 2.0 to 3.5 moles,

When the specific phenolic compound is 2- [bis {(5-isopropyl-4-hydroxy-2-methyl) phenyl} methyl] phenol, it is preferably 1.0 to 3.0 mol, more preferably 1.5 to 3.0 mol,

Certain phenolic compounds are 1- [1- (3- {1- (4-hydroxyphenyl) -1-methylethyl} -4,6-dihydroxyphenyl) -1-methylethyl] -3- (1- (3- {1- (4-hydroxyphenyl) -1-methylethyl} -4,6-dihydroxyphenyl) -1-methylethyl) benzene or 4,6-bis {1- (4-hydroxy Phenyl) -1-methylethyl} -1,3-dihydroxybenzene, Preferably it is 1.0-2.0 mol.

Examples of the solvent that can be used at this time include ketones and cyclic ethers. Specific examples of these solvents include acetone, methyl ethyl ketone, methyl isoamyl ketone, methyl isobutyl ketone, and the like. Examples of the cyclic ethers include 1,4-dioxane, 1,3,5-trioxane, and the like. In the case of using a solvent, the amount thereof to be used is preferably 100 to 2,000 parts by weight, more preferably 200 to 200 parts by weight based on 100 parts by weight of the total amount of the specific phenolic compound and 1,2-naphthoquinonediazidesulfonic acid halide. 1,000 parts by weight.

A basic compound can be used as said catalyst, Preferably it is triethylamine, tetramethylammonium chloride, tetramethylammonium bromide, pyridine, etc. The usage-amount of these catalysts becomes like this. Preferably it is 1 mol or more with respect to 1 mol of 1, 2- naphthoquinone diazide sulfonic-acid halides, More preferably, it is 1.05-1.2 mol.

The catalyst dropping temperature and the reaction temperature are preferably 0 to 50 ° C, more preferably 0 to 40 ° C, particularly preferably 10 to 35 ° C.

Moreover, reaction time becomes like this. Preferably it is 0.5 to 10 hours, More preferably, it is 1 to 5 hours, Especially 1 to 3 hours are preferable.

After the condensation reaction, the precipitate was removed by filtration, and then the filtrate was poured into a large amount of diluted acid aqueous solution, for example, 0.1 to 3.0 wt% dilute hydrochloric acid aqueous solution to precipitate the reaction product, and the precipitate was filtered to give a neutral filtrate. After washing with water, it is dried and the component [B] can be obtained.

These [B] components can be used individually or in combination of 2 or more types.

The use ratio of the component [B] is preferably 5 to 100 parts by weight, more preferably 10 to 50 parts by weight with respect to 100 parts by weight of the copolymer [A]. When the ratio is less than 5 parts by weight, the difference in solubility between the irradiated portion and the unirradiated portion of the alkaline aqueous solution serving as the developing solution is small, and patterning may be difficult, and the heat resistance of the resulting interlayer insulating film or microlens and Solvent resistance may become insufficient. On the other hand, when this ratio exceeds 100 weight part, the solubility to the said aqueous alkali solution in a radiation part may become inadequate and it may become difficult to develop.

In the present invention, a part of the component [B] can be replaced with a 1,2-quinonediazide compound other than the component [B].

Examples of the 1,2-quinonediazide compounds other than the component [B] include condensates of the following phenolic compounds or alcoholic compounds with 1,2-naphthoquinonediazidesulfonic acid halide.

As a phenolic compound or alcoholic compound which can be used here, for example, trihydroxy benzophenones, tetrahydroxy benzophenones, pentahydroxy benzophenones, hexahydroxy benzophenones, and (polyhydroxyphenyl Alkanes are mentioned.

Specific examples of these include 2,3,4-trihydroxybenzophenone, 2,4,6-trihydroxybenzophenone, and the like as trihydroxybenzophenones;

2,2 ', 4,4'-tetrahydroxybenzophenone, 2,3,4,3'-tetrahydroxybenzophenone, 2,3,4,4'-tetrahydroxy as tetrahydroxybenzophenones Benzophenone, 2,3,4,2'-tetrahydroxy-4'-methylbenzophenone, 2,3,4,4'-tetrahydroxy-3'-methoxybenzophenone and the like;

2,3,4,2 ', 6'-pentahydroxybenzophenone etc. as pentahydroxy benzophenone;

2,4,6,3 ', 4', 5'-hexahydroxybenzophenone, 3,4,5,3 ', 4', 5'-hexahydroxy benzophenone etc. as hexahydroxy benzophenone;

As (polyhydroxyphenyl) alkanes, bis (2,4-dihydroxyphenyl) methane, bis (p-hydroxyphenyl) methane, tri (p-hydroxyphenyl) methane, 1,1,1-tri ( p-hydroxyphenyl) ethane, bis (2,3,4-trihydroxyphenyl) methane, 2,2-bis (2,3,4-trihydroxyphenyl) propane, 1,1,3-tris ( 2,5-dimethyl-4-hydroxyphenyl) -3-phenylpropane, 4,4 '-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] Bisphenol, bis (2,5-dimethyl-4-hydroxyphenyl) -2-hydroxyphenylmethane, 3,3,3 ', 3'-tetramethyl-1,1'-spirobiindene-5,6, 7,5 ', 6', 7'-hexanol, 2,2,4-trimethyl-7,2 ', 4'-trihydroxypraban etc. are mentioned, respectively.

Further, 1,2-naphthoquinone diazide sulfonic acid amides in which the ester bond of the above-described parent nucleus is changed to an amide bond, for example, 2,3,4-trihydroxybenzophenone-1,2-naphthoquinone Diazide-4-sulfonic acid amide etc. are also used preferably.

As the 1,2-naphthoquinone diazide sulfonic acid halide, 1,2-naphthoquinone diazide sulfonic acid chloride is preferable.

