TWI394000B - Radiation sensitive resin composition, radiation sensitive dry film, interlayer dielectric film and a forming method thereof, and microlens and a forming method thereof - Google Patents

Description

Radiation-sensitive linear resin composition, radiation-sensitive linear dry film, interlayer insulating film and forming method thereof, and microlens and forming method thereof

The present invention relates to a radiation sensitive resin composition particularly for forming an interlayer insulating film and a microlens, an interlayer insulating film and a microlens formed of the radiation sensitive resin composition, and the interlayer insulating film and the micro A method of forming a lens.

An electronic component such as a thin film transistor (hereinafter referred to as "TFT") type liquid crystal display element, a magnetic head element, an integrated circuit element, or a solid-state imaging element is usually provided with an interlayer insulating film in order to insulate between wirings arranged in layers. The material for forming the interlayer insulating film is preferably a material having a small number of processes and having sufficient flatness in order to obtain a necessary pattern shape, and the radiation sensitive resin composition is widely used (for example, refer to Patent Document 1 and Patent Document 2).

Among the above-mentioned electronic components, for example, a TFT-type liquid crystal display element is formed on an interlayer insulating film to form a transparent electrode film, and is further manufactured by a process of forming a liquid crystal alignment film thereon, and an interlayer insulating film is formed in a process of forming a transparent electrode film. It must be exposed to high temperature conditions and exposed to the photoresist stripping liquid used to form the electrode pattern, and thus must have sufficient resistance to such.

In addition, in recent years, the TFT-type liquid crystal display device has been developed with a large screen, high brightness, high precision, high-speed response, and thinning, and it is required that the radiation-sensitive resin composition used for forming the interlayer insulating film must have high sensitivity. Further, it is required that the interlayer insulating film to be formed must have higher performance than conventional ones in terms of low dielectric constant, high light transmittance, and the like.

On the other hand, as an optical system of a color filter on a wafer of a facsimile machine, an electronic photocopier, a solid-state imaging device, or the like, or an optical system material of a fiber connector, a lens having a size of about 3 to 100 μm is regularly arranged. A microlens of diameter or a microlens array in which the microlenses are regularly arranged.

In the method of forming a microlens, it is known that after forming a photoresist pattern corresponding to a lens, heat treatment is performed to melt and flow, and a method of using the lens as a lens, a lens pattern of a molten flow as a mask, and dry etching are used. In the method of transferring the lens shape onto the substrate, a radiation sensitive resin composition is widely used to form such a lens pattern (for example, refer to Patent Document 3 and Patent Document 4).

Further, it is required that the radiation-sensitive resin composition used for forming the lens pattern has high sensitivity, and the subsequently formed microlens has a desired radius of curvature, high heat resistance, high light transmittance, and the like.

Further, the elements of the aforementioned microlenses are formed, and subsequently, in order to remove various insulating films on the pads (the wiring forming portions), it is necessary to provide the following processes, including coating the planarizing film and etching photoresist, so that the prescribed mask can be provided. After the radiation is irradiated, the image is developed, and the photoresist for etching is removed, the planarization film and various insulating films are removed by etching to expose the solder heat portion. Therefore, the microlens must have solvent resistance, heat resistance, and the like in the formation process of the planarization film or the photoresist for etching, and the etching process.

On the other hand, when the interlayer insulating film or the microlens thus obtained is formed in such a developing process, if the optimum time of the development time is slightly exceeded, the developing solution penetrates between the pattern and the substrate and is likely to be generated. Exfoliation, and in order to avoid this phenomenon, there are problems in that the development time, product yield, or productivity must be strictly controlled.

Thus, it is required that the radiation-sensitive resin composition used for forming the interlayer insulating film or the microlens has high sensitivity, and it is required that the pattern does not peel off even when the development time is exceeded for a predetermined time, and the formed interlayer is required. The insulating film has high heat resistance, high solvent resistance, low dielectric constant, high light transmittance, and the like. On the other hand, when forming a microlens, in addition to having a good molten shape (desired radius of curvature) as a microlens, In addition, it has been required to have high heat resistance, high solvent resistance, high light transmittance, and the like, and conventionally known radiation sensitive resin compositions have not sufficiently satisfied such various requirements.

Further, in the process of forming an interlayer insulating film or a microlens for a TFT-type liquid crystal display device, the radiation-sensitive resin composition used mostly contains an organic solvent, and must be coated by a spin coating method, a dipping method, a spray method, or the like. In order to obtain a predetermined film thickness, it takes time to find a suitable condition, and there is a problem in productivity, and it is also pointed out that there are environmental problems such as volatilization of an organic solvent. presence.

Therefore, it is strongly desired to develop a radiation sensitive resin composition, which is required to be laminated on a substrate as a dry film, by irradiating a predetermined amount of radiation, in comparison with the method of forming a conventional interlayer insulating film and a microlens. That is, the interlayer insulating film and the microlens can be easily formed.

[Patent Document 1] Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei.

The present invention has been developed based on the above circumstances, and the first object of the present invention is to provide a radiation-sensitive linear resin composition having a good development margin, which has high sensitivity to radiation and even exceeds the most suitable development time in the development process. Moreover, it can also form a good pattern shape.

A second object of the present invention is to provide a radiation sensitive resin composition capable of forming an interlayer insulating film having excellent solvent resistance, heat resistance, light transmittance, specific dielectric constant, etc., and capable of simultaneously forming It has a microlens with good shape, such as excellent solvent resistance, heat resistance, and light transmittance.

A third object of the present invention is to provide a radiation-sensitive linear dry film which is useful when forming an interlayer insulating film and a microlens having the above-described excellent characteristics.

A fourth object of the present invention is to provide a method of forming an interlayer insulating film and a microlens having the above-described excellent characteristics by a simple process including using a radiation-sensitive dry film.

Other objects and advantages of the present invention will be apparent from the following description.

According to the present invention, the first object is achieved by providing a radiation sensitive resin composition (hereinafter referred to as a radiation sensitive resin composition [I]) which is characterized by: [A An alkali-soluble copolymer, wherein the [A] alkali-soluble copolymer is composed of (a1) an unsaturated carboxylic acid and/or an unsaturated carboxylic anhydride, and (a2) has at least one structure selected from the group consisting of a tetrahydrofuran ring structure, a furan ring structure, and tetrahydrogen. a hydroquinone ring, a piper ring structure, an unsaturated compound of a group consisting of a structure represented by the following formula (1), and (a3) an unsaturated compound other than the above; and [B] 1,2-benzoquinone; Azide compound.

(wherein R is a hydrogen atom or a methyl group, and n is an integer of 2 to 10)

According to the present invention, the second aspect of the invention is achieved by providing a radiation-sensitive dry film which is provided with a radiation-sensitive layer composed of a radiation-sensitive resin composition [I] on a base film. to make.

According to the present invention, the third aspect of the invention is achieved by providing a radiation sensitive resin composition [I] (hereinafter referred to as "the composition for forming an interlayer insulating film") for forming an interlayer insulating film.

According to the invention, the fourth aspect of the invention is achieved by providing an interlayer insulating film which is formed of a composition for forming an interlayer insulating film.

According to the present invention, the fifth aspect of the invention is achieved by providing a method for forming an interlayer insulating film, comprising the steps of: (1) forming a film of a composition for forming an interlayer insulating layer on a substrate; (2) a process of irradiating at least a portion of the film with radiation; (3) a process of developing the film after the irradiation; and (4) a process of heating the film after development.

According to the present invention, the sixth aspect of the invention is achieved by providing a radiation sensitive linear resin composition [I] for forming a microlens (hereinafter referred to as "microlens forming composition"). This is achieved by providing a microlens which is formed of a composition for forming a microlens.

According to the present invention, the eighth aspect of the present invention is achieved by providing a method for forming a microlens, comprising the steps of: (1) a process for forming a film for forming a composition for forming a microlens on a substrate; (2) a process in which at least a part of the film is irradiated with radiation; (3) a process of developing the film after the irradiation; and (4) a process of heating the film after development.

The invention is described in detail below.

Radiation-sensitive resin composition [I] -[A]copolymer -

The [A] component of the radiation sensitive resin composition [I] is an alkali-soluble copolymer (hereinafter referred to as "A" copolymer) which is composed of: (a1) unsaturated carboxylic acid and/or An unsaturated carboxylic anhydride (hereinafter, collectively referred to as "(a1) unsaturated compound"); (a2) having at least one structure selected from the group consisting of a tetrahydrofuran ring structure, a tetrahydropyran ring structure, a piper ring structure, and the foregoing An unsaturated compound having a structural group represented by the formula (1) (hereinafter referred to as "(a2) unsaturated compound"); and (a3) an unsaturated compound other than the above (hereinafter referred to as "(a3) unsaturated) Compound").

(a1) The unsaturated compound may, for example, be an unsaturated monocarboxylic acid, an unsaturated dicarboxylic acid, or an anhydrate thereof, or a mono[(meth)acryloxyalkylalkyl ester of a polyvalent carboxylic acid. A mono(meth)acrylate having a polymer of a carboxyl group and a hydroxyl group at both terminals, an unsaturated polycyclic compound having a carboxyl group, or an anhydride thereof.

Specific examples of the (a1) unsaturated compound may be, for example, (meth)acrylic acid, crotonic acid or the like of the unsaturated monocarboxylic acid; maleic acid or antibutene of the unsaturated dicarboxylic acid or an anhydride thereof. Diacid, citraconic acid, mesaconic acid, itaconic acid, or anhydrate of such compounds; etc.; mono[(meth)acryloxyalkyl]ester of polyvalent carboxylic acid has succinic acid mono[2- (Meth) propylene methoxyethyl ester], phthalic acid mono [2-(methyl) propylene methoxyethyl ester], etc.; mono(meth) acrylate having a polymer having a carboxyl group and a hydroxyl group at both terminals There are ω-carboxypolycaprolactone mono(meth)acrylate, etc.; an unsaturated polycyclic compound having a carboxyl group or an anhydride thereof, which may be exemplified by 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 anhydrate, and the like.

