KR100858446B1 - Radiation sensitive resin composition, interlayer dielectric and microlens, and method for producing thereof - Google Patents

Abstract

A radiation sensitive composition having high radiation sensitivity, having a developing margin capable of forming a better pattern even when the optimum developing time is exceeded in the developing step, and easily forming a patterned thin film excellent in adhesion, and the same It is to provide an interlayer insulating film and a microlens formed from.

Radiation-sensitive resin containing an unsaturated carboxylic acid and / or unsaturated carboxylic anhydride, an epoxy group containing unsaturated compound, a phenol skeleton containing unsaturated compound, and the copolymer of unsaturated compounds other than the said compound, and 1, 2-quinonediazide compound Composition.

Description

Radiation-sensitive resin composition, interlayer insulating film and microlens, and a method of manufacturing the same {RADIATION SENSITIVE RESIN COMPOSITION, INTERLAYER DIELECTRIC AND MICROLENS, AND METHOD FOR PRODUCING THEREOF}

1 is a schematic view of the cross-sectional shape of a microlens.

TECHNICAL FIELD This invention relates to a radiation sensitive resin composition, an interlayer insulation film and a microlens, and their manufacturing method.

In an electronic component such as a thin film transistor (hereinafter referred to as "TFT") type liquid crystal display device, a magnetic head device, an integrated circuit device, or a solid state image pickup device, an interlayer insulating film is generally formed to insulate between wirings arranged in layers. It is. As a material which forms an interlayer insulation film, since the number of processes for obtaining the required pattern shape is small, and it is preferable to have sufficient flatness, the radiation sensitive resin composition is used widely (refer patent document 1 and patent document 2).

Among the electronic components, for example, a TFT type liquid crystal display element is manufactured through a process of forming a transparent electrode film on the interlayer insulating film and then forming a liquid crystal alignment film thereon, so that the interlayer insulating film is used for forming a transparent electrode film. In order to be exposed to a high temperature condition or to a stripping solution of a resist used for pattern formation of an electrode, sufficient resistance to these is required.

In recent years, in the TFT type liquid crystal display device, there are trends such as large screen, high brightness, high definition, high speed response, and thinning, and have high sensitivity as a composition for forming an interlayer insulating film used therein, and having a low dielectric constant in the interlayer insulating film to be formed. In high transmittance and the like, conventionally, high performance has been demanded.

On the other hand, a microlens having a lens diameter of about 3 to 100 µm as an imaging optical system of an on-chip color filter such as a facsimile, an electronic copying machine, a solid-state imaging device, or 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 the lens is formed and then melt-flowed by heat treatment, and used as it is as a lens, or by dry etching using a melt-flowed lens pattern as a mask. Background Art A method of transferring a lens shape is known. The radiation sensitive resin composition is widely used for formation of the said lens pattern (refer patent document 3 and patent document 4).

However, in order to remove the various insulating films on the bonding pads, which are wiring forming portions, the device in which the microlenses or the microlens arrays are formed as described above is coated with a planarization film and an etching resist film and exposed using a predetermined mask. It develops and removes the etching resist of a bonding pad part, and then removes a planarization film and various insulating films by etching, and exposes a bonding pad part. Therefore, in the microlens or the microlens array, solvent resistance and heat resistance are required in the film forming step and the etching step of the planarization film and the etching resist.

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

In addition, the interlayer insulating film and the microlens obtained in this way have a developing solution that penetrates between the pattern and the substrate and easily peels off when the developing time is excessively slightly larger than the optimum time in the developing step when forming them. It was necessary to strictly control the developing time, and there was a problem in terms of yield of the product.

Thus, when forming an interlayer insulation film and a microlens from a radiation sensitive resin composition, it is required to have a high sensitivity as a composition, and peeling of a pattern generate | occur | produces even if the developing time becomes more than predetermined time in the image development process during a formation process. In addition, it exhibits good adhesion, and the interlayer insulating film formed therefrom requires high heat resistance, high solvent resistance, low dielectric constant, high transmittance, and the like, and on the other hand, when forming a microlens, a good melt shape as a microlens (predetermined Radius of curvature), 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.

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

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

[Patent Document 3] Japanese Patent Application Laid-Open No. 6-18702

[Patent Document 4] Japanese Patent Application Laid-Open No. 6-136239

This invention is made | formed based on the above circumstances. Therefore, it is an object of the present invention to easily form a patterned thin film having high radiation sensitivity, having a developing margin capable of forming a better pattern even when the optimum developing time is exceeded in the developing step, and having excellent adhesion. It is providing the radiation sensitive composition which can be performed.

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

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.

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

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

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

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

(a2) Epoxy group containing unsaturated compound (Hereinafter, it may be called "compound (a2).),

(a3) the following formula (I)

(Wherein R ¹ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R ² to R ⁶ are the same or different, a hydrogen atom, a hydroxyl group or an alkyl group having 1 to 4 carbon atoms, B is a single bond,- COO- or -CONH-, m is an integer of 0 to 3, provided that at least one of R ² to R ⁶ is a hydroxyl group.)

Phenolic skeleton-containing unsaturated compound represented by

, And

(a4) Copolymers (hereinafter referred to as "copolymer [A]") of unsaturated compounds other than (a1), (a2) and (a3) (hereinafter may be referred to as "compound (a4)"). There is this.), And

(B) A 1,2-quinone diazide compound (Hereinafter, it may be called "[B] component.) Is contained, It is achieved by the radiation sensitive resin composition characterized by the above-mentioned.

The objects and advantages of the present invention in the second,

It is achieved by the method for forming an interlayer insulating film or microlens, which comprises the following steps in the order described below.

(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 process.

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

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), compound (a3) and compound (a4) in the presence of a polymerization initiator in a solvent. The copolymer [A] used in the present invention preferably has 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). Is 5 to 40% by weight, particularly preferably 5 to 25% by weight. When the copolymer having less than 5% by weight of this structural unit is used, it is difficult to dissolve it in the aqueous alkali solution during the development step, while the copolymer having more than 40% by weight tends to have too high solubility in the aqueous alkali solution.

Compound (a1) is an unsaturated carboxylic acid and / or unsaturated carboxylic anhydride having radical polymerizability, for example, monocarboxylic acid, dicarboxylic acid, anhydride of dicarboxylic acid, mono carboxylic acid [(Meth) acryloyloxyalkyl] ester, the mono (meth) acrylate of the polymer which has a carboxyl group and a hydroxyl group at both terminals, the polycyclic compound which has a carboxyl group, its anhydride, etc. are mentioned.

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, succinic acid mono [2- (meth) acryloyloxyethyl], phthalic acid mono [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 a polycyclic compound which has a carboxyl group, and its anhydride, For example, 5-carboxy bicyclo [2.2.1] hept-2-ene, 5, 6- dicarboxy bicyclo [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 these, anhydrides of monocarboxylic acid and dicarboxylic acid are preferably used, and acrylic acid, methacrylic acid and maleic anhydride are particularly preferably used in terms 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 (a2) based on the sum of the repeating units derived from the compounds (a1), (a2), (a3) and (a4). Preferably it is 10 to 80% by weight, particularly preferably 30 to 80% by weight. When this structural unit is less than 10 weight%, the heat resistance and surface hardness of the obtained interlayer insulation film and microlens tend to fall, and when the quantity of this structural unit exceeds 80 weight%, the storage stability of a radiation sensitive resin composition This tends to be lowered.

