TWI480594B - The manufacturing method of microlenses - Google Patents

Description

Microlens manufacturing method

The present invention relates to a method for producing a microlens and a composition for forming a microlens upper film. More specifically, the present invention relates to a solid-state imaging device represented by CCD and CMOS, and more particularly to a method for manufacturing a microlens in which a gap between adjacent microlenses in a solid-state imaging device using a microlens is a narrow pitch and a method thereof A composition for forming a microlens upper film to be used.

In recent years, the photographic elements have progressed with high definition and high pixelation every year, and the size of the light-receiving elements has been lowered, and the decrease in sensitivity has become a problem. Further, the reduction in the size of the microlens and the gap between the lenses become noises, which further causes problems.

In order to improve the sensitivity and improve the noise reduction or the light collection efficiency, it is preferable to dispose the microlens without a gap. It is proposed in Japanese Laid-Open Patent Publication No. 2006-41467 or JP-A-2006-156898, but the manufacturing method thereof is not specific. It is revealed that it is almost manufactured by etching.

A further problem is that it is difficult to process by etching, as the thickness of the microlens is reduced and the size is lowered.

(disclosure of the invention)

An object of the present invention is to provide a solid-state imaging device represented by CCD and CMOS, and in particular, a method for manufacturing a microlens having a narrow pitch in which adjacent microlenses are used in a solid-state imaging device using a microlens, and a method thereof A composition for forming a microlens upper film.

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

According to the present invention, the above objects and advantages of the present invention are achieved by a method of manufacturing a microlens, which is a method for manufacturing a microlens from a radiation sensitive resin composition on a substrate, characterized in that it comprises The following steps are: (a) a step of coating a photosensitive radiation resin composition for forming a microlens on a substrate; (b) a step of performing patterning by exposure and development; and (c) a diagram on the substrate. a step of coating a composition for forming a microlens upper film and (d) a step of performing heat treatment.

According to the present invention, the above objects and advantages of the present invention are attained by a composition comprising a polymer and used for forming a microlens film; and the polymer containing at least one selected from the group consisting of carboxylic acids An acid group of a group consisting of a sulfonic acid group and a phosphoric acid group.

(The best form for implementing the invention)

Hereinafter, the method of producing the microlens of the present invention will be described in detail.

The method for producing a microlens according to the present invention comprises the steps of: (a) applying a photosensitive radiation resin composition for forming a microlens on a substrate; (b) performing exposure and development; a step of patterning; (c) a step of coating a composition for forming a microlens upper film on a pattern on the substrate; and (d) a step of performing heat treatment.

The substrate in the step (a) is, for example, a photoelectric conversion element in which a transparent resin layer such as a color filter film, a high refractive index resin layer, an antireflection film layer, or a flattening film layer is disposed. In this case, the coating method is not particularly limited, and for example, a coating method such as a spin coating method, a rod coating method, or a roll coating method can be used. The film thickness is not particularly specified, but it is preferably 0.05 to 10 μm. Generally, prebaking is carried out at 50 to 120 ° C to cause a solvent to be formed to form a film.

Then, in the step (b), first, exposure is performed on the film. Examples of the radiation used for the exposure include visible light; ultraviolet rays such as g-line and i-line, far-ultraviolet rays such as ArF excimer lasers and KrF excimer lasers; X-rays such as synchrotron rays; and electron beams. Various radiation lines.

After exposure, the image can be developed by an alkali imaging solution to form a desired pattern. Examples of the development method include spray development, spray development, immersion development, paddle development, and the like. The development conditions should be 20~40°C for 10 seconds~5 minutes. The alkali developing solution may, for example, be an aqueous solution which is dissolved in water so as to have a concentration of about 0.05 to 5% by weight, such as sodium hydroxide, potassium hydroxide, aqueous ammonia or tetramethylammonium hydroxide. A water-soluble organic solvent such as methanol or ethanol, a surfactant, or the like may be appropriately added to the aqueous alkali solution. After the image is washed, it is washed with water and air dried.

After the development, after coating, washing, and drying of the composition for forming a microlens upper film, the 1,2-naphthoquinonediazide compound remaining in the linear composition of the radiation radiation can be converted into, for example, by irradiation with ultraviolet rays. A carboxylic acid compound.

Then, in the step (c), application of the composition for forming a microlens upper film is performed. The same method of applying the radiation-sensitive linear composition is not particularly limited, and a coating method such as a spin coating method, a rod coating method, or a roll coating method can be used. The film thickness of the composition for forming a microlens upper film is preferably from 1 to 500 nm, more preferably from 2 to 400 nm, and the solvent may be used for pre-baking or for removal. The above composition for forming a layer film is washed with water. Since the composition for forming an overlayer film of the present invention has an acid group as described later, the acid group reacts with a functional group in the microlens composition. Therefore, the excess composition for forming an overlayer film is removed by washing, but not all of the composition for forming an upper layer film is washed and removed. After the cleaning, the composition for forming an overlayer film is removed, and the composition for forming a film of the microlens is left in the subsequent step (d), whereby the meltability of the lens can be sufficiently controlled. The composition for forming an overlayer film as described above can also sufficiently exhibit the function as an upper layer film of the microlens upper film of the present invention.

Thereafter, in the step (d), the pattern is melted to form a microlens, and at the same time, the characteristics as a permanent film are sufficiently exhibited to perform heat treatment. The heat treatment conditions are not particularly limited, and for example, an oven, a hot plate, a far-infrared furnace or the like is used, and it is preferably treated at 100 to 300 ° C for 30 seconds to 30 minutes.