Among these (a1) unsaturated compounds, an anhydride of a monocarboxylic acid or a dicarboxylic acid is preferred, and in terms of copolymerization reactivity, solubility in an alkali liquid, and easy availability, (methyl) Acrylic acid and maleic acid are particularly preferred.

The (a1) unsaturated compound may be used singly or in combination of two or more.

In the [A] copolymer, the content of the repeating unit derived from the (a1) unsaturated compound is preferably from 5 to 40% by weight, particularly preferably from 10 to 30% by weight, based on the total repeating unit. In this case, when the content of the repeating unit is less than 5% by weight, the solubility in the alkali developing solution tends to decrease. On the other hand, when the content is more than 40% by weight, the solubility in the alkali developing solution becomes Too big a tendency.

Specific examples of the (a2) unsaturated compound may be exemplified by a compound having a tetrahydrofuran ring structure: tetrahydrofurfuryl (meth)acrylate, tetrahydrofurfuryl ester of 2-(meth)acryloxypropionic acid, tetrahydrofuran. -3-yl (meth) acrylate, etc.; compounds having a furan ring structure are decyl (meth) acrylate, 2-methyl-5-(furan-3-yl)-1-penten-3-one , 1-(furan-2-yl)-3-buten-2-one, 1-(furan-2-yl)-3-methoxy-3-buten-2-one, 6-(furan- 2-yl)-2-methyl-1-hexen-3-one, 6-(furan-2-yl)-1-hexen-3-one, 6-(furan-2-yl)-6- Methyl-1-hepten-3-one, [2-(furan-2-yl)-1-methyl]ethyl (meth) acrylate, etc.; a compound having a tetrahydropyran ring structure has tetrahydrogen Piperan-2-yl (meth) acrylate, (tetrahydropyran-2-yl)methyl (meth) acrylate, 2,6-dimethyl-8-(tetrahydropyran-2-yl Oxy)-1-octene-3-one, 1-(tetrahydropyran-2-yloxy)-3-buten-2-one, etc.; having a piper ring Compounds are 4- (1,4-bis -5-Sideoxy-6-heptenyl)-6-methyl-2-piperidine, 4-(1,5-di -6-o-oxy-7-octenyl)-6-methyl-2-piperidin or the like; a compound having the structure represented by the above formula (1) is diethylene glycol mono(meth)acrylate, Dipropylene glycol mono (meth) acrylate, triethylene glycol mono (meth) acrylate, tripropylene glycol mono (meth) acrylate, tetraethylene glycol mono (meth) acrylate, tetrapropylene glycol mono (methyl ) Acrylate and the like.

Among these (a2) unsaturated compounds, tetrahydrofurfuryl (meth) acrylate, tetrahydrofuran-3-yl (meth) acrylate is used to enhance the sensitivity of the radiation sensitive resin composition and to expand the development margin. Ester, decyl (meth) acrylate, methyl (tetrahydromethane-2-yl) (meth) acrylate, 1-(tetrahydropyran-2-yloxy)-3-butene-2- A ketone, diethylene glycol mono(meth)acrylate, triethylene glycol mono(meth)acrylate or the like is preferred.

The (a2) unsaturated compound may be used singly or in combination of two or more.

In the [A] copolymer, the content of the repeating unit derived from the (a2) unsaturated compound is preferably from 5 to 50% by weight, particularly preferably from 10 to 40% by weight, based on the total repeating unit. In this case, when the content of the repeating unit is less than 5% by weight, the sensitivity tends to be lowered. On the other hand, when the content is more than 50% by weight, the solubility in the alkali developing solution tends to be too large.

(a3) The unsaturated compound is not particularly limited as long as it can be copolymerized with the (a1) unsaturated compound and the (a2) unsaturated compound, and examples thereof include alkyl (meth)acrylates and alicyclic rings (for example). Methyl) acrylates, (meth) acrylates having hydroxyl groups, (meth) acrylates having epoxy groups, aryl (meth) acrylates, unsaturated dicarboxylic acid diesters, double rings An unsaturated compound, a maleimide-based compound, an aromatic vinyl compound, a conjugated diene compound, or the like.

Specific examples of the (a3) unsaturated compound may be exemplified by (meth)acrylic acid alkyl esters such as methyl (meth)acrylate, ethyl (meth)acrylate, and n-propyl (meth)acrylate. Isopropyl acrylate, n-butyl (meth)acrylate, second butyl (meth)acrylate, tert-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, (a) Isodecyl acrylate, lauryl (meth)acrylate, n-tridecyl (meth)acrylate, stearyl (meth)acrylate, etc.; alicyclic (meth) acrylates with (meth)acrylic acid Cyclohexyl ester, 2-methylcyclohexyl (meth)acrylate, sulphide [5.2.1.0 ^{2 , 6} ]decane-8-yl (meth) acrylate, 2-(shen ring [5.2.1.0 ^{2 , 6} ]decane-8-yloxy)ethyl (meth)acrylate, isodecyl (meth)acrylate, etc.; (meth)acrylate having a hydroxyl group is hydroxymethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, (meth)acrylic acid 2 ,3-dihydroxypropyl ester, 2-(methyl)propenyloxy Dehydration glycerin, 4-hydroxyphenyl (meth) acrylate, etc.; (meth) acrylates having epoxy groups include glycidyl (meth) acrylate, glycyl propyl α-ethyl acrylate, Glycidyl α-n-propyl acrylate, glycidyl α-n-butyl acrylate, 3,4-epoxybutyl (meth)acrylate, 6,7-epoxyheptyl (meth)acrylate, 6-ethyl acrylate 6,7-epoxyheptyl ester; (meth)acrylic acid aryl esters are phenyl (meth) acrylate, benzyl (meth) acrylate, etc.; unsaturated dicarboxylic acid diesters are cis Diethyl phthalate, diethyl fumarate, diethyl itaconate, etc.; bicyclic unsaturated compounds are bicyclo [2.2.1] hept-2-ene, 5-methyl bicyclo [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- Third butoxycarbonylbicyclo[2.2.1]hept-2-ene, 5-cyclohexyloxycarbonylbicyclo[2.2.1]hept-2-ene, 5-phenoxycarbonylbicyclo [2.2.1] Hept-2-ene, 5,6-di(t-butoxycarbonyl)bicyclo[2.2.1]hept-2-ene, 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-bis(hydroxymethyl)bicyclo[2.2.1]hept-2-ene, 5,6-di(hydroxyethyl)bicyclo[2.2.1]hept-2-ene, 5-hydroxy-5-A Bicyclo[2.2.1]hept-2-ene, 5-hydroxy-5-ethylbicyclo[2.2.1]hept-2-ene, 5-hydroxymethyl-5-methylbicyclo[2.2.1]g 2-ene and the like; maleimide-based compounds are N-phenyl maleimide, N-cyclohexyl maleimide, N-benzyl butadiene Amine, N-succinimide-3-oxenimide benzoate, N-succinimide-4-butyleneimine butyrate, N-amber Amino-6-methyleneimide hexanoate, N-succinimide-3-butyleneimine phenylpropionate, N-(9-acridinyl)-n-butene Diterpenoid, etc.; aromatic vinyl compounds have styrene, α-A Styrene, m-methylstyrene, p-methylstyrene, vinyl toluene, p-methoxystyrene, o-vinylbenzylepoxypropyl ether, m-vinylbenzylepoxypropyl ether, pair a vinyl benzyl epoxypropyl ether or the like; the conjugated diene compound may be 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene or the like; The compound may be (meth)acrylonitrile, vinyl chloride, vinylidene chloride, (meth)acrylamide, vinyl acetate or the like.

Among these (a3) unsaturated compounds, alkyl (meth)acrylates, alicyclic (meth)acrylates, (meth)acrylates having epoxy groups, bicyclic unsaturated compounds, and The butylenediamine-based compound, the aromatic vinyl compound, and the conjugated diene compound are preferred, and the (meth)acrylic acid is the third in terms of copolymerization reactivity and solubility in the alkali solution. Butyl ester, 2-methylcyclohexyl (meth)acrylate, sulfon [5.2.1.0 ^{2 , 6} ]decane-8-yl (meth) acrylate, isodecyl (meth) acrylate, (A) Glycidyl acrylate, bicyclo [2.2.1] hept-2-ene, N-phenyl maleimide, N-cyclohexyl maleimide, styrene, p-methoxy Styrene, p-vinylbenzyl epoxidized propyl ether, and 1,3-butadiene are particularly preferred.

The (a3) unsaturated compound may be used singly or in combination of two or more.

In the [A] copolymer, the content of the repeating unit derived from the (a3) unsaturated compound is preferably from 5 to 70% by weight, particularly preferably from 5 to 50% by weight, based on the total repeating unit. In this case, when the content of the repeating unit is less than 5% by weight, the storage stability of the radiation-sensitive resin composition obtained tends to be deteriorated. On the other hand, when it is more than 70% by weight, it is in the alkali developing solution. Solubility tends to decrease.

The preferred [A] copolymer of the present invention, more specifically, may be exemplified by at least one (a1) unsaturated compound selected from the group consisting of (meth)acrylic acid and maleic anhydride, and at least One selected from the group consisting of tetrahydrofurfuryl (meth) acrylate, tetrahydrofuran-3-yl (meth) acrylate, decyl (meth) acrylate, (tetrahydromethane-2-yl) (meth) acrylate Esters, 1-(tetrahydropyran-2-yloxy)-3-buten-2-one, diethylene glycol mono(meth)acrylate, and triethylene glycol mono(meth)acrylate The unsaturated compound represented by the group (a2) and at least one selected from the group consisting of: tert-butyl (meth)acrylate, 2-methylcyclohexyl (meth)acrylate, and sulphide [5.2.1.0 ^{2 , 6} ]decane-8-yl (meth) acrylate, isodecyl (meth) acrylate, glycidyl (meth) acrylate, bicyclo [2.2.1] hept-2-ene, N-phenyl Composition of maleimide, N-cyclohexylmethyleneimine, styrene, p-methoxystyrene, p-vinylbenzylepoxypropyl ether, and 1,3-butadiene A copolymer composed of an unsaturated compound represented by the group (a3).