When 1,2-quinonediazide compounds other than this [B] component are synthesize | combined by condensation, it can carry out on the conditions similar to the condensation of said component [B].

The 1,2-quinonediazide compounds other than this [B] component can be used individually or in combination of 2 or more types.

In the present invention, when a 1,2-quinonediazide compound other than the [B] component is used together with the component [B], the amount of the 1,2-quinonediazide compound other than the component [B] is [B]. It is 70 weight% or less normally, Preferably it is 65 weight% or less, More preferably, it is 60 weight% or less with respect to the sum total of the usage-amount of a 1, 2- quinonediazide compound other than a component and [B] component. When 1,2-quinonediazide compounds other than [B] component are used exceeding this value, the advantageous effect of this invention, especially high transparency may not be exhibited.

Other ingredients

The radiation-sensitive resin composition of the present invention contains the above-mentioned copolymers [A] and [B] as essential components, but if necessary, [C] a thermosensitive acid-producing compound and [D] at least one ethylenic compound. The polymerizable compound which has an unsaturated double bond, epoxy resins other than [E] copolymer [A], [F] surfactant, or [G] adhesion | attachment adjuvant can be contained.

The said (C) thermosensitive acid production compound can be used in order to improve heat resistance and hardness. Specific examples thereof include onium salts such as sulfonium salts, benzothiazonium salts, ammonium salts and phosphonium salts.

Specific examples of the sulfonium salt include alkylsulfonium salts, benzylsulfonium salts, dibenzylsulfonium salts, substituted benzylsulfonium salts, and the like.

Specific examples thereof include 4-acetophenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium hexafluoroarsenate, and dimethyl-4- (benzyloxy as alkylsulfonium salts. Carbonyloxy) phenylsulfonium hexafluoroantimonate, dimethyl-4- (benzoyloxy) phenylsulfonium hexafluoroantimonate, dimethyl-4- (benzoyloxy) phenylsulfonium hexafluoroarsenate, Dimethyl-3-chloro-4-acetoxyphenylsulfonium hexafluoroantimonate and the like;

Benzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, benzyl-4-hydroxyphenylmethylsulfonium hexafluorophosphate, 4-acetoxyphenylbenzylmethylsulfonium hexafluoroantimo as the benzylsulfonium salt Nate, benzyl-4-methoxyphenylmethylsulfonium hexafluoroantimonate, benzyl-2-methyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, benzyl-3-chloro-4-hydroxy Phenylmethylsulfonium hexafluoroarsenate, 4-methoxybenzyl-4-hydroxyphenylmethylsulfonium hexafluorophosphate and the like;

Dibenzyl-4-hydroxyphenylsulfonium hexafluoroantimonate, dibenzyl-4-hydroxyphenylsulfonium hexafluorophosphate, 4-acetoxyphenyl dibenzylsulfonium hexafluoro antimony as dibenzylsulfonium salt Monate, Dibenzyl-4-methoxyphenylsulfonium hexafluoroantimonate, Dibenzyl-3-chloro-4-hydroxyphenylsulfonium hexafluoroarsenate, dibenzyl-3-methyl-4- Hydroxy-5-tert-butylphenylsulfonium hexafluoroantimonate, benzyl-4-methoxybenzyl-4-hydroxyphenylsulfonium hexafluorophosphate and the like;

P-chlorobenzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, p-nitrobenzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, p-chlorobenzyl- as substituted benzylsulfonium salt 4-hydroxyphenylmethylsulfonium hexafluorophosphate, p-nitrobenzyl-3-methyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, 3,5-dichlorobenzyl-4-hydroxyphenylmethyl Sulfonium hexafluoro antimonate, o-chlorobenzyl-3-chloro-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, and the like.

Specific examples of the benzothiazonium salt include 3-benzylbenzothiazonium hexafluoroantimonate, 3-benzylbenzothiazonium hexafluorophosphate, 3-benzylbenzothiazonium tetrafluoroborate, 3- (p-meth Benzyl, such as oxybenzyl) benzothiazonium hexafluoroantimonate, 3-benzyl-2-methylthiobenzothiazonium hexafluoroantimonate, 3-benzyl-5-chlorobenzothiazonium hexafluoroantimonate A benzothiazonium salt is mentioned.

Among them, sulfonium salts and benzothiazonium salts are preferably used, and 4-acetoxyphenyldimethylsulfonium hexafluoroarsenate, benzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, 4- Acetoxyphenylbenzylmethylsulfonium hexafluoroantimonate, dibenzyl-4-hydroxyphenylsulfonium hexafluoroantimonate, 4-acetoxyphenylbenzylsulfonium hexafluoroantimonate, 3-benzylbenzo Tiazonium hexafluoroantimonate is preferably used.

Examples of these commercially available products include Sunaid SI-L85, SI-L110, SI-L145, SI-L150, and SI-L160 (manufactured by Sanshin Chemical Co., Ltd.).

The use ratio of the component [C] is preferably 20 parts by weight or less, and more preferably 5 parts by weight or less based on 100 parts by weight of the copolymer [A]. When this usage amount exceeds 20 weight part, precipitates may precipitate in a coating film formation process, and may interrupt the coating film formation.

The polymerizable compound having one or more ethylenically unsaturated double bonds of [D] (hereinafter also referred to as "D component") is, for example, monofunctional (meth) acrylate, difunctional (meth) acrylate or trifunctional or more (Meth) acrylate is mentioned preferably.