The compound (a2) is an epoxy group-containing unsaturated compound having radical polymerizability, for example, glycidyl acrylate, glycidyl methacrylate, glycidyl α-ethyl acrylate, glycidyl α-propyl acrylate, α Glycidyl n-butylacrylate, 3,4-epoxybutyl acrylate, methacrylic acid-3,4-epoxybutyl, acrylic acid-6,7-epoxyheptyl, methacrylic acid-6,7-epoxyheptyl, α -Ethyl acrylate-6,7-epoxyheptyl, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether, etc. are mentioned. 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. These compounds (a2) are used individually or in combination.

Copolymer [A] used in the present invention is preferably a structural unit derived from compound (a3) based on the sum of repeating units derived from compounds (a1), (a2), (a3) and (a4). Preferably it is 1 to 50% by weight, particularly preferably 3 to 40% by weight. When this structural unit is less than 1 weight%, there exists a tendency for the sensitivity of a radiation sensitive resin composition to fall, and when it exceeds 50 weight%, in the developing process in formation of an interlayer insulation film or a microlens, Its solubility tends to be too large.

Compound (a3) is an unsaturated compound which contains a phenol skeleton and has radical polymerizability, and is a following formula (I)

(Wherein R ¹ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R ² to R ⁶ are the same or different, a hydrogen atom, a hydroxyl group or an alkyl group having 1 to 4 carbon atoms, B is a single bond,- COO- or -CONH-, m is an integer of 0 to 3, provided that at least one of R ² to R ⁶ is a hydroxyl group.)

It is represented by

The compound represented by said formula (I) can be classified into the compound represented by following formula (1)-(5) by definition of B and m.

(In formula (1), n is an integer of ^1-3 , and the definition of R <^1> , R <^2> , R <^3> , R <^4> , R <^5> , and R <^6> is the same as Formula (I).)

(In formula (2), definition of R <^1> , R <^2> , R <^3> , R <^4> , R <^5> , and R <^6> is the same as said Formula (I).)

(In formula (3), n is an integer of 1-3. The definition of R <^1> , R <^2> , R <^3> , R <^4> , R <^5> , and R <^6> is the same as said Formula (I).)

(In formula (4), the definition of R <^1> , R <^2> , R <^3> , R <^4> , R <^5> , and R <^6> is the same as said Formula (I).)

(In formula (5), definition of R <^1> , R <^2> , R <^3> , R <^4> , R <^5> , and R <^6> is the same as said Formula (I).)

Among these, N- (3,5-dimethyl-4-hydroxybenzyl) (meth) acrylamide, N- (4-hydroxyphenyl) (meth) acrylamide, 4-hydroxybenzyl (meth) acrylate, 4-hydroxyphenyl (meth) acrylate, o-hydroxystyrene, m-hydroxystyrene, p-hydroxystyrene, α-methyl-o-hydroxystyrene, α-methyl-m-hydroxystyrene, α -Methyl-p-hydroxystyrene is preferably used in view of increasing the sensitivity of the radiation-sensitive resin composition, widening the development margin, and improving heat resistance. These are used individually 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 it is 5 to 70% by weight, particularly preferably 5 to 50% by weight. When this structural unit is less than 5 weight%, there exists a tendency for the storage stability of a radiation sensitive resin composition to fall, and when it exceeds 70 weight%, the aqueous alkali solution in the image development process in formation of an interlayer insulation film or a microlens. It may become difficult to dissolve in.

The compound (a4) is not particularly limited as long as it is an unsaturated compound having radical polymerizability. For example, methacrylic acid alkyl ester, acrylic acid alkyl ester, methacrylic acid cyclic alkyl ester, methacrylic acid ester having a hydroxyl group, acrylic acid cyclic alkyl ester, methacrylic acid aryl ester, acrylic acid aryl ester, unsaturated dicarboxylic acid diester, Bicyclo unsaturated compounds, maleimide compounds, unsaturated aromatic compounds, conjugated dienes, tetrahydrofuran skeleton, furan skeleton, tetrahydropyran skeleton, pyran skeleton, unsaturated compounds having a skeleton represented by the following formula (6) and other unsaturated compounds Can be mentioned.

(In formula (6), R ⁷ is a hydrogen atom or a methyl group.)

As these specific examples, as methacrylic acid alkyl ester, for example, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate, t-butyl methacrylate, 2-ethylhexyl Methacrylate, isodecyl methacrylate, n-lauryl methacrylate, tridecyl methacrylate, n-stearyl methacrylate and the like;

As acrylic acid alkyl ester, For example, methyl acrylate, isopropyl acrylate, etc .;

As methacrylic acid cyclic alkylester, for example, cyclohexyl methacrylate, 2-methylcyclohexyl methacrylate, tricyclo [5.2.1.0 ^2,6 ] decane-8-yl methacrylate, tricyclo [5.2. 1.0 ^2,6 ] decane-8- ^yloxyethyl methacrylate, isobornyl methacrylate, and the like; As methacrylic acid ester which has a hydroxyl group, For example, hydroxymethyl methacrylate, 2-hydroxyethyl methacrylate, 3-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, diethylene glycol monometha Methacrylate, 2,3-dihydroxypropyl methacrylate, 2-methacryloxyethylglycoside, 4-hydroxyphenyl methacrylate, and the like;

As acrylic acid cyclic alkylester, For example, cyclohexyl acrylate, 2-methylcyclohexyl acrylate, tricyclo [5.2.1.0 ^2,6 ] decane-8-yl acrylate, tricyclo [5.2.1.0 ^2,6 ] Decan-8-yloxyethyl acrylate, isobonyl acrylate and the like;

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

As acrylic acid aryl ester, For example, phenyl acrylate, benzyl acrylate;

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

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-methoxybicyclo [2.2.1] hept-2-ene, 5-ethoxybicyclo [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-t-butoxycarbonylbicyclo [2.2.1] hept-2-ene, 5-cyclohexyl ox Cycarbonylbicyclo [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-ethylbicycle [2.2.1] hept-2-ene, and 5-hydroxy-5-methyl-bicyclo [2.2.1] hept-2-ene;

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 Propionate, 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 unsaturated compounds containing a tetrahydrofuran skeleton, for example, tetrahydrofurfuryl (meth) acrylate, 2-methacryloyloxy-propionic acid tetrahydrofurfuryl ester, 3- (meth) acryloyloxy tetrahydro Furan-2-one and the like;

As unsaturated compounds containing furan skeletons, 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, acrylic acid 2-furan-2-yl-1-methyl-ethylester, 6- (2-furyl) -6-methyl-1-hepten-3-one Etc;

As unsaturated compounds containing tetrahydropyran skeletons, for example (tetrahydropyran-2-yl) methylmethacrylate, 2,6-dimethyl-8- (tetrahydropyran-2-yloxy) -octo-1 -En-3-one, 2-methacrylic acid tetrahydropyran-2-yl ester, 1- (tetrahydropyran-2-oxy) -butyl-3-en-2-one and the like;

As unsaturated compounds containing pyran skeletons, 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-pyrone and the like;

As an unsaturated compound containing the skeleton represented by the said Formula (6), For example, polyethyleneglycol (n = 2-10) mono (meth) acrylate, polypropylene glycol (n = 2-10) mono (meth) acryl Rate and the like;

As another unsaturated compound, an acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, vinyl acetate is mentioned, for example.