Specific examples of the copolymer [A] of the present invention include (meth)acrylic acid/tetrahydrofurfuryl (meth)acrylate/paraben [5.2.1.0 ^{2 , 6} ]decane-8- (meth) acrylate / glycidyl (meth) acrylate / styrene copolymer, (meth) acrylate / tetrahydrofurfuryl (meth) acrylate / sulphide [5.2.1.0 ^{2 , 6} ] 癸Alkan-8-yl (meth) acrylate / glycidyl (meth) acrylate / styrene / p-vinylbenzyl epoxy propyl ether copolymer, (meth) acrylic acid / (meth) acrylic acid Hydroquinone / (tetrahydropyran-2-yl) methyl (meth) acrylate / sulphide [5.2.1.0 ^{2 , 6} ] decane-8-yl (meth) acrylate / N-cyclohexyl cis Butyleneimine/styrene copolymer, (meth)acrylic acid/diethylene glycol mono(meth)acrylate/shencyclo [5.2.1.0 ^{2 , 6} ]decane-8-yl (methyl) Acrylate/glycidyl (meth)acrylate/styrene copolymer, (meth)acrylic acid/diethylene glycol monomethyl)acrylate/isodecyl (meth)acrylate/shen ring [5.2.1.0 ^{2, 6]} decan-8-yl (meth) acrylate / p-vinylbenzyl glycidyl ether copolymer, (meth) acrylic acid / diethylene Mono (meth) acrylate / reference ring [5.2.1.0 ^{2, 6]} decan-8-yl (meth) acrylate / (meth) acrylate, glycidyl methacrylate copolymers, (meth) acrylic acid / three Ethylene glycol mono(meth)acrylate/cyclohexene [5.2.1.0 ^{2 , 6} ]decane-8-yl(meth)acrylate/glycidyl (meth)acrylate/styrene copolymer.

The average molecular weight (hereinafter referred to as "Mw") of [A] copolymer converted to polystyrene is usually 2 × 10 ³ to 1 × 10 ⁵ , preferably 5 × 10 ³ to 5 × 10 ⁴ . In this case, when the Mw of the [A] copolymer is less than 2 × 10 ³ , the development margin or the residual film ratio is lowered, and the pattern shape and heat resistance of the interlayer insulating film or the microlens are deteriorated. When the other direction is larger than 1 × 10 ⁵ , the sensitivity may be lowered, and the pattern shape of the interlayer insulating film or the microlens, heat resistance, and the like may be impaired.

Further, the molecular weight distribution defined by the ratio (Mw/Mn) of the Mw of the [A] copolymer to the number average molecular weight (hereinafter referred to as "Mn") in terms of polystyrene is usually 5.0 or less and 3.0 or less. It is better. When Mw/Mn is more than 5.0, the pattern shape of the interlayer insulating film or the microlens tends to be deteriorated.

The radiation sensitive resin composition [I] containing a copolymer having such Mw and Mw/Mn can easily form a pattern of a predetermined shape without causing development residue during development.

In the radiation sensitive resin composition [I], the [A] copolymer may be used singly or in combination of two or more.

[A] Copolymer can be polymerized by using, in a suitable solvent, in the presence of a radical polymerization initiator, for example, (a1) an unsaturated compound, (a2) an unsaturated compound, and (a3) an unsaturated compound. And manufacturing.

Examples of the solvent used in the polymerization include alcohols, ethers, glycol ethers, ethylene glycol alkyl ether acetates, diethylene glycols, propylene glycol ethers, and propylene glycol alkyl ethers. Acetate, propylene glycol alkyl ether propionate, aromatic hydrocarbon, ketone, ester, and the like.

Specific examples of such solvents include methanol, ethanol, benzyl alcohol, 2-phenylethanol, 3-phenyl-1-propanol, etc.; ethers are tetrahydrofuran; glycol ethers are B. Glycol monomethyl ether, ethylene glycol monoethyl ether, etc.; ethylene glycol alkyl ether acetates are ethylene glycol methyl ether acetate, ethylene glycol ethyl ether acetate, ethylene glycol positive Ethyl ether acetate, ethylene glycol n-butyl ether acetate, etc.; diethylene glycols are diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, Diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, etc.; propylene glycol ethers include propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether, etc. ; propylene glycol alkyl ether acetates are propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol n-propyl ether acetate, propylene glycol n-butyl ether acetate, etc.; propylene glycol alkyl ether propionic acid The esters include propylene glycol methyl ether propionate, propylene glycol ethyl ether propionate, propylene glycol n-propyl ether propionate, propylene glycol n-butyl ether propionate, etc.; There are toluene, xylene, etc.; ketones are methyl ethyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone, etc.; esters are methyl acetate, ethyl acetate, acetic acid Ester, n-butyl acetate, methyl hydroxyacetate, ethyl hydroxyacetate, n-propyl glycolate, n-butyl glycolate, methyl lactate, ethyl lactate, n-propyl lactate, n-butyl lactate, 3-hydroxyl Methyl propionate, ethyl 3-hydroxypropionate, n-propyl 3-hydroxypropionate, n-butyl 3-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, 2-hydroxy-2- Ethyl methacrylate, methyl 2-hydroxy-3-methylbutanoate, methyl methoxyacetate, ethyl methoxyacetate, n-propyl methoxyacetate, n-butyl methoxyacetate, Methyl ethoxyacetate, ethyl ethoxyacetate, n-propyl ethoxyacetate, n-butyl ethoxyacetate, methyl n-propoxyacetate, ethyl n-propoxyacetate, n-propoxy N-propyl acetate, n-butyl n-propoxyacetate, methyl n-butoxyacetate, ethyl n-butoxyacetate, n-propyl n-butoxyacetate, n-butyl n-butoxyacetate, 2- Methyl methoxypropionate, ethyl 2-methoxypropionate, n-propyl 2-methoxypropionate, n-butyl 2-methoxypropionate, methyl 2-ethoxypropionate, Ethyl 2-ethoxypropionate, n-propyl 2-ethoxypropionate, n-butyl 2-ethoxypropionate, methyl 2-n-propoxypropionate, 2-n-propoxypropane Ethyl acetate, n-propyl 2-n-propoxypropionate, n-butyl 2-n-propoxypropionate, methyl 2-n-butoxypropionate, ethyl 2-n-butoxypropionate, 2- n-Butoxypropionate n-propyl ester, n-butyl 2-n-butoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3-methoxypropane N-propyl acrylate, n-butyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, n-propyl 3-ethoxypropionate, 3-B N-butyl oxypropionate, methyl 3-n-propoxypropionate, ethyl 3-n-propoxypropionate, n-propyl 3-n-propoxypropionate, 3-n-propoxypropionic acid N-butyl ester, methyl 3-n-butoxypropionate, ethyl 3-n-butoxypropionate, n-propyl 3-n-butoxypropionate, n-butyl 3-n-butoxypropionate, etc. .

Among these solvents, ethylene glycol alkyl ether acetates, diethylene glycols, propylene glycol ethers, propylene glycol alkyl ether acetates, etc., preferably diethylene glycol dimethyl ether, diethylene glycol Alcohol ethyl methyl ether, propylene glycol monomethyl ether, and propylene glycol methyl ether acetate are preferred.

Further, examples of the radical polymerization initiator used in the polymerization include, for example, 2,2'-azobisisobutyronitrile and 2,2'-azo-(2,4-dimethylvaleronitrile). An azo compound such as 2,2'-azo-(4-methoxy-2,4-dimethylvaleronitrile); benzamidine peroxide, lauric acid peroxide, and tert-butylperoxytrimethyl An organic peroxide such as acetate or 1,1'-bis-(t-butylperoxy)cyclohexane; hydrogen peroxide or the like. When a peroxide is used as the radical polymerization initiator, it can also be used together with a reducing agent as a redox type initiator.

Further, in the above polymerization, in order to adjust the molecular weight of the [A] copolymer, a molecular weight modifier may also be used.

Specific examples of the molecular weight modifier include halogenated hydrocarbons such as chloroform and carbon tetrabromide; n-hexyl mercaptan, n-octyl mercaptan, n-dodecyl mercaptan, and third (dodecyl) mercaptan. Thiols such as thioethylene glycol; xanthogen such as dimethylxanthine sulfide and diisopropylxanthine disulfide; onion olefin, α-methylstyrene dimer, and the like.

-[B] 1,2-benzoquinonediazide -

The [B] component of the radiation sensitive resin composition [I] is a 1,2-benzoquinonediazide compound which generates an acid by irradiation of radiation, and is a compound having a phenolic hydroxyl group or an alcoholic hydroxyl group (hereinafter) A condensate of a 1,2-naphthoquinonediazidesulfonic acid halide referred to as a "mother core".

The core compound may, for example, be a 3-yldiphenyl ketone, a tetrahydroxydiphenyl ketone, a pentahydroxydiphenyl ketone, a hexahydroxydiphenyl ketone or a (polyhydroxyphenyl)alkane. Hydrocarbons.

Specific examples of the parent core compound can be exemplified, and the 3-diphenyl ketones are 2,3,4-3-yldiphenyl ketone, 2,4,6-3-yldiphenyl ketone, etc.; Hydroxydiphenyl ketones are 2,2',4,4'-tetrahydroxydiphenyl ketone, 2,3,4,3'-tetrahydroxydiphenyl ketone, 2,3,4,4'-four Hydroxydiphenyl ketone, 2,3,4,2'-tetrahydroxy-4'-methyldiphenyl ketone, 2,3,4,4'-tetrahydroxy-3'-methoxydiphenyl ketone Etc.; pentahydroxydiphenyl ketones are 2,3,4,2',6'-pentahydroxydiphenyl ketone; hexahydroxydiphenyl ketones are 2,4,6,3',4', 5'-hexahydroxydiphenyl ketone, 3,4,5,3',4',5'-hexahydroxydiphenyl ketone, etc.; (polyhydroxyphenyl)alkane hydrocarbons have double (2,4- Dihydroxyphenyl)methane, bis(p-hydroxyphenyl)methane, cis (p-hydroxyphenyl)methane, 1,1,1-paraxyl (p-hydroxyphenyl)ethane, bis(2,3,4-3 -phenyl)methane, 2,2-bis(2,3,4-3-phenyl)propane, 1,1,3-gin(2,5-dimethyl-4-hydroxyphenyl)-3- Phenylpropane, 4,4'-[1-{4-(1-[4-hydroxyphenyl]-1-methylethyl)phenyl}ethylidene]bisphenol, bis(2,5-di Methyl-4- Hydroxyphenyl)-2-hydroxyphenylmethane, 3,3,3',3'-tetramethyl-1,1'-spirobiguanidine-5,6,7,5',6',7'- Hexanol, 2,2,4-trimethyl-7,2',4'-3-ylflavone, etc.; the other parent compound other than the above has 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-hydroxyphenyl}-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 or the like.