The preferred radiation-sensitive linear resin composition used in the present invention is, for example, (A) an alkali-soluble resin, (B) 1,2-naphthoquinonediazide compound, and (C) having at least one in a molecule. A compound composed of an epoxy group.

(A) alkali soluble resin

The alkali-soluble resin used in the present invention is a resin soluble in an aqueous alkali solution, and examples thereof include a novolak resin, a copolymer of α,β-unsaturated carboxylic acid (hereinafter referred to as "copolymer I"), and a hydroxystyrene compound. A nucleated bromine (hereinafter referred to as "brominated polymer II") of a polymer or a copolymer thereof with styrene is preferred.

The novolak resin is obtained by condensing an aldehyde with an aldehyde in the presence of a phenolic acid catalyst. The phenol type may be a cresol such as phenol, m-cresol or phosphocresol; 2,5-xylenol, 3,5-xylenol, 3,4-xylenol, 2,3-di Xylenol such as cresol; m-ethylphenol, p-ethylphenol, phosphorus ethylphenol, alkylphenol such as p-tert-butylphenol; p-methoxyphenol, m-methoxyphenol, 3,5 -dimethoxyphenol, 2-methoxy-4-methylphenol, m-ethoxyphenol, p-ethoxyphenol, m-propoxyphenol, p-propoxyphenol, m-butoxyphenol, pair Alkoxyphenols such as third butoxyphenol; bisalkylphenols such as 2-methyl-4-isopropylphenol; m-chlorophenol, p-chlorophenol, chlorophenol, dihydroxybiphenyl, double A hydroxyaromatic compound such as phenol A, phenylphenol, resorcinol or naphthol.

Further, as the aldehyde, for example, formaldehyde, paraformaldehyde, acetaldehyde, propionaldehyde, benzaldehyde, phenylacetaldehyde, α-phenylpropanal, β-phenylpropanal, o-hydroxybenzaldehyde, m-hydroxybenzaldehyde can be used. , p-hydroxybenzaldehyde, phosphochlorobenzaldehyde, m-chlorobenzaldehyde, p-chlorobenzaldehyde, o-nitrobenzaldehyde, m-nitrobenzaldehyde, p-nitrobenzaldehyde, o-methylbenzaldehyde, m-methylbenzaldehyde And p-methylbenzaldehyde, p-ethylbenzaldehyde, p-n-butylbenzaldehyde, furfural, chloroacetaldehyde, and the like, such as chloroacetaldehyde, diethyl acetal, and the like. Among these, formaldehyde should be used.

The aldehyde is preferably used in an amount of 0.7 to 3 moles, more preferably at a ratio of 1.1 to 2 moles, relative to the phenolic 1 mole.

The acid catalyst is preferably used, for example, hydrochloric acid, sulfuric acid, formic acid, acetic acid, oxalic acid or the like.

The amount of the acidic catalyst to be used is preferably 1 × 10 ^-4 to 5 × 10 ^-1 per 1 mol of the total amount of the phenols and aldehydes (hereinafter referred to as "reaction materials").

In the condensation reaction, water is generally used as the reaction medium, but the phenol used in the condensation reaction is not dissolved in the aqueous solution of the aldehyde, and when it is not uniform from the initial stage of the reaction, a hydrophilic solvent can be used as the reaction medium.

Examples of such a solvent include alcohols such as methanol, ethanol, ethanol, and butanol; 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 to be used is preferably from 50 to 1,000 parts by weight per 100 parts by weight of the reaction raw material.

The reaction temperature at the time of the condensation reaction can be appropriately adjusted depending on the reactivity of the reaction raw material. It is preferably 10 to 150 ° C, more preferably 70 to 130 ° C, and the copolymer I is obtained by radically polymerizing an α,β-unsaturated carboxylic acid with another radically polymerizable compound in a solvent.

The α,β-unsaturated carboxylic acid may, for example, be a monocarboxylic acid such as acrylic acid, methacrylic acid or crotonic acid; or a dicarboxylic acid such as maleic acid, fumaric acid, citraconic acid, mesaconic acid or itaconic acid. Wait.

Further, as the other radical polymerizable compound, for example, an acid anhydride such as maleic anhydride or itaconic anhydride can be used; a monocarboxylic acid monoester such as monoethyl maleate, monoethyl fumarate or monoethyl itaconate a conjugated diene such as 1,3-butadiene, isoprene, chlorobutene, dimethyl-1,3-butadiene, etc.; a monoolefin-based unsaturated compound such as methyl methacrylate, Ethyl methacrylate, n-butyl methacrylate, dibutyl methacrylate, alkyl methacrylate of butyl methacrylate, methyl acrylate, alkyl acrylate of isopropyl acrylate, methyl Cyclohexyl acrylate, 2-methylcyclohexyl methacrylate, methacrylic acid cyclic alkyl ester, cyclohexyl acrylate, 2-methylcyclohexyl acrylate, cyclic alkyl acrylate, phenyl methacrylate, Aryl methacrylate methacrylate, phenyl acrylate, acrylate aryl acrylate, styrene, α-methyl styrene, o-methyl styrene, m-methyl benzene Ethylene, p-methylstyrene, p-methoxystyrene, acrylonitrile, methyl Acrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, vinyl acetate, and the like.