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 ( Meta) acrylate, polyethylene glycol (n = 2-10) mono (meth) acrylate, 3- (meth) acryloyloxytetrahydrofuran-2-one, 1- (tetrahydropyran-2-oxy)- Butyl-3-en-2-one and furfuryl (meth) acrylate are preferred in view of copolymerization reactivity and solubility in aqueous alkali solution. These compounds (a4) are used individually or in combination.

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 copolymer, methacrylic acid / methacrylic acid glycidyl / 1- (tetrahydropyran-2-oxy)- Butyl-3-en-2-one / N-cyclohexylmaleimide / p-methoxystyrene / N- (3,5-dimethyl-4-hydroxybenzyl) methacrylamide copolymer, methacrylic acid / methacryl Shanglycidyl / tricyclo [5.2.1.0 ^2,6 ] decane-8-yl methacrylate / styrene / N-phenylmaleimide / N- (4-hydroxyphenyl) methacrylamide copolymer, methacrylic acid Methacrylate glycidyl / tricyclo [5.2.1.0 ^2,6 ] decane-8-yl methacrylate / n-lauryl methacrylate / 3-methacryloyloxytetrahydrofuran-2-one / N- (4-hydroxyphenyl) methacrylamide aerial Copolymer, methacrylic acid / methacrylate glycidyl / styrene / 2-methylcyclohexyl acrylate / 1- (tetrahydropyran-2-oxy)-butyl-3-en-2-one / 4-hydroxybenzyl Methacrylate copolymer, methacrylic acid / methacrylate glycidyl / tricyclo [5.2.1.0 ^2,6 ] decane-8-ylmethacrylate / p-methoxystyrene / 4-hydroxybenzyl methacrylate Copolymer, methacrylic acid / tricyclo [5.2.1.0 ^2,6 ] decane-8-ylmethacrylate / glycidyl methacrylate / styrene / p-vinylbenzylglycidyl ether / tetrahydrofurfurylmethacryl Rate / 4-hydroxyphenyl methacrylate copolymer, methacrylic acid / methacrylate glycidyl / N-cyclohexylmaleimide / 3-methacryloyloxytetrahydrofuran-2-one / tetrahydrofurfuryl Methacrylate / 4-hydroxyphenyl methacrylate copolymer, methacrylic acid / methacrylate glycidyl / tetrahydrofurfuryl methacrylate / N-phenylmaleimide / α-methyl-p-hydroxystyrene copolymer, methacrylic acid / methacrylate glycidyl / tricyclo [5.2.1.0 ^2,6 ] decane-8-ylmethacrylate / N- Cyclohexyl maleimide / n-lauryl methacrylate / (alpha)-methyl- p-hydroxy styrene copolymer is 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 . When Mw is less than 2x10 <^3> , development margin may become inadequate, the residual film ratio of a film obtained etc. may fall, or the pattern shape, heat resistance, etc. of an interlayer insulation film or microlens obtained may be inferior, On the other hand, when it exceeds 1 * 10 <^5> , a sensitivity may fall or a pattern shape may be inferior. 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 obtained interlayer insulation film or microlens may be inferior. The radiation sensitive resin composition containing said copolymer [A] can easily form a predetermined pattern shape, without developing developing residue at the time of image development.

As a solvent used for manufacture of copolymer [A], an alcohol, an ether, glycol ether, ethylene glycol alkyl ether acetate, diethylene glycol, propylene glycol monoalkyl ether, propylene glycol alkyl ether acetate, propylene glycol alkyl ether pro, for example is used. Cypionate, aromatic hydrocarbon, ketone, ester, etc. are mentioned.

As these specific examples, As alcohol, For example, methanol, ethanol, benzyl alcohol, 2-phenylethyl alcohol, 3-phenyl-1-propanol;

Tetrahydrofuran etc. as ethers;

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

As ethylene glycol alkyl ether acetate, For example, methyl cellosolve acetate, ethyl cellosolve acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monoethyl ether acetate, etc .; As diethylene glycol, For example, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, etc .;

As propylene glycol monoalkyl ether, For example, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, etc .;

As a propylene glycol alkyl ether propionate, For example, propylene glycol methyl ether propionate, propylene glycol ethyl ether propionate, propylene glycol propyl ether propionate, propylene glycol butyl ether propionate, etc .;

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

As an aromatic hydrocarbon, For example, toluene, xylene, etc .;

As a ketone, For example, methyl ethyl ketone, cyclohexanone, 4-hydroxy-4-methyl- 2-pentanone, etc .;

As the ester, for example, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, hydroxyacetic acid Methyl, ethyl hydroxy acetate, hydroxy butyl acetate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, methyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, propyl hydroxypropionate, 3-hydroxy Butyl propionate, methyl 2-hydroxy-3-methylbutyrate, methyl methoxy acetate, ethyl methoxy acetate, methoxy propyl acetate, methoxy butyl acetate, methyl ethoxy acetate, ethyl ethoxy acetate, ethoxy propyl acetate, Butyl ethoxy acetate, methyl propoxy acetate, ethyl propoxy acetate, propyl propoxy acetate, butyl propoxy acetate, methyl butoxy acetate, ethyl butoxy acetate, butyl butoxy acetate, butyl butoxy acetate, 2-methoxypropionic acid Methyl, 2-methoxypropion Ethyl Acid, 2-Methoxy Propionate, 2-Methoxy Propionate, 2-Ethoxy Propionate, 2-Ethoxy Propionate, 2-Ethoxy Propionate, 2-Ethoxy Propionate, 2-Butoxypropionate Methyl, ethyl 2-butoxypropionate, propyl 2-butoxypropionate, butyl 2-butoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate Methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, propyl 3-ethoxypropionate, butyl 3-ethoxypropionate, methyl 3-propoxypropionate, ethyl 3-propoxypropionate, 3-propoxypropionate, Ester, such as 3-butyl propoxypropionate, 3-butoxy methyl propionate, 3-butoxy ethyl propionate, 3-butoxy propyl propionate, and 3-butyl butyl propionate, is mentioned, respectively.

Among these, ethylene glycol alkyl ether acetate, diethylene glycol, propylene glycol monoalkyl ether, and propylene glycol alkyl ether acetate are preferable, and in particular, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, propylene glycol methyl ether, and propylene glycol Ethyl ether, propylene glycol methyl ether acetate and methyl 3-methoxypropionate are preferable.

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, you may use a peroxide together with a reducing agent 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, (alpha) -methylstyrene dimer, etc. are mentioned.

[B] component

[B] component used by this invention is a 1, 2- quinonediazide compound which generate | occur | produces a carboxylic acid by irradiation of a radiation, A phenolic compound or an alcoholic compound (henceforth "mother nucleus"), Condensates of 1,2-naphthoquinone diazide sulfonic acid halide can be used.

Examples of the mother core include trihydroxybenzophenone, tetrahydroxybenzophenone, pentahydroxybenzophenone, hexahydroxybenzophenone, (polyhydroxyphenyl) alkane, and other mother cores.