Among these core compounds, 2,3',4,4'-tetrahydroxydiphenyl ketone, 4,4'-[1-{4-(1-[4-hydroxyphenyl]-1- Methyl ethyl)phenyl}ethylidene]bisphenol is particularly preferred.

Further, the 1,2-naphthoquinonediazidesulfonic acid halide is preferably 1,2-naphthoquinonediazidesulfonium chloride, and specific examples thereof include 1,2-naphthoquinonediazide- 4-sulfonyl chloride, 1,2-naphthoquinonediazide-5-sulfonyl chloride, etc., among which 1,2-naphthoquinonediazide-5-sulfonyl chloride is particularly preferred.

Further, a 1,2-naphthoquinonediazidesulfonamide such as a 2,3,4-3-yl group which is obtained by changing an ester bond in the above 1,2-benzoquinonediazide compound to a guanamine bond. Diphenyl ketone-1,2-naphthoquinonediazide-4-sulfonamide or the like can also be suitably used as the 1,2-benzoquinonediazide compound.

In the radiation sensitive resin composition [I], the 1,2-benzoquinonediazide compound may be used singly or in combination of two or more.

When the condensation reaction of the 1,2-benzoquinonediazide compound is carried out, it is preferred to use 1,2-naphthoquinonediazidesulfonium halogen to be equivalent to 30 to 85 mol% relative to the total hydroxyl number of the core compound. It is preferably 50 to 75 mol%.

The aforementioned condensation reaction can be carried out by a well-known method.

The ratio of use of the radiation sensitive resin composition [I], 1,2-benzoquinonediazide compound is preferably from 5 to 100% by weight, based on 100% by weight of the [A] copolymer, and from 10 to 50. Better. In this case, when the use ratio of the 1,2-benzoquinonediazide compound is less than 5% by weight, the difference in solubility between the irradiated portion of the radiation and the unirradiated portion in the alkali developing solution is small, and the pattern is not easily formed. The obtained interlayer insulating film or microlens may have insufficient heat resistance or solvent resistance. On the other hand, when it is more than 100% by weight, the solubility of the irradiated portion of the radiation in the developing solution may be lowered or not. The possibility of easy visualization.

-Other ingredients -

The radiation sensitive linear resin composition [I] contains the above-mentioned [A] copolymer and [B] 1,2-benzoquinone bismuth gas compound as essential components, but may further contain a heat-sensitive acid generating compound as necessary, and a compound having at least one polymer unsaturated bond (hereinafter referred to as "polymerizable compound", [A] epoxy resin other than copolymer (hereinafter referred to as "other epoxy resin"), an adhesion aid, a surfactant, and the like .

The heat-sensitive acid generating compound is a component which generates an acid by heating, and has a function of further improving the heat resistance and surface hardness of the obtained interlayer insulating film and the microlens.

Examples of the thermosensitive acid-generating compound include an onium salt compound, a benzothiazolium compound, an ammonium salt compound, and an onium salt such as an anthracene compound, among which an onium salt compound and a benzothiazolium compound are used. good.

Examples of the onium salt compound include alkyl phosphonium salts, benzyl phosphonium salts, dibenzyl phosphonium salts, substituted benzyl phosphonium salts, and the like.

Specific examples of the phosphonium salt compound may be exemplified by the alkyl sulfonium salt being dimethyl-4-ethyl phenyl phenyl hexafluoroantimonate or dimethyl-4-ethoxy phenyl hexafluoro arsenate. Acid salt, dimethyl-4-(benzyloxycarbenyloxy)phenylphosphonium hexafluoroantimonate, dimethyl-4-(benzylideneoxy)phenylphosphonium hexafluoroantimonate, Dimethyl-4-(benzylideneoxy)phenylphosphonium hexafluoroarsenate, dimethyl-3-chloro-4-ethenyloxyphenylphosphonium hexafluoroantimonate, etc.; benzyl sulfonium salt Benzyl (4-hydroxyphenyl)(methyl)phosphonium hexafluoroantimonate, benzyl (4-hydroxyphenyl)(methyl)phosphonium hexafluorophosphate, benzyl (4-ethyloxyl) Phenyl)(methyl)phosphonium hexafluoroantimonate, benzyl (4-methoxyphenyl)(methyl)phosphonium hexafluoroantimonate, benzyl (2-methyl-4-hydroxyphenyl) (methyl)phosphonium hexafluoroantimonate, benzyl (3-chloro-4-hydroxyphenyl)(methyl)phosphonium hexafluoroarsenate, etc.; dibenzylsulfonium salt with dibenzyl-4-hydroxyl Phenylphosphonium hexafluoroantimonate, dibenzyl-4-hydroxyphenylphosphonium hexafluorophosphate, dibenzyl-4-ethenyloxyphenylphosphonium hexafluoroantimonate, dibenzyl-4-methyl Oxyphenyl Hexafluoroantimonate, dibenzyl-3-chloro-4-hydroxyphenylphosphonium hexafluoroarsenate, dibenzyl-3-methyl-4-hydroxy-5-t-butylphenylphosphonium Fluoride, benzyl-4-methoxybenzyl-4-hydroxyphenylphosphonium hexafluorophosphate, etc.; substituted benzyl sulfonium salts are 4-methoxybenzyl (4-hydroxyphenyl) ( Methyl) sulfonium hexafluorophosphate, 4-chlorobenzyl (4-hydroxyphenyl) (methyl) hexafluoroantimonate, 4-nitrobenzyl (4-hydroxyphenyl) (methyl) hydrazine Hexafluoroantimonate, 4-nitrobenzyl (4-hydroxyphenyl)(methyl)phosphonium hexafluorophosphate, 4-nitrobenzyl (3-methyl-4-hydroxyphenyl) (methyl Hexafluoroantimonate, 3,5-dichlorobenzyl (4-hydroxyphenyl)(methyl)phosphonium hexafluoroantimonate, 2-chlorobenzyl (3-chloro-4-hydroxyphenyl) (Methyl) hexafluoroantimonate or the like.

Specific examples of the benzothiazolium salt compound include 3-benzylbenzothiazolium hexafluoroantimonate, 3-benzylbenzothiazolium hexafluorosulfate, and 3-benzylbenzothiazole. Tetrafluoroborate, 3-(p-methoxybenzyl)benzothiazolium hexafluoroantimonate, 3-benzyl-2-methylthiazolium hexafluoroantimonate, 3-benzyl-5- a benzylbenzothiazolium salt such as chlorobenzothiazolium hexafluoroantimonate.

Among these thermosensitive acid generating compounds, dimethyl-4-acetoxyphenyl hexafluoroantimonate, benzyl (4-hydroxyphenyl) (methyl) hexafluoroantimonate, Benzyl (4-acetoxyphenyl)(methyl)phosphonium hexafluoroantimonate, dibenzyl-4-hydroxyphenylphosphonium hexafluoroantimonate, dibenzyl-4-ethenyloxybenzene Based on hexafluoroantimonate, 3-benzylbenzothiazolium hexafluoroantimonate, commercially available products of such compounds include SANEIDO SI-L85, same as SI-L110, and the same SI- L145, the same as SI-L150, the same SI-L160 (above, Sanxin Chemical Industry Co., Ltd.).

The above-mentioned thermosensitive acid generating compounds may be used singly or in combination of two or more kinds.

The amount of the thermosensitive acid generating compound to be used is preferably 20% by weight or less, more preferably 5% by weight or less based on 100% by weight of the [A] copolymer. In this case, when the amount of the thermosensitive acid generating compound used is more than 20% by weight, the coating process of the composition solution described later may easily cause precipitates and may hinder the formation of the film.

In addition, the polymerizable compound has a function of further improving the heat resistance and surface hardness of the interlayer insulating film and the microlens obtained from the radiation sensitive resin composition [I], and for example, a monofunctional (meth) acrylate, A difunctional (meth) acrylate or a trifunctional or higher (meth) acrylate is preferred.

Specific examples of the monofunctional (meth) acrylate include 2-hydroxyethyl (meth)acrylate, diethylene glycol diethyl ether (meth) acrylate, and isodecyl (meth) acrylate. 3-methoxybutyl (meth)acrylate, 2-hydroxypropyl 2-methoxypropyl-phenoxy phthalate, and the like. Commercial products of such compounds include, for example, ARONIX M-101, M-111, M-114 (above, East Asia Synthetic Co., Ltd.), KAYARAD TC-110S, and TC-120S (above). , Japan Chemicals Co., Ltd., BISCOAT 158, and 2311 (above, Osaka Organic Chemical Industry Co., Ltd.).

Specific examples of the bifunctional (meth) acrylate include ethylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, and 1,9-decanediol. (Meth) acrylate, tetraethylene glycol di(meth) acrylate, polypropylene glycol di(meth) acrylate, bisphenoxyethanol hydrazine di(meth) acrylate, and the like. Commercial products of such compounds include, for example, ARONIX M-210, M-240, M-6200 (above, East Asia Synthetic Co., Ltd.), KAYARAD HDDA, HX-220, and R-604. (above, Nippon Kayaku Co., Ltd.), BISCOAT 260, 312, and 335HP (above, Osaka Organic Chemical Industry Co., Ltd.).

