WO2008069159A1

WO2008069159A1 - Method for producing microlens

Info

Publication number: WO2008069159A1
Application number: PCT/JP2007/073276
Authority: WO
Inventors: Mibuko Shimada; Fumiko Yonezawa
Original assignee: Jsr Corporation
Priority date: 2006-11-28
Filing date: 2007-11-27
Publication date: 2008-06-12
Also published as: TWI480594B; TW200827154A

Abstract

Disclosed is a method for producing a microlens, which comprises a step for applying a radiation-sensitive resin composition over a substrate, a step for performing patterning through exposure and development, a step for applying a composition for forming a microlens upper film, and a step for performing a heat treatment. This method enables to produce microlenses with a narrow pitch between adjacent microlenses. The composition for forming a microlens upper film contains a polymer having at least one acid group selected from the group consisting of a carboxylic acid group, a sulfonic acid group and a phosphoric acid group.

Description

Technical Document Microlens Manufacturing Method Technical Field

The present invention relates to a method for producing a microphone mouth lens and a composition for forming a microphone mouth lens upper layer film. More specifically, in a solid-state image pickup device represented by a CCD or a CMOS, particularly in a solid-state image pickup device using a microphone mouth lens, a method for manufacturing a microphone mouth lens in which a gap between adjacent microphone mouth lenses is a narrow pitch, and the method used therefor. The present invention relates to a composition for forming a lens upper layer film. Background art

In recent years, image sensors have become increasingly finer and more pixelated year by year, and the size of the light receiving element has decreased, resulting in a problem of reduced sensitivity. Furthermore, as the microlens size decreases, the gap between the lenses causes noise, which is a further problem.

In order to improve sensitivity, reduce noise, and increase light collection efficiency, it is ideal to arrange microlenses without gaps. Japanese Patent Laid-Open No. 2 0 06-4 1 4 6 7 Although it has been proposed in Japanese Patent No. 1 5 6 8 98, the manufacturing method is not specifically shown, and in most cases it is manufactured by etching.

A further problem is that the processing by etching becomes difficult as the microlens film becomes thinner and the size decreases. Disclosure of the invention

An object of the present invention is to provide a method for manufacturing a microphone mouth lens in which a gap between adjacent microphone mouth lenses is a narrow pitch in a solid-state image pickup device represented by a CCD or a CMOS, particularly a solid-state image pickup device using a microlens, and a microphone therefor An object of the present invention is to provide a composition for forming a mouth lens upper layer film.

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 method for producing a microlens from a radiation-sensitive resin composition on a substrate, comprising: (a) a method for forming a microlens on a substrate. A step of applying a radiation-sensitive resin composition, (b) a step of patterning by exposure and development, (c) a step of applying a composition for forming a microlens upper layer film on a pattern on a substrate, and (d) This is achieved by a method of manufacturing a microphone mouth lens, which includes a step of performing a heat treatment.

According to the present invention, the above-mentioned objects and advantages of the present invention are, secondly, containing a polymer containing at least one acid group selected from the group consisting of a carboxylic acid group, a sulfonic acid group, and a phosphoric acid group. This is achieved by the composition used for forming the lens upper layer film. Brief Description of Drawings

FIG. 1 is a schematic cross-sectional view of adjacent microlenses. BEST MODE FOR CARRYING OUT THE INVENTION

Hereinafter, the manufacturing method of the microphone mouth lens of the present invention will be described in detail.

The method for producing a microlens of the present invention includes, as described above, (a) a step of applying a radiation-sensitive resin composition for forming a microphone aperture lens on a substrate, and (b) a pattern by performing exposure and development. (C) a step of applying a composition for forming a microlens upper layer film on a pattern on a substrate, and (d) a step of performing a heat treatment.

Examples of the substrate in the step (a) include a photoelectric conversion element in which a transparent resin layer such as a color filter, a high refractive index resin layer, an antireflection film layer, and a planarization film layer is disposed. At this time, the coating method is not particularly limited, and for example, a coating method such as a spin coating method, a non-coating method, or a roll coating method can be used. The film thickness is not particularly limited, but is preferably 0.05 to 10 m. Usually, the film is formed by pre-baking at 50 to 120 to volatilize the solvent.

Next, in step (b), first, the film is exposed. Radiation used for exposure Examples of rays include: visible rays; ultraviolet rays such as g rays and i rays; far ultraviolet rays such as Ar F excimer lasers and K r F excimer lasers; X rays such as synchrotron radiation; Can be mentioned.

After the exposure, development is performed with an alkaline developer to form a desired pattern. Examples of development methods include shower development, spray development, immersion development, and paddle development. The development conditions are preferably 20 to 40 and about 10 seconds to 5 minutes. As an alkaline developer, for example, sodium hydroxide, potassium hydroxide, ammonia water or tetramethylammonium hydroxide is dissolved in water so that the concentration is about 0.05 to 5% by weight. An aqueous solution may be mentioned. For example, a water-soluble organic solvent such as methanol or ethanol, a surfactant, or the like may be appropriately added to these aqueous solutions. After development, wash with water and air dry.

After development or after application of the composition for forming the microlens upper layer film, washing with water, and drying, the 1,2-mononaphthoquinonediazide compound remaining in the radiation-sensitive composition is converted into an indenecarboxylic acid compound, for example, by irradiating ultraviolet rays. Can be made. Next, in the step (c), the microlens upper layer film-forming composition is applied. The coating method is not particularly limited as in the case of the radiation sensitive resin composition. For example, a coating method such as a spin coating method, a bar coating method, or a roll coating method can be used. The film thickness of the microlens upper layer film-forming composition is preferably as solid content:! ~ 500 nm, more preferably 2 ~ 400 nm, and pre-baking for the purpose of volatilizing the solvent, In order to remove the composition for the upper layer film more than necessary, it may be washed with water. Since the composition for forming an upper layer film of the present invention has an acid group as described later, this acid group reacts with a functional group in the microphone mouth lens composition. Therefore, although the excess upper layer film-forming composition is removed by washing, the upper layer film-forming composition is not completely removed by washing. Even after washing and removing the excess upper layer forming composition, the upper layer forming composition remaining on the microlens sufficiently controls the melt property of the lens in the subsequent step (d). be able to. Such a remaining composition for forming an upper layer film also provides an upper layer film that sufficiently functions as the upper layer film of the microlens in the present invention. - Thereafter, in the step (d), the pattern is melted to form a microlens, and heat treatment is performed in order to sufficiently exhibit the characteristics as a permanent film. The heat treatment conditions are not particularly limited. For example, an oven, a hot plate, a far-infrared furnace or the like is used, and the treatment is preferably performed at 100 to 300 for 30 seconds to 30 minutes. Preferred radiation-sensitive resin compositions used in the present invention include, for example, (A) an alkali-soluble resin, (B) 1,2-naphthoquinonediazide compound, and (C) a compound having at least one epoxy group in the molecule. Become.

(A) Alkali-soluble resin

The strength-soluble resin used in the present invention is a resin that is soluble in the strength strength aqueous solution. For example, a nopolac resin, α,; 8-unsaturated carboxylic acid copolymer (hereinafter referred to as “copolymer I”). And a nuclear brominated polymer of a copolymer of hydroxystyrenes or a copolymer thereof with styrenes (hereinafter referred to as “brominated polymer II”) may be mentioned as preferred.

The nopolac resin is obtained by condensing phenols with an aldehyde in the presence of an acidic catalyst. These phenols include, for example, cresols such as phenol, m-cresol, o-cresol; xylenols such as 2,5-xylenol, 3,5-xylenol, 3,4-xylenol, 2,3-xylenol; Alkylphenols such as cetylphenol, p-ethylphenol, o-ethylphenol, p — t —butylphenol; p-methoxyphenol, m —methoxyphenol, 3,5-dimethoxyphenol, 2-methoxy-4-methylphenol, m-ethoxy Alkoxyphenols such as phenol, p-ethoxyphenol, m-propoxyphenol, p-propoxyphenol, m-butoxyphenol, p-t-butoxyphenol; bisalkylphenols such as 2-methyl-4-alkylpropylphenol; m —Black and white It can be used p- black port phenol, o- black port phenol, dihydroxy Biff enyl, Bisufueno Le eight, phenylalanine phenol, resorcinol, a hydroxy aromatic compound of naphthol.

