KR20080080453A - Radiation-sensitive resin composition, interlayer insulation film and microlens, and process for producing them - Google Patents

Abstract

A radiation-sensitive resin composition is provided to realize high radiation sensitivity, to form a high-quality pattern shape even when a development step is performed for over the optimal development time, and to form a patterned thin film with excellent adhesion. A radiation-sensitive resin composition comprises: [A] a copolymer of (a1) at least one selected from unsaturated carboxylic acids and anhydrides thereof, (a2) an unsaturated compound containing at least one of epoxy and oxetanyl, (a3) at least one selected from acryloylmorpholine and methacryloylmorpholine, and (a4) at least one unsaturated compound other than (a1), (a2) and (a3), selected from alkyl methacrylate, cycloalkyl methacrylate, alkyl acrylate, cycloalkyl acrylate, aryl acrylate, aryl methacrylate, unsaturated dicarboxylate, hydroxymethacrylate, hydroxylacrylate, bicyclic unsaturated compounds, maleimide compounds, unsaturated aromatic compounds, conjugated dienes, unsaturated compounds having a tetrahydropyran backbone, unsaturated compounds having a furan backbone, unsaturated compounds having a tetrahydropyran backbone, unsaturated compounds having a pyran backbone, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide and vinyl acetate; and [B] 1,2-quinonediazide compound.

Description

Radiation-sensitive resin composition, interlayer insulating film and microlens, and manufacturing method thereof {RADIATION-SENSITIVE RESIN COMPOSITION, INTERLAYER INSULATION FILM AND MICROLENS, AND PROCESS FOR PRODUCING THEM}

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 image pickup elements are generally provided with an interlayer insulating film to insulate between layers arranged in layers. have. 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 (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 further forming a liquid crystal alignment film thereon, so that the interlayer insulating film is used in the process of forming a transparent electrode film. In order to be exposed to high temperature conditions or to the stripper 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 the 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, high performance is required.

On the other hand, a microlens having a lens diameter of about 3 to 100 µm or a microlens as an optical system material of an imaging optical system of an on-chip color filter such as a facsimile, an electron copier, a solid-state imaging device, or an optical fiber connector is regularly used. The microlens array arranged in this manner is used.

To form a microlens or microlens array, a resist pattern corresponding to a lens is formed and then melt-flowed by heat treatment to be used as a lens, or by a dry etching using a melt-flowed lens pattern as a mask. The method of transferring a shape is known. The radiation sensitive resin composition is widely used for formation of the said lens pattern (refer Unexamined-Japanese-Patent No. 6-18702 and Unexamined-Japanese-Patent No. 6-136239).

By the way, the device in which the microlens or the microlens array is formed as described above is then coated with a planarization film and an etching resist film to remove various insulating films on the bonding pads, which are wiring forming portions, and is exposed and developed using a desired mask. To remove the etching resist of the bonding pad portion, and then to remove the planarization film and various insulating films by etching to expose the bonding pad portion. Therefore, solvent resistance and heat resistance are required for the microlens or 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 in this way, if the developing time exceeds a little more than the optimum time, the developing solution penetrates easily between the pattern and the substrate, causing easy peeling. It is necessary to strictly control the problem, 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 be highly sensitive, and in the developing step during the forming step, pattern peeling does not occur even when the developing time is more than a predetermined time. High heat resistance, high solvent resistance, low dielectric constant, high transmittance, high adhesion, etc. are required for the interlayer insulating film formed therefrom, while exhibiting good adhesion. Radius), high heat resistance, high solvent resistance, and high transmittance are required. There is no known radiation-sensitive resin composition that satisfies such a requirement.

This invention is made | formed based on the above circumstances. Therefore, an object of the present invention is to provide a patterned thin film having high radiation sensitivity, having a developing margin which can still form a good pattern shape even when the optimum developing time is exceeded in the developing process, and having excellent adhesion. It is to provide a radiation sensitive composition.

Another object of the present invention is to form an interlayer insulating film having high heat resistance, high solvent resistance, high transmittance, low dielectric constant, and high adhesion when used for forming an interlayer insulating film, and high when used for forming a microlens. It is providing the radiation sensitive resin composition which can form the microlens which has a transmittance | permeability and a favorable melt shape.

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

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, firstly,

(A) (a1) one or more selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic anhydrides (hereinafter sometimes referred to as "compound (a1)"),

(a2) unsaturated compounds containing at least one of an epoxy group and an oxetanyl group (hereinafter sometimes referred to as "compound (a2)"),

(a3) at least one selected from the group consisting of acryloyl morpholine and methacryloyl morpholine (hereinafter sometimes referred to as "compound (a3)")

(a4) Methacrylic acid alkyl ester, methacrylic acid cyclic alkyl ester, acrylic acid alkyl ester, acrylic acid cyclic alkyl ester, acrylic acid aryl ester, methacrylic, different from all of the compounds (a1), (a2) and (a3). Acid aryl ester, unsaturated dicarboxylic acid diester, hydroxymethacrylic acid ester, hydroxyacrylic acid ester, bicyclo unsaturated compound, maleimide compound, unsaturated aromatic compound, conjugated diene, unsaturated compound having tetrahydrofuran skeleton, furan skeleton In the group consisting of an unsaturated compound having a compound, an unsaturated compound having a tetrahydropyran skeleton, an unsaturated compound having a pyran skeleton, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide and vinyl acetate One or more other unsaturated compounds selected (hereinafter "compound (a4)") If a copolymer (hereinafter, referred to "copolymer [A]") for that), and

[B] 1,2-quinonediazide compound (hereinafter sometimes referred to as "[B] component")

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

The objects and advantages of the present invention are second,

The following steps are included in the order described below, which is achieved by a method for forming an interlayer insulating film or microlens.

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

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

(3) developing process, and

(4) heating step.

In addition, the object and advantages of the present invention is third,

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

The present invention provides a radiation sensitive composition having high radiation sensitivity, having a development margin that can still form a good pattern shape even when the optimum development time is exceeded in the development process, and easily forming a patterned thin film excellent in adhesion. To provide.

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), compound (a3) and compound (a4) in the presence of a polymerization initiator in a solvent.

The compound (a1) is one or more selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic anhydrides having radical polymerizability, for example, anhydrides of monocarboxylic acids, dicarboxylic acids and dicarboxylic acids. And mono [(meth) acryloyloxyalkyl] esters of polyhydric carboxylic acids, mono (meth) acrylates of polymers having carboxyl groups and hydroxyl groups at both ends, polycyclic compounds having carboxyl groups, and anhydrides thereof. .

As these specific examples, As monocarboxylic acid, For example, acrylic acid, methacrylic acid, crotonic acid, etc .;

As the dicarboxylic acid, for example, maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid and the like;

As anhydride of dicarboxylic acid, For example, anhydride of the compound illustrated as said dicarboxylic acid;

As mono [(meth) acryloyloxyalkyl] ester of polyhydric carboxylic acid, For example, monosuccinate mono [2- (meth) acryloyloxyethyl], mono phthalate [2- (meth) acryloyloxyethyl ] Etc;

As mono (meth) acrylate of the polymer which has a carboxyl group and a hydroxyl group in both terminal, For example, (omega) -carboxypolycaprolactone mono (meth) acrylate etc .;

As the polycyclic compound having a carboxyl group and anhydrides thereof, for example, 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. Each can be mentioned.

Among them, anhydrides of monocarboxylic acid and dicarboxylic acid are preferably used, and acrylic acid, methacrylic acid and maleic anhydride are particularly preferably used in view of copolymerization reactivity, solubility in an aqueous alkali solution and availability. These compounds (a1) are used individually or in combination.

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 compounds (a1), (a2), (a3) and (a4). Preferably it is 1 to 80% by weight, particularly preferably 5 to 40% by weight. When this structural unit is less than 1 weight%, there exists a tendency for the adhesiveness of the interlayer insulation film and microlenses obtained to fall, and when the quantity of this structural unit exceeds 80 weight%, the storage stability of a radiation sensitive resin composition will be It tends to be lowered.

Compound (a2) is an unsaturated compound containing at least one of an epoxy group and an oxetanyl group which have radical polymerizability.

As an epoxy-group-containing unsaturated compound, glycidyl acrylate, glycidyl methacrylate, the glycidyl (alpha)-ethyl acrylate, the glycidyl (alpha)-n-propyl acrylate, the glycidyl (alpha)-n-butyl acrylate, and acrylic acid are mentioned, for example. -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-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether and the like. Of these, methacrylic acid glycidyl, methacrylic acid-6,7-epoxyheptyl, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether, 3,4 -Epoxycyclohexyl methacrylate etc. are used preferably at the point which raises heat resistance and surface hardness of copolymerization reactivity and the obtained interlayer insulation film or microlens.