The copolymerization ratio of the α,β-unsaturated carboxylic acid of the copolymer I is preferably from 5 to 40% by weight, particularly preferably from 15 to 30% by weight, based on the copolymer. If it is less than 5% by weight, the obtained copolymer is hardly dissolved in an aqueous alkali solution, so that development residue is liable to occur, and it is difficult to produce a sufficient photoresist pattern. On the other hand, when it exceeds 40% by weight, the solubility of the obtained copolymer in an aqueous alkali solution is too large, and it is difficult to prevent dissolution of the unexposed portion, that is, film development.

Further, the other radical polymerizable compound is preferably a conjugated diene or a monoolefin unsaturated compound in terms of the properties of the obtained copolymer.

When the conjugated diene is used, the flexibility imparted to the copolymer can be imparted to the copolymer, so that the copolymer is soft, and the copolymer is not cracked, and the yield of the product can be remarkably improved. Further, the adhesion of the copolymer to the substrate becomes high. Further, when the copolymerization amount of the copolymer of the conjugated diene is increased, the melting temperature of the obtained copolymer moves toward the low temperature side.

Further, since the copolymer contains a monoolefin-based unsaturated compound, the mechanical properties of the copolymer can be appropriately controlled, and the solubility in the aqueous alkali solution can be finely adjusted by the relationship of the components soluble in the aqueous alkali solution described above.

As the monoolefin-based unsaturated compound, for example, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, second butyl methacrylate, and butyl methacrylate may be used. ; methyl acrylate, isopropyl acrylate of isopropyl acrylate; cycloalkyl methacrylate of cyclohexyl methacrylate, 2-methylcyclohexyl methacrylate, etc.; cyclohexyl acrylate, 2-methyl acrylate a cyclic alkyl acrylate such as cyclohexyl ester; an aryl methacrylate such as phenyl methacrylate or benzyl methacrylate; an acrylate aryl ester such as phenyl acrylate or benzyl acrylate; a diester of a dicarboxylic acid such as diethyl acrylate, diethyl fumarate or diethyl itaconate; methacrylic acid such as 2-hydroxyethyl methacrylate or 2-hydroxypropyl methacrylate; Hydroxyalkyl ester; styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, p-methoxystyrene, acrylonitrile, methacrylonitrile, Chlorinated ethylene, vinylidene chloride, acrylamide, methacrylamide, acetic acid Alkenyl esters.

These compounds may be used alone or in combination of two or more. In view of the influence of the monoolefin-based unsaturated compound on each characteristic, the copolymerization amount is preferably from 25 to 90% by weight, particularly from 30 to 80% by weight, based on the copolymer. The content of the monoolefin-based unsaturated compound is less than 25% by weight, and the total amount of the α,β-unsaturated carboxylic acid, which is a component of the conjugated diolefin-based compound or the aqueous alkali solution, which is contained in the resin, is increased. Therefore, it is difficult to control the mechanical properties of the resin or the alkali developability, and if it exceeds 90% by weight, the solubility of the resin to the aqueous alkali solution is relatively small, which is not preferable.

The solvent used for the production of the copolymer I may, for example, be an alcohol such as methanol or ethanol; an ether such as tetrahydrofuran; a glycol ether such as ethylene glycol monomethyl ether; or a cellosolve such as methyl cellosolve acetate. Ester; others are aromatic hydrocarbons, ketones, esters, and the like.

As the polymerization catalyst in the radical polymerization, a general radical polymerization initiator can be used, and examples thereof include 2,2'-azobisisobutylation and 2,2'-azobis-(2,4-di). Nitrogen compound such as methylpentyl), 2,2'-azobis-(4-methoxy-2,4-dimethylpentyl); benzammonium peroxide, lauryl peroxide, An organic peroxide such as t-butylperoxytrimethylacetate or 1,1-bis-(t-butylperoxy)cyclohexane; and hydrogen peroxide. When a peroxide is used for the radical polymerization initiator, a reducing agent may be combined to serve as a redox-type initiator.

The brominated polymer II is preferably used, for example, to have the following formula (II) The structural unit (II) or the structural unit (II) shown and the following formula (III)

Here, R ₁ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and R ₂ represents a hydrogen atom, a methyl group or a methoxy group, and is represented by a structural unit (III), and then the structural unit (II) is An alkali-soluble polymer in which 100 to 70 mol% of the polymer is replaced by nuclear bromine according to the total of the structural unit (II) or the structural unit (III).

The method for producing the brominated polymer II is, for example, a method of copolymerizing a hydroxystyrene with a styrene to obtain a precursor polymer, followed by bromination of the polymer (hereinafter referred to as "direct method"); A method in which a compound having another functional group protects a hydroxyl group of a hydroxystyrene and copolymerized with a styrene, and then converted into a hydroxyl group by an appropriate method to obtain a precursor polymer, and then brominated the polymer (hereinafter referred to as "indirect" law"). In the present invention, any method may be used as long as the microlens is formed, and any method may be used.

Further, the position of the hydroxyl group may be any, but it is preferred that the double bond to styrene is at the p-position.

The precursor polymer may, for example, be a homopolymer composed only of the structural unit represented by the above formula (II) and a structural unit represented by the above formula (II) and a structure represented by the above formula (III). a copolymer composed of units.

The copolymerization ratio in the precursor polymer is preferably 70 mol% or more, particularly preferably 85 mol% or more, based on the hydroxystyrene.

If it is less than 70 mol%, the obtained copolymer is hardly dissolved in an aqueous alkali solution, so that development residue is liable to occur, and it is difficult to produce a pattern necessary for the microlens.