Examples of aldehydes include formaldehyde, paraformaldehyde, Acetaldehyde, Propylaldehyde, Benzaldehyde, Phenylacetaldehyde, α-Phenylpropylaldehyde, 8-Phenylpropylaldehyde, ο-Hydroxybenzaldehyde, m-Hydroxybenzaldehyde, p-Hydroxybenzaldehyde, o-Clorobenzaldehyde, m—Black mouth benzaldehyde, p—Black mouth benzaldehyde, o—Nitrobensaldehyde, m—Nitto mouth benzaldehyde, p—Nitrobenzaldehyde, o—Methylbenzaldehyde, m—Methyl Benzaldehyde, p-methylbenzaldehyde, p-ethylbenzaldehyde, p-n-butylbenzaldehyde, furfural, chloroacetaldehyde and their acetals, such as chloroacetaldehyde, decylacetal It can be used. Of these, formaldehyde is preferably used.

Aldehydes are preferably used in a proportion of 0.7 to 3 mol, more preferably 1.1 to 2 mol, per mol of phenols.

As the acidic catalyst, for example, hydrochloric acid, sulfuric acid, formic acid, acetic acid and oxalic acid can be preferably used.

The amount of these acidic catalysts used is preferably ¹ X 10 — ^{4 to} 5 X 10 0-1 per mole of the total amount of phenols and aldehyde (hereinafter referred to as “reaction raw material”).

In the condensation reaction, water is usually used as the reaction medium. However, if the phenols used in the condensation reaction do not dissolve in the aldehyde aqueous solution and become heterogeneous from the beginning of the reaction, a hydrophilic solvent is used as the reaction medium. Can be used.

Examples of such a solvent include alcohols such as methanol, ethanol, propanol, and butyl alcohol; ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; and cyclic ethers such as tetrahydrofuran and dioxane.

The amount of the reaction medium used is preferably 50 to 1,000 parts by weight per 100 parts by weight of the reaction raw material.

The reaction temperature during the condensation reaction can be appropriately adjusted according to the reactivity of the reaction raw materials. Preferably it is 10 to 15 Ot :, more preferably 70 to 1 30. Copolymer I can be obtained by radical polymerization of α, ι6-unsaturated carboxylic acid and another radical polymerizable compound in a solvent.

Examples of the α, j8-unsaturated carboxylic acid include monocarboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid; dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid, and itaconic acid. Can be mentioned.

Other radical polymerizable compounds include, for example, acid anhydrides such as maleic anhydride, itaconic anhydride, etc .; dicarboxylic acid monoesters such as monoethyl maleate, monoethyl fumarate, monoethyl itaconate, etc .; conjugated diolefins, for example 1,3-Butadiene, isoprene, black-opened plane, dimethyl-1,3-butylene, etc .; monoolefin-unsaturated compounds such as methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate, t Methacrylic acid alkyl esters such as methyl methacrylate, methyl acrylate, acrylic acid alkyl esters such as isopropyl acrylate, methacrylic acid cyclic such as cyclohexyl methacrylate, 2-methylcyclohexyl methacrylate Alkyl ester such as alkyl ester, cyclohexyl acrylate, 2-methyl acrylate, cyclic alkyl ester such as hexyl acrylate, phenyl acrylate, phenyl acrylate, phenyl acrylate, phenyl acrylate Acrylate, aryl ester such as benzyl acrylate, styrene, α-methyl styrene, o-methyl styrene, m-methyl styrene, p-methyl styrene, p-methoxy styrene, acrylonitrile, methacrylonitrile, vinyl chloride, chloride Vinylidene, acrylamide, methacrylic amide, vinyl acetate, etc. can be used.

The copolymerization ratio of the α, ι6-unsaturated carboxylic acid in the copolymer I is preferably 5 to 40% by weight, particularly preferably 15 to 30% by weight, based on the copolymer. If it is less than 5% by weight, the resulting copolymer is difficult to dissolve in an alkaline aqueous solution, so that a development residue is likely to occur, and it is difficult to form a sufficient resist pattern. On the other hand, if it exceeds 40% by weight, the solubility of the resulting copolymer in an aqueous solution of alcohol will be too great, and it will be difficult to prevent dissolution of unexposed areas, that is, film development. Further, as the other radical polymerizable compound, a synergistic diolefin or monoolefin-unsaturated compound is preferable from the properties of the resulting copolymer.

By using this conjugated diolefin, it is possible to give the copolymer the unique flexibility of the rubber, so that the copolymer is flexible, the copolymer is not cracked, and the yield of the product is significantly improved. Can do. In addition, the adhesion of the copolymer to the substrate is increased. Furthermore, when the copolymerization amount of conjugated diolefin is increased, the melting temperature of the obtained copolymer shifts to a lower temperature side.

In addition, by including a monoolefin-unsaturated compound in the copolymer, the mechanical properties of the copolymer are appropriately controlled. It is possible to finely adjust the solubility in water.

Examples of monoolefin-unsaturated compounds include methyl methacrylate alkyl esters such as methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate, and t-butyl methacrylate; methyl acrylate and isopropyl acrylate. Acrylic acid alkyl esters such as cyclohexyl methacrylate, 2-methylcyclohexyl methacrylate, and other cyclic acid cyclic alkyl esters; Cyclohexyl acrylate, acrylic acid cyclic alkyl esters such as 2-methylcyclohexyl methacrylate, and the like Methacrylic acid aryl ester such as phenyl methacrylate and benzyl methacrylate; acrylic acid aryl ester such as phenyl acrylate and benzyl acrylate; jetyl maleate, fuma Diesters of dicarboxylic acids such as cetyl acrylate and decyl itaconate; hydroxyalkyl esters of methacrylic acid such as 2-hydroxyethyl methacrylate and 2-hydroxypropyl methacrylate; styrene, α-methylstyrene, ο— Methyl styrene, m-methyl styrene, p-methyl styrene, vinyl toluene, p-methoxy styrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, vinyl acetate and the like can be used.

These compounds can be used alone or in combination of two or more. mono Considering the influence of the olefinic unsaturated compound on various properties, the preferred copolymerization amount is 25 to 90% by weight, particularly preferably 30 to 80% by weight, based on the copolymer. If the content of the monoolefin-unsaturated compound is less than 25% by weight, α, which is a component soluble in other components in the resin, that is, a conjugated diolefin-based compound or an alkaline aqueous solution, 6-unsaturated carboxylic acid content Therefore, it is difficult to control the mechanical properties of the resin and the developability of the resin. On the other hand, if it exceeds 90% by weight, the solubility of the resin in the aqueous solution of alcohol will be reduced, which is not preferable. Solvents used in the production of Copolymer I include, for example, alcohols such as methanol and ethanol; ethers such as tetrahydrofuran; glycol ethers such as ethylene glycol monomethyl ether; cellosolve esters such as methyl solvate acetate; Group hydrocarbons, ketones, esters and the like.

As a polymerization catalyst in radical polymerization, usual radical polymerization initiators can be used. For example, 2, 2'-azobisisobutyronitrile, 2, 2, azobis- (2, 4-dimethylvaleronitrile), 2, 2 Azo compounds such as 4-methoxy-1-2,4-dimethylvaleronitrile; benzoylberoxide, lauroyl peroxide, tert-butylperoxybivalate, 1,1-bis-1, ) Organic peroxides such as hexane hexane and hydrogen peroxide can be mentioned. When a peroxide is used as a radical polymerization initiator, a redox initiator may be combined with a reducing agent.

Examples of the brominated polymer I I include, for example, the following formula (I I)

— (-CH ₂ — CH ^ — Structural unit (II) or structural unit (II) represented by the following formula (III)

Here, represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, R ₂ represents a hydrogen atom, a methyl group or a methoxy group,

And the structural unit (II) accounts for 100 to 70 mol% based on the total of the structural unit (II) and the structural unit (III). Preferably used is an al force resoluble polymer. The brominated polymer II can be produced by, for example, copolymerizing hydroxystyrenes and styrenes to obtain a precursor polymer and then brominating the polymer (hereinafter referred to as “direct method”), hydroxy After copolymerization with styrene using a compound in which the hydroxyl group of styrene is protected with another functional group, the polymer is brominated after conversion to hydroxyl group using an appropriate method to obtain a precursor polymer Method (hereinafter referred to as “indirect method”). In the present invention, any method may be used as long as no adverse effect occurs when the microlens is formed. The hydroxyl group may be located at any position, but is preferably located at the P position with respect to the double bond of styrene.

Examples of the precursor polymer include a homopolymer composed only of the structural unit represented by the above formula (II) and a copolymer composed of the structural unit represented by the above formula (II) and the structural unit represented by the above formula (III). Can do.

The copolymerization ratio in the precursor polymer is preferably 70 mol% or more, particularly preferably 85 mol% or more for hydroxystyrenes.

When it is less than 70 mol%, the obtained copolymer is difficult to dissolve in an alkaline aqueous solution. Therefore, it is difficult to produce a pattern necessary for the microlens because the development residue is likely to occur. Examples of styrenes for obtaining a precursor polymer by the direct method include styrene, hypermethylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, p-vinyltoluene, and .p-methoxystyrene. . Examples of the hydroxystyrenes include o-hydroxystyrene, m-hydroxystyrene, and p-hydroxystyrene.