As an epoxy group containing unsaturated compound, 3- (methacryloyloxymethyl) oxetane, 3- (methacryloyloxymethyl) -3-ethyl oxetane, 3- (methacryloyloxymethyl)-, for example 2-methyl oxetane, 3- (methacryloyloxymethyl) -2-trifluoromethyloxetane, 3- (methacryloyloxymethyl) -2-pentafluoroethyloxetane, 3- (meta Chryloyloxymethyl) -2-phenyloxetane, 3- (methacryloyloxymethyl) -2,2-difluorooxetane, 3- (methacryloyloxymethyl) -2,2,4 -Trifluorooxetane, 3- (methacryloyloxymethyl) -2,2,4,4-tetrafluorooxetane, 3- (methacryloyloxyethyl) oxetane, 3- (methacryl Loyloxyethyl) -3-ethyloxetane, 2-ethyl-3- (methacryloyloxyethyl) oxetane, 3- (methacryloyloxyethyl) -2-trifluoromethyloxetane, 3 -(Methacryloyloxyethyl) -2-pentafluoroethyloxetane, 3- (methacryloyloxyethyl) -2-phenyloxetane, 2,2-difluoro-3- ( Methacryloyloxyethyl) oxetane, 3- (methacryloyloxyethyl) -2,2,4-trifluorooxetane, 3- (methacryloyloxyethyl) -2,2,4, 4-tetrafluorooxetane etc. are mentioned. These compounds (a2) are used alone or in combination.

The copolymer [A] used in the present invention is preferably a structural unit derived from the compound (a2) based on the sum of the repeating units derived from the compounds (a1), (a2), (a3) and (a4). Preferably from 5 to 70% by weight, particularly preferably from 10 to 60% by weight. When this structural unit is less than 5 weight%, there exists a tendency for the heat resistance, sclerosis | hardenability, and surface hardness of a radiation sensitive resin composition to fall, and when it exceeds 70 weight%, there exists a tendency for the storage stability of a radiation sensitive resin composition to fall. have.

Compound (a3) is acryloyl morpholine and / or methacryloyl morpholine.

In a compound (a3), acryloyl morpholine can improve a polymerization conversion rate by copolymerizing with the acrylate in the other unsaturated compound represented by a compound (a4). As these specific examples, for example, methyl acrylate, ethyl acrylate, n-propyl acrylate, i-propyl acrylate, n-butyl acrylate, sec-butyl acrylate, t-butyl acrylate, cyclohexyl acryl Latex, 2-methylcyclohexylacrylate, tricyclo [5.2.1.0 ^2,6 ] decane-8-ylacrylate (hereinafter referred to as "dicyclopentanylacrylate"), tricyclo [5.2.1.0 ^2,6 ] Decan-8-yloxyethyl acrylate, isobornyl acrylate, phenyl acrylate, benzyl acrylate, tetrahydrofurfuryl acrylate, 3-acryloyloxy tetrahydrofuran-2-one, furfuryl acryl The rate etc. are mentioned.

The copolymer [A] used in the present invention is preferably a structural unit derived from the compound (a3) based on the sum of the repeating units derived from the compounds (a1), (a2), (a3) and (a4). Preferably 1 to 50% by weight, particularly preferably 1 to 30% by weight. When this structural unit exceeds 50 weight%, there exists a tendency for the storage stability of a radiation sensitive resin composition to fall.

Compound (a4) is an unsaturated compound having radical polymerizability, and is alkyl methacrylate, methacrylic acid cyclic alkyl ester, acrylic acid alkyl ester, acrylic acid cyclic alkyl ester, acrylic acid aryl ester, methacrylic acid aryl ester, unsaturated dicar Acid diester, hydroxymethacrylic acid ester, hydroxyacrylic acid ester, bicyclo unsaturated compound, maleimide compound, unsaturated aromatic compound, conjugated diene, tetrahydrofuran skeleton, furan skeleton, tetrahydropyran skeleton or pyran skeleton Unsaturated compounds or other unsaturated compounds.

As methacrylic acid alkyl ester, for example, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate, t-butyl methacrylate, 2-ethylhexyl methacrylate, iso Decyl methacrylate, n-lauryl methacrylate, tridecyl methacrylate, n-stearyl methacrylate, and the like; As the cyclic ester of methacrylic acid, for example, cyclohexyl methacrylate, 2-methylcyclohexyl methacrylate, tricyclo [5.2.1.0 ^2,6 ] decane-8-ylmethacrylate (hereinafter referred to as "dicyclo Fentanyl methacrylate "), tricyclo [5.2.1.0 ^2,6 ] decane-8-yloxyethyl methacrylate, isobornyl methacrylate and the like; As alkyl acrylate, For example, methyl acrylate, ethyl acrylate, n-propyl acrylate, i-propyl acrylate, n-butyl acrylate, sec-butyl acrylate, t-butyl acrylate, etc .; As a cyclic ester of acrylic acid, for example, cyclohexyl acrylate, 2-methylcyclohexyl acrylate, tricyclo [5.2.1.0 ^2,6 ] decane-8-yl acrylate (hereinafter referred to as "dicyclopentanyl acrylate" Tricyclo [5.2.1.0 ^2,6 ] decane-8-yloxyethyl acrylate, isoboroyl acrylate and the like; As acrylic acid aryl ester, For example, phenyl acrylate, benzyl acrylate; As methacrylic acid aryl ester, For example, phenyl methacrylate, benzyl methacrylate; As unsaturated dicarboxylic acid diester, For example, diethyl maleate, diethyl fumarate, diethyl itaconic acid; As hydroxy methacrylate ester, For example, hydroxymethyl methacrylate, 2-hydroxyethyl methacrylate, 3-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, diethylene glycol mono Methacrylate, 2,3-dihydroxypropyl methacrylate, 2-methacryloxyethyl glycoside, 4-hydroxyphenyl methacrylate, and the like; As the hydroxyacrylic acid ester, for example, hydroxymethyl acrylate, 2-hydroxyethyl acrylate, 3-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, diethylene glycol monoacrylate, 2,3- Dihydroxypropyl acrylate, 2-acryloxyethyl glycoside, 4-hydroxyphenyl acrylate, and the like;

As the bicyclo unsaturated compound, for example, 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] hep 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-butoxycarbo Nylbicyclo [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, 5,6-di (cyclohexyloxycarbonyl) bicyclo [2.2.1] hept-2 -Yen and the like;

As the maleimide compound, for example, N-phenylmaleimide, N-cyclohexyl maleimide, N-benzyl maleimide, N- (4-hydroxyphenyl) maleimide, N- (4-hydroxybenzyl) maleimide , N-succinimidyl-3-maleimidebenzoate, N-succinimidyl-4-maleimide butyrate, N-succinimidyl-6-maleimide caproate, N-succinimidyl-3-maleimide pro Cypionate, N- (9-acridinyl) maleimide and the like;

As an unsaturated aromatic compound, For example, styrene, (alpha) -methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, p-methoxy styrene etc .; As the conjugated diene, for example, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene and the like; As an unsaturated compound containing a tetrahydrofuran skeleton, it is tetrahydrofurfuryl (meth) acrylate, 2-methacryloyloxy- propionic acid tetrahydrofurfuryl ester, 3- (meth) acryloyloxy tetrahydro, for example. Furan-2-one and the like; As unsaturated compounds containing a furan skeleton, for example, 2-methyl-5- (3-furyl) -1-penten-3-one, furfuryl (meth) acrylate, 1-furan-2-butyl-3- En-2-one, 1-furan-2-butyl-3-methoxy-3-en-2-one, 6- (2-furyl) -2-methyl-1-hexen-3-one, 6-furan -2-yl-hex-1-en-3-one, 2-furan-2-yl-1-methyl-ethylester, 6- (2-furyl) -6-methyl-1-hepten-3-one Etc; As unsaturated compounds containing a tetrahydropyran skeleton, for example, (tetrahydropyran-2-yl) methylmethacrylate, 2,6-dimethyl-8- (tetrahydropyran-2-yloxy) -oct-1 -En-3-one, 2-methacrylic acid tetrahydropyran-2-ylester, 1- (tetrahydropyran-2-oxy) -butyl-3-en-2-one and the like; As unsaturated compounds containing a pyran skeleton, for example, 4- (1,4-dioxa-5-oxo-6-heptenyl) -6-methyl-2-pyrone, 4- (1,5-dioxa- 6-oxo-7-octenyl) -6-methyl-2-pyron etc. are mentioned, respectively. Other unsaturated compounds are acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide or vinyl acetate.

Of 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 [5.2.1.0 ^{2 , 6} ] decane-8-ylmethacrylate, p-methoxystyrene, 2-methylcyclohexylacrylate, 1,3-butadiene, bicyclo [2.2.1] hept-2-ene, tetrahydrofurfuryl ( Meth) acrylate, polyethylene glycol (n = 2 to 10) mono (meth) acrylate, 3- (meth) acryloyloxytetrahydrofuran-2-one, 1- (tetrahydropyran-2-oxy)- Butyl-3-en-2-one and furfuryl (meth) acrylate are particularly preferred in view of copolymerization reactivity and solubility in aqueous alkali solution. These compounds (a4) are used alone or in combination.