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 Toa Synthetic), KAYARAD TC-110S, and TC-120S (above, Nippon Kayaku Corporation | KK Co., Ltd., biscoat 158, copper 2311 (above, Osaka Organic Chemical Industry Co., Ltd. product), 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, bisphenoxyethanol fluorene diacrylate, bisphenoxy ethanol fluorene diacrylate, and the like. As these commercial items, for example, Alonics M-210, M-240, M-6200 (above, Toa Synthetic Co., Ltd.), KAYARAD HDDA, HX-220, R-604 (above, Nippon Kayaku Co., Ltd., Biscot 260, 312, 335 HP (above, Osaka Organic Chemical Industry Co., Ltd. product) etc. are mentioned.

As said trifunctional or more than (meth) acrylate, a trimethylol propane tri (meth) acrylate, a pentaerythritol tri (meth) acrylate, a tri ((meth) acryloyloxyethyl) phosphate, a pentaeryte, for example Lithol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, etc. are mentioned, As a commercial item thereof, for example, Alonics M-309, copper M-400, M-405, M-450, M-7100, M-8030, M-8060 (above, manufactured by Doa Synthetic Co., Ltd.), KAYARAD TMPTA, DDP DPHA, DDPCA-20, East 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 Organic Chemical Industrial Co., Ltd.) etc. are mentioned.

Among these, trifunctional or higher (meth) acrylates are preferably used, and trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate and dipentaerythritol hexa (meth) acrylate are particularly preferred. desirable.

These monofunctional, difunctional or trifunctional or more (meth) acrylates are used alone or in combination. The use ratio of the component [D] is preferably 50 parts by weight or less, and more preferably 30 parts by weight or less with respect to 100 parts by weight of the copolymer [A].

By containing [D] component in such a ratio, the heat resistance, surface hardness, etc. of the interlayer insulation film or microlens obtained from the radiation sensitive resin composition of this invention can be improved. When this usage amount exceeds 50 weight part, film roughness may generate | occur | produce in the process of forming the coating film of a radiation sensitive resin composition on a board | substrate.

Epoxy resins other than the above-mentioned [E] copolymer [A] (hereinafter also referred to as "E component") are not limited so long as they do not affect compatibility, but preferably bisphenol A type epoxy resins, phenol novolac type epoxy resins, Cresol novolak-type epoxy resin, cyclic aliphatic epoxy resin, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, heterocyclic epoxy resin, resin which co-polymerized glycidyl methacrylate, etc. are mentioned. have. Among these, bisphenol A type epoxy resins, cresol novolac type epoxy resins, glycidyl ester type epoxy resins, and the like are preferable.

The use ratio of the component [E] is preferably 30 parts by weight or less based on 100 parts by weight of the copolymer [A]. By containing [E] component in such a ratio, the heat resistance, surface hardness, etc. of the protective film or insulating film obtained from the radiation sensitive resin composition of this invention can be improved further. When this ratio exceeds 30 weight part, when forming the coating film of a radiation sensitive resin composition on a board | substrate, the film thickness uniformity of a coating film may become inadequate.

Moreover, although copolymer [A] can also be called "epoxy resin", it differs from [E] component by the point which has alkali solubility.

In the radiation sensitive resin composition of the present invention, the above-mentioned [F] surfactant may be further used in order to improve applicability. As the [F] surfactant that can be used here, a fluorine-based surfactant, a silicone-based surfactant, and a nonionic surfactant can be preferably used.

Specific examples of the fluorine-based surfactant include 1,1.2,2-tetrafluorooctyl (1,1,2.2-tetrafluoropropyl) ether, 1,1,2,2-tetrafluorooctylhexyl ether, and octaethylene glycol Di (1,1,2,2-tetrafluorobutyl) ether, hexaethylene glycol (1,1,2,2,3,3-hexafluoropentyl) ether, octapropylene glycoldi (1,1,2 , 2-tetrafluorobutyl) ether, hexapropylene glycol di (1,1,2,2,3,3-hexafluoropentyl) ether, sodium perfluorododecylsulfonate, 1,1,2,2, Sodium fluoroalkylbenzenesulfonates, in addition to 8,8,9,9,10,10-decafluorododecane, 1,1,2,2,3,3-hexafluorodecane and the like; Fluoroalkyloxyethylene ethers; Fluoroalkylammonium iodides, fluoroalkylpolyoxyethylene ethers, perfluoroalkylpolyoxyethanols; Perfluoroalkyl alkoxylates; Fluorine-based alkyl esters and the like. These commercially available products include BM-1000, BM-1100 (above, manufactured by BM Chemi Corporation), Mega Pack F142D, Copper F172, Copper F173, Copper F183, Copper F178, Copper F191, Copper F471 (above, Dainippon Ink Industries, Inc. Kogyo Co., Ltd.), Flowride FC-170C, FC-171, FC-430, FC-431 (above, Sumitomo 3M Co., Ltd.), Supron S-112, Copper S-113, Copper S-131 , S-141, S-145, S-382, SSC-101, SSC-102, SSC-103, SSC-104, SSC-105, SSC-106 (Asahi Glass Co., Ltd.) ) Manufacture), F-top EF301, copper 303, copper 352 (manufactured by Shin-Kita Chemical Co., Ltd.), SH-28PA, SH-190, SH-193, SZ-6032, SF-8428, DC-57, DC-190 (Toray Dow Corning Silicon Co., Ltd. product) etc. are mentioned.

As said silicone type surfactant, Toray silicon DC3PA, copper DC7PA, copper SH11PA, copper SH21PA, copper SH28PA, copper SH29PA, copper SH30PA, copper FS-1265-300 (above, Toray Dow Corning Silicone Co., Ltd.) Manufactured by TSF-4440, TSF-4300, TSF-4445, TSF-4446, TSF-4460, TSF-4452 (above, GE Toshiba Silicone Co., Ltd. product), etc. are mentioned.

As said nonionic surfactant, For example, polyoxyethylene alkyl ether, such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, 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 No. 57, 95 (made by Kyoeisha Chemical Co., Ltd.), etc. can be used.