Examples of precursor monomers of hydroxystyrenes for obtaining brominated polymer II by the indirect method include p-benzyloxystyrene, p-tert-butoxystyrene, p-tert-butoxycarbonyloxystyrene, p — Tert-Butyldimethylsiloxystyrene, p-acetoxystyrene, etc. can be used. Examples of styrenes that can be used include styrene, α-methylstyrene, o_methylstyrene, m-methylstyrene, p-methylstyrene, p-vinyltoluene, and p-methoxystyrene.

Then, a precursor polymer can be obtained by subjecting the hydroxystyrenes to an appropriate treatment, for example, hydrolysis.

In addition, a radical polymerization initiator, an anion polymerization initiator, or the like can be used as a polymerization catalyst for producing the precursor monomer and styrene copolymer. Brominated polymer II can be obtained by adding bromine dropwise after dissolving the precursor polymer in an organic solvent such as carbon tetrachloride and taking care that the reaction temperature does not exceed 30. it can. The bromination rate in this case is preferably 5 mol% or more with respect to 100 mol% of benzene nuclei. If it is less than 5 mol%, the desired strength-resolving property may not be obtained. Commercially available resins include Maruzalin Petrochemical Co., Ltd. Marcarinka — M, Marcarinka IMB, P HM- C, Nippon Soda Co., Ltd. VP polymer, Toho Chemical Co., Ltd. parahydroxystyrene, Toyo Gosei Co., Ltd. Parahydroxystyrene and the like can be mentioned.

The molecular weight of the above Al-soluble resin is not particularly limited as long as the solution of the composition of the present invention can be uniformly applied, but it is preferably 5 in terms of weight average molecular weight. 0 0 to 1 0 0, 0 0 0, more preferably 1, 0 0 0 to 7 0, 0 0 0 is there.

(B) 1,2-Naphthoquinonediazide compound

The photosensitizer used in the present invention can impart heat resistance / solvent resistance to the composition by a reaction with an alcohol-soluble resin and an epoxy compound. 1,2-Naphthoquinonediazide compounds, for example, 1,2-naphthoquinonediazide sulfonic acid esters include, for example, condensates of phenolic compounds or alcoholic compounds with 1,2-naphthoquinonediazide sulfonic acid halides. . As the 1,2-naphthoquinone diazide sulfonic acid halide, 1,2-naphthoquinone diazide sulfonic acid halide is preferable.

Examples of the phenolic compound or alcoholic compound include dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, penoxyhydroxybenzophenone, hexahydroxybenzophenone, and (polyhydroxyphenone). Enyl) Alkanes.

Specific examples thereof include, for example, 4,4′-dihydroxydiphenylmethane, 4,4′-dihydroxydiphenyl ether, etc. as dihydroxybenzophenone:

Examples of trihydroxybenzophenone include 2, 3, 4-trihydroxybenzophenone, 2, 4, 6-trihydroxybenzophenone, etc .;

Tetrahydroxybenzophenone includes 2, 2 ', 4, 4' — tetrahydrobenzobenzophenone, 2, 3, 4, 3 '— tetrahydroxybenzophenone, 2, 3, 4, 4, Tetrahydroxybenzophenone, 2, 3, 4, 2, —tetrahydroxy-4, 1-methylbenzophenone, 2, 3, 4, 4, 4-tetrahydroxy-1 3 ′ —methoxybenzophenone, etc .;

Pen Yun hydroxybenzophenone includes 2, 3, 4, 2 ', 6, one pen Yun hydroxybenzophenone, etc .;

Hexahydroxybenzophenone includes 2, 4, 6, 3 ', 4', 5, monohexahydroxybenzophenone, 3, 4, 5, 3 4 ', 5, monohexahydroxybenzophenone, etc .; (Polyhydroxyphenyl) Alkanes include 2-methyl-2- (2,4-dihydroxyphenyl) 1-41- (4-hydroxyphenyl) 7-hydroxychroman, 2- [bis {(5_isopropyl 1-hydroxy-2-phenyl) methyl] phenol, 1- [1- (3-— {1- (4-hydroxyphenyl) — 1-methylethyl} -4, 6-dihydroxyphenyl) — 1 —Methylethyl] 1 3— (1— (3— {1- (4-hydroxyphenyl) 1 1-methylethyl} 1 4,6-dihydroxyphenyl) 1 1-methylethyl) benzene, and 4, 6-bis { 1- (4-Hydroxyphenyl) 1 1 1-methylethyl} — 1,3-dihydroxybenzene, bis (2,4-dihydroxyphenyl) methane, bis (p-hydroxyphenyl) methane, 1, 1-bis ( 4-hydroxy Phenyl) — 1-phenylphenyl, 1,3-bis [1— (4-hydroxyphenyl) -1/1 methylethyl] benzene, 1,4-bis [1- (4-hydroxyphenyl) 1-11 methylethyl] benzene , 4, 6-bis [1 (4-hydroxyphenyl) 1 1-methylethyl] -1,3-dihydroxybenzene, 1, 1 bis (4-hydroxyphenyl) — 1 1 [4 1 [1 — (4-Hydroxyphenyl) 1-methylphenyl] phenyl] ethane, tri (p-hydroxyphenyl) methane, 1, 1, 1 monotri (p-hydroxyphenyl) ethane, bis (2, 3, 4-trihydroxyphenyl) methane, 2, 2-bis (2, 3, 4_trihydroxyphenyl) propan, 1, 1, 3-tris (2, 5-dimethyl-4-hydroxyphenyl) 1 — Phenylpropane, 4, 4,-[1— [4 1 [ 1 1 [4-hydroxyphenyl] 1 1-methylethyl] phenyl] ethylidene] bisphenol, bis (2,5-dimethyl-4-hydroxyphenyl) 1 2-hydroxyphenylmethane, 3, 3, 3, 3 ' —Tetramethyl-1,1, -Spirobiindene-1,6,7,5 ', 6', 7, —Hexanol, 2,2,4_trimethyl _7,2 ', 4'—Trihydr Can be mentioned respectively.

In the condensation reaction, 1,2-naphthoquinonediazide sulfonic acid halide corresponding to 30 to 85 mol%, more preferably 50 to 70 mol% is preferably added to the number of HH groups in the phenolic compound or alcoholic compound. Can be used Monkey.

Examples of the solvent that can be used at this time include ketones and cyclic ethers. Specific examples of these include ketones such as acetone, methyl ethyl ketone, methyl isoamyl ketone, and methyl isobutyl ketone, and cyclic ethers such as 1,4 monodioxane, 1,3,5-trioxane and the like. Each can be mentioned. When a solvent is used, the amount used is preferably 10 to 5 to 100 parts by weight with respect to a total of 100 parts by weight of the above phenolic compound or alcoholic compound and 1,2-naphthoquinonediazidesulfonic acid halide. 0 parts by weight.

A basic compound can be used as the catalyst. Preferable examples include triethylamine, tetramethylammonium chloride, tetramethylammonium bromide, and pyridine. The amount of these catalysts used is preferably 1 mol or more, more preferably 1.05 to 1.2 mol, per 1 mol of 1,2-naphthoquinone diazide sulfonic acid halide.

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

The reaction time is preferably 0.5 to 10 hours, more preferably 1 to 5 hours. ~ 3 hours is preferred.

After the condensation reaction, the precipitate is filtered, and the filtrate is put into a large amount of 0.1 to 3.0% by weight dilute aqueous hydrochloric acid solution to precipitate the reaction product. Thereafter, the precipitate is filtered, washed with water until the filtrate becomes neutral, and then dried to obtain the component (B).

These components (B) can be used alone or in combination of two or more.

(B) The component is represented by the following formula (I): 1, 1 bis (4-hydroxyphenyl) _ 1 1 [4 1 [1- (4-hydroxyphenyl) 1-methylethyl] phenyl] A condensate of ethane and 1,2-naphthoquinonediazide sulfonic acid ester is particularly preferred.

(Here, the three D's are the same or different and represent 1,2-naphthoquinonediazido 4-monosulfonyl group or 1,2-naphthoquinone diazido 5-sulfonyl group.)

The proportion of the component (B) used is preferably 5 to 100 parts by weight, more preferably 10 to 50 parts by weight with respect to 100 parts by weight of the alkali-soluble resin. When this ratio is less than 5 parts by weight, the amount of indenecarboxylic acid produced by irradiation decreases, so the difference in solubility in an alkaline aqueous solution cannot be made before and after irradiation. In some cases, the heat resistance and solvent resistance of the resulting microlens may be insufficient. When the amount exceeds 100 parts by weight, most of the 1,2-naphthoquinonediazidosulfonic acid ester added by short-time irradiation still remains in the form as it is, so the insolubilizing effect in the aqueous solution is too high. May be difficult to develop.