As these specific examples, it is trihydroxy benzophenone, For example, 2,3,4- trihydroxy benzophenone, 2,4,6- trihydroxy benzophenone etc .;

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

As pentahydroxy benzophenone, For example, 2,3,4,2 ', 6'- pentahydroxy benzophenone etc .;

As hexahydroxybenzophenone, for example, 2,4,6,3 ', 4', 5'-hexahydroxybenzophenone, 3,4,5,3 ', 4', 5'-hexahydroxybenzo Phenone and the like;

As (polyhydroxyphenyl) alkanes, for example, 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'-trihydroxyflavan and the like;

As other parent nuclei, for example, 2-methyl-2- (2,4-dihydroxyphenyl) -4- (4-hydroxyphenyl) -7-hydroxychroman, 2- [bis {(5- Isopropyl-4-hydroxy-2-methyl) phenyl} methyl], 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, 4,6-bis {1- (4-hydroxyphenyl) -1-methylethyl} -1,3-dihydroxybenzene is mentioned.

In addition, 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-naphthoquinonedia Zide-4-sulfonic acid amide etc. are also used preferably.

Of these mother cores, 2,3,4,4'-tetrahydroxybenzophenone, 4,4 '-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene Bisphenol is preferable.

As the 1,2-naphthoquinone diazide sulfonic acid halide, 1,2-naphthoquinone diazide sulfonic acid chloride is preferable, and specific examples thereof include 1,2-naphthoquinone diazide-4-sulfonic acid chloride and 1 And 2-naphthoquinone diazide-5-sulfonic acid chloride, among which it is preferable to use 1,2-naphthoquinone diazide-5-sulfonic acid chloride.

In the condensation reaction, 1,2-naphthoquinone diazide sulfonic acid halide corresponding to the number of OH groups in the phenolic compound or the alcoholic compound is preferably 30 to 85 mol%, more preferably 50 to 70 mol%. It is available.

Condensation reaction can be performed by a well-known method.

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, and more preferably 10 to 50 parts by weight based on 100 parts by weight of the copolymer [A]. When this ratio is less than 5 parts by weight, the difference in solubility between the irradiated portion and the unirradiated portion of the radiation to the alkaline aqueous solution serving as the developing solution is small, so that 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.

Other ingredients

Although the radiation sensitive resin composition of this invention contains said copolymer [A] and [B] component as an essential component, other [C] thermosensitive acid generating compound and [D] at least 1 ethylene as needed. The polymerizable compound which has a sex unsaturated double bond, epoxy resins other than [E] copolymer [A], [F] adhesion | attachment adjuvant, or [G] surfactant can be contained.

Said thermosensitive acid generating 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.

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-acetoxy phenylbenzylmethylsulfonium 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.

Specific examples of the benzothiazonium salt include 3-benzylbenzothiazonium hexafluoroantimonate, 3-benzylbenzothiazonium hexafluorophosphate, 3-benzylbenzothiazonium tetrafluoroborate, 3- (p-methoxybenzyl ) Benzylbenzo, such as benzothiazonium hexafluoro antimonate, 3-benzyl-2-methylthiobenzothiazonium hexafluoro antimonate, and 3-benzyl-5-chlorobenzothiazonium hexafluoro antimonate 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-benzyl Benzothiazolium hexafluoroantimonate is preferably used.

Examples of such commercially available products include San-Aid SI-L85, East SI-L110, East SI-L145, East SI-L150, East SI-L160 (manufactured by Sanshin Kakagaku Kogyo Co., Ltd.), and the like.

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]. In the case where the amount of use exceeds 20 parts by weight, precipitates may precipitate in the coating film forming step, which may interfere with the coating film formation.

As a polymeric compound (Hereinafter, it may be called "D component.") Which has at least 1 ethylenically unsaturated double bond which is the said [D] component, For example, monofunctional (meth) acrylate and bifunctional (meth) ) Acrylate or (meth) acrylate more than trifunctional is mentioned preferably.

As said monofunctional (meth) acrylate, 2-hydroxyethyl (meth) acrylate, carbitol (meth) acrylate, isobonyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, for example And 2- (meth) acryloyloxyethyl-2-hydroxypropyl phthalate, and the like. As these commercial items, for example, Aronix M-101, copper M-111, copper M-114 (above, product made by Toagosei Co., Ltd.), KAYARAD TC-110S, and copper TC-120S (above, Nihon Kayakaku ( Ltd.), Biscot 158, East 2311 (above, Osaka Yuki Kagaku Kogyo Co., Ltd.), etc. are mentioned.

As said bifunctional (meth) acrylate, ethylene glycol (meth) acrylate, 1, 6- hexanediol di (meth) acrylate, 1, 9- nonane diol di (meth) acrylate, polypropylene glycol is mentioned, for example. Di (meth) acrylate, tetraethylene glycol di (meth) acrylate, bisphenoxyethanol fluorene diacrylate, bisphenoxy ethanol fluorene diacrylate, and the like. As these commercial items, for example, Aronix M-210, M-240, M-6200 (above, Toagosei Co., Ltd.), KAYARAD HDDA, HX-220, R-604 (above, Nihon) Kayaku Co., Ltd., biscoat 260, copper 312, copper 335HP (above, Osaka Yuki Kagaku Kogyo Co., Ltd. product) etc. are mentioned.

As said (meth) acrylate more than trifunctional, a trimethol propane tri (meth) acrylate, a pentaerythritol tri (meth) acrylate, a tri ((meth) acryloyloxyethyl) phosphate, a pentaerythritol tetra, for example (Meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, etc. are mentioned, As a commercial item, it is Aronix M-309, M-400, copper, for example. M-405, M-450, M-7100, M-8030, M-8060 (above, manufactured by Toagosei Co., Ltd.), KAYARAD TMPTA, East DPHA, East DPCA-20, East DPCA-30, East DPCA-60, East DPCA-120 (above, made by Nihon Kayaku Co., Ltd.), Biscot 295, East 300, East 360, East GPT, East 3PA, East 400 (above, Osaka Yukikagaku Kogyo Co., Ltd.) 1) etc. can be 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 individually 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 an 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 copolymer [A] which is the said [E] component (Hereinafter, it may be called "E component.") Are not limited unless there is an influence on compatibility. Preferably, bisphenol A type epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, cyclic aliphatic epoxy resin, glycidyl ester type epoxy resin, glycidylamine type epoxy resin, heterocyclic epoxy resin, glyc The resin etc. which co-polymerized the cyl methacrylate are mentioned. Of these, bisphenol A epoxy resins, cresol novolac epoxy resins, glycidyl ester epoxy resins and the like are particularly 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.

Moreover, 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.