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

These [F] surfactants are used with respect to 100 weight part of copolymers [A], Preferably it is 5 weight part or less, More preferably, it is used in 2 weight part or less. When the usage-amount of [F] surfactant exceeds 5 weight part, when a coating film is formed on a board | substrate, the film roughness of a coating film may arise easily.

In the radiation sensitive resin composition of this invention, in order to improve adhesiveness with a base, [G] adhesion | attachment adjuvant can also be used. As this [G] adhesion | attachment adjuvant, a functional silane coupling agent is used preferably, For example, the silane coupling agent which has reactive substituents, such as a carboxyl group, a methacryloyl group, an isocyanate group, an epoxy group, is mentioned. Specifically, trimethoxysilylbenzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanatepropyltriethoxysilane, γ-glycidoxypropyltrimethoxy Silane, (beta)-(3,4-epoxycyclohexyl) ethyltrimethoxysilane, etc. are mentioned. Such [G] adhesion aid is preferably used in an amount of 20 parts by weight or less, and more preferably 10 parts by weight or less, based on 100 parts by weight of the copolymer [A]. When the amount of the adhesion aid exceeds 20 parts by weight, development residues are likely to occur in the development step.

Radiation-sensitive resin composition

The radiation sensitive resin composition of this invention is manufactured by mixing uniformly the above-mentioned copolymer [A] and [B] components, and the other components added arbitrarily as mentioned above. Usually, the radiation sensitive resin composition of this invention is melt | dissolved in a suitable solvent, and is used in a solution state. For example, the radiation sensitive resin composition of a solution state can be manufactured by mixing a copolymer [A] and a [B] component and the other component added arbitrarily at a predetermined ratio.

As a solvent used for manufacture of the radiation sensitive resin composition of this invention, it is a thing which melt | dissolves each component of the copolymer [A] and [B] components, and the other components arbitrarily mix | blended uniformly, and does not react with each component. Used.

As such a solvent, the same thing as what was illustrated as a solvent which can be used in order to manufacture copolymer [A] mentioned above is mentioned.

Among these solvents, glycol ethers, ethylene glycol alkyl ether acetates, esters, and diethylene glycols are preferably used in view of solubility of each component, reactivity with each component, ease of coating film formation, and the like. Among these, diethylene glycol ethyl methyl ether, diethylene glycol dimethyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, methyl methoxy propionate and ethoxy propionic acid ether can be particularly preferably used.

Moreover, in order to raise the in-plane uniformity of a film thickness with the said solvent, you may use together a high boiling point solvent. As a high boiling point solvent which can be used together, for example, N-methylformamide, N, N-dimethylformamide, N-methylformanilide, N-methylacetoamide, N, N-dimethylacetoamide, N-methyl Pyrrolidone, dimethyl sulfoxide, benzyl ethyl ether, dihexyl ether, acetonyl acetone, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, oxalic acid Diethyl, diethyl maleate, gamma -butyrolactone, ethylene carbonate, propylene carbonate, phenyl cellosolve acetate and the like. Among these, N-methylpyrrolidone, γ-butyrolactone, and N, N-dimethylacetoamide 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 may 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. have. When the usage-amount of a high boiling point solvent exceeds this usage-amount, the film thickness uniformity, a sensitivity, and a residual film ratio of a coating film may fall.

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

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

Interlayer insulating film, microlens formation

Next, the method of forming the interlayer insulation film and microlens of this invention using the radiation sensitive resin composition of this invention is stated. The method for forming an interlayer insulating film or microlens of the present invention includes at least the following steps.

(1) forming a coating film of the radiation sensitive composition of the present invention on a substrate;

(2) irradiating at least a part of the coating film with radiation;

(3) developing process, and

(4) heating step.

(1) Process of forming the coating film of the radiation sensitive composition of this invention on a board | substrate

In the process of said (1), the composition solution of this invention is apply | coated to the surface of a board | substrate, and preliminary baking removes a solvent and forms the coating film of a radiation sensitive resin composition.

As a kind of substrate which can be used for this invention, a glass substrate, a silicon wafer, and the board | substrate with which the various metal was formed in these surfaces are mentioned.

It does not specifically limit as a coating method of a composition solution, For example, the appropriate method, such as the spray method, the roll coating method, the rotation coating method, the bar coating method, can be used. As conditions for preliminary baking, although it changes also with the kind, usage ratio, etc. of each component, it is about 30 to 15 minutes at 60-110 degreeC normally.

As a film thickness of the coating film formed, it is a value after prebaking, and when forming an interlayer insulation film, 3-6 micrometers is preferable, and when forming a microlens, 0.5-3 micrometers is preferable.

(2) irradiating at least a part of the coating film with radiation

In the step (2), the formed coating film is irradiated through a mask having a predetermined pattern, and then patterned by removing the irradiated portion of the radiation by developing with a developer. Examples of the radiation used at this time include ultraviolet rays, far ultraviolet rays, X-rays, charged particle beams, and the like.

As said ultraviolet-ray, g line | wire (wavelength 436 nm), i line | wire (wavelength 365 nm), etc. are mentioned, for example. As far ultraviolet rays, KrF excimer laser etc. are mentioned, for example. As X-ray, a synchrotron radiation etc. are mentioned, for example. As a charged particle beam, an electron beam etc. are mentioned, for example.

Among these, ultraviolet rays are preferable, and radiation including g rays and / or i rays is particularly preferable.

As an exposure amount, it is preferable to set it as 50-1,500 J / m <2> when forming an interlayer insulation film, and 50-2,000 J / m <2> when forming a microlens.