(C) Compound having at least one epoxy group in the molecule

The epoxy compound used in the present invention is a compound that reacts with a carboxylic acid generated by irradiation of radiation, and has an action of imparting heat resistance and solvent resistance and an action of imparting adhesion. In the above case, the epoxy compound is preferably a compound having two or more epoxy groups in the molecule. Bisphenol A type epoxy resin commercially available products such as Epicot 1001, 1002, 1003, 1004, 1007, 1009, 1010 (manufactured by Yuka Shell Epoxy Co., Ltd.); Bisphenol F type As an epoxy resin commercial product, for example, Epicoat 807

(Oilized Shell Epoxy Co., Ltd.) Bisphenol AD type epoxy resin; Commercially available products such as Epnocoat 152 and 154 (Oka Shell Epoxy Co., Ltd.), EP PN-201, 202 (Nippon Kayaku Co., Ltd.); For example, EOC N-102S, 103S, 104S, 1020, 1025, 1027 (manufactured by Nippon Kayaku Co., Ltd.); Epicot 180 S 75 (manufactured by Yuka Shell Epoxy Co., Ltd.) Commercially available cycloaliphatic epoxy resins such as CY-175, 177, 179 (CI BA—GE I GY), ERL-4234, 4299, 4221, 4206 (UCC); Glycidyl ester epoxy resin Commercially available products include, for example, Shodyne 508 (manufactured by Showa Denko KK), Araldite CY—182, 192, 184 (CI BA—GE I GY), Epiclon 200, 400 (large) (Manufactured by Nippon Ink Co., Ltd.), Epicot 871, 872 Luepoxy Co., Ltd.), ED-5661, 5662 (Celanese Coatings Co., Ltd.); Commercially available glycidylamine epoxy resins such as tetraglycidyl diaminodiphenylmethane, triglycidyl para-aminophenol Nord, triglycidyl metaaminophenol, diglycidyl dilin, diglycidyl toluidine, tetraglycidyl methyl xylylenediamine, diglycidyl tribromaniline, tetraglycidyl bisaminomethylcyclohexane; heterocyclic epoxy Examples of commercially available resins include Alaldite PT810 (manufactured by CI BA-G EI GY), Epicoat RXE-15 (manufactured by Yuka Shell Epoxy Co., Ltd.), EP I TEC (manufactured by Nissan Chemical Co., Ltd.), etc. it can.

In addition, compounds having an epoxy group and an alkoxysilyl group in the molecule are also preferably used. For example, glycidoxypropyl trimethoxysilane, glycidoxypropyltriethoxysilane, glycidoxypropylmethyldimethoxysilane, glycidoxypropylmethyljetoxysilane, 2- (3,4-epoxycyclohexyl) etheryltri Examples include methoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethylmethyldimethoxysilane, and the like.

Also, many of the epoxy compounds listed here are high molecular weight compounds, but are used in the present invention. The epoxy compound to be used is not limited by the molecular weight, and may be a low molecular weight material such as bisphenol A or bisphenol F diglycidyl ether.

Of these, phenol nopolac type epoxy resins, cruzol novolak type epoxy resins, cycloaliphatic epoxy resins, and glycidyl ester epoxy resins are preferred because they are difficult to color after heat treatment.

The amount of the epoxy compound used is preferably 1 to 100 parts by weight, more preferably 2 to 80 parts by weight with respect to the alkali-soluble resin (A).

If the amount is less than 1 part by weight, the reaction with the carboxylic acid produced by irradiation with radiation will not proceed sufficiently, and the heat-resistant deformation of the formed microphone mouth lens will not be sufficient. On the other hand, when the amount exceeds 100 parts by weight, the melting point of the composition as a whole is lowered, and it becomes difficult to widen the temperature range of the heat treatment to be carried out when producing the microphone mouth lens.

Other ingredients

In the radiation sensitive resin composition of the present invention, a surfactant can be further blended.

Examples of the surfactant include a fluorine-based leveling agent, a silicone-based leveling agent, and an ether-based or ester-based leveling agent. Specifically, as (trade name, the same shall apply hereinafter), for example, FTX-218 (manufactured by Neos Co., Ltd.); BM1 000, BM1100 (manufactured by BM-CHEM IE); Megafuck F 142D, F 172, F 173, F 183 (Dainippon Ink Chemical Co., Ltd.), Florad FC-135, FC-170C, FC-430, F-431 (Sumitomo Suriem Co., Ltd.), F force 772, F force 777, F force 30, F force 31, F force 34, F force 35, F force 36, F force 39, F force 83, F force 86, F force 88 (manufactured by F power chemicals) ; Floren series (manufactured by Kyoeisha Chemical Co., Ltd.); FC series (manufactured by Sumitomo 3EM); Fluoronar TF series (manufactured by Toho Chemical Co., Ltd.), SH-28A (manufactured by Toray Dow Corning Co., Ltd.), BYK series of Big Chemie; S s hme go series (manufactured by S s hme gma nn); Surfynol (manufactured by Nissin Chemical Industry Co., Ltd.); Emargen, homogenol (manufactured by Kao Corporation), etc.

The amount of these surfactants used is preferably in the range of 0.005 to 5 parts by weight, more preferably 0.001 to 2 parts by weight per 100 parts by weight of the alkali-soluble resin (A). It is.

Solvent

The radiation sensitive resin composition used in the present invention can be easily prepared by uniformly mixing the components described above. When mixing, it is usually dissolved in an appropriate solvent and used in the form of a solution. As the solvent to be used, an alkali-soluble resin, a 1,2-naphthoquinonediazide compound, an epoxy compound, and other compounds can be uniformly dissolved, and those that do not react with each component are used.

Examples of such solvents include alcohols such as methanol and ethanol; ethers such as tetrahydrofuran; glycol ethers such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether; and ethylene glycols such as methyl solvate sorbate and cetyl solvate sorb acetate. Alkyl ether acetates; alkyl ethers of diethylene glycol such as diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, and jetylene glycol dimethyl ether; propylene glycol alkyl ether acetates such as propylene glycol methyl ether acetate and propylene glycol propyl ether acetate; Aromatic hydrocarbons such as toluene and xylene; methyl ethyl , Cyclohexanone, ketones such as 4-hydroxy-4-monomethyl-1,2-pentanone, etc .; 2-ethyl hydroxypropionate, 2-hydroxymethyl 2-methylpropionate, 2-hydroxy-2-methylpropionate Ethyl acetate ethyl, Ethyl hydroxy acetate, Methyl 2-hydroxy-3-methylbutanoate, Methyl 3-methoxypropionate, Ethyl 3-methoxypropionate, Ethyl 3-ethoxypropionate, Methyl 3-ethoxypropionate, Ethyl acetate And esters such as butyl acetate can be used. In addition, N-methylformaldehyde, N, N-dimethylformaldehyde, N-methylacetamide, N, N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, benzylethyl ether, dihexyl ether, acetonylacetone, isophorone, cabronic acid, strong prillic acid, 1-year-old octanol, 1-nonanol, benzyl High-boiling solvents such as alcohol, benzyl acetate, ethyl benzoate, jetyl oxalate, jetyl maleate, alpha-ptyrolactone, ethylene carbonate, propylene carbonate, and phenyl sorbate solvate can also be added.

Among these solvents, because of solubility, reactivity with each component, and ease of forming a coating film, glycol ethers such as ethylene glycol monoethyl ether; ethylene glycol alkyl ether acetates such as ethyl cellosolve acetate; 2-Esters such as ethyl hydroxypropionate; alkyl ethers of jetylene glycol such as diethylene glycol monomethyl ether are preferred.

In preparing the composition solution, for example, a solution of an alkali-soluble polymer, a solution of 1,2_naphthoquinonediazide compound, a solution of an epoxy compound, and a solution of other compounding agents are prepared separately, and these are prepared immediately before use. It is also possible to mix the solutions in a predetermined ratio.

The composition solution prepared as described above can be used after being filtered using Millipore Filament having a pore size of 0.2 / m.

Composition for forming an upper layer film of a microphone mouth lens

Hereinafter, the composition for forming an upper layer film of the microphone mouth lens of the present invention will be described.

The composition for forming a microlens upper layer film of the present invention comprises a polymer containing one or more acid groups selected from the group consisting of carboxylic acid groups, sulfonic acid groups and phosphoric acid groups. The shape of the microlens can be controlled by applying it on the microphone mouth lens. These acid group-containing polymers are not particularly defined, but (i) a copolymer obtained by polymerizing an acid group-containing monomer containing an acid group and (mouth) other monomers. It is preferable that

(I) Acid group-containing monomer

The carboxylic acid group-containing compound may be, for example, α, / 3-unsaturated carboxylic acid, and examples thereof include acrylic acid, methylacrylic acid, crotonic acid and the like. Nocarboxylic acids; dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid, and itaconic acid.