The copolymer [A] used in the present invention is preferably a structural unit derived from the compound (a4) based on the sum of the repeating units derived from the compounds (a1), (a2), (a3) and (a4). Preferably from 10 to 80% by weight, particularly preferably from 20 to 70% by weight. When this structural unit is less than 10 weight%, there exists a tendency for the heat resistance and surface hardness of the interlayer insulation film or microlens obtained to fall, and when the quantity of this structural unit exceeds 80 weight% of a radiation sensitive resin composition, There exists a tendency for storage stability to fall.

As a preferable specific example of the copolymer [A] used by this invention, methacrylic acid / tricyclo [5.2.1.0 ^2,6 ] decane-8-yl methacrylate / glycidyl methacrylate / 2- Methylcyclohexylacrylate / N- (3,5-dimethyl-4-hydroxybenzyl) methacrylamide / acryloyl morpholine copolymer, methacrylic acid / methacrylic acid glycidyl / 1- (tetrahydropyran 2-oxy) -butyl-3-en-2-one / N-cyclohexylmaleimide / p-methoxystyrene / 3-ethyl-3-methacryloyloxymethyloxetane / N- (3,5 -Dimethyl-4-hydroxybenzyl) methacrylamide / acryloyl morpholine copolymer, methacrylic acid / tricyclo [5.2.1.0 ^2,6 ] decane-8-ylmethacrylate / styrene / N-phenylmaleic Mid / N- (4-hydroxyphenyl) methacrylamide / acryloyl morpholine copolymer, methacrylic acid / methacrylic acid glycidyl / tricyclo [5.2.1.0 ^2,6 ] decane-8-ylmeta Acrylate / n-lauryl methacrylate / 3- Tacryloyloxytetrahydrofuran-2-one / N- (4-hydroxyphenyl) methacrylamide / acryloyl morpholine copolymer, methacrylic acid / methacrylic acid glycidyl / styrene / 2-methylcyclo Hexylacrylate / 1- (tetrahydropyran-2-oxy) -butyl-3-en-2-one / 4-hydroxybenzyl methacrylate / acryloyl morpholine copolymer, methacrylic acid / methacrylic acid Glycidyl / tricyclo [5.2.1.0 ^2,6 ] decane-8-ylmethacrylate / p-methoxystyrene / 4-hydroxybenzylmethacrylate / acryloylmorpholine copolymer, methacrylic acid / Tricyclo [5.2.1.0 ^2,6 ] decane-8-yl methacrylate / glycidyl methacrylate / styrene / p-vinylbenzyl glycidyl ether / tetrahydrofurfuryl methacrylate / 4-hydroxyphenyl Methacrylate / acryloyl morpholine copolymer, methacrylic acid / methacrylate glycidyl / N-cyclohexylmaleimide / α-methyl-p-hydroxystyrene / tet Hydrofurfuryl methacrylate / acryloyl morpholine copolymer, methacrylic acid / methacrylate glycidyl / N-cyclohexylmaleimide / 3-ethyl-3-methacryloyloxymethyloxetane / 3- Methacryloyloxytetrahydrofuran-2-one / tetrahydrofurfuryl methacrylate / 4-hydroxyphenylmethacrylate / acryloyl morpholine copolymer, methacrylic acid / glycidyl methacrylate / 3 -Ethyl-3-methacryloyloxymethyloxetane / tetrahydrofurfurylmethacrylate / N-phenylmaleimide / α-methyl-p-hydroxystyrene / acryloyl morpholine copolymer, methacrylic acid / Glycidyl methacrylate / 3-ethyl-3-methacryloyloxymethyloxetane / tricyclo [5.2.1.0 ^2,6 ] decane-8-ylmethacrylate / N-cyclohexylmaleimide / n- Lauryl methacrylate / alpha -methyl- p-hydroxy styrene copolymer / acryloyl morpholine, etc. are mentioned.

The polystyrene reduced weight average molecular weight (hereinafter referred to as "Mw") of the copolymer [A] used in the present invention is preferably 2 × 10 ³ to 1 × 10 ⁵ , more preferably 5 × 10 ³ to 5 × 10 ⁴ . If Mw is less than 2 × 10 ³ , the development margin may become insufficient, and the remaining film ratio of the resulting film may be reduced, or the pattern shape, heat resistance, etc. of the resulting interlayer insulating film or microlens may be deteriorated, while 1 × 10. ^When it exceeds ⁵ , the sensitivity may decrease or the pattern shape may fall. In addition, the molecular weight distribution (hereinafter referred to as "Mw / Mn") is preferably 5.0 or less, and more preferably 3.0 or less. When Mw / Mn exceeds 5.0, the pattern shape of the resulting interlayer insulating film or microlens may fall. The radiation sensitive resin composition containing the said copolymer [A] can form a predetermined pattern shape easily, without developing residue when developing.

The copolymer (A) can be synthesized, for example, by polymerizing an unsaturated compound (a1), an unsaturated compound (a2), an unsaturated compound (a3) and an unsaturated compound (a4) in the presence of a radical polymerization initiator in a suitable solvent.

As a solvent used for the said superposition | polymerization, alcohol, an ether, ethylene glycol ether, ethylene glycol alkyl ether acetate, diethylene glycol alkyl ether, propylene glycol monoalkyl ether, propylene glycol alkyl ether acetate, propylene glycol alkyl ether propionate, for example , Aromatic hydrocarbons, ketones, esters and the like.

Specific examples of these solvents include methanol, ethanol, benzyl alcohol, 2-phenylethanol, 3-phenyl-1-propanol, and the like as alcohols; As ether, tetrahydrofuran and the like; As ethylene glycol ether, Ethylene glycol monomethyl ether, Ethylene glycol monoethyl ether, etc .; Examples of ethylene glycol alkyl ether acetates include ethylene glycol methyl ether acetate, ethylene glycol ethyl ether acetate, ethylene glycol n-propyl ether acetate, ethylene glycol n-butyl ether acetate, and the like; As diethylene glycol alkyl ether, Diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, etc .;

As propylene glycol monoalkyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether, etc .; As propylene glycol alkyl ether acetates, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol n-propyl ether acetate, propylene glycol n-butyl ether acetate, etc .; As propylene glycol alkyl ether propionate, propylene glycol methyl ether propionate, propylene glycol ethyl ether propionate, propylene glycol n-propyl ether propionate, propylene glycol n-butyl ether propionate, etc .; As an aromatic hydrocarbon, toluene, xylene, etc .; As the ketone, methyl ethyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone and the like;

Examples of the esters include methyl acetate, ethyl acetate, propyl acetate, butyl acetate, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate and hydroxyacetic acid. Methyl, ethyl hydroxyacetate, butyl hydroxyacetate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, 3-hydroxypropionate methyl, 3-hydroxypropionate, 3-hydroxypropionic acid propyl, 3-hydroxypropionic acid Butyl, 2-hydroxy-3-methyl butyrate, methyl methoxyacetate, ethyl methoxyacetate, methoxyacetic acid propyl, butyl acetate, ethoxyacetic acid, ethyl ethoxyacetate, ethoxyacetic acid propyl Butyl oxyacetate, methyl propoxy acetate, ethyl propoxy acetate, propyl propoxy acetate, butyl propoxy acetate, methyl butoxy acetate Ethyl butoxy acetate, propyl butoxy acetate, butyl butoxy acetate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, 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, 3-methoxy methyl propionate, 3-methoxy ethylpropionate, 3-methoxy propylpropionate, 3-methoxy butyl propionate, 3-ethoxy propylpropionate, 3-ethoxy propylpropionate, 3-ethoxy propylpropionate, 3 Butyl ethoxypropionate, methyl 3-propoxypropionate, ethyl 3-propoxypropionate, propyl 3-propoxypropionate, butyl 3-propoxypropionate, methyl 3-butoxypropionate, 3-butoxypropionic acid Butyl, can be given a 3-butoxy-propionic acid propyl, 3-butoxy-propionic acid butyl ester, etc., respectively.

Among 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 among these are preferred. Methyl ether acetate is particularly 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- (2, 4- dimethylvaleronitrile), 2,2'- azobis- (4-methoxy-2 Azo compounds, such as (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, a peroxide can be used together with a reducing agent, and it can be set as a redox type initiator.

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; Terpinolene, the (alpha) -methylstyrene dimer, etc. are mentioned.

[B] component

As a 1, 2- quinone diazide compound of the [B] component used by this invention, a 1, 2- benzoquinone diazide sulfonic acid ester, a 1, 2- naphthoquinone diazide sulfonic acid ester, 1, 2-- Benzoquinone diazide sulfonic acid amide, 1,2-naphthoquinone diazide sulfonic acid amide, and the like.