(3) developing process

Developers used for the development include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, ammonia, ethylamine, n-propylamine, diethylamine, diethylaminoethanol, di-n-propylamine, tri Ethylamine, methyldiethylamine, dimethylethanolamine, triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, pyrrole, piperidine, 1,8-diazabicyclo [5,4,0]- Aqueous solutions of alkalis, such as 7-undecene and 1, 5- diazabicyclo [4, 3, 0] -5-nonane, can be used. Moreover, the aqueous solution which added water-soluble organic solvents, such as methanol and ethanol, and surfactant in appropriate quantity to the aqueous solution of said alkalis, or the various organic solvent which melt | dissolves the composition of this invention can be used as a developing solution. As the developing method, a suitable method such as a liquid immersion method, a dipping method, a rocking immersion 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 is usually performed between 30 and 120 seconds.

Moreover, since the peeling will generate | occur | produce in the pattern formed when the development time exceeds about 20-25 second at the optimal value in the conventionally known radiation sensitive resin composition, it was necessary to strictly control the development time, but the radiation sensitive resin composition of this invention In this case, even if the excess time from the optimum developing time is 30 seconds or more, good pattern formation is possible, and there is an advantage in product yield.

(4) heating process

The patterned thin film after the (3) developing step performed as described above is preferably subjected to a washing process by, for example, running water washing, and more preferably irradiating the entire surface with radiation by a high pressure mercury lamp or the like (after Exposure) to decompose the 1,2-quinonediazide compound remaining in the thin film, and then heat-process (post-calcination) the thin film by a heating apparatus such as a hot plate or an oven to cure the thin film. The process is performed. The exposure amount in the said post-exposure process becomes like this. Preferably it is about 2,000-5,000 J / m <2>. In addition, the baking temperature in this hardening process is 120-250 degreeC, for example. Although heating time changes with kinds of heating apparatus, it can be set as 5 to 30 minutes, when carrying out heat processing on a hotplate, for example, and 30 to 90 minutes when carrying out heat processing in an oven. At this time, the step firing method etc. which perform two or more heating processes 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 is apparent from the Examples described later.

Interlayer insulation film

The interlayer insulating film of the present invention formed as described above has good adhesion to a substrate, excellent solvent resistance and heat resistance, high transmittance and low dielectric constant, and can be suitably used as an interlayer insulating film for electronic components.

Microlens

The microlens of the present invention formed as described above has good adhesion to a substrate, excellent solvent resistance and heat resistance, and high transmittance and good melt shape, and can be suitably used as a microlens of a solid-state imaging device. have.

The microlens of the present invention has a semiconvex lens shape as shown in Fig. 1A.

<Example>

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

Synthesis Example of Copolymer [A]

Synthesis Example 1

In a flask equipped with a cooling tube and a stirrer, 10 parts by weight of 2,2'-azobis (2,4-dimethylvaleronitrile) and 250 parts by weight of diethylene glycol ethylmethyl ether were added. 5 parts by weight of styrene, 22 parts by weight of methacrylic acid, 28 parts by weight of tricyclo [5.2.1.0 ^2,6 ] decane-8-ylmethacrylate, 45 parts by weight of glycidyl methacrylate and α-methylstyrene After adding 5 parts by weight of dimer and replacing with nitrogen, stirring was started gently. The temperature of the solution was raised to 70 ° C., and this temperature was maintained for 4 hours to obtain a polymer solution containing the copolymer [A-1].

The polystyrene reduced weight average molecular weight (Mw) of the copolymer [A-1] was 8,000. In addition, the solid content concentration of the polymer solution obtained here was 29.8 weight%.

Synthesis Example 2

In a flask equipped with a cooling tube and a stirrer, 7 parts by weight of 2,2'-azobis (2,4-dimethylvaleronitrile) and 200 parts by weight of diethylene glycol ethylmethyl ether were added. 18 parts by weight of methacrylic acid, 6 parts by weight of styrene, 10 parts by weight of tricyclo [5.2.1.0 ^2,6 ] decane-8-ylmethacrylate, 33 parts by weight of glycidyl methacrylate, p-vinylbenzyl 33 parts by weight of glycidyl ether and 3 parts by weight of α-methylstyrene dimer were added thereto, followed by nitrogen substitution, followed by gentle stirring. The temperature of the solution was raised to 70 ° C., and this temperature was maintained for 5 hours to obtain a polymer solution containing a copolymer [A-2].

The polystyrene reduced weight average molecular weight (Mw) of the copolymer [A-2] was 11,000. In addition, the solid content concentration of the polymer solution obtained here was 31.5 weight%.

Synthesis Example 3

In a flask equipped with a cooling tube and a stirrer, 6 parts by weight of 2,2'-azobis (2,4-dimethylvaleronitrile) and 200 parts by weight of diethylene glycol ethylmethyl ether were added. Then 7 parts by weight of methacrylic acid, 27 parts by weight of glycidyl methacrylate, 6 parts by weight of tricyclo [5.2.1.0 ^2,6 ] decane-8-ylmethacrylate, p-vinylbenzyl glycidyl ether 30 By weight, 30 parts by weight of 2-hydroxyethyl methacrylate and 3 parts by weight of α-methylstyrene dimer were added thereto, followed by nitrogen substitution, followed by gentle stirring. The temperature of the solution was raised to 70 ° C., and this temperature was maintained for 4.5 hours to obtain a polymer solution containing the copolymer [A-3].

The polystyrene reduced weight average molecular weight (Mw) of the copolymer [A-3] was 13,000. Moreover, the solid content concentration of the polymer solution obtained here was 32.7 weight%.

Synthesis Example 4

8.5 parts by weight of 2,2'-azobis (2,4-dimethylvaleronitrile) and 220 parts by weight of diethylene glycol ethylmethyl ether were placed in a flask equipped with a cooling tube and a stirrer. 15 parts by weight of methacrylic acid, 35 parts by weight of glycidyl methacrylate, 30 parts by weight of tricyclo [5.2.1.0 ^2,6 ] decane-8-ylmethacrylate, and 10 parts of p-vinylbenzyl glycidyl ether Part by weight, 10 parts by weight of n-lauryl methacrylate and 3 parts by weight of α-methylstyrene dimer were added thereto, followed by nitrogen substitution, followed by gentle stirring. The temperature of the solution was raised to 70 ° C., and this temperature was maintained for 4.5 hours to obtain a polymer solution including the copolymer [A-4].