Examples of the sulfonic acid group-containing compound include vinyl sulfonic acid, allyl sulfonic acid, P-styrene sulfonic acid, allyloxybenzene sulfonic acid, methallyloxybenzene sulfonic acid, 4-monosulfopropyl methacrylate, and the following formula (IV): Examples include acrylamide derivatives that give structural units (referred to as “acrylamide derivatives (iv)”).

(IV) (i v)

[In the formulas (IV) and U v), R ³ represents a hydrogen atom or a monovalent organic group, and R ⁴ represents a divalent organic group. ]

In the formula (IV), the monovalent organic group of R ^{3 and} the divalent organic group of R ⁴ can be linear, branched or cyclic.

The monovalent organic group of R ³ is preferably a group having 1 to 12 carbon atoms. Examples thereof include a carboxyl group; a cyano group; a methyl group, an ethyl group ′, an n-propyl group, an i-propyl group, an n —Butyl group, i-butyl group, sec-butyl group, t-butyl group, n-pentyl group, n-hexyl group and other alkyl groups having 1 to 12 carbon atoms; carboxymethyl group, 2-carboxyethyl group A carboxyalkyl group having 2 to 12 carbon atoms such as a 2-carboxypropyl group, a 3-carboxypropyl group, a 2-stroxybutyl group, a 3-carboxybutyl group, and a 4-carboxybutyl group; a methoxycarbonyl group and a ethoxycarbonyl group N-propoxycarbonyl group, i-propoxycarbonyl group, n-butoxycarbonyl group, t-butoxycarbonyl, etc. A coxycarbonyl group; an acyloxy group having 2 to 12 carbon atoms such as an acetyloxy group, a propionyloxy group, a buenoyloxy group, a benzoyloxy group;

Arenyl group having 6 to 12 carbon atoms such as phenyl group and cumenyl group; Aralkyl group having 7 to 12 carbon atoms such as benzyl group and α-methylbenzyl group; Methoxy group, ethoxy group, η-propoxy group, i 1 Alkoxyl group having 1 to 12 carbon atoms such as propoxy group, n_butoxy group, t-butoxy group, etc .; methoxymethyl group, ethoxymethyl group, 2-methoxychetyl group, 2_ethoxyethyl group, 2-methoxypropyl group, 3 —Methoxypropyl group, 2-methoxybutyl group, 3-methoxybutyl group, 4-methoxybutyl group, etc., C2-C12 alkoxyalkyl group; cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, etc. Cycloalkyl groups having 3 to 12 carbon atoms, substituted derivatives of these groups, and the like.

In the formula (IV), R ³ is preferably a hydrogen atom, a methyl group or the like.

Further, the divalent organic group of R ⁴ is preferably a group having 1 to 12 carbon atoms, and examples thereof include a methylene group, an ethylene group, a 1,2-propylene group, a 1,3-propylene group, 1,1-dimethylethylene group, 1-methyl-1,3-propylene group, 1,4-butylene group, 1_methyl-1,4-butylene group, 2-methyl-1,4-butylene group, 1,5-pentylene group 1, 1-dimethyl-1,4-butylene group, 2,2-dimethyl-1,4-butylene group, 1,2-dimethyl-1,4-butylene group, 1,6-hexylene group, 1,3-cyclohexane Examples thereof include a pentylene group and a 1,4-cyclohexylene group.

Of these divalent organic groups, 1,1-dimethylethylene group is particularly preferred. Specific examples of acrylamide derivatives U V)

2- (meth) acrylamide-2-methylpropanesulfonic acid, 2_α-carboxyacrylamide-2-methylpropanesulfonic acid, 2-α-carboxymethylacrylamide-2-methylpropanesulfonic acid, 2-α-methoxy Carbon acrylamide 2-methylpropane sulfonic acid, 2-α-acetyl silylamide 2-methyl propane sulfonic acid, 2-α-phenyl acrylamido 2-methyl propane sulfonic acid, 2_Hydrenyl acrylamide-2- Me Tylpropanesulfonic acid, 2-a-methoxyacrylamide-2-methylpropansulfonic acid, 2-a- (2-methoxyethyl) acrylamide-2-methylpropane sulfonic acid, 2-a-cyclohexylacrylamide-2- Examples thereof include methylpropane sulfonic acid, 2-a-cyanacrylamide-2-methylpropanesulfonic acid, and the like.

Examples of the phosphoric acid group-containing compound include vinyl phosphoric acid, allylic phosphoric acid, p-styrene phosphoric acid.

Etc.

Other monomers (mouth) include, for example, acid anhydrides, such as maleic anhydride, hydrous itaconic acid, etc .; dicarboxylic acid monoesters, such as monoethyl maleate, monoethyl fumarate, monoethyl itaconate, etc .; conjugated diolefins For example, 1,3-butadiene, isoprene, black-prene, dimethyl-1,3-butadiene, etc .; monoolefin-unsaturated compounds such as methyl methacrylate, ethyl methacrylate, n_butyl methacrylate, sec_butyl methacrylate, t-butyl methacrylate Methacrylic acid alkyl esters such as acrylate, methyl acrylate, alkyl acrylates such as isopropyl acrylate, cyclohexyl methacrylate, 2-methylcyclohexyl methacrylate cyclic alkyl Acrylic acid cyclic alkyl esters such as stear, cyclohexyl acrylate, 2-methylcyclohexyl acrylate, phenyl methacrylate, methyl acrylate esters such as benzyl methacrylate, phenyl acrylate, benzyl acrylate, etc. Acrylic acid aryl ester, styrene, a-methyl styrene, o-methyl styrene, m-methyl styrene, p-methyl styrene, p-methoxy styrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, Methacrylamide, vinyl acetate, difluoromethyl (meth) acrylate, trifluoromethyl (meth) acrylate — 卜;

2,2,2-difluoroethyl (meth) acrylate, 2,2,2_trifluoroethyl (meth) acrylate, pen fluorethyl (meth) acrylate; 1- (Trifluoromethyl) ethyl (meth) acrylate, 2- (trifluoromethyl) ethyl (meth) acrylate, 2, 2, 3, 3-tetrafluoro-n-propyl (meth) acrylate, (Peneven fluoroethyl) Methyl (meth) acrylate, di (trifluoromethyl) methyl (meth) acrylate, heptafluoro n-propyl (meth) acrylate, 1-methyl-2,2,3,3-tetrafluoropropyl (meth) Acrylate, 1_ (Peneven Fluoroetil) Ethyl (Meth) Acrylate, 2-— (Pen Even Fluoroetil) Ethyl (Meth) Acrylate, 2, 2, 3, 3, 4, 4—Hexafluoro n-Butyl (Meth) Acrylate, (Heptofluoro-n-propyl) Methyl (meth) acrylate, Nonafluoro-n-butyl (Meth) acrylate, 1,1 dimethyl-2,2,3,3-tetrafluoropropyl (meth) acrylate, 1,1-dimethyl-2,2,3,3,3-pentafluoropropyl (meth) acrylate , 2— (Hep Even Fluoro n-Propyl) Ethyl (meth) acrylate, 2, 2, 3, 3, 4, 4, 5, 5—Octofluoro-n-pentyl (meth) acrylate group, (Nonafluo mouth) _n—Butyl) Methyl (meth) acrylate, perfluoro n-pentyl (meth) acrylate, 1, 1-dimethyl 1, 2, 3, 3, 4, 4 Hexafluorobutyl (meth) acrylate, 1, 1-dimethyl — 2, 2, 3, 3, 4, 4, 4 Heptobutyl fluorobutyl (meth) acrylate, 2— (Nonafluoro-n-butyl) ethyl (meth) acrylate, 2, 2, 3, 3, 4, 4, 5 , 5, 6, 6—decafluoro-n —Hexyl (meth) acrylate, (perfluoro-n-pentyl) methyl (meth) acrylate, perfluoro-n-hexyl (meth) acrylate, 1,1-dimethyl-1, 2, 2, 3, 3, 4, 4, 5, 5—octafluoropentyl (meth) acrylate, 1, 1-dimethyl _2, 2, 3, 3, 4,

4, 5, 5, 5—nonafluoropentyl (meth) acrylate, 2— (perfluoro n-pentyl) ethyl (meth) acrylate, 2, 2, 3, 3, 4, 4,