In order to further improve applicability, surfactant which is the said [F] component can be used for the radiation sensitive resin composition of this invention. As [F] surfactant which can be used here, a fluorochemical surfactant, silicone type surfactant, and 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 perfluorododecyl sulfonate, 1,1,2 Sodium fluoroalkylbenzenesulfonate, such as 2,8,8,9,9,10,10-decafluorododecane and 1,1,2,2,3,3-hexafluorodecane; Fluoroalkyloxyethylene ethers; Fluoroalkylammonium iodides, fluoroalkylpolyoxyethylene ethers, perfluoroalkylpolyoxyethanols; Perfluoroalkylalkoxylates; Fluorine-based alkyl esters and the like. As these commercial items, BM-1000, BM-1100 (above, manufactured by BM Chemie Co., Ltd.), Mega Pack F142D, East F172, East F173, East F183, East F178, East F191, East F471 (above, Dainippon Ink & Chemical Co., Ltd.) Co., Ltd.), Floroid FC-170C, FC-171, FC-430, FC-431 (above, Sumitomos Rem Co., Ltd.), Saffron S-112, S-113, S-131 , S-141, S-145, S-382, SSC-101, SSC-102, SSC-103, SSC-104, SSC-105, SSC-106 (Asahi Glass Ltd.), 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 ( (Trade name), 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 Nos. 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] surfactant is 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 a [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 | substrate, the adhesion | attachment adjuvant which is a [G] component can also be used. As such [G] adhesion 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, trimethoxysilyl benzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-glycidoxypropyl Trimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and the like. 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, the development residue may easily occur in the development step.

Radiation-sensitive resin composition

The radiation sensitive resin composition of this invention is prepared by uniformly mixing said copolymer [A] and [B] component, 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, Preferably it is used in solution state. For example, the radiation-sensitive resin composition in a solution state can be prepared by mixing the copolymer [A] and the component [B] and other components optionally added in a predetermined ratio.

As a solvent used for preparation of the radiation sensitive resin composition of this invention, it is a thing which melt | dissolves each component of the copolymer [A] and [B] component and the other components arbitrarily mix | blended, and 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 these, 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.

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, 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, maleic acid Diethyl, gamma -butyrolactone, ethylene carbonate, propylene carbonate, phenyl cellosolve acetate, and the like. Among these, N-methylpyrrolidone, γ-butyrolactone, and N, N-dimethylacetamide are preferable.

When using a high boiling point solvent together as a solvent of the radiation sensitive resin composition of this invention, the usage-amount shall 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. Can be. 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.

In the case where the radiation-sensitive resin composition of the present invention is prepared in a solution state, the ratio of components (ie, the total amount of the copolymer [A] and [B] components and other components optionally added) other than the solvent in the solution is Although it can set arbitrarily according to a purpose of use, a value of predetermined film thickness, etc., Preferably it is 5-50 weight%, More preferably, it is 10-40 weight%, More preferably, it is 15-35 weight%.

The composition solution thus prepared can be used for use after being filtered using a Millipore filter having a pore diameter 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 is demonstrated using the radiation sensitive resin composition of this invention. The method for forming an interlayer insulating film or microlens of the present invention includes the following steps in the order described below.

(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 process.

(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 board | substrate surface, Preferably a solvent is removed by performing prebaking, and the coating film of a radiation sensitive resin composition is formed.

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

The coating method of the composition solution is not particularly limited, and for example, a suitable method such as spraying, roll coating, spin coating (spin coating), slit die coating, bar coating or inkjet can be adopted. In particular, the spin coating method and the slit die coating method are preferable. The conditions for the 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 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 process of said (2), after irradiating a radiation to the formed coating film through the mask which has a predetermined | prescribed pattern, patterning is performed by developing by using a developing solution and removing the irradiation part of radiation. 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, when forming an interlayer insulation film, it is desirable to set it as 50-1,500 J / m <2> 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, An aqueous solution of an alkali (basic compound) such as 0] -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 quantity to the aqueous solution of said alkali, 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 set as 30 to 120 second, for example.

Moreover, since the peeling will generate | occur | produce in the formed pattern when the developing time exceeds about 20-25 second from the optimal value, the radiation-sensitive resin composition conventionally known was required to strictly control the developing time, but the radiation of the present invention In the case of the resin composition, 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 step (3) carried out as described above, the patterned thin film is preferably rinsed with, for example, running water washing, and more preferably irradiated with radiation of a high-pressure mercury lamp to the entire surface (post exposure). By decomposing the 1,2-quinonediazide compound remaining in the thin film, the heat treatment (post-baking) of the thin film is performed by a heating apparatus such as a hot plate or an oven, thereby curing the thin film. 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 a heating apparatus, it can be set as 5 to 30 minutes, for example, when heat processing on a hotplate, and 30 to 90 minutes when 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 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 so as to be clear 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, low dielectric constant, and can be suitably used as an interlayer insulating film of an electronic component.

Microlenses

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

In addition, the shape of 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

7 parts by weight of 2,2'-azobis (2,4-dimethylvaleronitrile) and 200 parts by weight of diethylene glycol ethylmethyl ether were added to a flask equipped with a cooling tube and a stirrer. 14 parts by weight of methacrylic acid, 16 parts by weight of tricyclo [5.2.1.0 ^2,6 ] decane-8-ylmethacrylate, 20 parts by weight of 2-methylcyclohexyl acrylate, and 40 parts by weight of glycidyl methacrylate 10 parts by weight of N- (3,5-dimethyl-4-hydroxybenzyl) methacrylamide and 3 parts by weight of α-methylstyrene dimer were added and nitrogen-substituted, followed by slow stirring. The temperature of the solution was raised to 70 ° C, and this temperature was maintained for 4 hours to obtain a polymer solution containing a copolymer [A-1].

The polystyrene reduced weight average molecular weight (Mw) of the copolymer [A-1] was 8,000 and molecular weight distribution (Mw / Mn) was 2.3. In addition, the solid content concentration of the polymer solution obtained here was 34.4 weight%.

Synthesis Example 2

9 parts by weight of 2,2'-azobis (2,4-dimethylvaleronitrile) and 220 parts by weight of diethylene glycol ethylmethyl ether were added to a flask equipped with a cooling tube and a stirrer. 12 parts by weight of methacrylic acid, 12 parts by weight of p-methoxystyrene, 15 parts by weight of 1- (tetrahydropyran-2-oxy) -butyl-3-en-2-one, and glycidyl methacrylate 40 Parts by weight, 10 parts by weight of N-cyclohexylmaleimide, 10 parts by weight of N- (3,5-dimethyl-4-hydroxybenzyl) methacrylamide, and 3 parts by weight of α-methylstyrene dimer, followed by nitrogen replacement. , Began to stir slowly. The temperature of the solution was raised to 70 ° C, and this temperature was maintained for 4 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 8,100 and molecular weight distribution (Mw / Mn) was 2.4. In addition, the solid content concentration of the polymer solution obtained here was 32.7 weight%.

Synthesis Example 3

7 parts by weight of 2,2'-azobis (2,4-dimethylvaleronitrile) and 220 parts by weight of diethylene glycol ethylmethyl ether were added to a flask equipped with a cooling tube and a stirrer. 6 parts by weight of styrene, 16 parts by weight of methacrylic acid, 18 parts by weight of tricyclo [5.2.1.0 ^2,6 ] decane-8-yl methacrylate, 10 parts by weight of N-phenylmaleimide, and methacrylate 40 parts by weight of cylyl, 10 parts by weight of N- (4-hydroxyphenyl) methacrylamide and 3 parts by weight of? -Methylstyrene dimer were added and nitrogen-substituted, followed by slow 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 a copolymer [A-3].