The weight average molecular weight (Mw) of copolymers [A-4] was 8,000. In addition, the solid content concentration of the polymer solution obtained here was 31.5 weight%.

Synthesis Example of Component

Synthesis Example 5

36.41 g of 2-methyl-2- (2,4-dihydroxyphenyl) -4- (4-hydroxyphenyl) -7-hydroxychroman in a flask equipped with a stirrer, a dropping port and a thermometer under light shielding ( 100 mmol), 85.49 g (300 mmol) of 1,2-naphthoquinone diazide-5-sulfonic acid chloride and 735 mL of acetone were added and dissolved homogeneously. Subsequently, 33.37 g (330 mmol) of triethylamine was added dropwise over 30 minutes while maintaining the temperature of the solution at 20 to 30 ° C, followed by reacting at the same temperature for 2 hours.

The precipitate was removed by filtration, the filtrate was poured into a large excess of 1% by weight aqueous hydrochloric acid solution to precipitate the product, which was separated by filtration, washed with water until the filtrate became neutral, and then washed at 40 ° C. in a vacuum dryer for one day. Dried to [B-1] (2-methyl-2- (2,4-dihydroxyphenyl) -4- (4-hydroxyphenyl) -7-hydroxychroman (1.0 mol) and 1,2- Condensate of naphthoquinonediazide-5-sulfonic acid chloride (3.0 mol)).

Synthesis Examples 6 to 8

The synthesis and the amount of the specific phenol compound and the amount of 1,2-naphthoquinone diazide-5-sulfonic acid chloride in Synthesis Example 5 were carried out in the same manner as in Synthesis Example 5, except that [B- 2] to [B-4].

Synthesis Example of 1,2-quinonediazide compounds other than [B] component

Synthesis Examples 9 and 10

In Synthesis Example 5, the amount of 1,2-naphthoquinone diazide-5-sulfonic acid chloride used in the amount of the phenolic compounds shown in Table 1 below in Table 1 in place of the specific phenolic compounds is shown in Table 1. [B-5] and [b-6] were obtained in the same manner as in Synthesis example 5 except for the above.

<Example 1>

[Manufacture of a radiation sensitive resin composition]

A solution containing polymer [A-1] as the component [A] synthesized in Synthesis Example 1 above, as an amount corresponding to 100 parts by weight of the polymer [A-1] (solid content), and the component [B] above 20 parts by weight of [B-1] synthesized in 5 was dissolved in diethylene glycol ethyl methyl ether so that the solid content concentration was 30% by weight, and then filtered through a membrane filter having a diameter of 0.2 µm to obtain a solution of the radiation-sensitive resin composition ( S-1) was prepared.

<Examples 2 to 9>

[Manufacture of a radiation sensitive resin composition]

In Example 1, it carried out similarly to Example 1 except having used the kind and quantity shown in following Table 2 as a component [A] and a component [B], and the solution (S-2)-(of a radiation sensitive resin composition) S-9) was prepared.

In addition, in Examples 5-9, description of [B] component shows using 2 types of 1,2-quinonediazide compounds together, respectively.

<Examples 10 to 18, Comparative Examples 1 and 2>

<Performance evaluation as an interlayer insulation film>

The various characteristics as an interlayer insulation film were evaluated as follows using the radiation sensitive resin composition manufactured as mentioned above. In addition, the composition used by Comparative Examples 1 and 2 is a commercial item (made by Tokyo Oka Co., Ltd.) of the composition of m / p-cresol novolak and 1,2-naphthoquinone diazide-5-sulfonic acid ester.

[Evaluation of sensitivity]

After applying the composition of Table 3 to a silicon substrate using a spinner, it prebaked at 90 degreeC for 2 minutes on the hotplate, and formed the coating film of 3.0 micrometers in film thicknesses. After exposure by changing exposure time with Canon PLA-501F exposure machine (ultra high pressure mercury lamp) through the pattern mask which has a predetermined | prescribed pattern to the obtained coating film, it was made into the tetramethylammonium hydroxide aqueous solution of the density | concentration shown in Table 3. It was developed by liquid immersion at 25 ° C. for 90 seconds. The resultant was washed with ultrapure water for 1 minute and dried to form a pattern on the wafer. The exposure amount required for complete dissolution of the space pattern of the line and space (10: 1) of 3.0 mu m was measured. This value is shown in Table 3 as the sensitivity. When this value is 1000 J / m <2> or less, it can be said that a sensitivity is favorable.

[Evaluation of development margin]

After applying the composition shown in Table 3 using a spinner on a silicon substrate, it was prebaked at 90 DEG C on a hot plate for 2 minutes to form a coating film having a film thickness of 3.0 mu m. In the "[evaluation of sensitivity]" using the PLA-501F exposure machine (ultra-high pressure mercury lamp) by Canon Corp. via the mask which has a pattern of a line and space (10: 1) of 3.0 micrometers in the obtained coating film. It exposed at the exposure amount corresponded to the value of the measured sensitivity, and it developed by the liquid immersion method at 25 degreeC for 90 second with the tetramethylammonium hydroxide aqueous solution of the density | concentration shown in Table 3. Subsequently, flowing water was washed with ultrapure water for 1 minute and dried to form a pattern on the wafer. At this time, the developing time required for the line width to be 3 占 퐉 is shown in Table 3 as the optimum developing time. In addition, the time from the optimum development time to further development of the 3.0 탆 line pattern was measured and shown in Table 3 as the development margin. When this value is 30 second or more, it can be said that a developing margin is favorable.