5, 5, 6, 6, 7, 7 _dodecafluoro-n-heptyl (meth) acrylate, (perfluoro-n-hexyl) methyl (meth) acrylate, perfluoro-n-heptyl (meth) acrylate, 2- (perfluoro- n-hexyl) Le (meta) alkyl relay, 2, 2, 3, 3, 4, 4, 5, 5, 6, 6, 7, 7, 8, 8—tetradecafluoro-n-year-old octyl (meth) acrylate, (Perful Oro n-heptyl) Methyl (meth) acrylate, Perfluoro-n-octyl (meth) acrylate, 2- (Perfluoro-n-heptyl) Ethyl (meth) acrylate, 2, 2, 3, 3, 4, 4, 5, 5, 6, 6, 7, 7, 8, 8, 9, 9 One hexade force fluoro-n-nonyl (meth) acrylate, (perfluoro n-year-old octyl) methyl (meth) acrylate, perfluoro n_nonyl ( Me evening) Acrylate, 2_ (perfluoro-n-year-old octyl) Ethyl (meth) Acrylee, 2, 2, 3, 3, 4, 4, 5, 5, 6, 6, 7, 7, 8, 8, 9 , 9, 10, 10—Octodecafluoro-n-decyl (meth) acrylate, (full Low n- nonyl) methyl (meth) Akurireto, perfluoro chromatography n- decyl

(Meta) Acrylate

In addition to fluoroalkyl (meth) acrylates with 1 to 10 carbon atoms in the fluoroalkyl group such as 2, 2, 2-trifluoroethyl α-carboxyacrylate, (pentafluoroethyl) methyl α α force Xyacrylate;

2, 2, 2—trifluoroethyl α- (carboxymethyl) acrylate,

(Penyu Fluoroethyl) Methyl _α_ (Carboxymethyl) acrylate; 2, 2, 2-trifluoroethyl 留-(methoxycarbonyl) acrylate,

(Peneven Fluoroethyl) Methyl-α- (Methoxycarbonyl) acrylate; 2, 2, 2-Trifluoroethyl- α- (Acetyloxy) acrylate, (Pentafluoroethyl) Methyl-α- (Acetyloxy) acrylate;

2, 2, 2_Trifluoroethyl-α-phenyl acrylate, (Pen evening fluorethyl) Methyl-α-phenyl acrylate, 2, 2, 2-trifluoroethyl α-benzyl acrylate, (Pen Fluoroethyl) Methyl-α-benzyl acrylate, 2, 2, 2-trifluoroethyl mono-α-ethoxyacrylate,

(Penyu Fluoroetil) Methyl 1α-ethoxyacrylate;

2, 2, 2—trifluoroethyl a— (2-methoxyethyl) acrylate,

(Penyu Fluoroetil) Methyl mono a_ (2-Methoxyethyl) acrylate; 2, 2, 2 _trifluoroethyl mono-alpha-cyclohexyl acrylate, (Penyu fluorethyl) methyl-alpha-cyclohexyl acrylate;

2,2,2-Trifluoroethyl cyanosilane, (Penyu Fluoroethyl) methyl mono α-cyanoacrylate, and the like.

In the present invention, the acid group of the acid group-containing compound is preferably sulfonic acid, and the acid group-containing monomer is preferably 2- (meth) acrylamide-2-methylpropanesulfonic acid. Other monomers are preferably 2,2,2-trifluoroethyl acrylate and 2- (perfluoro-η-year-old octyl) ethyl (meth) acrylate. Further, the preferred range of the component (i) is 0.5 to 90 parts by weight, more preferably 1 to 80 parts by weight, when (i) + (mouth) = 100 parts by weight.

The polymer containing one or more acid groups selected from the group consisting of a carboxylic acid group, a sulfonic acid group, and a phosphoric acid group of the present invention can be mixed with a radiation-sensitive resin composition forming a microphone mouth lens. In order to suppress it, it is preferable to contain water in part or all of the solvent.

Further, the polymer containing one or more acid groups selected from the group consisting of carboxylic acid groups, sulfonic acid groups and phosphoric acid groups of the present invention preferably contains a (meth) acrylic resin.

An additive can be blended in the composition for forming an upper layer film of the microphone mouth lens of the present invention as long as the performance of the present invention is not impaired. A surfactant can be blended as an additive.

For example, Surflon S-111, S-112, S-113, S-121, S_131, S-132, S-141, S-145. , S-38 1, S-393, manufactured by Seimi Chemical Co., Ltd .;

Cover 100, 100C, 150, 150CH, AK :, 51, 250, 251, 222F, 300, 222F, 250, 251, 222F, 300, 310, FTX- 212M, FTX-2 09F, FTX- 213F, FTX- 233 F, FTX- 245 F, etc. Made by Neos Co., Ltd .;

F-top EF-103, EF-112, EF-121, EF-122A, EF-122B, EF-122C, EF_123C, EF_123A, EF-123B, EF-352, EF_802 EF-132, EF-352, EF-802, Gemco Corporation;

Florade FC_4430, manufactured by Sumitomo 3EM Co., Ltd .;

BM1000, BM1100, or more BM—made by CHEMI E;

F force 30, F force 31, F force 34, F force 35, F force 36, F force 39, F force 83, F force 86, F force 88, F force 772, F force 777, or more ;

Surfinore 104, 104E, 420, 440, 465, SE, SE-F, 61, 82, 504, 2502, DF 58, DF 110D, DF 110L, DF37, DF75, DF210, CT111, CT121, CT131, CT136, GA, TG, TGE, E104, PD_001, PD-002W, PD-004, EXP400 1 , EXP4051, Dynol 604, Orphin B, P, Y, D, STG, SPC, E1004, E1010, AK-02, and more

Floren series manufactured by Kyoeisha Chemical Co., Ltd .;

FC series manufactured by Sumitomo 3EM;

Fluoronal TF series manufactured by Toho Chemical Co., Ltd .;

BYK series made by Bicchemi;

S s hme go shi U—s S s hme gma n n company;

Emargen,

Examples include homogenol and more manufactured by Kao Corporation.

Surfactants can be used alone or in admixture of two or more. The compounding amount of the surfactant is preferably 50 parts by weight or less, more preferably 0.01 to 40 parts by weight, still more preferably 0.1 to 30 parts by weight per 100 parts by weight of the component (b) + (mouth). It is a quantity part. If it exceeds 50 parts by weight, the radiation-sensitive resin composition for forming a microlens may be dissolved, and if it is less than 0.01 part by weight, the radiation-sensitive resin composition for forming a microlens may be dissolved. The applicability decreases.

The following strength compounds can be added as other additives. The acid group can be neutralized by adding an alkaline compound to the polymer containing at least one acid group selected from the group consisting of the carboxylic acid group, the sulfonic acid group, and the phosphoric acid group. Neutralization suppresses self-decomposition during long-term storage at room temperature of the polymer containing the acid group, so that the storage stability with the composition for forming the upper layer film of the microphone mouth lens is further improved and processed. It can be used universally by solving the above handling problems and corrosion problems.

The purpose of adding an alkaline compound is to control pH. Examples of the alkaline compound include alkali metal hydroxides such as sodium hydroxide, potassium hydroxide, and lithium hydroxide; sodium methoxide, sodium ethoxide, potassium methoxide, sodium tert-butoxide, and potassium tert-butoxy. Alkali metal alkoxides such as sid; carbonates such as sodium carbonate, potassium carbonate, lithium carbonate; methyllithium, ethyllithium, n-butyllithium, sec-butyllithium, amyllithium, propylsodium, methylmagnesium chloride, ethylmagnesium bromide , Organometallic compounds such as propylmagnesium iodide, jetylmagnesium, jetylzinc, triethylaluminum, triisobutylaluminum; ammonia, trimethylamido , Triethylamine, Tripropylamine, Triptylamamine, Tripentylamine, Trihexylamine, Trioctylamine, Triethanolamine, Diethanolamine, N, N-dimethylamino ether, 2-Amino-2-methyl Examples include amines such as propanol, tetramethylammonium hydroxide, pyridine, aniline and piperazine; and metal compounds such as sodium, lithium, potassium, calcium and zinc. These basic compounds can be used alone or in combination of two or more. Among these basic compounds, triethylamine, triethanolamine, tetramethylammonium Muhydroxide is preferred.

The above strength-reducing compounds can be used alone or in admixture of two or more. The compounding amount of the alkaline compound is preferably 1 part by weight or more, more preferably 5 parts by weight or more with respect to 100 parts by weight of (i) + (mouth) component. By adding the alkaline compound in the above-mentioned addition amount, the composition for forming the microlens upper layer film is neutralized, thereby suppressing the self-decomposition during long-term storage of the polymer containing the acid group at room temperature. The storage stability of the composition for forming the lens upper layer film is improved, and the problem of handling in processing and the problem of corrosion can be solved and it can be used for general purposes.