The polystyrene reduced weight average molecular weight (Mw) of the copolymer [A-3] was 8500 and molecular weight distribution (Mw / Mn) was 2.2. In addition, the solid content concentration of the polymer solution obtained here was 32.2 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 added to a flask equipped with a cooling tube and a stirrer. 15 parts by weight of methacrylic acid, 15 parts by weight of tricyclo [5.2.1.0 ^2,6 ] decane-8-ylmethacrylate, 40 parts by weight of glycidyl methacrylate, 3-methacryloyloxytetrahydro 10 parts by weight of furan-2-one, 10 parts by weight of n-lauryl methacrylate, 10 parts by weight of N- (4-hydroxyphenyl) methacrylamide, and 3 parts by weight of α-methylstyrene dimer were added and nitrogen-substituted. After that, stirring began slowly. 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 a copolymer [A-4].

The polystyrene reduced weight average molecular weight (Mw) of the copolymer [A-4] was 7,700 and molecular weight distribution (Mw / Mn) was 1.8. In addition, the solid content concentration of the polymer solution obtained here was 31.9 weight%.

Synthesis Example 5

7 parts by weight of 2,2'-azobis (2,4-dimethylvaleronitrile) and 200 parts by weight of diethylene glycol ethylmethyl ether were added to a flask equipped with a cooling tube and a stirrer. 10 parts by weight of styrene, 15 parts by weight of methacrylic acid, 40 parts by weight of glycidyl methacrylate, 10 parts by weight of 2-methylcyclohexyl acrylate, 1- (tetrahydropyran-2-oxy) -butyl-3 10 parts by weight of -en-2-one, 15 parts by weight of 4-hydroxybenzyl methacrylate, and 3 parts by weight of? -Methylstyrene dimer were added and nitrogen-substituted, followed by slow stirring. The temperature of the solution was raised to 70 ° C, and this temperature was maintained for 4 hours to obtain a polymer solution containing a copolymer [A-5].

The polystyrene reduced weight average molecular weight (Mw) of the copolymer [A-5] was 8,300 and molecular weight distribution (Mw / Mn) was 2.1. In addition, the solid content concentration of the polymer solution obtained here was 33.9 weight%.

Synthesis Example 6

8 parts by weight of 2,2'-azobis (2,4-dimethylvaleronitrile) and 200 parts by weight of diethylene glycol ethylmethyl ether were added to a flask equipped with a cooling tube and a stirrer. 10 parts by weight of p-hydroxy styrene, 15 parts by weight of methacrylic acid, 20 parts by weight of tricyclo [5.2.1.0 ^2,6 ] decane-8-ylmethacrylate, 40 parts by weight of glycidyl methacrylate, 15 parts by weight of 4-hydroxybenzyl methacrylate and 3 parts by weight of? -Methylstyrene dimer were added and nitrogen-substituted, followed by slow 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 a copolymer [A-6].

The polystyrene reduced weight average molecular weight (Mw) of copolymer [A-6] was 7,600, and molecular weight distribution (Mw / Mn) was 2.0. In addition, solid content concentration of the polymer solution obtained here was 34.5 weight%.

Synthesis Example 7

7.5 parts by weight of 2,2'-azobis (2,4-dimethylvaleronitrile) and 230 parts by weight of diethylene glycol ethylmethyl ether were added to a flask equipped with a cooling tube and a stirrer. 5 parts by weight of styrene, 15 parts by weight of methacrylic acid, 5 parts by weight of tricyclo [5.2.1.0 ^2,6 ] decane-8-ylmethacrylate, 40 parts by weight of glycidyl methacrylate, p-vinylbenzyl 15 parts by weight of glycidyl ether, 10 parts by weight of tetrahydrofurfuryl methacrylate, 10 parts by weight of 4-hydroxyphenyl methacrylate, and 3 parts by weight of? -Methylstyrene dimer were added and nitrogen-substituted, followed by slow stirring. it 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-7].

The polystyrene reduced weight average molecular weight (Mw) of the copolymer [A-7] was 8,500 and molecular weight distribution (Mw / Mn) was 2.3. In addition, the solid content concentration of the polymer solution obtained here was 32.8 weight%.

Synthesis Example 8

7 parts by weight of 2,2'-azobis (2,4-dimethylvaleronitrile) and 200 parts by weight of diethylene glycol ethylmethyl ether were added to a flask equipped with a cooling tube and a stirrer. 12 parts by weight of methacrylic acid, 40 parts by weight of glycidyl methacrylate, 23 parts of tetrahydrofurfuryl methacrylate, 5 parts by weight of 3-methacryloyloxytetrahydrofuran-2-one, and N- 10 weight part of cyclohexyl maleimide, 10 weight part of 4-hydroxyphenyl methacrylates, and 3 weight part of (alpha) -methylstyrene dimers were thrown in and nitrogen-substituted, and stirring was started slowly. 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-8].

The polystyrene reduced weight average molecular weight (Mw) of the copolymer [A-8] was 8,000 and molecular weight distribution (Mw / Mn) was 2.2. In addition, the solid content concentration of the polymer solution obtained here was 32.4 weight%.

Synthesis Example 9

8.5 parts by weight of 2,2'-azobis (2,4-dimethylvaleronitrile) and 220 parts by weight of diethylene glycol ethylmethyl ether were added to a flask equipped with a cooling tube and a stirrer. 15 parts by weight of methacrylic acid, 40 parts by weight of glycidyl methacrylate, 20 parts by weight of tricyclo [5.2.1.0 ^2,6 ] decane-8-yl methacrylate, 15 parts by weight of N-phenylmaleimide, α 10 parts by weight of -methyl-p-hydroxystyrene and 3 parts by weight of? -Methylstyrene dimer were added and nitrogen-substituted, followed by slow 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-9].

The polystyrene reduced weight average molecular weight (Mw) of the copolymer [A-9] was 7,900 and molecular weight distribution (Mw / Mn) was 2.3. In addition, the solid content concentration of the polymer solution obtained here was 32.0 weight%.

Synthesis Example 10

8 parts by weight of 2,2'-azobis (2,4-dimethylvaleronitrile) and 220 parts by weight of diethylene glycol ethylmethyl ether were added to a flask equipped with a cooling tube and a stirrer. 11 parts by weight of methacrylic acid, 12 parts by weight of tetrahydrofurfuryl methacrylate, 40 parts by weight of glycidyl methacrylate, 15 parts by weight of N-cyclohexylmaleimide, 10 parts by weight of lauryl methacrylate, α- 10 parts by weight of methyl-p-hydroxystyrene and 3 parts by weight of? -Methylstyrene dimer were added and nitrogen-substituted, followed by slow 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-10].

The polystyrene reduced weight average molecular weight (Mw) of the copolymer [A-10] was 8,000 and the molecular weight distribution (Mw / Mn) was 2.3. In addition, the solid content concentration of the polymer solution obtained here was 31.9 weight%.

Comparative Synthesis Example 1

8 parts by weight of 2,2'-azobis (2,4-dimethylvaleronitrile) and 220 parts by weight of diethylene glycol ethylmethyl ether were added to a flask equipped with a cooling tube and a stirrer. Subsequently, 20 parts by weight of styrene, 20 parts by weight of methacrylic acid, 40 parts by weight of glycidyl methacrylate, and 20 parts by weight of phenylmaleimide were added and nitrogen-substituted, followed by slow stirring. 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-1].

The polystyrene reduced weight average molecular weight (Mw) of the copolymer [a-1] was 7,500 and molecular weight distribution (Mw / Mn) was 2.4. In addition, the solid content concentration of the polymer solution obtained here was 30.6 weight%.