The styrene in the case where the precursor polymer is obtained by a direct method may, for example, be styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, p-vinyltoluene, or the like. Methoxystyrene and the like. Further, examples of the hydroxystyrenes include o-hydroxystyrene, m-hydroxystyrene, and p-hydroxystyrene.

The precursor monomer of the hydroxystyrene when the brominated polymer II is obtained by an indirect method can be, for example, p-benzyloxystyrene, p-tert-butoxystyrene or p-tert-butoxycarbonyl. Oxystyrene, p-tert-butyldimethylformyloxystyrene, p-ethoxylated styrene, and the like. Next, examples of the styrene include styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, p-vinyltoluene, and p-methoxystyrene.

Next, a precursor polymer can be obtained by subjecting the hydroxystyrenes to a suitable treatment such as hydrolysis.

Further, as a polymerization catalyst for producing a copolymer of a precursor monomer and a styrene, for example, a radical polymerization initiator, an anionic polymerization initiator, or the like can be used.

The brominated polymer II is obtained by dissolving a precursor polymer in an organic solvent such as carbon tetrachloride, and taking care to prevent the reaction temperature from exceeding 30 ° C while dropping bromine. The bromination ratio at this time is 5 mol% or more with respect to 100 mol% of the benzene nucleus. If it is less than 5 mol%, the desired alkali solubility may not be obtained. Commercially available resins include, for example, Marukalyncur M, Marukalyncur MB, PHM-C, COS polymer manufactured by Japan Soda Co., Ltd., hydroxy styrene manufactured by Toho Chemical Co., Ltd., Toyo Synthetic Co., Ltd. Preparation of p-hydroxystyrene and the like.

The molecular weight of the above-mentioned alkali-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 a weight average molecular weight of 500 to 100,000, more preferably 1,000 to 70,000.

(B) 1,2-naphthoquinonediazide compound

The sensitizer used in the present invention can impart heat resistance and solvent resistance to the composition by the reaction of an alkali water-soluble resin and an epoxy compound. The 1,2-naphthoquinonediazide compound may, for example, be a 1,2-naphthoquinonediazide sulfonate such as a phenolic compound or an condensate of an alcoholic compound and a halogenated 1,2-naphthoquinonediazidesulfonic acid. Better. Preferably, the halogenated 1,2-naphthoquinonediazidesulfonic acid is preferably 1,2-naphthoquinonediazidesulfonic acid chloride.

The above phenolic compound or alcoholic compound may, for example, be dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, pentahydroxybenzophenone, hexahydroxybenzophenone or (polyhydroxybenzene). Alkane.

Specific examples of such may be, for example, dihydroxybenzophenone-based 4,4'-dihydroxydiphenylmethane, 4,4'-dihydroxydiphenyl ether, etc.; trihydroxybenzophenone-2 , 3,4-trihydroxybenzophenone, 2,4,6-trihydroxybenzophenone, etc.; tetrahydroxybenzophenone 2,2',4,4'-tetrahydroxybenzophenone, 2,3,4,3'-tetrahydroxybenzophenone, 2,3,4,4'-tetrahydroxybenzophenone, 2,3,4,2'-tetrahydroxy-4'-methyl Benzophenone; 2,3,4,4'-tetrahydroxy-3'-methoxybenzophenone; etc.; pentahydroxybenzophenone 2,3,4,2',6'-pentahydroxydiene Benzophenone, etc.; hexahydroxybenzophenone 2,4,6,3',4',5'-hexahydroxybenzophenone, 3,4,5,3',4',5'-six Hydroxybenzophenone, etc.; (polyhydroxyphenyl) alkane 2-methyl-2(2,4-dihydroxyphenyl)-4-(4-hydroxyphenyl)-7-hydroxycoumarin, 2 -[Bis{(2-isopropyl-4-hydroxy-2-methyl)phenyl}methyl]phenol, 1-[1-(3-{1-(4-hydroxyphenyl)-1-methyl Benzyl}-4,6-dihydroxyphenyl)-1-methylethyl]-3-(1-(3-{1-(4-hydroxyphenyl)-1 -methylethyl}-4,6-dihydroxyphenyl)-1-methylethyl)benzene, and 4,6-bis{1-(4-hydroxyphenyl)-1-methylethyl} -1,3-dihydroxybenzene, bis(2,4-dihydroxyphenyl)methane, bis(p-hydroxyphenyl)methane, 1,1-bis(4-hydroxyphenyl)-1-phenylethane , 1,3-bis[1-(4-hydroxyphenyl)-1-methylethyl]benzene, 1,4-bis[1-(4-hydroxyphenyl)-1-methylethyl]benzene 4,6-bis[1-(4-hydroxyphenyl)-1-methylethyl]-1,3-dihydroxybenzene, 1,1-bis(4-hydroxyphenyl)-1-[4 -[1-(4-hydroxyphenyl)-1-methylethyl]phenyl]ethane, tris(p-hydroxyphenyl)methane, 1,1,1-tris(p-hydroxyphenyl)ethane, Bis(2,3,4-trihydroxyphenyl)methane, 2,2-bis(2,3,4-trihydroxyphenyl)propane, 1,1,3-tris(2,5-dimethyl- 4-hydroxyphenyl)-3-phenylpropane, 4,4'-[1-[4-[1-[4-hydroxyphenyl]-1-methylethyl]phenyl]vinyl]bisphenol , bis(2,5-dimethyl-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'-trihydroxy flavan like.

In the condensation reaction, a halogenated 1,2-naphthoquinonediazide sulfonate equivalent to 30 to 85 mol%, more preferably 50 to 70 mol%, may be used relative to the OH group in the phenolic compound or the alcohol compound. acid.