[Evaluation of solvent resistance]

After applying the composition shown in Table 3 using a spinner on a silicon substrate, it was prebaked at 90 DEG C on a hot plate for 2 minutes to form a coating film having a film thickness of 3.0 mu m. The obtained coating film was exposed so that accumulated irradiation amount might be 3,000 J / m <2> by Canon PLA-501F exposure machine (ultra high pressure mercury lamp), and this silicon substrate was heated in 220 degreeC for 1 hour, and the cured film was obtained. The film thickness (T1) of the obtained cured film was measured. After the silicon substrate on which the cured film was formed was immersed in dimethyl sulfoxide for 20 minutes at a temperature controlled at 70 ° C., the film thickness t1 of the cured film was measured, and the film thickness change rate by immersion {| t1-T1 | / T1} × 100 [%] was calculated. The results are shown in Table 4 below. It can be said that solvent resistance is favorable when this value is 5% or less.

In the evaluation of solvent resistance, since the patterning of the formed film is unnecessary, the radiation irradiation step and the developing step were omitted, and only the coating film forming step, the post-firing step and the heating step were used for evaluation.

[Evaluation of Heat Resistance]

In the same manner as the above evaluation of the solvent resistance, a cured film was formed, and the film thickness (T2) of the obtained cured film was measured. Subsequently, after further baking this cured film board | substrate at 240 degreeC in the clean oven for 1 hour, the film thickness (t2) of this cured film was measured, and the film thickness change rate by further baking {| t2-T2 | / T2} x 100 [%] was calculated. The results are shown in Table 4. When this value is 5% or less, it can be said that heat resistance is favorable.

[Evaluation of transparency]

In evaluating the above solvent resistance, a cured film was formed on the glass substrate in the same manner except that a glass substrate "Corning 7059 (manufactured by Corning)" was used in place of the silicon substrate. The light transmittance of the glass substrate which has this cured film was measured at the wavelength of 400-800 nm using the spectrophotometer "150-20 type double beam (the Hitachi company make)." Table 4 shows the values of the minimum light transmittance at this time. When this value is 95% or more, transparency can be said to be favorable.

[Evaluation of relative dielectric constant]

The composition shown in Table 3 was apply | coated using the spinner on the board | substrate made from SUS304 polished, and it baked preliminarily on a hotplate at 90 degreeC for 2 minutes, and formed the coating film of 3.0 micrometers in film thicknesses. The cured film was obtained by exposure to the obtained coating film so that the accumulated irradiation amount might be 3.000 J / m <2> with Canon PLA-501F exposure machine (ultra high pressure mercury lamp), and baking this board | substrate at 220 degreeC in clean oven for 1 hour.

About this cured film, the Pt / Pd electrode pattern was formed by the vapor deposition method, and the sample for dielectric constant measurement was produced. The dielectric constant of the board | substrate was measured by CV method using this board | substrate at the frequency of the frequency of 10 kHz using the HP16451B electrode manufactured by Yokogawa Hewlett-Packard Co., Ltd., and the HP4284A Precision LCR meter. The results are shown in Table 4. It can be said that the dielectric constant is good when this value is 3.6 or less.

In the evaluation of the dielectric constant, since the patterning of the formed film is unnecessary, the irradiation step and the developing step were omitted, and only the coating film forming step, the post-firing step and the heating step were used for evaluation.

[Evaluation of Adhesiveness]

In the same manner as in the above evaluation of transparency, a cured film was formed on a glass substrate "Corning 7059 (manufactured by Corning)". After performing a pressure cooker test (120 degreeC, 100% of humidity, 4 hours) with respect to the glass substrate which has this cured film, adhesive evaluation was performed according to the JISK5400 check tape method.

Table 4 shows the number of the remaining checkers without peeling among the 100 checkers.

<Examples 19 to 27, Comparative Examples 3 and 4>

<Evaluation as a micro lens>

Using the radiation sensitive resin composition prepared as described above, various characteristics as microlenses were evaluated as follows. In addition, evaluation of heat resistance, evaluation of transparency, and evaluation of adhesiveness can refer to the result in performance evaluation as the said interlayer insulation film.

In addition, the composition used by the comparative examples 3 and 4 are all the commercial items (made by Tokyo Oka Co., Ltd.) of the composition of m / p-cresol novolak and 1,2-naphthoquinone diazide-5-sulfonic acid ester.

[Evaluation of sensitivity]

After applying the composition shown in Table 5 on the silicon substrate using a spinner, it was prebaked on a hot plate at 90 ° C. for 2 minutes to form a coating film having a film thickness of 3.0 μm. The exposure time was changed by the Nikon Corporation NSR 1755i7A reduced projection exposure machine (NA = 0.50, (lambda == 365 nm) through the pattern mask which has a predetermined | prescribed pattern to the obtained coating film, and it exposed, and the tetramethylammonium of the density shown in Table 3 was exposed. It developed by the liquid immersion method at 25 degreeC with hydroxide aqueous solution for 1 minute. Washed with water and dried to form a pattern on the wafer. The exposure time required for the space line width of the 0.8 μm line and space pattern (1: 1) to be 0.8 μm was measured. This value is shown in Table 5 as the sensitivity. When this value is 2,500 J / m <2> or less, it can be said that a sensitivity is favorable.