Solvent

In the present invention, a predetermined amount of the microlens upper layer film-forming composition is dissolved in a solvent at a solid content concentration of, for example, 0.1 to 10% by weight, and then filtered through a filter with a pore diameter of about 0.1. To prepare a solution. As a solvent used for preparing the composition solution for forming the microlens upper layer film, a solvent capable of dissolving each component constituting the composition, for example, water, monohydric alcohol such as methanol, ethanol, isopropanol, etc. , Ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, jetylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol methyl ether acetate, propylene glycol ether ether Acetate, propylene glycol propyl ether acetate, methyl ethyl ketone, cyclohexanone, methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, 2-hydroxy-2-ethyl ethyl propionate, methyl 3-methoxypropionate, 3_ethoxy ethyl propionate, ethoxy acetate ethyl, ethyl oxyacetate, 2_hydroxy_methyl 3-methylbutyrate, 3-methyl-3-methoxybutyl Acetate, 3-methyl-3-methoxybutyl propionate, 3-methyl-3-methoxybutyl butyrate, ethyl acetate, butyl acetate, methyl 3-methylpropionate, ethyl pyruvate, benzyl ether, di Hexyl ether, acetonyl acetone, isophorone, caproic acid, strong prillic acid, benzyl acetate, ethyl benzoate, Use can be made of ethyl oxalate, cetyl maleate, aptilolactone, ethylene carbonate, propylene carbonate, ethylene glycol monophenyl ether acetate and the like.

These solvents are used alone or in combination of two or more.

Among the solvents, those containing 10% by weight or more of water and Z or monohydric alcohol are preferable.

As described above, according to the present invention, the lens is heat-treated after applying the microlens upper layer film-forming composition, thereby functioning as a melt control agent for controlling the melt property of the lens, and without any gap on the substrate. Lenses can be formed. In other words, the present invention utilizes the reaction of the extreme surface layer of the lens, and the microphone mouth lens can be formed without any gap regardless of the size and film thickness of the lens.

The composition for forming a microlens upper layer film of the present invention is only applied after patterning, and has an advantage that the shape of the lens can be controlled by a simple process. The composition for an upper layer film of the microphone mouth lens of the present invention can further improve storage stability by containing an alcoholic compound. Example

EXAMPLES Next, the present invention will be described more specifically with reference to examples. However, the present invention is not limited by these examples.

Unless otherwise specified, “%” means “% by weight”.

Synthesis example 1

After the atmosphere in the flask was replaced with nitrogen, 500 g of a propylene glycol monomethyl ether solution in which 10 g of 2,2′-azobisisoptyronitrile was dissolved was charged. Subsequently, 25 g of styrene and 47. 5 g of P-tert-butoxystyrene were charged, and then gently stirred. Polymerization started at 70, and this temperature was maintained for 12 hours, and then the solution was gradually returned to room temperature. Acetone was then added to adjust the solution concentration to 15% by weight and then dripped into 10 times the amount of methanol to solidify the reaction product. After thoroughly washing this coagulated material with methanol, propylene glycol monomethyl ether The sample was redissolved in 500 g of a solution and coagulated again with a large amount of methanol.

After this re-dissolution-coagulation operation was performed three times, the obtained coagulated product was vacuum-dried at 60 for 48 hours to obtain the desired copolymer.

Thereafter, 200 g of this copolymer was placed in a flask, and a 15 wt% solution was obtained using 1,133 g of propylene glycol monomethyl ether solution. Thereafter, the flask was placed in an oil bath at 120 ° C., and the solution was refluxed at the boiling point while stirring the solution under a nitrogen bubble. Using a dropping funnel, 200 g of a 7.2% hydrochloric acid aqueous solution was slowly added dropwise over 60 minutes, taking care not to precipitate the polymer, and then refluxed for another 5 hours.

After confirming that the hydrolysis was complete by infrared spectroscopy (IR), the solution was gradually returned to room temperature, diluted with acetone, and dripped into 10 times the amount of ultrapure water to solidify. Thereafter, the filtrate was thoroughly washed with ultrapure water until it became neutral, and the obtained white polymer was dried at 60 for 48 hours to obtain a polymer.

Synthesis example 2

In a flask purged with nitrogen, 100 g of the alkali-soluble polymer obtained in Synthesis Example 1 was dissolved in 400 g of carbon tetrachloride, and then 50 g of bromine was added while making sure that the reaction temperature did not exceed 30. It dropped using the dropping funnel. Thereafter, stirring was continued for 3 hours. The precipitated product was filtered off, dissolved in 400 g of acetone, and gradually added to 10 times the amount of ultrapure water to precipitate the polymer. Filtered, washed with water, was again dissolved in acetone, precipitated with 10 4% NaHC_〇 polymer in addition to the ₃ aqueous solution L. After Filtration and 2 4 hours and vacuum dried at N a HC_〇 ₃ after 40 was completely removed by thoroughly washing the polymer.

Bromination was confirmed by measuring the infrared absorption spectrum and newly appearing absorption of 740 cm- ¹ derived from C-Br.

(1) Preparation Example 1 of Radiation Sensitive Resin Composition

After dissolving 10.0 g of the alkali-soluble polymer obtained in Synthesis Example 2 in diethylene glycol dimethyl ether 13. O g, 4′-hydroxy 2, 3, 4-trihydroxybenzophenone 0.4 g, 1, 1 _Bis (4-hydroxyphenol 1) [4 1 [1 (4-Hydroxyphenyl) _ 1-methylethyl] phenyl] 1,2_ naphthoquinonediazide 1-5-sulfonic acid 2.5 molar condensate 3.0 g Glycidoxyprovir trimethoxysilane 0.2 g, Hexamethoxy melamine lg, Epicot 152 (manufactured by Japan Epoxy Resin Co., Ltd.) 0.5 g, Ethyl lactate 10.0 g dissolved in pore size 0 A radiation sensitive resin composition (1) was prepared by filtration through a 2 / m Millipore filter.

Similarly, except that the alkali-soluble polymer P-hydroxystyrene (Marcalinker M, manufactured by Maruzen Petrochemical Co., Ltd.) was changed to 10 g, all were prepared with the same composition to obtain a radiation-sensitive resin composition (2).

Similarly, after dissolving Marcalinker PHM- C 10.0 g in diethylene glycol dimethyl ether 13. O g, 4 '—hydroxy 2, 3, 4-trihydroxybenzophenone 0.4 g, 1, 1-bis (4 —Hydroxyphenyl) 1 [4 1 [1 1 (4-Hydroxyphenyl) 1 1-methylethyl] phenyl] ethane and 1,2-naphthoquinonediazide 1-5-sulfonic acid 3.0 molar condensate 3.0 g , Glycidoxyprovir trimethoxysilane 0.2 g, Hexamethoxymelamine 1 g, Epicoat 152 (Japan Epoxy Resin Co., Ltd.) 1.0 g, Lactic acid ethyl 120. O g A radiation sensitive resin composition (3) was prepared by filtration through a 0.2 / zm Millipore filter.

Similarly, after dissolving 0.0 g of Marcalinker Ml in diethylene glycol dimethyl ether 13. O g, 4'-hydroxy 2,3,4-trihydroxybenzazophenone 0.4 g, 1,1-bis (4-hydroxyl Enyl) 1 1- [4— [1— (4-hydroxyphenyl) 1 1-methylethyl] phenyl] ethane and 1,2-naphthoquinonediazido 5-sulfonic acid 3.0 molar condensate 3.0 g Glycidoxypropyl-trimethoxysilane 0.2 g, Hexamethoxymelamine 1 g, Epicoat 152 (Japan Epoxy Resin Co., Ltd.) 1.5 g, Ethyl lactate 120. A radiation-sensitive resin composition (4) was prepared by filtration through a Milliporefil / m 2.

Synthesis example 3 After the atmosphere in the flask was replaced with nitrogen, 25 O.O g of a diethylene glycol dimethyl ether solution in which 7.0 g of 2,2′-azobis (2,4-dimethylvaleronitryl) was dissolved was charged. Subsequently, 5.0 g of styrene, 22.0 g of methacrylic acid, 20.2 g of dicyclopentaneyl methacrylate, 28.2 g of glycidyl methacrylate, and 45.0 g of glycidyl methacrylate were charged, and then gently stirring was started. Polymerization was started at 70, and this temperature was maintained for 6 hours. Then, the polymerization was terminated to obtain a polymerization solution having a solid content concentration of 30%.

(1) Preparation example 2 of radiation sensitive resin composition

After diluting the copolymer solution 33.3 g (copolymer 10 g) obtained in Synthesis Example 3 with 162.0 g of jetylene glycol dimethyl ether, 1,1 bis (4-hydroxyphenyl) one [4 — [1— (4-Hydroxyphenyl) 1 1 1 methyl ethenyl] ethane] and 1,2-naphthoquinonediazido 5-sulfonic acid 3.0 mol condensate 3.0 g, glycidoxyprovir Trimethoxysilane 0.5 g, SH-28PA (manufactured by Toray Dow Corning Silicone Co., Ltd.) 0.005 g was dissolved and filtered through a Millipore filter with a pore size of 0.2 / m to obtain a radiation sensitive resin composition (5). Prepared.