The solvent which can be used at this time is, for example, a ketone or a cyclic ether. Specific examples of such a ketone include acetone, methyl ethyl ketone, methyl isoamyl ketone, and methyl isobutyl ketone. The cyclic ether may, for example, be 1,4-dioxane or 1,3,5-trid. Oxane and the like. When a solvent is used, it is preferably used in an amount of from 100 to 500 parts by weight based on 100 parts by weight of the total of the phenolic compound or the alcohol compound and the halogenated 1,2-naphthoquinonediazidesulfonic acid.

A basic compound can be used as the catalyst. Preferred examples thereof include triethylamine, tetramethylammonium chloride, tetramethylammonium bromide, and pyridine. The amount of such catalyst used is preferably 1 mole or more, more preferably 1.05 to 1.2 moles, per mole of the halogenated 1,2-naphthoquinonediazidesulfonic acid.

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

Further, the reaction time is preferably 0.5 to 10 hours, more preferably 1 to 5 hours, and particularly preferably 1 to 3 hours.

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

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

The component (B) is particularly preferably 1,1-bis(4-hydroxyphenyl)-1-[4-[1-(4-hydroxyphenyl)-1-methyl group represented by the following formula (I). A condensate of ethyl]phenyl]ethane and 1,2-naphthoquinonediazide sulfonate.

(Here, the three D groups are the same or different and represent 1,2-naphthoquinonediazide-4-sulfonyl or 1,2-naphthoquinonediazide-5-sulfonyl)

The use ratio of the component (B) is preferably from 5 to 100 parts by weight, more preferably from 10 to 50 parts by weight, per 100 parts by weight of the alkali-soluble resin. When the ratio is less than 5 parts by weight, the amount of the carboxylic acid formed by irradiation with radiation becomes small, so that the solubility of the aqueous alkali solution cannot be differentiated before and after the irradiation of the radiation, and the patterning becomes difficult, and In some cases, the heat resistance and solvent resistance of the obtained microlens become insufficient. Further, if it exceeds 100 parts by weight, most of the 1,2-naphthoquinonediazidesulfonate added in a short period of irradiation with radiation is not present in its direct form, so that it may be insolubilized in an aqueous alkali solution. It is too high to make development difficult.

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

The epoxy compound used in the present invention is a compound which reacts with a carboxylic acid generated by irradiation with a radiation, and has an effect of imparting heat resistance and solvent resistance, and imparting an adhesive property. In the case of the above, the epoxy compound is preferably a compound having two or more epoxy groups in the molecule, and examples thereof include the following. Commercial products of bisphenol A type epoxy resin may, for example, be Epicote 1001, 1002, 1003, 1004, 1007, 1009, 1010 (manufactured by Oiled Shell Epoxy Co., Ltd.); and bisphenol F type epoxy resin may be, for example, commercially available products. Epicote 807 (made by Oiled Shell Epoxy Co., Ltd.) bisphenol AD type epoxy resin; phenol novolak type epoxy resin commercially available products such as Epicote 152, 154 (oiled Shell Epoxy), EPPN-201 202 (manufactured by Nippon Kayaku Co., Ltd.); a commercial product of a cresol novolac type epoxy resin, for example, EOCN-102S, 103S, 104S, 1020, 1025, 1027 (manufactured by Nippon Kayaku Co., Ltd.); Epicote 180S 75 (manufactured by Oiled Shell Epoxy Co., Ltd.); a commercially available product of a cyclic aliphatic epoxy resin, for example, CY-175, 177, 179 (manufactured by CIBA-GEIGY Co., Ltd.), ERL-4234, 4299, 4221 4206 (manufactured by UCC); a commercially available product of a water-reducing oleyl ester-based epoxy resin, for example, Shodyne 508 (manufactured by Showa Denko KK), Araldite CY-182, 192, 184 (manufactured by CIBA-GEIGY Co., Ltd.), Epichlon 200 , 400 (made by Dainippon Ink Co., Ltd.), Epicote 871, 872 (made by Oiled Shell Epoxy Co., Ltd.), ED-5661, 5662 (Celanese Coating), shrinkable oil-based amine epoxy resin The product may, for example, be glycidyldiaminediphenylmethane, triglycidylaminophenol, triglycidylaminophenol, diglycidylaniline, diglycidyltoluidine, tetraglycidyl In the case of a heterocyclic epoxy resin, for example, Araldite PT 810 (manufactured by CIBA-GEIGY Co., Ltd.) may be used as a heterocyclic epoxy resin. , Epicote RXE-15 (oiled shell Epoxy (share) system), EPITEC (Nissan Chemical (share) system).

Further, it is also preferred to use a compound having an epoxy group and an alkoxymethylcarbonyl group in the molecule. For example, glycidoxypropyltrimethoxydecane, glycidoxypropyltriethoxydecane, glycidoxypropylmethyldimethoxydecane, glycidoxypropyl Methyldiethoxydecane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxynonane, 2-(3,4-epoxycyclohexyl)ethyltriethoxydecane, 2 -(3,4-Epoxycyclohexyl)ethylmethyldimethoxydecane, and the like.

Further, many of the epoxy compounds exemplified herein are high molecular weight bodies, but the epoxy compound used in the present invention is not limited by molecular weight, and may be, for example, bisphenol A or bisphenol F diglycidyl ether. Low molecular weight body.