Example 1

[Preparation of radiation sensitive resin composition]

The solution containing polymer [A-1] as the component [A] synthesized in Synthesis Example 1 above was used in an amount corresponding to 100 parts by weight of the polymer [A-1] (solid content) and 4,4 as component [B]. '-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol (1.0 mole) and 1,2-naphthoquinone diazide-5-sulfonic acid chloride 30 parts by weight of a (2.0 mol) condensate (B-1) was mixed, 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, followed by radiation sensitivity. The solution (S-1) of the resin composition was prepared.

Examples 2 to 36, Comparative Examples 1 to 4

[Preparation of radiation sensitive resin composition]

In Example 1, it carried out similarly to Example 1 except having used the kind and quantity as Table 1 as component [A] and [B], and the solution of a radiation sensitive resin composition (S-2 ) To (S-36) and (s-1) to (s-4) were prepared.

In Example 8, the description of the component [B] indicates that two kinds of 1,2-quinonediazide compounds were used in combination.

Example 37

In Example 1, the composition was prepared like Example 1 except having melt | dissolved in diethylene glycol ethyl methyl ether so that solid content concentration might be 15weight%, and the solution (S-37) of the radiation sensitive resin composition was prepared. .

Example 38

In Example 1, except having melt | dissolved in diethylene glycol ethyl methyl ether / propylene glycol monomethyl ether acetate = 6/4 so that solid content concentration might be 20 weight%, the composition was prepared like Example 1, and a radiation sensitive resin composition Solution (S-38) was prepared.

In Table 1, the abbreviated-name of a component shows the following compound.

(B-1): 4,4 '-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol (1.0 mole) and 1,2-naphtho Condensate of quinonediazide-5-sulfonic acid chloride (2.0 moles)

(B-2): 4,4 '-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol (1.0 mole) and 1,2-naphtho Condensate of quinonediazide-5-sulfonic acid chloride (1.0 mole)

(B-3): 2,3,4,4'-tetrahydroxybenzophenone (1.0 mol) and 1,2-naphthoquinone diazide-5-sulfonic acid ester (2.44 mol)

(F): SH-28PA (product made by Toray Dow Corning Silicone)

Examples 38-77, Comparative Examples 5-10

<Performance evaluation as an interlayer insulating film>

The various characteristics as an interlayer insulation film were evaluated as follows using the radiation sensitive resin composition prepared as mentioned above. In addition, the composition used by the comparative examples 3 and 4 is a commercial item (made by Tokyooka Co., Ltd.) of the composition of both m / p-cresol novolak and a 1, 2- naphthoquinone diazide-5-sulfonic acid ester.

[Evaluation of sensitivity]

After applying the composition shown in Table 2 using a spinner about Examples 38-75 and Comparative Examples 5-10 on a silicon substrate, and using a slit die coater about Examples 76-77, It prebaked on the hotplate for minutes, 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 pattern in the obtained coating film, tetramethylammonium hydroxide of the density shown in Table 2 was performed. When the developer of 25 degreeC, 0.4%, and 0.5% of density | concentration was used for aqueous solution, it developed for 80 seconds and the puddle method for 50 second, when using the developer of 2.38% concentration. Water flow was washed with ultrapure water for 1 minute, dried, and a pattern was formed on the wafer. The exposure amount required in order for the space pattern of the line-and-space (10: 1) of 3.0 micrometers to melt | dissolve completely was measured. This value is shown in Table 2 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]

On the silicon substrate, after applying the composition shown in Table 2 using the spinner about Examples 38-75 and Comparative Examples 5-10, and about the Examples 76-77 using the slit die coater, at 90 degreeC It prebaked on the hotplate for 2 minutes, and formed the coating film of 3.0 micrometers in thickness. The obtained coating film was measured by the above-mentioned "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. Exposure was performed at the exposure amount corresponding to the value of sensitivity, and it developed by the puddle method by changing 25 degreeC and developing time with the tetramethylammonium hydroxide aqueous solution of the density | concentration shown in Table 2. Subsequently, flowing water was washed with ultrapure water for 1 minute, dried, and a pattern was formed on the wafer. At this time, the developing time required for the line width to be 3 占 퐉 is shown in Table 2 as the optimum developing time. In addition, when developing was continued from the optimum developing time, the time until the line pattern of 3.0 micrometers was peeled off was measured, and it showed in Table 2 as image development margin. When this value is 30 seconds or more, the development margin can be said to be good.

[Evaluation of solvent resistance]

After the composition shown in Table 2 was apply | coated using a spinner about Examples 38-75 and Comparative Examples 5-10 on a silicon substrate, and about the Examples 76-77 using the slit die coater, It prebaked on the hotplate for minutes, 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 set to 3,000 J / m <2> with Canon PLA-501F exposure machine (super high pressure mercury lamp), and this silicon substrate was heated at 220 degreeC in clean oven 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 2. When this value is 5% or less, it can be said that solvent resistance is favorable.

In addition, since the patterning of the film to be formed is not necessary in evaluation of solvent resistance, the radiation irradiation process and the development process were abbreviate | omitted, and only the coating film formation process, the postbaking process, and the heating process were provided for evaluation.

[Evaluation of heat resistance]

The cured film was formed like the evaluation of the above solvent resistance, 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 clean oven for 1 hour, the film thickness t2 of the said 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 2. When this value is 5% or less, it can be said that heat resistance is favorable.

[Evaluation of transparency]

In evaluation of said solvent resistance, the cured film was formed on the glass substrate similarly except having used the glass substrate "Corning 7059 (made by Corning Corporation)" instead 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 (made by Hitachi Seisakusho)." Table 2 shows the values of the minimum light transmittance at that time. When this value is 90% or more, transparency can be said to be favorable.

[Evaluation of relative dielectric constant]

After applying the composition shown in Table 2 on the polished SUS304 board | substrate using the spinner about Examples 38-75 and Comparative Examples 5-10, and using the slit die coater about Examples 76-77, 90 It prebaked on the hotplate for 2 minutes at ° C, and formed the coating film with a film thickness of 3.0 micrometers. The cured film was obtained by exposure to the obtained coating film so that the accumulated irradiation amount might become 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 said board | substrate was measured by CV method using the HP16451B electrode made from Yokogawa Hewlett-Packard Co., Ltd., and the HP4284A flash zone LCR meter at the frequency of 10 kHz. The results are shown in Table 2. When this value is 3.6 or less, the dielectric constant is good.

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

Examples 78-115, Comparative Examples 11-16

<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 and transparency can refer to the result in the performance evaluation as the said interlayer insulation film.

In addition, the composition used by Comparative Examples 6 and 7 is a commercial item (made by Tokyooka Co., Ltd.) of the composition of both m / p-cresol novolak and a 1, 2- naphthoquinone diazide-5-sulfonic acid ester.