Specific examples thereof include 2,3,4-trihydroxybenzophenone-1,2-naphthoquinoneazide-4-sulfonic acid ester and 2,3,4-trihydroxybenzophenone-1,2-naphthoquinone Diazide-5-sulfonic acid ester, 2,3,4-trihydroxybenzophenone-1,2-naphthoquinone diazide-6-sulfonic acid ester, 2,3,4-trihydroxybenzophenone-1,2 Naphthoquinone diazide-7-sulfonic acid ester, 2,3,4-trihydroxybenzophenone-1,2-naphthoquinone diazide-8-sulfonic acid ester, 2,4,6-trihydroxybenzophenone -1,2-naphthoquinone diazide-4-sulfonic acid ester, 2,4,6-trihydroxybenzophenone-1,2-naphthoquinone diazide-5-sulfonic acid ester, 2,4,6-tri Hydroxybenzophenone-1,2-naphthoquinonediazide-6-sulfonic acid ester, 2,4,6-trihydroxybenzophenone-1,2-naphthoquinonediazide-7-sulfonic acid ester, 2,4 Trihydroxy benzophenes such as 6-trihydroxybenzophenone-1,2-naphthoquinone diazide-8-sulfonic acid ester Discussion 1,2-naphthoquinonediazidesulfonic acid ester;

2,2 ', 4,4'-tetrahydroxybenzophenone-1,2-naphthoquinone diazide-4-sulfonic acid ester, 2,2', 4,4'-tetrahydroxybenzophenone-1,2 Naphthoquinone diazide-5-sulfonic acid ester, 2,2 ', 4,4'-tetrahydroxybenzophenone-1,2-naphthoquinone diazide-6-sulfonic acid ester, 2,2', 4, 4'-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-7-sulfonic acid ester, 2,2 ', 4,4'-tetrahydroxybenzophenone-1,2-naphthoquinonediazide- 8-sulfonic acid ester, 2,3,4,3'-tetrahydroxybenzophenone-1,2-naphthoquinone diazide-4-sulfonic acid ester, 2,3,4,3'-tetrahydroxybenzophenone- 1,2-naphthoquinone diazide-5-sulfonic acid ester, 2,3,4,3'-tetrahydroxybenzophenone-1,2-naphthoquinone diazide-6-sulfonic acid ester, 2,3,4 , 3'-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-7-sulfonic acid ester, 2,3,4,3'-tetrahydroxybenzophenone-1,2-naphthoquinonediazide- 8-sulfonic acid ester Le, 2,3,4,4'-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonic acid ester, 2,3,4,4'-tetrahydroxybenzophenone-1,2 Naphthoquinone diazide-5-sulfonic acid ester, 2,3,4,4'-tetrahydroxybenzophenone-1,2-naphthoquinone diazide-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-naphthoquinone diazide-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-naphthoquinonedia Zide-6-sulfonic acid ester, 2,3,4,2'-tetrahydroxy-4'-methylbenzophenone-1,2-naphthoquinone diazide-7- sulfonic acid ester, 2,3,4,2 ' Tetrahydroxy-4'-methylbenzophenone-1 , 2-naphthoquinone diazide-8-sulfonic acid ester, 2,3,4,4'-tetrahydroxy-3'-methoxybenzophenone-1,2-naphthoquinone diazide-4-sulfonic acid ester, 2,3,4,4'-tetrahydroxy-3'-methoxybenzophenone-1,2-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-naphthoquinone Tetrahydroxy benzophene, such as a diazide-7-sulfonic acid ester and 2,3,4,4'- tetrahydroxy-3'-methoxy benzophenone-1,2-naphthoquinone diazide-8-sulfonic acid ester Discussion 1,2-naphthoquinone diazide sulfonic acid ester;

2,3,4,2 ', 6'-pentahydroxybenzophenone-1,2-naphthoquinone diazide-4-sulfonic acid ester, 2,3,4,2', 6'-pentahydroxybenzophenone -1,2-naphthoquinone diazide-5-sulfonic acid ester, 2,3,4,2 ', 6'-pentahydroxybenzophenone-1,2-naphthoquinone diazide-6-sulfonic acid ester, 2 , 3,4,2 ', 6'-pentahydroxybenzophenone-1,2-naphthoquinonediazide-7-sulfonic acid ester, 2,3,4,2', 6'-pentahydroxybenzophenone- 1,2-naphthoquinone diazide sulfonic acid ester of pentahydroxy benzophenone, such as a 1, 2- naphthoquinone diazide-8- sulfonic acid ester;

2,4,6,3 ', 4', 5'-hexahydroxybenzophenone-1,2-naphthoquinone diazide-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-naphthoquinone Diazide-6-sulfonic acid ester, 2,4,6,3 ', 4', 5'-hexahydroxybenzophenone-1,2-naphthoquinone diazide-7-sulfonic acid ester, 2,4,6, 3 ', 4', 5'-hexahydroxybenzophenone-1,2-naphthoquinone diazide-8-sulfonic acid ester, 3,4,5,3 ', 4', 5'-hexahydroxybenzophenone -1,2-naphthoquinone diazide-4-sulfonic acid ester, 3,4,5,3 ', 4', 5'-hexahydroxybenzophenone-1,2-naphthoquinone diazide-5- Sulfonic acid ester, 3,4,5,3 ', 4', 5'-hexahydroxybenzophenone-1,2-naphthoquinonediazide-6-sulfonic acid ester, 3,4,5,3 ', 4' , 5'-hexahydroxybenzophenone-1,2-naphthoquinonediazide-7-sulfonic acid ester, 3,4,5,3 ', 4', 5'-hexahydroxybenzophenone-1,2- Naphthoquinonedia Hexahydro-hydroxy-benzophenone 1,2-naphthoquinonediazide sulfonic acid ester, such as de-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-naphthoquinone diazide-6-sulfonic acid ester, bis (2,4-dihydroxyphenyl) methane-1,2 Naphthoquinone diazide-7-sulfonic acid ester, bis (2,4-dihydroxyphenyl) methane-1,2-naphthoquinone diazide-8-sulfonic acid ester, bis (p-hydroxyphenyl) methane- 1,2-naphthoquinone diazide-4-sulfonic acid ester, bis (p-hydroxyphenyl) methane-1,2-naphthoquinone diazide-5-sulfonic acid ester, bis (p-hydroxyphenyl) methane- 1,2-naphthoquinone diazide-6-sulfonic acid ester, bis (p-hydroxyphenyl) methane-1,2-naphthoquinone diazide-7-sulfonic acid ester, bis (p-hydroxyphenyl) methane- 1,2-naphthoquinonediazide-8-sulfonic acid ester, tri (p-hydroxyphenyl) methane-1,2-naphthoquinone Azide-4-sulfonic acid ester, tri (p-hydroxyphenyl) methane-1,2-naphthoquinone diazide-5-sulfonic acid ester, tri (p-hydroxyphenyl) methane-1,2-naphthoquinone Diazide-6-sulfonic acid ester, tri (p-hydroxyphenyl) methane-1,2-naphthoquinone diazide-7-sulfonic acid ester, tri (p-hydroxyphenyl) methane-1,2-naphthoquinone Diazide-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 Naphthoquinone diazide-5-sulfonic acid ester, 1,1,1-tri (p-hydroxyphenyl) ethane-1,2-naphthoquinone diazide-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-trihydroxyphenyl) methane-1,2-naphthoquinone diazide-4-sulfonic acid ester, bis (2,3,4-trihydroxyphenyl) methane- 1,2-naphthoquinone diazide-5-sulfonic acid ester, bis (2,3,4-trihydroxyphenyl) methane-1,2-naphthoquinone diazide-6-sulfonic acid ester, bis (2,3 , 4-trihydroxyphenyl) methane-1,2-naphthoquinonediazide-7-sulfonic acid ester, bis (2,3,4-trihydroxyphenyl) methane-1,2-naphthoquinonediazide- 8-sulfonic acid ester, 2,2-bis (2,3,4-trihydroxyphenyl) propane-1,2-naphthoquinonediazide-4-sulfonic acid ester, 2,2-bis (2,3,4-trihydroxyphenyl Propane-1,2-naphthoquinonediazide-5-sulfonic acid ester, 2,2-bis (2,3,4-trihydroxyphenyl) propane-1,2-naphthoquinonediazide-6-sulfonic acid Ester, 2,2-bis (2,3,4-trihydroxyphenyl) propane-1,2-naphthoquinonediazide-7-sulfonic acid ester, 2,2-bis (2,3,4-trihydrate Oxyphenyl) propane-1,2-naphthoquinonediazide-8-sulfonic acid ester,