In this case, it is also difficult to color from the heat treatment, and it is preferably a phenol novolac type epoxy resin, a cresol novolac type epoxy resin, a cyclic aliphatic epoxy resin, or a glycidyl ester epoxy resin.

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

When the amount is less than 1 part by weight, the reaction with the carboxylic acid formed by irradiation with radiation is extremely difficult, and the heat distortion resistance of the formed microlens is hard to be sufficient. On the other hand, when it exceeds 100 parts by weight, the melting point of the entire composition is lowered, and it is difficult to expand the temperature range of the heat treatment performed when the microlens is produced.

Other blending agents

A surfactant can be further formulated in the sensitive radiation linear resin composition of the present invention.

The surfactant may, for example, be a fluorine-based leveling agent, a polyfluorene-based leveling agent, an ether-based or ester-based leveling agent. Specifically, for example, FTX-218 (manufactured by Neos Co., Ltd.); BM 1000, BM 1100 (manufactured by BM-CHEMIE Co., Ltd.); Magafack F142D, F172, F173, and F183 (Daily Ink Chemical Industry) (share) system, Fluraid FC-135, FC-170C, FC-430, FC-431 (Sumitomo 3M (share) system), EFC 772, 777, 30, 31, 34, 35, 36, 39, 83, 86, 88 (manufactured by EFC Chemicals); Florene series (Kyoeisha Chemical Co., Ltd.); FC series (Sumitomo 3M (share) system); Fluonal TF series (Toho Chemical Co., Ltd.), SH-28A ( Toray Dow corning (share) system, BYK company's BYK series; Sshmego series (made by Sshmegmann); Safinol (Nissin Chemical Industry Co., Ltd.); Emalgen, Homogenol (King).

The amount of the surfactant to be used is preferably from 0.005 to 5 parts by weight, more preferably from 0.001 to 2 parts by weight, per 100 parts by weight of the alkali-soluble resin (A).

Solvent

The radiation sensitive linear resin composition used in the present invention can be easily prepared by uniformly mixing the above components. At the time of mixing, it is usually dissolved in a suitable solvent and supplied as a solution. The solvent to be used may be an alkali-soluble resin, a 1,2-naphthoquinone quinone compound, an epoxy compound, or other formulation, and may be used without being reacted with each component.

As such a solvent, for example, an alcohol such as methanol or ethanol; an ether such as tetrahydrofuran; a glyceryl ether such as ethylene glycol monomethyl ether or ethylene glycol monoethyl ether; methyl cellosolve acetate or ethyl group; Ethylene glycol alkyl ether acetate such as cellosolve acetate; diethylene glycol such as diethylene glycol monomethyl ether, diethylene glycol monoethyl ether or diethylene glycol dimethyl ether Alkyl ether; propylene glycol alkyl ether acetate such as propylene glycol methyl ether acetate or propylene glycol propyl ether acetate; aromatic hydrocarbon such as toluene or xylene; methyl ethyl ketone, cyclohexanone, Ketones such as 4-hydroxy-4-methyl-2-pentanone; ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate Ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3-ethoxy Ethyl propyl propionate, methyl 3-ethoxypropionate, ethyl acetate, butyl acetate, etc. Further, N-methylformaldehyde, N,N-dimethylformaldehyde, N-methyl may also be added. Ethylamine, N,N-dimethyl B Indoleamine, N-methylpyrrolidone, dimethyl hydrazine, benzyl ethyl ether, dihexyl ether, acetonitrile acetone, isophorone, caproic acid, octanoic acid, 1-octanol, 1-nonanol, benzene Methyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, phenyl cellosolve acetate, etc. High boiling point solvent.

Among these solvents, solubility, compatibility with each component, and ease of formation of a coating film are suitable, and glycol ethers such as ethylene glycol monoethyl ether; ethyl cellosolve acetate, etc. are suitable. An ethylene glycol alkyl ether acetate; an ester of ethyl 2-hydroxypropionate; an alkyl ether of diethylene glycol such as diethylene glycol monomethyl ether.

Further, when the composition solution is prepared, a solution of, for example, an alkali-soluble polymer, a solution of a 1,2-naphthoquinonediazide compound, a solution of an epoxy compound, and a solution of another formulation may be separately prepared before use. These solutions are mixed at a specific ratio.

The composition solution prepared as described above can be used after being filtered using a Millipore filter membrane having a pore size of 0.2 μm or the like.

Microlens upper film forming composition

Hereinafter, the composition for forming a microlens upper film of the present invention will be described.

The composition for forming a microlens upper film of the present invention is composed of a 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. The shape of the microlens can be controlled by coating on the microlens. The polymer containing the acid group-containing monomer is not particularly limited, but is preferably a copolymer obtained by polymerizing (1) an acid group-containing monomer having an acid group and (2) a monomer other than the other.

(1) Monomers containing acid groups

The compound containing a carboxylic acid is, for example, an α,β-unsaturated carboxylic acid, and examples thereof include monocarboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid; maleic acid, fumaric acid, citraconic acid, and Zhongkang Dicarboxylic acid such as acid or itaconic acid.

Examples of the compound containing a sulfonic acid group include vinylsulfonic acid, allylsulfonic acid, p-styrenesulfonic acid, allyloxybenzenesulfonic acid, methacryloxybenzenesulfonic acid, and 4-sulfobutylmethacrylate. Or the acrylamide derivative "propylene amide derivative (iv)" which has a structural unit represented by the following formula (IV).

[In the formulae (IV) and (iv), 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 may be linear, branched or cyclic.