Specific examples of the trifunctional or higher functional (meth) acrylate include 3-methylpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, and tris[(methyl). Propylene methoxyethyl] sulfate, neopentyltetrakis (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, etc. Commercially available products such as ARONIX M-309, M-400, M-405, M-450, M-7100, M-8030, M-8060 (above, East Asia) Synthetic (stock) system, KAYARAD TMPTA, DPHA, DPCA-20, DPCA-30, DPCA-60, DPCA-120 (above, Nippon Chemical Co., Ltd.), BISCOAT 295, same 300, Same as 360, with GPT, with 3PA, with 400 (above, Osaka Organic Chemical Industry Co., Ltd.).

Among these polymerizable compounds, a trifunctional or higher (meth) acrylate is preferable, and 3-methylpropane tri(meth)acrylate, neopentyltetrakis(meth)acrylate, and dinoxin are used. Pentaerythritol hexa(meth) acrylate is preferred.

These polymerizable compounds may be used singly or in combination of two or more kinds.

The amount of the polymerizable compound to be used is preferably 50% by weight or less based on 100% by weight of the [A] copolymer, and more preferably 30% by weight or less. In this case, when the amount of the polymerizable compound used is more than 50% by weight, there is a possibility that film formation may occur in the film formation process.

In addition, the other epoxy resin has a function of further improving the heat resistance and surface hardness of the interlayer insulating film and the microlens obtained from the radiation sensitive resin composition [I], as long as it is combined with the radiation sensitive resin composition [ When the component contained in I] has no problem of compatibility, it is not particularly limited, and examples thereof include bisphenol A type epoxy resin, resol type epoxy resin, and cresol resol type epoxy resin. , a cyclic aliphatic epoxy resin, a copolymer of glycidyl methacrylate, among which bisphenol A type epoxy resin, cresol resol type epoxy resin, glycidyl ester type epoxy Resin or the like is preferred.

The above other epoxy resins may be used singly or in combination of two or more.

Further, the [A] copolymer having an epoxy group may be referred to as "epoxy resin", but is different from other epoxy resins in terms of alkali solubility.

The amount of the other epoxy resin used is preferably 30% by weight or less based on 100% by weight of the [A] copolymer, and more preferably 15% by weight or less. At this time, when the amount of the other epoxy resin used is more than 30% by weight, the film thickness uniformity of the film may be lowered.

In addition, the adhesion promoter has a function of further improving the adhesion between the interlayer insulating film obtained from the radiation sensitive resin composition [I] and the adhesion between the microlens and the substrate, and has a carboxyl group, a methacryl fluorenyl group, and an ethylene group. A functional decane coupling agent which is a reactive substituent such as a group, an isocyanate group or an epoxy group is preferred.

Specific examples of the functional decane coupling agent include trimethoxydecyl benzoic acid, γ-methacrylic acid methoxy propyl trimethoxy decane, vinyl triethoxy decane, and vinyl trimethyl hydrazine. Oxydecane, γ-isocyanate propyl triethoxy decane, γ-glycidoxypropyl trimethoxy decane, β-(3,4-ethoxycyclohexyl)ethyltrimethoxydecane, and the like.

These functional decane coupling agents may be used singly or in combination of two or more.

The amount of the adhesion aid to be used is preferably 20% by weight or less based on 100% by weight of the [A] copolymer, and more preferably 10% by weight or less. At this time, if the amount of other adhesion aids used is more than 20% by weight, there is a possibility that development remains easily in the developing process.

Further, the surfactant has a component which further enhances the applicability of the composition solution to be described later, and a fluorine-based surfactant, a quinone-based surfactant, and a nonionic surfactant are preferred.

Specific examples of the fluorosurfactant include 1,1,2,2-tetrafluoro-n-octyl (1,1,2,2-tetrafluoro-n-propyl)ether, 1,1,2. , 2-tetrafluoro-n-octyl (n-hexyl) ether, octaethylene glycol di(1,1,2,2,-tetrafluoro-n-butyl)ether, hexaethylene glycol di(1,1,2, 2,3,3-hexafluoro-n-pentyl)ether, octapropylene glycol bis(1,1,2,2,-tetrafluoro-n-butyl)ether, hexapropylene glycol di(1,1,2,2,3 ,3-hexafluoro-n-pentyl)ether, sodium perfluorododecylsulfonate, 1,1,2,2,8,8,9,9,10,10-decafluorododecane, 1,1 Other than 2,2,3,3-hexafluorodecane, etc., sodium fluoroalkylbenzenesulfonate, fluoroalkyloxyvinyl ether, fluoroalkylammonium iodide, fluoroalkyl polyoxyethylene ether And perfluoroalkyl polyoxyethylene alcohols, perfluoroalkyl alkoxides, fluoroalkanes, etc., and commercially available products of such fluorosurfactants include, for example, BM-1000, the same - 1100 (above, BM Chemie), MEGAFAK F142D, F172, F173, F178, F183, F191, F471 (above, Dainippon Ink Chemical Industry Co., Ltd.), FRORAD FC-170C, FC-171, with FC-430, with FC-431 (above, Sumitomo 3M (share) system), SARFRON S-112, same S-113, same S-131, same S-141, same S-145, same S-382, same SC-101, same SC-102, same SC-103 In the same way, SC-104, SC-105, SC-106 (above, Asahi Glass Co., Ltd.), EFTOP EF301, EF303, EF352 (above, New Akita Chemicals Co., Ltd.).

Examples of the lanthanoid surfactant include commercially available products such as DC3PA, 7PA, FS-1265, SF-8428, SH11PA, 21PA, 28PA, 29PA, 30PA, and 190. Same as -193, SZ-6032 (above, TORAY-Dow Corning Silicone), TSF-4300, same -4440, same -4445, same -4446, same -4452, same -4460 (above, GE Toshiba Silicones (share) system, etc.

The nonionic surfactant may be exemplified by, for example, polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether; polyoxyethylene n-octyl Polyoxyethylene aryl ethers such as phenyl ether and polyoxyethylene n-decyl phenyl ether; polyoxyethylene dialkyl esters such as polyoxyethylene dilaurate and polyoxyethylene distearate Examples of the product to be sold include, for example, (meth)acrylic copolymer POLYFLOW NO. 57, and the same as No. 95 (above, Coron Chemical Co., Ltd.).

These surfactants may be used singly or in combination of two or more.

The amount of the surfactant to be used is preferably 5% by weight or less, more preferably 2% by weight or less based on 100% by weight of the [A] copolymer. At this time, when the amount of the other surfactant used is more than 5% by weight, the film formation process may be likely to cause film roughness.

- Modulation of the radiation sensitive resin composition [I] -

The radiation sensitive resin composition [I] can be prepared by uniformly mixing the above [A] copolymer and [B] 1,2-benzoquinone quinone compound, and optionally containing other components, preferably as a dissolution. A composition solution of a suitable solvent is used.

The solvent used for the preparation of the composition solution can be used by uniformly dissolving each component constituting the radiation sensitive resin composition [I] without reacting with each component.

The solvent may be, for example, the same as the solvent exemplified for the polymerization in the production of the [A] copolymer, and the solubility of each component and the reactivity with each component. In terms of easiness of coating operation, etc., alcohols, glycol ethers, ethylene glycol alkyl ether acetates, diethylene glycols, propylene glycol alkyl ethers, propylene glycol alkyl ether acetates, esters Preferably, benzyl alcohol, 2-phenylethanol, 3-phenyl-1-propanol, ethylene glycol ethyl ether acetate, ethylene glycol n-butyl ether acetate, diethylene glycol dimethyl Ether, dipropylene glycol diethyl ether, diethylene glycol ethyl methyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, methyl 2-methoxypropionate, 2-ethoxypropyl Ethyl acetate or the like is preferred.

Further, in order to increase the film thickness uniformity of the film, a high boiling point solvent may be used in combination with the above solvent.

Such a high boiling point solvent may, for example, be N-methylformamide, N,N-dimethylformamide, N-methylformamide, N-methylacetamide, N,N- Dimethylacetamide, N-methylpyrrolidone, dimethylhydrazine, benzyl (ethyl) ether, di-n-hexyl ether, acetone acetone, isophorone, hexanoic acid, octanoic acid, 1-octyl Alcohol, 1-nonanol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, ethylene glycol phenyl ether Acetate and the like.

Among these high boiling point solvents, N-methylpyrrolidone, γ-butyrolactone, N,N-dimethylacetamide or the like is preferred.

These surfactants may be used singly or in combination of two or more.

The amount of the high boiling point solvent used in the preparation of the composition solution is usually 50% by weight or less, preferably 40% by weight or less, and preferably 30% by weight or less based on the total solvent. In this case, when the amount of the other high-boiling point solvent used is more than 50% by weight, the sensitivity, the film thickness uniformity of the film, or the residual film ratio may be lowered.

The solid content concentration of the composition solution can be appropriately set according to the purpose of use of the radiation sensitive resin composition [I], the desired film thickness, and the like, and is usually 5 to 60% by weight, preferably 10 to 55% by weight. 20 to 50% by weight is more preferred.

The composition solution thus prepared can be used, for example, by filtration using a micropore filter having a pore size of about 0.2 μm.

The radiation sensitive resin composition [I] is preferably used as a composition solution or as a radiation sensitive dry film, and is particularly preferably used for forming an interlayer insulating film and a microlens.

Dry radiation linear dry film

The radiation sensitive dry film of the present invention is obtained by providing a radiation sensitive layer composed of a radiation sensitive resin composition [I] on a base film.

When the radiation-sensitive dry film is formed, it is preferred that the radiation-sensitive resin composition [I] is used as a composition solution, and after being coated on the base film, a radiation-sensitive layer composed of a radiation-sensitive linear dry film can be formed by drying. .

The base film used for the radiation-sensitive dry film is preferably a flexible synthetic resin film such as polyethylene terephthalate (PET), polyethylene, polypropylene, polycarbonate, or polyvinylidene chloride.

The thickness of the base film can be appropriately selected in accordance with the purpose of use of the radiation-sensitive dry film, etc., and preferably in the range of 15 to 125 μm.

When the composition solution is applied to the base film, an appropriate coating method by an applicator, a bar coater, a roll coater, a curtain coater or the like can be employed.