1,1,3-tris (2,5-dimethyl-4-hydroxyphenyl) -3-phenylpropane-1,2-naphthoquinonediazide-4-sulfonic acid ester, 1,1,3-tris (2 , 5-dimethyl-4-hydroxyphenyl) -3-phenylpropane-1,2-naphthoquinonediazide-5-sulfonic acid ester, 1,1,3-tris (2,5-dimethyl-4-hydroxy Phenyl) -3-phenylpropane-1,2-naphthoquinonediazide-6-sulfonic acid ester, 1,1,3-tris (2,5-dimethyl-4-hydroxyphenyl) -3-phenylpropane-1 , 2-naphthoquinonediazide-7-sulfonic acid ester, 1,1,3-tris (2,5-dimethyl-4-hydroxyphenyl) -3-phenylpropane-1,2-naphthoquinonediazide- 8-sulfonic acid ester, 4,4 '-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol-1,2-naphthoquinonediazide-4 Sulfonic acid ester, 4,4 '-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol-1,2-naphthoquinonediazide-5- Sulfonic acid ester, 4,4 '-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bis Nol-1,2-naphthoquinonediazide-6-sulfonic acid ester, 4,4 '-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol -1,2-naphthoquinonediazide-7-sulfonic acid ester, 4,4 '-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol- 1,2-naphthoquinone diazide-8-sulfonic acid ester,

Bis (2,5-dimethyl-4-hydroxyphenyl) -2-hydroxyphenylmethane-1,2-naphthoquinonediazide-4-sulfonic acid ester, bis (2,5-dimethyl-4-hydroxyphenyl ) -2-hydroxyphenylmethane-1,2-naphthoquinonediazide-5-sulfonic acid ester, bis (2,5-dimethyl-4-hydroxyphenyl) -2-hydroxyphenylmethane-1,2- Naphthoquinone diazide-6-sulfonic acid ester, bis (2,5-dimethyl-4-hydroxyphenyl) -2-hydroxyphenylmethane-1,2-naphthoquinone diazide-7-sulfonic acid ester, bis ( 2,5-dimethyl-4-hydroxyphenyl) -2-hydroxyphenylmethane-1,2-naphthoquinonediazide-8-sulfonic acid ester, 3,3,3 ', 3'-tetramethyl-1, 1'-spirobiindene-5,6,7,5 ', 6', 7'-hexanol-1,2-naphthoquinone diazide-4-sulfonic acid ester, 3,3,3 ', 3'- Tetramethyl-1,1'-spirobiindene-5,6,7,5 ', 6', 7'-hexanol-1,2-naphthoquinonediazide-5-sulfonic acid ester, 3,3,3 ', 3'-tetramethyl-1,1'-spirobiindene-5,6,7,5', 6 ', 7'-hexanol-1,2-naphthoquinonedia De-6-sulfonic acid ester, 3,3,3 ', 3'-tetramethyl-1,1'-spirobiindene-5,6,7,5', 6 ', 7'-hexanol-1,2 Naphthoquinonediazide-7-sulfonic acid ester, 3,3,3 ', 3'-tetramethyl-1,1'-spirobiindene-5,6,7,5', 6 ', 7'-hexane All-1,2-naphthoquinonediazide-8-sulfonic acid ester, 2,2,4-trimethyl-7,2 ', 4'-trihydroxyflavan-1,2-naphthoquinonediazide-4 Sulfonic acid esters, 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 Such as, 2-naphthoquinone diazide-7-sulfonic acid, 2,2,4-trimethyl-7,2 ', 4'-trihydroxyflavan-1,2-naphthoquinone diazide-8-sulfonic acid 1,2-naphthoquinone diazide sulfonic acid ester of (polyhydroxyphenyl) alkane is mentioned.

These 1,2-quinonediazide compounds 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 based on 100 parts by weight of the copolymer [A]. When the ratio is less than 5 parts by weight, the amount of acid generated by irradiation of the radiation is small, so that the difference in solubility in the aqueous alkali solution that becomes the developer between the irradiation portion and the unirradiated portion of the radiation tends to be difficult to pattern. . 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, when this ratio exceeds 100 weight part, since unreacted [B] component remains in large quantities by irradiation of the radiation for a short time, the insolubilization effect to the said aqueous alkali solution is too high and it tends to become difficult to develop. have.

Other ingredients

Although the radiation sensitive resin composition of this invention contains the said copolymer [A] and [B] components as an essential component, other [C] thermosensitive acid production compound and [D] one or more ethylenically unsaturated as needed. It may contain a polymeric compound which has a double bond, another epoxy resin different from [E] copolymer [A], [F] surfactant, or [G] adhesion | attachment adjuvant.

The heat-sensitive acid-producing compound [C] can be used 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.

As these specific examples, as alkylsulfonium salt, 4-acetophenyl dimethylsulfonium hexafluoro antimonate, 4-acetoxy phenyl dimethylsulfonium hexafluoro arsenate, dimethyl-4- (benzyloxycarba, for example) Bonyloxy) phenylsulfonium hexafluoroantimonate, dimethyl-4- (benzoyloxy) phenylsulfonium hexafluoroantimonate, dimethyl-4- (benzoyloxy) phenylsulfonium hexafluoroarsenate, dimethyl 3-chloro-4-acetoxyphenylsulfonium hexafluoroantimonate, etc .;

As the benzylsulfonium salt, for example, benzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, benzyl-4-hydroxyphenylmethylsulfonium hexafluorophosphate, 4-acetoxyphenylbenzylmethylsulfonium hexa Fluoroantimonate, benzyl-4-methoxyphenylmethylsulfonium hexafluoroantimonate, benzyl-2-methyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, benzyl-3-chloro 4-hydroxyphenylmethylsulfonium hexafluoroarsenate, 4-methoxybenzyl-4-hydroxyphenylmethylsulfonium hexafluorophosphate, etc .;

As the dibenzylsulfonium salt, for example, dibenzyl-4-hydroxyphenylsulfonium hexafluoroantimonate, dibenzyl-4-hydroxyphenylsulfonium hexafluorophosphate, 4-acetoxyphenyl dibenzylsulfonium Hexafluoroantimonate, 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;

As the substituted benzylsulfonium salt, for example, p-chlorobenzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, p-nitrobenzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, p -Chlorobenzyl-4-hydroxyphenylmethylsulfonium hexafluorophosphate, p-nitrobenzyl-3-methyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, 3,5-dichlorobenzyl-4- Hydroxyphenylmethylsulfonium hexafluoroantimonate, o-chlorobenzyl-3-chloro-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, and the like.

As a specific example of the said benzothiazonium salt, 3-benzyl benzothiazonium hexafluoro antimonate, 3-benzyl benzothiazonium hexafluoro phosphate, 3-benzyl benzothiazonium tetrafluoro borate, 3- (p-methoxy Benzyl benzo, such as benzyl) benzothiazonium hexafluoroantimonate, 3-benzyl-2-methylthiobenzothiazonium hexafluoroantimonate, 3-benzyl-5-chlorobenzothiazonium hexafluoroantimonate A thiazonium salt is mentioned.

Of these, 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 Thiazolium hexafluoroantimonate is preferably used.

Examples of these commercially available products include sun-aid SI-L85, SI-L110, SI-L145, SI-L150, and SI-L160 (manufactured by Sanshin Kagaku Kogyo 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 it may interfere with coating film formation.

As a polymeric compound (Hereinafter, it may be called "D component") which has one or more ethylenically unsaturated double bond which is the said [D] component, For example, monofunctional (meth) acrylate and bifunctional (meth) An acrylate or trifunctional or more than (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, Aronix M-101, copper M-111, copper M-114 (above, manufactured by Toagosei Co., Ltd.), KAYARAD TC-110S, and copper TC-120S (above, Nippon Kayaku ( Ltd.), Biscot 158, East 2311 (above, Osaka Yuki Chemical Co., Ltd. make), etc. are mentioned.

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

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

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

These monofunctional, bifunctional or trifunctional or more (meth) acrylates are used alone or in combination. The use ratio of component [D] is 50 weight part or less with respect to 100 weight part of copolymers [A], More preferably, it is 30 weight part or less.

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 arise in the process of forming the coating film of a radiation sensitive resin composition on a board | substrate.

Other epoxy resins (hereinafter, sometimes referred to as "E component") different from the copolymer [A] which is the said [E] component are not limited, unless there is an influence on compatibility. Preferably, bisphenol-A epoxy resin, phenol novolak-type epoxy resin, cresol novolak-type epoxy resin, cyclic aliphatic epoxy resin, glycidyl ester type epoxy resin, glycidylamine type epoxy resin, heterocyclic epoxy resin, glyc The resin etc. which co-polymerized the cyl methacrylate are mentioned. Among these, bisphenol-A epoxy resin, cresol novolak-type epoxy resin, glycidyl ester-type epoxy resin, etc. are especially 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 a 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.

On the other hand, although copolymer [A] can also be called "epoxy resin", it differs from [E] component by the point which has alkali solubility. [E] component is alkali-insoluble.