The monovalent organic group of R ³ is preferably a group having 1 to 12 carbon atoms, and examples thereof include a carboxyl group; a cyano group; a methyl group, an ethyl group, a n-propyl group, an isopropyl group, an n-butyl group, and an isobutyl group. a carbon number of 1 to 12 alkyl groups such as a second butyl group, a third butyl group, a n-pentyl group or a n-hexyl group; a carboxymethyl group, a 2-carboxyethyl group, a 2-carboxypropyl group, a 3-carboxypropyl group, and 2 a carboxyalkyl group having 2 to 12 carbons such as carboxybutyl, 3-carboxybutyl or 4-carboxybutyl; methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl, isopropoxycarbonyl, Alkoxycarbonyl group having a carbon number of 2 to 12 such as a n-butoxycarbonyl group or a tert-butoxycarbonyl group; a carbon number of an acetonitrile-based oxygen group, a acrylonitrile-oxygen group, a butyl fluorenyloxy group, or a benzylideneoxy group; a decyloxy group of 12; an aryl group having 6 to 12 carbon atoms such as a phenyl group or a trimethylphenyl group; an aralkyl group having 7 to 12 carbon atoms such as a benzyl group or an α-methylbenzyl group; a methoxy group; Ethoxyl, n-propoxy, isopropoxy, n-butoxy, isobutoxy and the like having 1 to 12 alkoxy groups; methoxymethyl, ethoxymethyl, 2-methoxy Ethyl ethyl, 2-ethoxyethyl, 2-methoxypropyl, 3-methoxypropyl, 2-methoxybutyl, 3-methoxybutyl a carbon number of 2 to 12 alkoxyalkyl groups such as 4-methoxybutyl group; a cycloalkyl group having 3 to 12 carbon atoms such as a cyclopentyl group, a cyclohexyl group, a cycloheptyl group or a cyclooctyl group; or Substituted derivatives, etc.

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, and 1 ,1-dimethylmethylene, 1-methyl-1,3-propanylene, 1,4-butene, 1-methyl-1,4-butylidene, 2-methyl-1 , 4-butylene, 1,5-pentylene, 1,1-dimethyl-1,4-butylene, 2,2-dimethyl-1,4-butene, 1,2 a dimethyl-1,4-butylene group, a 1,6-hexylene group, a 1,3-cyclopentylene group, a 1,4-cyclohexylene group or the like.

Among these divalent organic groups, a 1,1-dimethylethylene group is particularly preferable.

Specific examples of the acrylamide derivative (iv) include, for example,

2-(Methyl)propenylamine-2-methylpropanesulfonic acid, 2-α-carboxypropenylamine-2-methylpropanesulfonic acid, 2-α-carboxymethylpropenylamine-2-methyl Propanesulfonic acid, 2-α-methoxycarbonylpropenylamine-2-methylpropanesulfonic acid, 2-α-ethenyloxypropenylamine-2-methylpropanesulfonic acid, 2-α-phenyl Acrylamide-2-methylpropanesulfonic acid, 2-α-benzylpropenylamine-2-methylpropanesulfonic acid, 2-α-methoxypropenylamine-2-methylpropanesulfonic acid, 2-α-(2-methoxyethyl)propenylamine-2-methylpropanesulfonic acid, 2-α-cyclohexylpropenylamine-2-methylpropanesulfonic acid, 2-α-cyanopropene Indole-2-methylpropanesulfonic acid and the like.

Examples of the compound containing a phosphorus group include vinyl phosphoric acid, allyl phosphoric acid, and p-styrene phosphoric acid.