The film thickness of the radiation-sensitive layer of the radiation-sensitive dry film can be appropriately selected in accordance with the purpose of use of the radiation-sensitive dry film, and the value after drying is preferably in the range of 2 to 10 μm.

The radiation sensitive dry film thus formed may be deposited on the radiation sensitive layer by laminating the film while not in use.

The cover film is a material that can be removed when the radiation-sensitive dry film is used. Therefore, the cover film must have a suitable mold release property, and it is not easily peeled off when it is not used, and can be easily peeled off when it is used. The cover film which meets such conditions can be coated or plated with, for example, a bismuth-based release agent on a film such as PET, polypropylene or polyethylene. The thickness of the cover film is not particularly limited, and is preferably, for example, about 15 μm.

Interlayer insulating film and microlens

The interlayer insulating film and the microlens of the present invention are each formed of a radiation sensitive resin composition [I].

The interlayer insulating film of the present invention is suitably used for an electronic component such as a TFT liquid crystal display device, a magnetic head device, an integrated circuit device, or a solid-state imaging device, and is further suitable for the microlens of the present invention and the microlenses are regularly arranged. The microlens array is an imaging optical system or a fiber optic connector optical material for use in a color filter on a wafer such as a facsimile machine, an electronic photocopier, or a solid-state imaging device, and is extremely suitable.

Interlayer insulating film and method of forming microlens

The method for forming an interlayer insulating film of the present invention and the method for forming a microlens include the steps described below: (1) a process of forming a film of the radiation sensitive resin composition [I] on a substrate; (2) a process for forming a film of the radiation sensitive resin composition [I] on the substrate a process of irradiating at least a part of radiation (hereinafter referred to as "exposure"); (3) a process of developing the film after exposure; and (4) a process of heating the film after development.

Hereinafter, these processes will be described in order.

-(1) Process -

In the process, the radiation sensitive resin composition [I] is preferably applied as a composition solution onto the surface of the substrate, and then dried to form a film of the radiation sensitive resin composition [I].

The coating method may employ an appropriate coating method by an applicator, a bar coater, a roll coater, a curtain coater or the like.

Further, when the film of the radiation sensitive linear resin composition [I] is formed by using a radiation-sensitive dry film, when the film is covered with a cover film, it is removed by a normal pressure hot roll pressure bonding method or a vacuum heat roll pressure bonding method. Vacuum hot plate pressure bonding method is a pressure-sensitive method, which will sense the radiation dry film so that the radiation-sensitive layer is on the substrate side, and apply pressure and adhesion to the substrate while applying appropriate heat and pressure. The dry film is transferred onto the surface of the substrate, and then the base film is peeled off to form a film of the radiation sensitive resin composition [I].

- (2) Process -

In this process, at least a part of the film of the film of the radiation sensitive resin composition [I] formed is exposed. When only a part of the film is exposed, it is usually exposed by a mask having a predetermined pattern.

Examples of the radiation used for the exposure include X-rays such as g-rays (wavelength 436 nm), i-rays (wavelength 365 nm), X-rays such as far-ultraviolet rays such as KrF excimer lasers, and synchrotron radiation. Charged particle lines such as lines. Among these radiations, ultraviolet rays are preferred, and radiation containing g-line and/or i-line is particularly preferable.

When the interlayer insulating film is formed, the exposure amount is preferably in the range of 50 to 1,500 J/m ² , and in the case of forming the microlens, it is preferably in the range of 50 to 2,000 J/m ² .

-(3) Process -

In this process, the film of the radiation-sensitive resin composition [I] after exposure is subjected to development processing to remove the exposed portion to form a predetermined pattern.

The developing solution used for the development treatment is preferably, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, ammonia, ethylamine, n-propylamine, Diethylamine, diethylaminoethanol, di-n-propylamine, triethylamine, methyldiethylamine, dimethylethanolamine, triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, pyrrole, piperidine, a base such as 1,8-diazabicyclo[5,4,0]-7-undecene or 1,5-diazabicyclo[4,3,0]-5-nonene (basic compound) As the aqueous solution, various organic solvents capable of dissolving the film of the radiation sensitive resin composition [I] may be used as the developing solution.

Further, an appropriate amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant may be added to the aqueous alkali solution.

As the developing method, an appropriate method such as a liquid-filling method, a dipping method, a shaking dipping method, or a shower method can be employed.

Although the development time varies depending on the composition of the radiation-sensitive resin composition [I], it can be set, for example, in the range of 30 to 120 seconds.

In the conventionally known radiation-sensitive resin composition, since the development time is more than about 20 to 25 seconds, the formed pattern may be peeled off, and the development time must be strictly controlled, but the radiation of the present invention is linear. The resin composition [I] can form a good pattern even if the development time is more than 30 seconds than the optimum value, and is advantageous in terms of product yield or productivity.

- (4) Process -

In the process, the film forming the predetermined pattern is preferably treated by washing, and further preferably exposed to radiation (post exposure) by a high pressure mercury lamp or the like to remninate in the film. After the 1,2-benzoquinonediazide compound is subjected to decomposition treatment, the film is subjected to heat treatment (post-baking) by a heating device such as a hot plate or an oven to cure the film. Further, when the microlens is formed, the formed pattern is melted and flowed by post-baking to form a predetermined shape.

The exposure amount after exposure is preferably about 2,000 to 5,000 J/m ² .

Further, the heating temperature in the post-baking is, for example, about 120 to 250 °C. The heating time varies depending on the heating machine. It can be set to 5 to 30 minutes on, for example, a hot plate, and 30 to 90 minutes in an oven. At this time, it is also possible to carry out the heating process twice or more by the stage baking.

In this manner, a pattern-like film corresponding to the target interlayer insulating film or the microlens can be formed on the surface of the substrate, and the shape of the obtained microlens is a semi-convex lens shape as shown in a of FIG.

The radiation sensitive resin composition [I] of the present invention has high sensitivity to radiation and has a good development margin, and can form a good pattern shape even if the development process is larger than the development time, and is particularly suitable for use in electronic parts. An interlayer insulating film, a solid-state imaging element, or the like is used as the microlens.

Further, the interlayer insulating film of the present invention has excellent solvent resistance, heat resistance, light transmittance, specific dielectric constant, and the like.

Further, the microlens of the present invention has excellent solvent resistance, heat resistance, light transmittance, and a good melt shape.

Further, the method for forming the interlayer insulating film of styrene and the method for forming the microlens can form a favorable pattern even when the development time is longer than the development time, and the interlayer insulating film and the microlens having the above-described excellent characteristics can be easily formed. Further, in such a forming method, by using a radiation-sensitive dry film, it is advantageous in terms of productivity in order to find suitable conditions for obtaining a predetermined film thickness, and it is also possible to easily form interlayers. The insulating film and the microlens do not cause environmental problems due to volatilization of the organic solvent.

[Examples]

The present invention will be more specifically described below by showing examples, but the present invention is not limited to the following examples. In this part and % is the basis of weight.

[A] Synthesis of copolymer Synthesis Example 1

In a flask equipped with a cooling tube and a stirrer, 5 parts of 2,2'-azobis(2,4-dimethylvaleronitrile) and 250 parts of diethylene glycol ethyl methyl ether were added, followed by Add 14 parts of methacrylic acid, 30 parts of tetrahydrofurfuryl (meth) acrylate, 11 parts of cyclohexene [5.2.1.0 ^{2 , 6} ] decane-8-yl (meth) acrylate, 45 parts of methacrylic acid ring Oxypropyl propyl ester, 5 parts of styrene, and 3 parts of α-methylstyrene dimer, after being substituted with nitrogen, began to stir slowly, raising the temperature of the solution to 70 ° C, and maintaining the temperature at this temperature for 4 hours for polymerization. A solution of the [A] copolymer (solid content concentration: 29.8%) was obtained.

The [A] copolymer had Mw of 3.5 × 10 ⁴ and Mw / Mn of 2.2. This [A] copolymer was referred to as "copolymer (A-1)".

Synthesis Example 2

In a flask equipped with a cooling tube and a stirrer, 3 parts of 2,2'-azobis(2,4-dimethylvaleronitrile) and 200 parts of diethylene glycol ethyl methyl ether were added, followed by Add 18 parts of methacrylic acid, 20 parts of tetrahydrofurfuryl (meth) acrylate, 30 parts of (tetrahydropyran-2-yl)methyl methacrylate, 11 parts of ginseng [5.2.1.0 ^{2 , 6} ] 癸Alkan-8-yl (meth) acrylate, 15 parts of N-cyclohexylmethylene iodide, 6 parts of styrene, 3 parts of -α-methylstyrene dimer, after being replaced by nitrogen, start The mixture was stirred slowly, the temperature of the solution was raised to 70 ° C, and polymerization was carried out for 5 hours at this temperature to obtain a solution of the [A] copolymer (solid content concentration: 31.5%).

The [A] copolymer had Mw of 3.1 × 10 ⁴ and Mw / Mn of 2.5. This [A] copolymer was referred to as "copolymer (A-2)".

Synthesis Example 3

In a flask equipped with a cooling tube and a stirrer, 3 parts of 2,2'-azobis(2,4-dimethylvaleronitrile) and 200 parts of diethylene glycol ethyl methyl ether were added, followed by Add 16 parts of methacrylic acid, 30 parts of diethylene glycol monomethacrylate, 18 parts of isodecyl methacrylate, 6 parts of cyclohexene [5.2.1.0 ^{2 , 6} ]decane-8-yl (methyl) Acrylate, 30 parts of p-vinylbenzylepoxypropyl ether, 3 parts of α-methylstyrene dimer, after being replaced by nitrogen, began to slowly stir to raise the temperature of the solution to 70 ° C. The temperature was maintained for 4.5 hours to carry out polymerization to obtain a solution of the [A] copolymer (solid content concentration: 32.7%).

The [A] copolymer had Mw of 2.9 × 10 ⁴ and Mw / Mn of 1.8. This [A] copolymer was referred to as "copolymer (A-3)".