[Evaluation of development margin]

After applying the composition of Table 5 to a silicon substrate using a spinner, it prebaked at 90 degreeC for 2 minutes on the hotplate, and formed the coating film of 3.0 micrometers in film thicknesses. It corresponds to the value of the sensitivity measured by said "[evaluation of sensitivity]" with the Nikon Corporation NSR 1755i7A reduction projection exposure machine (NA = 0.50, (lambda == 365 nm) through the pattern mask which has a predetermined | prescribed pattern in the obtained coating film. It exposed at the exposure amount and developed by the liquid immersion method in 25 degreeC for 1 minute with tetramethylammonium hydroxide aqueous solution of the density | concentration shown in Table 4. Washed with water and dried to form a pattern on the wafer. Table 5 shows the development time necessary for the space line width of the 0.8 µm line-and-space pattern (1: 1) to be 0.8 µm. Moreover, the time (development margin) until the pattern of width 0.8 micrometer peels when the image development is continued further from the optimal image development time was measured, and it shows in Table 5 as a development margin. When this value is 30 second or more, it can be said that a developing margin is favorable.

[Evaluation of solvent resistance]

After applying the composition of Table 5 to a silicon substrate using the spinner, it prebaked at 90 degreeC for 2 minutes on the hotplate, and formed the coating film of 3.0 micrometers in film thicknesses. The obtained coating film was exposed so that accumulated irradiation amount might be 3,00 J / m <2> by Canon PLA-501F exposure machine (ultra-high pressure mercury lamp), and this silicon substrate was heated in 220 degreeC for 1 hour, and the cured film was heated. Got it. The film thickness (T3) of the obtained cured film was measured. After the silicon substrate on which the cured film was formed was immersed in isopropyl alcohol temperature controlled at 50 ° C. for 10 minutes, the film thickness t3 of the cured film was measured, and the film thickness change rate due to the immersion {| t3-T3 | / T3} × 100 [%] was calculated. The results are shown in Table 5.

In the evaluation of solvent resistance, since the patterning of the formed film is unnecessary, the radiation irradiation step and the developing step were omitted, and only the coating film forming step, the post-firing step and the heating step were used for evaluation.

[Formation of Micro Lens]

After applying the composition of Table 5 to a silicon substrate using a spinner, it prebaked at 90 degreeC for 2 minutes on the hotplate, and formed the coating film of 3.0 micrometers in film thicknesses. The obtained coating film was subjected to a pattern mask having a 4.0 µm dot and 2.0 µm space pattern, and the sensitivity measured in the "[evaluation of sensitivity]" by a Nikon Corporation NSR1755i7A reduced projection exposure machine (NA = 0.50, λ = 365 nm). It exposed at the exposure amount corresponding to a value, and it developed by the liquid immersion method at 25 degreeC for 1 minute in tetramethylammonium hydroxide aqueous solution of the density | concentration described as the developer concentration in evaluation of the sensitivity of Table 4. Washed with water and dried to form a pattern on the wafer. Then, it exposed by the Canon Co., Ltd. make PLA-501F exposure machine (ultra 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 flow the pattern to form a microlens.

Table 5 shows the dimensions (diameter) and the cross-sectional shape of the bottom (surface in contact with the substrate) of the formed microlenses. The dimension of the microlens bottom may be said to be good when it exceeds 4.0 μm and below 5.0 μm. Moreover, when this dimension is 5.0 micrometers or more, it will be in the state which adjoins adjacent lenses, and is unpreferable. In addition, in the schematic diagram shown in Fig. 1, the cross-sectional shape is good when the shape is a semi-convex lens such as (a). If the shape cannot be observed, it is defective.

The radiation-sensitive resin composition of the present invention has a high radiation sensitivity, has a developing margin that can still form a good pattern shape even after exceeding the optimum developing time in the developing step, and can easily form a patterned thin film excellent in adhesion. Can be.

The interlayer insulating film of the present invention formed from the above composition has good adhesion to a substrate, excellent solvent resistance and heat resistance, high transmittance and low dielectric constant, and can be suitably used as an interlayer insulating film of an electronic component.

In addition, the microlenses of the present invention formed from the upper composition have good adhesion to the substrate, are excellent in solvent resistance and heat resistance, and have high transmittance and good melt shape, and can be suitably used as microlenses of solid-state imaging devices. have.

Claims (7)

[A] (a1) unsaturated carboxylic acid and / or unsaturated carboxylic anhydride, (a2) epoxy group-containing unsaturated compounds, and (a3) copolymers of olefinically unsaturated compounds other than (a1) and (a2), and [B] 2-methyl-2- (2,4-dihydroxyphenyl) -4- (4-hydroxyphenyl) -7-hydroxychroman, 2- [bis {(5-isopropyl-4- Hydroxy-2-methyl) phenyl} methyl] phenol, 1- [1- (3- {1- (4-hydroxyphenyl) -1-methylethyl} -4,6-dihydroxyphenyl) -1- Methylethyl] -3- (1- (3- {1- (4-hydroxyphenyl) -1-methylethyl} -4,6-dihydroxyphenyl) -1-methylethyl) benzene and 4,6- Containing a condensate of at least one selected from bis {1- (4-hydroxyphenyl) -1-methylethyl} -1,3-dihydroxybenzene and 1,2-naphthoquinonediazidesulfonic acid halide A radiation sensitive resin composition characterized by the above-mentioned. The radiation sensitive resin composition according to claim 1, wherein the radiation sensitive resin composition is for forming an interlayer insulating film. (1) process of forming the coating film of the radiation sensitive resin composition of Claim 2 on a board | substrate, (2) irradiating at least a part of the coating film with radiation; (3) developing process, and (4) A method of forming an interlayer insulating film, comprising at least a heating step. An interlayer insulating film formed by the method of claim 3. The radiation sensitive resin composition according to claim 1, wherein the radiation sensitive resin composition is for forming a microlens. (1) Process of forming the coating film of radiation sensitive resin composition of Claim 5 on a board | substrate, (2) irradiating at least a part of the coating film with radiation; (3) developing process, and (4) A method for forming a microlens, comprising at least a heating step. A microlens formed by the method of claim 6.