Surfactant which is the said [F] component can be used for the radiation sensitive resin composition of this invention further in order to improve applicability | paintability. As [F] surfactant which can be used here, a fluorine-type surfactant, a silicone type surfactant, and a nonionic surfactant can be used preferably.

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, Octaethylene glycol di (1,1,2,2-tetrafluorobutyl) ether, hexaethylene glycol (1,1,2,2,3,3-hexafluoropentyl) ether, octapropylene glycol di (1, 1,2,2-tetrafluorobutyl) ether, hexapropylene glycol di (1,1,2,2,3,3-hexafluoropentyl) ether, sodium perfluorododecylsulfonate, 1,1,2 Sodium fluoroalkylbenzenesulfonate, in addition to 2,8,8,9,9,10,10-decafluorododecane, 1,1,2,2,3,3-hexafluorodecane and the like; Fluoroalkyloxyethylene ethers; Fluoroalkylammonium iodide, fluoroalkylpolyoxyethylene ether, perfluoroalkylpolyoxyethanol; Perfluoroalkylalkoxylates; Fluorine-type alkyl ester etc. are mentioned. As these commercial items, BM-1000, BM-1100 (above, BM Chemie Co., Ltd.), Mega Pack F142D, Copper F172, Copper F173, Copper F183, Copper F178, Copper F191, Copper F471 (or more) Kaku Kogyo Co., Ltd.), Florard FC-170C, FC-171, FC-430, FC-431 (above, Sumitomo 3M Co., Ltd.), Suplon S-112, S-113, S -131, S-141, S-145, S-382, SC-101, SC-102, SC-103, SC-104, SC-105, SC-106 (Asahi) Sue Co., Ltd. product, F-top EF301, copper 303, copper 352 (made by Shin Akita Kasei Co., Ltd.), etc. are mentioned.

As said silicone type surfactant, DC3PA, DC7PA, FS-1265, SF-8428, SH11PA, SH21PA, SH28PA, SH29PA, SH30PA, SH-190, SH-193, SZ-6032 (above, Toray Dow Corning silicone ( (Manufactured by Co., Ltd.), TSF-4440, TSF-4300, TSF-4445, TSF-4446, TSF-4460, TSF-4452 (above, manufactured by GE Toshiba Silicone Co., Ltd.). .

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 Nos. 57, 95 (manufactured by Kyoeisha Chemical Co., Ltd.) and the like can be used.

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

These [F] surfactants are preferably used in an amount of 5 parts by weight or less, and more preferably 2 parts by weight or less, based on 100 parts by weight of the copolymer [A]. When the usage-amount of [F] surfactant exceeds 5 weight part, when forming a coating film on a board | substrate, the film roughness of a coating film may become easy to produce.

In the radiation sensitive resin composition of this invention, in order to improve the adhesiveness with a base | substrate, the adhesion | attachment adjuvant which is a [G] component can also be used. As such [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, trimethoxy silyl benzoic acid, (gamma) -methacryloxypropyl trimethoxysilane, vinyl triacetoxysilane, vinyl trimethoxysilane, (gamma) -isocyanate propyl triethoxysilane, (gamma)-glycidoxy propyl trimeth Oxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and the like. Such [G] adhesion aid is used in an amount of preferably 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 adhesive aid exceeds 20 parts by weight, development residues are likely to occur in the developing step.

Radiation  Resin composition

The radiation sensitive resin composition of this invention is manufactured by uniformly mixing the said copolymer [A] and [B] components, and the other components added arbitrarily as mentioned above. The radiation sensitive resin composition of the present invention is preferably dissolved in a suitable solvent and used in a solution state. For example, the radiation sensitive resin composition of a solution state can be manufactured by mixing copolymer [A] and [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, the copolymer [A] and [B] component, and the other component mix | blended arbitrarily are melt | dissolved uniformly, and what does not react with each component is 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, alcohols, glycol ethers, ethylene glycol alkyl ether acetates, esters, and diethylene glycol are preferably used in view of solubility of each component, reactivity with each component, ease of coating film formation, and the like. Among them, benzyl alcohol, 2-phenylethyl alcohol, 3-phenyl-1-propanol, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, di Ethylene glycol dimethyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, methyl methoxy propionate, and ethoxy propionate can be used especially preferably.

In addition, a high boiling point solvent may be used in combination with the solvent in order to increase in-plane uniformity of the film thickness. As a high boiling point solvent which can be used together, it is N-methylformamide, N, N-dimethylformamide, N-methylformanilide, N-methylacetamide, N, N-dimethylacetamide, N-methylpi, for example. Ralidone, dimethyl sulfoxide, benzyl ethyl ether, dihexyl ether, acetonyl acetone, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl acetate, ethyl benzoate, diethyl oxalate, male Diethyl acid, gamma -butyrolactone, ethylene carbonate, propylene carbonate, phenyl cellosolve acetate, and the like. Of these, N-methylpyrrolidone, γ-butyrolactone, and N, N-dimethylacetamide are preferable.

When using a high boiling point solvent together as a solvent of the radiation sensitive resin composition of this invention, its usage-amount is preferably 50 weight% or less, More preferably, 40 weight% or less, More preferably, 30 weight weight with respect to solvent whole quantity. It can be made% or less. 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 (namely, the total amount of copolymer [A] and [B] components, and the other components added arbitrarily) is Although it can set arbitrarily according to a purpose of use, the value of desired film thickness, etc., Preferably it is 5 to 50 weight%, More preferably, it is 10 to 40 weight%, More preferably, it is 15 to 35 weight%.

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

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 demonstrated. The method for forming an interlayer insulating film or microlens of the present invention includes the following steps in the order described below.

(1) process of forming the coating film of the radiation sensitive resin composition of this invention on a board | 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 resin 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, Preferably it pre-bakes, and a solvent is removed and a coating film of a radiation sensitive resin composition is formed.

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

It does not specifically limit as a coating method of a composition solution, For example, the appropriate method, such as the spraying method, the roll coating method, the spin coating method (spin coating method), the slit die coating method, the bar coating method, the inkjet method, can be employ | adopted, In particular, the spin coating method and the slit die coating method are preferable. The conditions for prebaking also vary depending on the type of each component, the use ratio, and the like. For example, it can be made into about 30 to 15 minutes at 60-110 degreeC.

As a film thickness of the coating film formed, it is a value after prebaking, for example, when forming an interlayer insulation film, for example, 3-6 micrometers, and when forming a microlens, for example, 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 with a radiation through a mask having a predetermined pattern, and then developed by using a developing solution to remove the radiation portion of the patterning. 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 among these, 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

As a developing solution used for image development, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, ammonia, ethylamine, n-propylamine, diethylamine, diethylaminoethanol, di-n-propyl Amine, triethylamine, methyldiethylamine, dimethylethanolamine, triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, pyrrole, piperidine, 1,8-diazabicyclo [5.4.0] Aqueous solutions of alkali (basic compounds) 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 an appropriate amount in the said aqueous alkali solution, or the various organic solvent which melt | dissolves the composition of this invention can be used as a developing solution. As the developing method, for example, a suitable method such as a puddle method, a dipping method, a rocking dipping method or a shower method can be used. Although the developing time at this time changes with the composition of a composition, it can be made into 30 to 120 second, for example.

On the other hand, in the conventionally known radiation-sensitive resin composition, since the peeling occurs in the pattern formed when the developing time exceeds about 20 to 25 seconds from the optimum value, it is necessary to strictly control the developing time, but the radiation-sensitive resin composition of the present 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

After the development process (3) carried out as described above, the patterned thin film is preferably rinsed by, for example, running water washing, and more preferably irradiated with radiation on a whole surface by a high pressure mercury lamp (post exposure). By performing the decomposition | decomposition process of the 1, 2- quinonediazide compound which remain | survives in the said thin film, and heat-processing (post-baking) this thin film with a heating apparatus, such as a hotplate and oven, hardening process of the said thin film is performed. Do it. The exposure amount in the post-exposure step is preferably about 2,000 to 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 baking method etc. which perform two or more heating processes can also be used.

In this manner, 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.

Microlenses

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

On the other hand, the shape of the microlens of the present invention becomes a semi-convex lens shape as shown in Fig. 1A.

As described above, the radiation-sensitive resin composition of the present invention has a high radiation sensitivity, has a developing margin which can still form a good pattern shape even if the optimum developing time is exceeded in the developing step, and has a good pattern-like thin film Can be easily formed.

The interlayer insulating film of the present invention formed from the composition has good adhesion to the 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.