Synthesis Example 4

In a flask equipped with a cooling tube and a stirrer, 4 parts of 2,2'-azobis(2,4-dimethylvaleronitrile) and 220 parts of diethylene glycol ethyl methyl ether were added, followed by Add 20 parts of methacrylic acid, 20 parts of triethylene glycol monomethacrylate, 15 parts of cyclohexene [5.2.1.0 ^{2 , 6} ]decane-8-yl (meth) acrylate, 45 parts of methacrylic acid ring Oxypropyl propyl ester and 3 parts-α-methylstyrene dimer, after being substituted with nitrogen, start to stir slowly, raise the temperature of the solution to 70 ° C, and maintain the temperature at this temperature for 4.5 hours to obtain [A]. A solution of the copolymer (solid content concentration of 31.5%).

The [A] copolymer had Mw of 2.8 × 10 ⁴ and Mw / Mn of 1.9. This [A] copolymer was referred to as "copolymer (A-4)".

Synthesis of comparative copolymers Comparative Synthesis Example 1

In a flask equipped with a cooling tube and a stirrer, 4 parts of 2,2'-azobis(2,4-dimethylvaleronitrile) and 220 parts of diethylene glycol ethyl methyl ether were added, followed by Add 20 parts of methacrylic acid, 40 parts of glycidyl methacrylate, 20 parts of N-phenyl maleimide, 20 parts of styrene, after replacing with nitrogen, start stirring slowly to make the solution The temperature was raised to 70 ° C, and polymerization was carried out at this temperature for 5 hours to obtain a solution of a copolymer (solid content concentration: 30.6%).

The [A] copolymer had Mw of 2.65 × 10 ⁴ and Mw / Mn of 2.4. This copolymer was referred to as "copolymer (a-1)".

Modulation of composition solution Example 1

100 parts of the copolymer (A-1) (solid content) (as the [A] component, the solution of the [A] copolymer obtained in Synthesis Example 1), and 30 parts as the component [B] from 1.0 mol 4,4'-[1-{4-(1-[4-Hydroxyphenyl]-1-methylethyl)phenyl}ethylidene]bisphenol and 2.0 mol of 1,2-naphthoquinone The condensate of nitrogen-5-sulfonyl chloride was dissolved in diethylene glycol ethyl methyl ether to have a solid content of 30%, and then filtered using a membrane filter having a pore size of 0.2 μm to prepare a composition solution.

Examples 2 to 9 and Comparative Example 1

In the same manner as in Example 1, except that each component shown in Table 1 was used as the copolymer and the component [B], the composition solution was prepared. In the component [B] described in Example 8, two kinds of 1,2-benzoquinonediazide compounds were used in combination.

The components of Table 1 are as follows.

[B] ingredient

B-1: 1.0 mol 4,4'-[1-{4-(1-[4-hydroxyphenyl]-1-methylethyl)phenyl}ethylidene]bisphenol with 2.0 mol 1 , 2-naphthoquinonediazide-5-sulfonyl chloride condensate B-2: 1.0 mol 4,4'-[1-{4-(1-[4-hydroxyphenyl]-1-methyl Condensate of ethyl (ethyl) phenyl}ethylidene bisphenol with 1.0 mol of 1,2-naphthoquinonediazide-5-sulfonyl chloride B-3: 1.0 mol 2,3,4,4'- Condensate of tetrahydroxydiphenyl ketone with 2.44 mol 1,2-naphthoquinonediazide-5-sulfonyl chloride B-4: 1.0 mol 4,4'-[1-{4-(1-[ Condensate of 4-hydroxyphenyl]-1-methylethyl)phenyl}ethylidene]bisphenol with 2.0 mol of 1,2-naphthoquinonediazide-4-sulfonyl chloride

Other ingredients

F: SH-28PA (TORAY-Dow Corning Silicone)

Performance evaluation as interlayer insulating film Examples 10 to 18 and Comparative Examples 2 to 4

In Examples 10 to 18 and Comparative Example 2, each of the composition solutions prepared in Examples 1 to 9 and Comparative Example 1 was used, and in Comparative Example 3, a commercially available product (from m-cresol/p-cresol A) was used. (a composition of a phenolic resin and a 1,2-naphthoquinonediazide-5-sulfonate) (solution, trade name OFPR-800, manufactured by Tokyo Kasei Co., Ltd.), and Comparative Example 4 was used. Commercial product (composition composed of m-cresol/p-cresol resol resin and 1,2-naphthoquinonediazide-5-sulfonate) (solution, trade name OFPR-5000, Tokyo Yinghua) (Production), performance evaluation as an interlayer insulating film was carried out in the following order.

Sensitivity evaluation

Examples 10 to 18 and Comparative Example 2 were coated on a PET film having a thickness of 38 μm, and after coating each composition solution with an applicator, the coating film was dried at 90 ° C for 5 minutes to completely remove the solvent to obtain a film thickness of 4.0 μm. Radiation-sensitive dry film of the radiation layer. Subsequently, the radiation-sensitive film is laminated on the surface of the substrate by the radiation-sensitive layer, and the thermal radiation is linearly dried and transferred to the surface of the substrate by thermal compression bonding, and then the base film is peeled off to form on the substrate. A film having a film thickness of 4.0 μm. Further, in Comparative Example 3 and Comparative Example 4, each composition of a commercially available product was applied onto the surface of a tantalum substrate using a spin coater, and then prebaked on a hot plate at 90 ° C for 2 minutes to form a film thickness on the tantalum substrate. 4.0 micron film.

Next, a mask having a line width of 3.0 μm and a line and space of 10 to 1 is interposed, and a PLA-501F exposure machine made by CANON (light source: super high) Mercury lamp), after exposure of each film obtained by changing the exposure time, the solution was developed at 25 ° C for 90 seconds using a tetramethylammonium hydroxide aqueous solution at a concentration shown in Table 2. Subsequently, it was washed with running water for 1 minute with ultrapure water, dried, and patterned on the substrate.

At this time, the amount of exposure necessary for completely dissolving the pitch pattern (line width of 0.3 μm) was measured as the sensitivity. When the value is 1,000 J/m ² or less, it can be said that the sensitivity is good. The evaluation results are shown in Table 2.

Evaluation of Yu Yu

Each of Examples 10 to 18 and Comparative Example 2 was carried out in the same manner as in the order of "Evaluation of Sensitivity" in Examples 10 to 18 and Comparative Example 2, and a film having a film thickness of 4.0 μm was formed on the substrate. Further, Comparative Example 3 and Comparative Example 4 were carried out in the same manner as in the order of "Evaluation of Sensitivity" of Comparative Example 3 and Comparative Example 4, and a film having a film thickness of 4.0 μm was formed on the tantalum substrate.

Next, a mask having a line width of 3.0 μm and a line and space of 10 to 1 is interposed, and a PLA-501F exposure machine made by CANON (light source: super high) Mercury lamp), after exposure using an exposure amount equivalent to the sensitivity value measured by "Evaluation of Sensitivity", using a tetramethylammonium hydroxide aqueous solution having the concentration shown in Table 2, and developing at 25 ° C for 90 seconds using a liquid-filling method. . Subsequently, it was washed with running water for 1 minute with ultrapure water, dried, and patterned on the substrate.

At this time, the development time necessary for the line width of the line pattern of 3.0 μm was taken as the most suitable development time. The time until the most suitable development time is elapsed and the development is continued until the formed line pattern is peeled off is measured as a development margin. If the value is more than 30 seconds, it can be said to have a good development margin. The most suitable evaluation for the development time and development margin is shown in Table 2.

Solvent resistance evaluation

Each of Examples 10 to 18 and Comparative Example 2 was carried out in the same manner as in the order of "Evaluation of Sensitivity" in Examples 10 to 18 and Comparative Example 2, and a film having a film thickness of 4.0 μm was formed on the substrate. Further, Comparative Example 3 and Comparative Example 4 were carried out in the same manner as in the order of "Evaluation of Sensitivity" of Comparative Example 3 and Comparative Example 4, and a film having a film thickness of 4.0 μm was formed on the tantalum substrate.

Then, the PLA-501F exposure machine (light source: ultra-high mercury lamp) manufactured by CANON Co., Ltd. was exposed so that the cumulative exposure amount reached 3,000 J/m ² , and then the substrate was post-treated at 220 ° C in an oven. Bake for 1 hour to harden each film. Further, since the evaluation of the solvent resistance does not require a pattern, exposure and development can be omitted.

At this time, the film thickness (T1) of each film after curing was measured, and each of the hardened substrates was immersed in dimethylarylene having a temperature controlled at 70 ° C for 20 minutes, and then the film thickness of each film was measured ( T1), the film thickness change rate (| t1 - T1 | × 100 / T1) (%) due to immersion was calculated. When the value is 5% or less, it is said that the solvent resistance is good. The evaluation results are shown in Table 2.

Evaluation of heat resistance

In the same manner as the procedure of "evaluation of solvent resistance", each film was formed on a tantalum substrate to be cured.

At this time, the film thickness (T2) of each film after the hardening was measured, and the film thickness of each film was measured by further heating the cured ruthenium substrate at 240 ° C for 1 hour in a clean oven (t2). The film thickness change rate (| t2-T2 |×100/T2) (%) due to additional heating was calculated. When the value is 5% or less, it can be said that the heat resistant property is good. The evaluation results are shown in Table 2.

Transparency evaluation

In the same manner as in the "evaluation of solvent resistance", each film was formed on a glass substrate and cured, except that the glass substrate "CORNING 7059" (trade name, manufactured by Dow Corning Co., Ltd.) was used instead of the ruthenium substrate.

At this time, the light transmittance of the wavelength range of 400 to 800 nm was measured on the glass substrate having the hardened film using a spectrophotometer 150-20 type double beam manufactured by Hitachi, Ltd. In this case, when the lowest light transmittance in the wavelength range is 90% or more, the transparency is good. The evaluation results are shown in Table 2.

Evaluation of specific dielectric constant

In the same manner as in the "evaluation of solvent resistance", the respective films were formed on the SUS substrate and cured, except that the substrate made of SUS304 was replaced with a substrate made of SUS304. Subsequently, a Pt/Pd electrode pattern was formed on each of the films after hardening by a vapor deposition method to produce a sample for dielectric constant measurement. Further, since the evaluation of the specific dielectric constant does not require a pattern, exposure and development can be omitted.