[Evaluation of sensitivity]

About Examples 78-115 and Comparative Examples 11-16 on a silicon substrate, after apply | coating the composition of Table 3 using a spinner, it prebaked on a hotplate at 90 degreeC for 2 minutes, and formed the coating film of 2.0 micrometers in thickness. Formed. The exposure time was changed by using the Nikon Co., Ltd. NSR1755i7A 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, and it exposed, and the tetramethylammonium of the density shown in Table 3 was exposed. It developed by the puddle method at 25 degreeC with hydroxide aqueous solution for 1 minute. Rinsed with water and dried to form a pattern on the wafer. The exposure time required for the space line width of the 0.8 mu m line and space pattern (1 to 1) to 0.8 mu m was measured. Table 3 shows this value as the sensitivity. When this value is 2,000 J / m <2> or less, it can be said that a sensitivity is favorable.

[Evaluation of development margin]

About Examples 78-115 and Comparative Examples 11-16 on a silicon substrate, after apply | coating the composition of Table 3 using a spinner, it prebaked on a hotplate at 90 degreeC for 2 minutes, and formed the coating film of 2.0 micrometers in thickness. Formed. The exposure amount corresponding to the value of the sensitivity measured by said "evaluation of sensitivity" with the Nikon NSR1755i7A reduction projection exposure machine (NA = 0.50, (lambda == 365 nm) through the pattern mask which has a predetermined pattern in the obtained coating film. Exposure was performed and it developed by the puddle method at 25 degreeC for 1 minute with the tetramethylammonium hydroxide aqueous solution of the density | concentration shown in Table 3. Rinsed with water and dried to form a pattern on the wafer. Table 3 shows the development time required for the space line width of the 0.8 µm line and space pattern (1 to 1) to be 0.8 µm as the optimum development time. Moreover, the time (development margin) until the pattern of 0.8 micrometers in width was peeled off when developing was further continued from the optimal image development time was shown in Table 3 as image development margin. When this value is 30 seconds or more, the development margin can be said to be good.

[Evaluation of solvent resistance]

About Examples 78-115 and Comparative Examples 11-16 on a silicon substrate, after apply | coating the composition of Table 3 using a spinner, it prebaked on a hotplate at 90 degreeC for 2 minutes, and formed the coating film of 2.0 micrometers in thickness. Formed. It exposed to the obtained coating film so that accumulated irradiation amount might be 3,000 J / m <2> with Canon PLA-501F exposure machine (super high pressure mercury lamp), and this silicon substrate was heated at 220 degreeC in clean oven for 1 hour, and the cured film was obtained. 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 by immersion {| t3-T3 | / T3} × 100 [%] was calculated. The results are shown in Table 3. When this value is 5% or less, it can be said that solvent resistance is favorable.

In addition, since the patterning of the film to be formed is unnecessary in evaluation of solvent resistance, the radiation irradiation process and the development process were omitted, and only the coating film forming process, the postbaking process, and the heating process were used for evaluation.

[Formation of Micro Lens]

In Examples 78 to 115 and Comparative Examples 11 to 16 on the silicon substrate, the composition shown in Table 3 was applied using a spinner, and then prebaked on a hot plate at 90 ° C. for 2 minutes to form a coating film having a thickness of 2.0 μm. Formed. Of the sensitivity measured in said "evaluation of sensitivity" with the Nikon NSR1755i7A reduction projection exposure machine (NA = 0.50, (lambda == 365 nm) through the pattern mask which has a 4.0 micrometer dot and 2.0 micrometer space pattern in the obtained coating film. It exposed at the exposure amount corresponding to a value, and it developed by the puddle 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 3. Rinsed with water and dried to form a pattern on the wafer. Then, it exposed so that the accumulated irradiation amount might be 3,000 J / m <2> with Canon PLA-501F exposure machine (ultra high pressure mercury lamp). Thereafter, the plate was heated at 160 ° C. for 10 minutes and then heated at 230 ° C. for 10 minutes to melt flow the pattern to form a microlens.

Table 3 shows the dimensions (diameter) and the cross-sectional shape of the bottom (surface in contact with the substrate) of the formed microlenses. It can be said that the dimension of the microlens bottom is satisfactory when it exceeds 4.0 µm and less than 5.0 µm. In addition, when this dimension becomes 5.0 micrometers or more, it is a state which the adjacent lenses contact, and it is unpreferable. In addition, in the schematic diagram shown in FIG. 1, a cross-sectional shape is favorable when it is a semi-convex lens shape like (a), and it is bad in the case of substantially trapezoid shape like (b).

The radiation-sensitive resin composition of the present invention has a high radiation sensitivity, has a developing margin capable of forming a better pattern even when the optimum developing time is exceeded in the developing step, and facilitates a patterned thin film excellent in adhesion. Can be formed.

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

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

Claims (8)

[A] (a1) at least one of unsaturated carboxylic acid and unsaturated carboxylic anhydride, (a2) epoxy group-containing unsaturated compounds, (a3) the following formula (I)

(Wherein R ¹ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R ² to R ⁶ are the same or different, a hydrogen atom, a hydroxyl group or an alkyl group having 1 to 4 carbon atoms, B is a single bond,- COO- or -CONH-, m is an integer of 0 to 3, provided that at least one of R ² to R ⁶ is a hydroxyl group.) A phenol skeleton-containing unsaturated compound represented by (a4) copolymers of unsaturated compounds having radical polymerizability other than (a1), (a2) and (a3), and [B] 1,2-quinonediazide compound A radiation-sensitive resin composition comprising a. The radiation sensitive resin composition according to claim 1, which is for forming an interlayer insulating film. A method for forming an interlayer insulating film, which comprises the following steps in the order described below. (1) forming a coating film of the radiation sensitive composition according to claim 1 on a substrate; (2) irradiating at least a part of the coating film with radiation; (3) developing process, and (4) heating process. It is formed by the method of Claim 3, The interlayer insulation film characterized by the above-mentioned. The radiation sensitive resin composition according to claim 1, which is for forming microlenses. A method for forming a microlens, comprising the following steps in the order described below. (1) forming a coating film of the radiation sensitive composition according to claim 1 on a substrate; (2) irradiating at least a part of the coating film with radiation; (3) developing process, and (4) heating process. It is formed by the method of Claim 6, The microlens characterized by the above-mentioned. [A] (a1) at least one of unsaturated carboxylic acid and unsaturated carboxylic anhydride, (a2) epoxy group-containing unsaturated compounds, (a3) the following formula (I)

(Wherein R ¹ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R ² to R ⁶ are the same or different, a hydrogen atom, a hydroxyl group or an alkyl group having 1 to 4 carbon atoms, B is a single bond,- COO- or -CONH-, m is an integer of 0 to 3, provided that at least one of R ² to R ⁶ is a hydroxyl group.) A phenol skeleton-containing unsaturated compound represented by (a4) Methacrylic acid alkyl ester, acrylic acid alkyl ester, methacrylic acid cyclic alkyl ester, methacrylic acid ester having a hydroxyl group, acrylic acid cyclic alkyl ester, methacrylic acid aryl ester, acrylic acid aryl ester, unsaturated dicarboxylic acid diester, non Cyclounsaturated compound, maleimide compound, unsaturated aromatic compound, conjugated diene, tetrahydrofuran skeleton, furan skeleton, tetrahydropyran skeleton, pyran skeleton, formula (6)

(Wherein R ⁷ is a hydrogen atom or a methyl group) Copolymers of at least one unsaturated compound selected from the group consisting of unsaturated compounds having a skeleton represented by: acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, and vinyl acetate, and [B] 1,2-quinonediazide compound A radiation-sensitive resin composition comprising a.

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