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

<Example>

Although a synthesis example, an Example, and a comparative 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 1

In a flask equipped with a cooling tube and a stirrer, 7 parts by weight of 2,2'-azobis (2,4-dimethylvaleronitrile) and 220 parts by weight of propylene glycol monomethyl ether acetate were added. Then 22 parts by weight of methacrylic acid, 23 parts by weight of dicyclopentanyl methacrylate, 5 parts by weight of acryloyl morpholine, 50 parts by weight of 3-ethyl-3-methacryloyloxymethyloxetane and α-methylstyrene 3 weight part of dimers were put, and stirring was started slowly, replacing with nitrogen. The temperature of the solution was raised to 70 ° C. and heated at this temperature for 4 hours to obtain a polymer solution containing a copolymer [A-1]. Solid content concentration of the obtained polymer solution was 31.1 weight%, the weight average molecular weight of the polymer was 17,200, and molecular weight distribution (ratio of weight average molecular weight / number average molecular weight) was 1.9. 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 by Tosoh Corporation)).

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 220 parts by weight of diethylene glycol ethylmethyl ether were added. 13 parts by weight of methacrylic acid, 50 parts by weight of glycidyl methacrylate, 10 parts by weight of 3-ethyl-3-methacryloyloxymethyloxetane, 10 parts by weight of cyclohexylmaleimide, and acryloyl morpholine 10 parts by weight and 7 parts by weight of tetrahydrofurfuryl acrylate were added thereto, and stirring was started slowly with nitrogen substitution. The temperature of the solution was raised to 70 ° C, and heated at this temperature for 4 hours to obtain a polymer solution containing a copolymer [A-2]. Solid content concentration of the obtained polymer solution was 32.1 weight%, the weight average molecular weight of the polymer was 18,200, and molecular weight distribution was 1.8.

Synthesis Example 3

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. 11 parts by weight of methacrylic acid, 12 parts by weight of cyclohexylmaleimide, 9 parts by weight of α-methyl-p-hydroxystyrene, 50 parts by weight of glycidyl methacrylate, 3-ethyl-3-methacryloyl 10 parts by weight of oxymethyl oxetane, 5 parts by weight of acryloyl morpholine, 3 parts by weight of tetrahydrofurfuryl methacrylate and 3 parts by weight of α-methylstyrene dimer were added thereto, and stirring was started gently with nitrogen substitution. The temperature of the solution was raised to 70 ° C., and heated at this temperature for 5 hours to obtain a polymer solution containing a copolymer [A-3]. Solid content concentration of the obtained polymer solution was 32.4 weight%, the weight average molecular weight of the polymer was 21,200, and molecular weight distribution was 2.1.

Synthesis Example 4

In a flask equipped with a cooling tube and a stirrer, 8 parts by weight of 2,2'-azobis (2,4-dimethylvaleronitrile) and 220 parts by weight of diethylene glycol ethylmethyl ether were added. 10 parts by weight of styrene, 20 parts by weight of methacrylic acid, 20 parts by weight of 3-ethyl-3-methacryloyloxymethyloxetane, 30 parts by weight of glycidyl methacrylate, 8 parts by weight of acryloyl morpholine , 12 parts by weight of tetrahydrofurfuryl acrylate and 4.0 parts by weight of α-methylstyrene dimer were added thereto, and stirring was started gently with nitrogen substitution. The temperature of the solution was raised to 70 ° C, and heated at this temperature for 5 hours to obtain a polymer solution containing a copolymer [A-4]. Solid content concentration of the obtained polymer solution was 32.0 weight%, the weight average molecular weight of the polymer was 20,100, and molecular weight distribution was 1.9.

Comparative Synthesis Example 1

In a flask equipped with a cooling tube and a stirrer, 7 parts by weight of 2,2'-azobis (2,4-dimethylvaleronitrile) and 220 parts by weight of diethylene glycol methylethyl ether were added. Then, 23 parts by weight of methacrylic acid, 47 parts by weight of dicyclopentanyl methacrylate, 20 parts by weight of glycidyl methacrylate, and 2.0 parts by weight of α-methylstyrene dimer were added thereto, and gently stirring was started. The temperature of the solution was raised to 70 ° C., and the temperature was maintained for 5 hours to obtain a polymer solution containing a copolymer [A-1R]. Solid content concentration of the obtained polymer solution was 32.8 weight%, the weight average molecular weight of the polymer was 24,000, and molecular weight distribution was 2.3.

Comparative Synthesis Example 2

In a flask equipped with a cooling tube and a stirrer, 7 parts by weight of 2,2'-azobis (2,4-dimethylvaleronitrile) and 220 parts by weight of diethylene glycol methylethyl ether were added. Subsequently, 25 parts by weight of methacrylic acid, 35 parts by weight of dicyclopentanyl methacrylate, 40 parts by weight of 2-hydroxyethyl methacrylate, and 2.0 parts by weight of α-methylstyrene dimer were added thereto, and gently stirring was started. The temperature of the solution was raised to 70 ° C., and the temperature was maintained for 5 hours to obtain a polymer solution containing a copolymer [A-2R]. Solid content concentration of the obtained polymer solution was 32.8 weight%, the weight average molecular weight of the polymer was 25,000, and molecular weight distribution was 2.4.

Example 1

Preparation of radiation sensitive resin composition

Polymer solution containing the copolymer [A-1] obtained by the synthesis example 1 (it corresponds to 100 weight part (solid content) of copolymer [A-1]),

4,4 '-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol (1 mol) and 1,2-naphthoquinone as component [B] Condensate with diazide-5-sulfonic acid chloride (2 mol) (4,4 '-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol-1 (2-naphthoquinone diazide-5-sulfonic acid ester) 20 parts by weight and γ-methacryloxypropyltrimethoxysilane were mixed, and dissolved in propylene glycol monomethyl ether acetate so that the solid content concentration was 30% by weight. After that, the solution (S-1) of the radiation-sensitive resin composition was prepared by filtration with a Millipore filter having a pore size of 0.5 µm.

Evaluation of Interlayer Insulator

(I) Pattern  Formation of a thin film

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

The coating film obtained above was irradiated with the ultraviolet-ray whose intensity | strength at 365 nm is 10 mW / cm <^2> for 15 second using the predetermined pattern mask. Subsequently, it developed for 1 minute at 25 degreeC with the tetramethylammonium hydroxide 0.5 weight% aqueous solution, and then rinsed with pure water for 1 minute. Unnecessary parts were removed by these operations.

The pattern formed above was irradiated with ultraviolet light having an intensity of 10 mW / cm ² at 365 nm for 30 seconds, and then heated and cured at 220 ° C. for 60 minutes in an oven to obtain a patterned thin film having a thickness of 3 μm.

In addition, the same operation as described above was carried out except that the prebaking temperature was set at 90 ° C and 100 ° C to form three types of patterned thin films having different prebaking temperatures.

( II Evaluation of the resolution

(Circle) and the case which cannot be resolved were made into the case where the pattern (5 micrometer x 5 micrometer hole) taken out in the pattern thin film obtained by said (I) can be resolved. The results are shown in Table 1 below.

( III ) Heat resistance stability  evaluation

In the said (I), the thin film pattern formed at the prebaking temperature of 80 degreeC was heated at 220 degreeC for 60 minutes in oven. The change rate of the film thickness before and after heating is shown in Table 2 below. When the rate of dimensional change at this time is within 5% before and after heating, the heat-resistant dimensional stability is good, and when the rate of dimensional change exceeds 5%, it can be said to be defective.

( IV ) Evaluation of transparency

In the above (I), the 400 nm transmittance of the patterned thin film formed at a prebaking temperature of 80 ° C is measured using a spectrophotometer (150-20 type double beam (manufactured by Hitachi Seisakusho Co., Ltd.)), Transparency was evaluated. The results are shown in Table 2. In this case, when the transmittance is 90% or more, the transparency may be good, and when the transmittance is less than 90%, it may be called a defect.

(V) Thermochromic  evaluation

In the above (I), the substrate having the patterned thin film formed at a prebaking temperature of 80 ° C. is heated in an oven at 250 ° C. for 1 hour, and the heat discoloration resistance is evaluated by changing the transmittance of the patterned thin film before and after heating. It was. The evaluation result at this time is shown in Table 2. When the change rate is less than 5%, the heat discoloration resistance is good, and when the change rate is more than 5%, it can be said to be poor. In addition, the transmittance | permeability was calculated | required similarly to evaluation of (IV) transparency.

( VI ) Evaluation of Adhesion

In said (I), the adhesiveness of the patterned thin film formed at the prebaking temperature of 80 degreeC was evaluated by the checkerboard peeling test after a pressure cooker test (120 degreeC, 100% of humidity, 4 hours). The evaluation result at this time is shown in Table 2. The evaluation result was represented by the number of remaining checkerboard tick marks among 100 checkerboard tickmarks.

( VII Evaluation of Preservation Stability

The composition solution was heated in an oven at 40 ° C. for 1 week, and storage stability was evaluated by the change of the viscosity before and after heating. The viscosity change rate at this time is shown in Table 1. In the case where the rate of change is less than 5%, the storage stability is good, and in the case of 5% or more, the storage stability is poor.