At this time, the specific dielectric constant of each substrate at a frequency of 10 kHz was measured by a CR method using a HP16451B electrode manufactured by Yokogawa-Higashi Co., Ltd. and an HP4284A precision LCR meter. When the value is 3.6 or less, the specific dielectric constant can be said to be good. The evaluation results are shown in Table 2.

Performance evaluation as a microlens Examples 19 to 27 and Comparative Examples 5 to 7

In Examples 19 to 27 and Comparative Example 5, each of the composition solutions prepared in each of Examples 1 to 9 and Comparative Example 1 was used, and in Comparative Example 6, a commercially available product (from m-cresol/p-cresol resol resin) was used. A composition composed of 1,2-naphthoquinonediazide-5-sulfonate (solution, trade name OFPR-800, manufactured by Tokyo Kasei Co., Ltd.), and Comparative Example 7 used a commercial product. (Composition composed of m-cresol/p-cresol resol resin and 1,2-naphthoquinonediazide-5-sulfonate) (solution, trade name OFPR-5000, Tokyo Yinghua) The performance evaluation as a microlens was carried out in the following order. Moreover, the evaluation of heat resistance and transparency is referred to the "performance evaluation as an interlayer insulating film" mentioned above.

Sensitivity evaluation

Examples 19 to 27 and Comparative Example 5 were coated on a PET film having a thickness of 38 μm by coating each composition solution with an applicator, and then drying the coating film at 90 ° C for 5 minutes to completely remove the solvent to have a film thickness of 4.0 μm. Radiation-sensitive dry film of the radiation layer. Subsequently, the radiation-sensitive film is laminated on the surface of the substrate by the radiation-sensitive layer, and the thermal radiation is linearly dried and transferred to the surface of the substrate by thermal compression bonding, and then the base film is peeled off to form on the substrate. A film having a film thickness of 4.0 μm. Further, in Comparative Example 6 and Comparative Example 7, each composition of a commercially available product was applied onto the surface of a tantalum substrate using a spin coater, and then prebaked on a hot plate at 90 ° C for 2 minutes to form a film thickness on the tantalum substrate. 4.0 micron film.

Next, a reticle having a line width of 0.8 μm and a line and space of 1 to 1 is interposed, and the NSR1755 i 7A NSKA 755 i 7A is used to reduce the projection exposure machine (NA= 0.50, λ = 365 nm), and each of the obtained films was exposed for a change in exposure time, and then developed using a tetramethylammonium hydroxide aqueous solution having a concentration shown in Table 3, and developed at 25 ° C for 60 seconds using a liquid-filling method. Subsequently, it was washed with running water for 1 minute with ultrapure water, dried, and patterned on the substrate.

At this time, the amount of exposure necessary for completely dissolving the pitch pattern (line width of 0.8 μm) was measured as the sensitivity. When the value is 2,500 J/m ² or less, it can be said that the sensitivity is good. The evaluation results are shown in Table 3.

Evaluation of Yu Yu

Each of Examples 19 to 27 and Comparative Example 5 was carried out in the same manner as in the order of "Evaluation of Sensitivity" of Examples 19 to 27 and Comparative Example 5, and a film having a film thickness of 4.0 μm was formed on the substrate. Further, Comparative Example 6 and Comparative Example 7 were carried out in the same manner as in the order of "Evaluation of Sensitivity" of Comparative Example 6 and Comparative Example 7, and a film having a film thickness of 4.0 μm was formed on the ruthenium substrate.

Next, a mask having a line width of 0.8 μm and a line and space of 1 to 1 is interposed therebetween by a NIKON NSR1755 i 7A reduction projection exposure machine (NA=0.50). λ = 365 nm), after exposure time change was changed, and a tetramethylammonium hydroxide aqueous solution having a concentration shown in Table 3 was used, and development was carried out at 25 ° C for 90 seconds using a liquid-filling method. Subsequently, it was washed with running water for 1 minute with ultrapure water, dried, and patterned on the substrate.

At this time, the development time necessary for the line width of the line pattern to be 0.8 μm was taken as the most suitable development time. The time until the most suitable development time is elapsed and the development is continued until the formed line pattern is peeled off is measured as a development margin. If the value is more than 30 seconds, it can be said to have a good development margin. The evaluation that is most suitable for development time and development margin is shown in Table 3.

Solvent resistance evaluation

Each of Examples 19 to 27 and Comparative Example 5 was carried out in the same manner as in the order of "Evaluation of Sensitivity" of Examples 19 to 27 and Comparative Example 5, and a film having a film thickness of 4.0 μm was formed on the substrate. Further, Comparative Example 6 and Comparative Example 7 were carried out in the same manner as in the order of "Evaluation of Sensitivity" of Comparative Example 6 and Comparative Example 7, and a film having a film thickness of 4.0 μm was formed on the ruthenium substrate.

Then, the PLA-501F exposure machine (light source: ultra-high mercury lamp) manufactured by CANON Co., Ltd. was exposed so that the cumulative exposure amount reached 3,000 J/m ² , and then the substrate was post-treated at 220 ° C in an oven. Bake for 1 hour to harden each film. Further, since the evaluation of the solvent resistance does not require a pattern, exposure and development can be omitted.

At this time, the film thickness (T1) of each film after curing was measured, and each of the hardened substrates was immersed in dimethylarylene having a temperature controlled at 70 ° C for 20 minutes, and then the film thickness of each film was measured ( T1), the film thickness change rate (| t1 - T1 | × 100 / T1) (%) due to immersion was calculated. When the value is 5% or less, it is said that the solvent resistance is good. The evaluation results are shown in Table 3.

Evaluation of lens shape

Each of Examples 19 to 27 and Comparative Example 5 was carried out in the same manner as in the order of "Evaluation of Sensitivity" of Examples 19 to 27 and Comparative Example 5, and a film having a film thickness of 4.0 μm was formed on the substrate. Further, Comparative Example 6 and Comparative Example 7 were carried out in the same manner as in the order of "Evaluation of Sensitivity" of Comparative Example 6 and Comparative Example 7, and a film having a film thickness of 4.0 μm was formed on the ruthenium substrate.

Next, a photomask having a 4.0 micron dot (dot) and a 2.0 micron space pattern was interposed therebetween by a NIKON NSR1755 i 7A reduction projection exposure machine (NA=0.50, λ=365 nm). After exposure was carried out using an exposure amount equivalent to the sensitivity value measured by "Evaluation of Sensitivity", the aqueous solution of tetramethylammonium hydroxide having the concentration shown in Table 3 was used, and development was carried out at 25 ° C for 1 minute using a liquid-holding method. Subsequently, it was washed with running water for 1 minute with ultrapure water, dried, and patterned on the substrate.

Then, the PLA-501F exposure machine (light source: ultra-high mercury lamp) manufactured by CANON Co., Ltd. was exposed so that the cumulative exposure amount reached 3,000 J/m ² , and then heated at 160 ° C for 10 minutes on a hot plate. Further, the film was heated at 230 ° C for 10 minutes to form a microlens by melt-flowing the pattern.

At this time, the size of the bottom of the microlens (the diameter of the surface contacting the substrate) was measured by a scanning electron microscope, and the cross-sectional shape was observed. When the size of the bottom of the microlens is larger than 4.0 μm and smaller than 5.0 μm, the shape of the lens can be said to be good. Further, when the size is larger than 5.0 μm, it is not preferable because a contact state occurs between adjacent lenses. Further, in the pattern diagram shown in Fig. 1, the cross-sectional shape is good in the shape of a semi-convex lens as shown by a, and is not preferable in the case of a substantially flat shape as indicated by b. The evaluation results are shown in Table 3.

( ^* ) Contact between adjacent lenses is impossible to observe.

a. . . Semi-convex lens shape (good)

b. . . Semi-convex lens shape (poor)

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

Claims (10)

A radiation sensitive resin composition characterized by comprising: [A] an alkali-soluble copolymer, wherein the [A] alkali-soluble copolymer is composed of (a1) an unsaturated carboxylic acid and/or an unsaturated carboxylic anhydride, (a2) At least one structure is selected from the group consisting of a tetrahydrofuran ring structure, a furan ring structure, a tetrahydropyran ring, a piper ring structure, and an unsaturated compound of the group represented by the following formula (1), and (a3) other than the above a saturated compound; and [B] 1,2-benzoquinonediazide; (In the formula, R represents a hydrogen atom or a methyl group, and n is an integer of 2 to 10). A radiation-sensitive linear dry film comprising a radiation-sensitive layer composed of a radiation-sensitive resin composition of the first aspect of the patent application. The radiation sensitive resin composition of the first aspect of the patent application is for forming an interlayer insulating film. An interlayer insulating film formed of a radiation-sensitive resin composition of the third application of the patent application. A method for forming an interlayer insulating film, comprising the following system Process: (1) a process for forming a film of a radiation sensitive resin composition according to item 3 of the patent application scope; (2) a process of irradiating at least a part of the film with radiation; (3) a process for film development; and (4) a process for heating the film after development. The method for forming an interlayer insulating film according to claim 5, characterized in that in the (1) process, the radiation-sensitive layer of the radiation-sensitive dry film of the second aspect of the patent application is transferred onto the surface of the substrate. A film of a radiation-sensitive resin composition is formed on the substrate. The radiation sensitive linear resin composition of the first application of the patent scope is used for forming a microlens. A microlens formed by a radiation sensitive resin composition of claim 7 of the patent application. A method for forming a microlens, comprising the process of: (1) forming a film of a radiation sensitive resin composition according to item 7 of the patent scope; (2) irradiating at least a portion of the film. a process for radiging; (3) a process for developing the film after irradiation; and (4) a process for heating the film after development. The method for forming a microlens according to claim 9 is characterized in that in the (1) process, the radiation-sensitive layer of the radiation-sensitive dry film of the second aspect of the patent application is transferred onto the surface of the substrate, A film of a radiation-sensitive resin composition is formed on the substrate.