Examples 1-9

(1) A stainless steel autoclave equipped with a stirrer, thermometer, heater, monomer addition pump and nitrogen gas introduction device was charged with 140 parts by weight of ethylene glycol monobutyl ether, and the gas phase was replaced with nitrogen for 15 minutes. After that, the internal temperature was raised to 80. Then, while keeping the internal temperature at 80, 2_acrylamide-2-methylpropanesulfonic acid 10 parts by weight, perfluorooctylethyl acrylate 50 parts by weight, perfluoromethylethyl acrylate A mixture consisting of 40 parts by weight and 2 parts by weight of benzoyl peroxide was continuously added over 3 hours. After the addition was completed, the mixture was further reacted at 85 to 95 for 2 hours, and then cooled to 25T :. Thereafter, the reaction solution was vacuum-dried to remove the solvent to obtain a water-soluble resin having a solid concentration of 10% by weight. This water-soluble resin has an Mw of 3.0X 10 ⁴ and is a copolymer of 2_acrylamido-2-methylpropanesulfonic acid 2- (perfluoro-n-octyl) ethyl acrylate / perfluoromethyl ethyl acrylate Ratio is 10 70 1 0 (%). This water-soluble resin is referred to as “water-soluble resin (A-1)”.

(2) Water-soluble resin (A-1) After adding 100 parts by weight of Surfactor Surfinol 465 made by Air Products and adding water to a solids concentration of 1% by weight, the pore size is 0. The mixture was filtered through a 2 / zm membrane filter to obtain a lens upper layer composition (B-1).

Similarly, a composition for lens upper layer film (B-2) having a solid content concentration of 0.5% by weight was obtained. In the same manner, (A_ 1) 100 parts by weight of Surfactant Surfanol 465, 10 parts by weight of triethylamine, and water to further increase the solid content of the composition (B-3) to 1% by weight. Obtained.

(3) Spin-coating the radiation-sensitive resin composition (1) or (2) on a 6-inch diameter silicon wafer with a transparent resin layer, followed by 90 seconds on a hot plate at 100 seconds. To form a resist film having a desired thickness. Thereafter, exposure was performed for a predetermined time using a stepper NSR 220 5 1 1 2D (365 nm) manufactured by Nikon Corporation. Thereafter, development was carried out at 25 ° C. for 1 minute using a 1% by weight aqueous solution of tetramethylammonium hydroxide, followed by washing with water to form a resist pattern. Thickness 0. 3 zm Example 1-4, the dose at 7-9 is 1 90 m J cm ^2, an example 5 (thickness 0. 45 m) in 220m JZcm ^2, Example It was 25 Om J / cm ² at 6 (0.73 m).

Thereafter, the composition for forming the microlens upper layer film was spin-coated, washed with water, dried, and then again using Nikon Stepper NSR 2205 i 1 2D (365 nm) NAO. 63, Sigma 0. In step 6, the entire surface was exposed for a predetermined time. After that, it was baked at 200 for 4 minutes to form microlenses.

In order to confirm that the microlens upper layer film remains in this process, the photosensitive resin composition (2) was spin-coated on a 6-inch diameter silicon wafer with a transparent resin layer separately, and then 100 The resist film having a desired thickness was formed by pre-baking on a hot plate at 90 seconds for 90 seconds. After that, without exposure (without patterning), a 1% by weight aqueous solution of tetramethylammonium hydroxide was used for development for 25 1 minutes, and a process similar to that for forming a resist pattern was performed. afterwards The whole surface exposure without applying the composition for the microlens upper layer film (a), the one obtained by spin coating the composition for the microlens upper layer film, and the whole surface exposure (b), and the microlens upper layer A film composition (c) was prepared by spin coating, washing with water, drying, and drying the film composition, and was baked at 200 for 4 minutes to form an evening film. The surface contact angle of (a) is 72 degrees, the surface contact angle of (b) is 99 degrees, the surface contact angle of (c) is 100 degrees, and the difference in film thickness between (b) and (a) is 36 nm, ( The difference in film thickness between c) and (a) was 15 nm, confirming that the upper film remained.

Lens evaluation

1.Gap between lenses

Patterning with a mask size of 2 m square and a space of 0.3 m was performed by the above method, and the distance (/ m) between the microlenses was measured by SEM observation.

2, Melt property

As shown in Fig. 1, the lens cross-sectional area was used to evaluate the melt properties of the lens.

Of the cross-sectional area (A) of the lens, the area of the part having an independent radius of curvature (B) was determined.

(B / A) 80% or more of X I 00 (%) can be used as a lens, and less than 80% cannot be used as a lens.

3.Improved storage stability

After storing the specified number of days at the storage temperature shown in Table 1 below, gel permeation chromatography (GPC) (apparatus; HLC-8220 GPC (manufactured by Tosohichi Co., Ltd.), column; TSKgel GMPW, TSKg e 1 G 3000 PW was used to calculate the weight average molecular weight (Mw) of the microlens upper layer film composition with the solid content adjusted to 0.2%. The weight-average molecular weight is based on the above GPC, measured using ultrapure water / sodium sulfate Z-acetonitrile = 2100/15/900 as the elution solvent, at a column temperature of 25, and measured under analytical conditions of 2 ml Z. It is a value calculated using powdered polystyrene as a standard.

The results are shown in Table 2. table 1

Table 2

Comparative Examples 1 to 4

The microphone mouth lens used in the example was similarly formed without a lens upper layer film (Comparative Examples 1 and 2). In Comparative Example 1, the lens formation temperature was changed to 1600 at 4 ° C for 4 minutes, and Comparative Example 3 was designated. Further, Examples were used except that a 1% by weight aqueous solution of polyvinyl alcohol (manufactured by Wako Pure Chemical Industries, Ltd .; degree of saponification: 78 to 82%, average degree of polymerization: 1,500) was used as the upper layer film. The same method as 1 was used as Comparative Example 4.

The results are shown in Table 3.

Table 3

Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Radiation-sensitive resin composition (1) (2) (1) (1) Coating thickness after pre-baking (μm) 0. 45 0. 45 0 45 0. 45 Gap between lenses 0 0 0. 15 0 Melt property 20 40 100 0

Claims

The scope of the claims

1. (a) A step of applying a radiation-sensitive resin composition for forming a microlens on a substrate, (b) A step of patterning by exposure and development, (c) A microphone on a pattern on the substrate Applying a composition for forming a mouth lens upper layer film, and

(d) A method for manufacturing a microlens, including a step of performing a heat treatment.

2. The radiation-sensitive resin composition in step (a) contains (A) an alkali-soluble resin, (B) a 1,2-naphthoquinonediazide compound, and (C) a compound having at least one epoxy group in the molecule. The method for manufacturing the microphone mouth lens according to claim 1.

3. 1, 2_ naphthoquinonediazide compound (B) is represented by the following formula (I)

(Wherein three D's are the same or different and represent 1,2-naphthoquinonediazido 4_sulfonyl group or 1,2-naphthoquinonediazido 5-sulfonyl group). Manufacturing method of a micro lens.

4. The composition for forming a microlens upper layer film in the step (c) is composed of a compound containing at least one acid group selected from the group consisting of a carboxylic acid group, a sulfonic acid group and a phosphoric acid group. Of manufacturing a microphone mouth lens.

5. The method for producing a microlens according to claim 4, wherein the compound is water-soluble.

6. The method for manufacturing a microlens according to claim 1, wherein the gap between adjacent microlenses is 0.1 m or less.

7. A composition comprising a polymer containing at least one acid group selected from the group consisting of a carboxylic acid group, a sulfonic acid group and a phosphoric acid group, and used for forming a microlens upper layer film. -

8. The composition of claim 7, wherein the polymer is water soluble.

9. The composition according to claim 7, wherein the acid group is a sulfonic acid group.

10. The composition according to claim 7, wherein the polymer is a (meth) acrylic resin.

11. The composition according to claim 7, wherein the polymer contains a unit having a structure represented by the following formula (IV).

(IV)

[In the formula (IV), R ³ represents a hydrogen atom or a monovalent organic group, and R ⁴ represents a divalent organic group. ]

12. The composition according to claim 7, further comprising an alkaline compound.

13. Use of a polymer containing at least one acid group selected from the group consisting of a carboxylic acid group, a sulfonic acid group, and a phosphoric acid group for the formation of an upper layer film of a microphone mouth lens.

14. A microlens obtained by the method for producing a microlens according to any one of claims 1 to 6.