Evaluation of Microlenses

(I) formation of microlenses

The composition solution (S-1) was spin-coated on a 6-inch silicon substrate to a film thickness of 2.5 μm and prebaked at 70 ° C. for 3 minutes on a hot plate to form a coating film.

The ultraviolet-ray whose intensity | strength at 436 nm is 10 mW / cm <^2> was irradiated to the coating film obtained above using the predetermined pattern mask. Subsequently, after developing for 1 minute at 25 degreeC with the tetramethylammonium hydroxide 2.38 weight% aqueous solution, it rinsed with pure water for 1 minute. By this operation, unnecessary portions were removed and a pattern was formed.

After the 10 mW / cm ² of ultraviolet intensity at 436 ㎚ the pattern formed by the 200 mJ / cm ² irradiated, and further post-heated at 160 ℃ 10 bungan heated at 230 ℃ 10 bungan micro melt flow patterns The lens was formed.

( II Evaluation of sensitivity

Table 3 shows the lowest doses that can resolve the space line width of the 0.8 μm line-and-space pattern (10 to 1) of the microlens pattern after the melt flow obtained in the above (I). When this value is 100 mJ / cm <^2> or less, when a resolution is good and a sensitivity exceeds 100 mJ / cm < ² >, it may be said that it is a poor resolution.

( III ) Evaluation of transparency

A patterned thin film was formed on the glass substrate in the same manner as in the above (I).

About the glass substrate in which the microlens pattern after melt flow was formed, the transmittance | permeability of 400 nm is measured using the spectrophotometer (150-20 type double beam (made by Hitachi Seisakusho Co., Ltd.)), and transparency evaluation is performed. It was. Table 3 shows the transmittance at 400 nm at this time. When the transmittance is 90 to 100%, the transmittance is good, and when it is less than 90%, the transmittance can be said to be poor.

( IV ) Evaluation of Heat Transparency

The glass substrate having the patterned thin film formed in the above (III) was heated in an oven at 250 ° C. for 1 hour, and thermal transparency was evaluated by changing the transmittance of the patterned thin film before and after heating. The change rate of the transmittance at this time is shown in Table 3. When the rate of change is less than 5%, the heat-transparent transparency is good, and when it exceeds 5%, it can be said to be poor. In addition, the transmittance | permeability was calculated | required similarly to evaluation of (III) transparency.

(V) Evaluation of adhesiveness

The adhesiveness of the patterned thin film formed in said (I) was evaluated by the checkerboard peeling test after the pressure cooker test (120 degreeC, 100% of humidity, 4 hours). The evaluation results at this time are shown in Table 3. The evaluation result was represented by the number of remaining checkerboard tick marks among 100 checkerboard tickmarks.

( VII ) Solvent-resistant  evaluation

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 to evaluate a film thickness change. The change rate at this time is shown in Table 3. When the change rate is 0 to 5%, the solvent resistance is good, when it exceeds 5%, and when film thickness falls by melt | dissolution, solvent resistance can be said to be defective.

Example 2

Polymer solution containing the copolymer [A-2] obtained by the synthesis example 2 (it corresponds to 100 weight part (solid content) of copolymer [A-2]),

4,4 '-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol (1 mol) and 1,2-naphthoquinone as component [B] Condensate with diazide-5-sulfonic acid chloride (2 mol) (4,4 '-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol-1 (2-naphthoquinone diazide-5-sulfonic acid ester) 20 parts by weight and γ-methacryloxypropyltrimethoxysilane were mixed, and dissolved in propylene glycol monomethyl ether acetate so that the solid content concentration was 31% by weight. After making it, the solution (S-2) of the radiation sensitive resin composition was produced and evaluated by filtering by the Millipore filter of 0.5 micrometer of pore diameters. The results are shown in Tables 1-3.

Example 3

Polymer solution containing the copolymer [A-3] obtained by the synthesis example 3 (it corresponds to 100 weight part (solid content) of copolymer [A-3]),

4,4 '-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol (1 mol) and 1,2-naphthoquinone as component [B] Condensate with diazide-5-sulfonic acid chloride (2 mol) (4,4 '-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol-1 (2-naphthoquinone diazide-5-sulfonic acid ester) 18 parts by weight and γ-methacryloxypropyltrimethoxysilane were mixed and dissolved in propylene glycol monomethyl ether acetate so that the solid content concentration was 30% by weight. After making it, the solution (S-3) of the radiation sensitive resin composition was produced and evaluated by filtering by the Millipore filter of 0.5 micrometer of pore diameters. The results are shown in Tables 1-3.

Example 4

Polymer solution containing the copolymer [A-4] obtained by the synthesis example 4 (it corresponds to 100 weight part (solid content) of copolymer [A-4]),

4,4 '-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol (1 mol) and 1,2-naphthoquinone as component [B] Condensate with diazide-5-sulfonic acid chloride (2 mol) (4,4 '-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol-1 , 2-naphthoquinone diazide-5-sulfonic acid ester) 30 parts by weight, 4,4 '-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] 5 parts by weight of bisphenol and 5 parts by weight of γ-methacryloxypropyltrimethoxysilane were mixed, dissolved in propylene glycol monomethyl ether acetate so that the solid content concentration was 31% by weight, and filtered through a Millipore filter having a pore diameter of 0.5 μm. A solution (S-4) of the radiation sensitive resin composition was prepared and evaluated. The results are shown in Tables 1-3.

Comparative Example 1

A polymer solution (corresponding to 100 parts by weight (solid content) of a copolymer [A-1R]) containing the copolymer [A-1R] obtained in Comparative Synthesis Example 1,

4,4 '-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol (1 mol) and 1,2-naphthoquinone as component [B] Condensate with diazide-5-sulfonic acid chloride (2 mol) (4,4 '-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol-1 (2-naphthoquinone diazide-5-sulfonic acid ester) 30 parts by weight and γ-methacryloxypropyltrimethoxysilane were mixed and dissolved in propylene glycol monomethyl ether acetate so that the solid content concentration was 31% by weight. After that, the solution (S-1R) of the radiation-sensitive resin composition was prepared by filtration with a Millipore filter having a pore size of 0.5 µm and evaluated. The results are shown in Tables 1-3.

Comparative Example 2

A polymer solution (corresponding to 100 parts by weight (solid content) of a copolymer [A-2R]) containing a copolymer [A-2R] obtained in Comparative Synthesis Example 2,

4,4 '-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol (1 mol) and 1,2-naphthoquinone as component [B] Condensate with diazide-5-sulfonic acid chloride (2 mol) (4,4 '-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol-1 , 2-naphthoquinone diazide-5-sulfonic acid ester) 18 parts by weight and γ- methacryloxypropyl trimethoxysilane are mixed, and dissolved in propylene glycol monomethyl ether acetate so that the solid content concentration is 31% by weight. After filtration, the solution (S-2R) of the radiation-sensitive resin composition was prepared by filtration with a Millipore filter having a pore size of 0.5 µm and evaluated. The results are shown in Tables 1-3.

1 is a schematic diagram showing the shape of a microlens.

Claims (7)

(A) (a1) one or more selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic anhydrides, (a2) unsaturated compounds containing at least one of an epoxy group and an oxetanyl group, (a3) at least one member selected from the group consisting of acryloyl morpholine and methacryloyl morpholine, (a4) Methacrylic acid alkyl ester, methacrylic acid cyclic alkyl ester, acrylic acid alkyl ester, acrylic acid cyclic alkyl ester, acrylic acid aryl ester, methacrylic, different from all of the compounds (a1), (a2) and (a3). Acid aryl ester, unsaturated dicarboxylic acid diester, hydroxymethacrylic acid ester, hydroxyacrylic acid ester, bicyclo unsaturated compound, maleimide compound, unsaturated aromatic compound, conjugated diene, unsaturated compound having tetrahydrofuran skeleton, furan skeleton In the group consisting of an unsaturated compound having a compound, an unsaturated compound having a tetrahydropyran skeleton, an unsaturated compound having a pyran skeleton, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide and vinyl acetate Copolymers of one or more other unsaturated compounds selected, and [B] 1,2-quinonediazide compound A radiation-sensitive resin composition comprising a. The radiation sensitive resin composition of Claim 1 for forming an interlayer insulation film. A method of forming an interlayer insulating film, which comprises the following steps in the order described below. (1) process of forming the coating film of the radiation sensitive resin composition of Claim 1 on a board | substrate, (2) irradiating at least a part of the coating film with radiation; (3) developing process, and (4) heating step. An interlayer insulating film formed by the method according to claim 3. The radiation sensitive resin composition of Claim 1 for microlens formation. A method for forming a microlens, comprising the following steps in the order described below. (1) Process of forming the coating film of the radiation sensitive composition of Claim 1 on a board | substrate, (2) irradiating at least a part of the coating film with radiation; (3) developing process, and (4) heating step. A microlens formed by the method of claim 6.

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