Further, the other monomer (2) may, for example, be an acid anhydride such as maleic anhydride or itaconic anhydride; a dicarboxylic acid monoester such as monoethyl maleate, monoethyl fumarate or itaconic acid monoethyl Ester or the like; conjugated diene such as 1,3-butadiene, isobutylene, chloroprene, dimethyl-1,3-butadiene, etc.; monoolefin-based unsaturated compound such as methacrylic acid Ester, ethyl methacrylate, n-butyl methacrylate, second butyl methacrylate, alkyl methacrylate of butyl methacrylate, methyl acrylate, alkyl acrylate of isopropyl acrylate, Cyclohexyl methacrylate, cycloalkyl methacrylate of 2-methylcyclohexyl methacrylate, cyclohexyl acrylate, 2-methylcyclohexyl acrylate cyclic alkyl acrylate, methacrylic acid benzene Ester, aryl methacrylate, phenyl acrylate, acrylate acrylate, styrene, α-methyl styrene, o-methyl styrene, m-methyl styrene, P-methylstyrene, p-methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, partial Vinyl chloride, acrylamide, methacrylamide, vinyl acetate, difluoromethyl (meth)acrylate, trifluoromethyl (meth)acrylate; 2,2-difluoro(meth)acrylate Ethyl ester, 2,2,2-trifluoroethyl (meth)acrylate, pentafluoroethyl (meth)acrylate; 1-(trifluoromethyl)ethyl (meth) acrylate, 2-(three Fluoromethyl)ethyl (meth) acrylate, 2,2,3,3-tetrafluoro-n-propyl (meth) acrylate, (pentafluoroethyl) methyl (meth) acrylate, (Trifluoromethyl)methyl (meth) acrylate, heptafluoro-n-propyl (meth) acrylate, 1-methyl-2,2,3,3-tetrafluoropropyl (meth) acrylate , 1-(pentafluoroethyl)ethyl (meth) acrylate, 2-(pentafluoroethyl)ethyl (meth) acrylate, 2,2,3,3,4,4-hexafluoro-positive Butyl (meth) acrylate, (heptafluoro-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-(heptafluoro-n-propyl Ethyl (meth) acrylate, 2, 2, 3, 3, 4, 4, 5, 5 Octafluoro-n-pentyl (meth) acrylate, (nonafluoro-n-butyl) methyl (meth) acrylate, perfluoro-n-pentyl (meth) acrylate, 1,1-dimethyl-2, 2,3,3,4,4-hexafluorobutyl (meth) acrylate, 1,1-dimethyl-2,2,3,3,4,4,4-heptafluorobutyl (methyl Acrylate, 2-(nonafluoro-n-butyl)ethyl (meth) acrylate, 2,2,3,3,4,4,5,5,6,6-decafluoro-n-hexyl (methyl) Acrylate, (perfluoro-n-pentyl)methyl (meth) acrylate, perfluoro-n-hexyl (meth) acrylate, 1,1-dimethyl-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)acrylic acid Ester, 2-(perfluoro-n-pentyl)ethyl (meth) acrylate, 2,2,3,3,4,4,5,5,6,6,7,7-dodecyl-n-heptane (meth) acrylate, (perfluoro-n-hexyl) methyl (meth) acrylate, perfluoro-n-heptyl (meth) acrylate, 2-(perfluoro-n-hexyl) ethyl (meth) acrylate Ester, 2,2,3,3,4,4,5,5,6,6,7,7,8,8-tetradecafluoro-n-octyl (meth) acrylate, (perfluoro-n-heptyl) Methyl (meth) acrylate, perfluoro-n-octyl (meth) propylene Ester, 2-(perfluoro-n-heptyl)ethyl (meth) acrylate, 2,2,3,3,4,4,5,5,6,6,7,7,8,8,9, 9-hexadecafluoro-n-decyl (meth) acrylate, (perfluoro-n-octyl) methyl (meth) acrylate, perfluoro-n-decyl (meth) acrylate, 2-(perfluoro-n-octane Ethyl (meth) acrylate, 2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10-octadecyl fluoride A fluoroalkyl group such as n-decyl (meth) acrylate, (perfluoro-n-decyl)methyl (meth) acrylate or perfluoro-n-decyl (meth) acrylate has a carbon number of 1 to 10 Examples of the fluoroalkyl (meth) acrylate include 2,2,2-trifluoroethyl-α-carboxy acrylate and (pentafluoroethyl)methyl-α-carboxy acrylate; 2,2 , 2-trifluoroethyl-α-(carboxymethyl) acrylate, (pentafluoroethyl)methyl-α-(carboxymethyl) acrylate; 2,2,2-trifluoroethyl-α- (methoxycarbonyl) acrylate, (pentafluoroethyl)methyl-α-(methoxycarbonyl) acrylate; 2,2,2-trifluoroethyl-α-(ethyloxy) acrylate (pentafluoroethyl)methyl-α-(ethyloxy) acrylate; 2,2,2-trifluoroethyl-α-phenyl propylene Ester, (pentafluoroethyl)methyl-α-phenyl acrylate; 2,2,2-trifluoroethyl-α-phenyl methacrylate, (pentafluoroethyl)methyl-α-benzene Acrylate; 2,2,2-trifluoroethyl-α-ethoxy acrylate, (pentafluoroethyl)methyl-α-ethoxy acrylate; 2,2,2-trifluoroethyl -α-(2-methoxyethyl) acrylate, (pentafluoroethyl)methyl-α-(2-methoxyethyl) acrylate; 2,2,2-trifluoroethyl-α -cyclohexyl acrylate, (pentafluoroethyl)methyl-α-cyclohexyl acrylate; 2,2,2-trifluoroethyl-α-cyanoacrylate, (pentafluoroethyl)methyl-α - cyanoacrylate and the like.

In the present invention, the acid group of the acid group-containing compound is preferably a sulfonic acid, and the acid group-containing monomer is preferably 2-(meth) acrylamide-2-methylpropane sulfonic acid. The other monomer is preferably 2,2,2-trifluoroethyl acrylate or 2-(perfluoro-n-octyl)ethyl (meth) acrylate.

Further, the preferred range of the component (1) is (0) + (2) = 100 parts by weight, preferably 0.5 to 90 parts by weight, more preferably 1 to 80 parts by weight.

A 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 is a doping agent which suppresses formation of a linear radiation-sensitive resin composition with a microlens, and is preferably a solvent. Some or all of it contains water.

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

The composition for forming a microlens upper film of the present invention may be formulated with an additive as long as the properties of the present invention are not impaired. The additive is an adjustable surfactant.

The fluorine-based surfactant may be, for example, a product name of Sarflon S-111, S-112, S-113, S-121, S-131, S-132, S-141, S-145, S-381, S-. 393, above Semi chemical system; Ftergent 100, 100C, 150, 150CH, A-K, 501, 250, 251, 222F, 300, 222F, 250, 251, 222F, 300, 310, FTX-212M, FTX -209F, FTX-213F, FTX-233F, FTX-245F, above (stock) Neos system; EFTOP EF-103, EF-112, EF-121, EF-122A, EF-122B, EF-122C, EF-123A , EF-123B, EF-352, EF-802, EF-132, EF-352, EF-802, above (share) JEMCO system; Fluoraid FC-4430, above Sumitomo 3M (share) system; BM1000, BM1100, above BM-CHEMIE company; EFC 30, EFC 31, EFC 34, EFC 35, EFC 36, EFC 39, EFC 83, EFC 86, EFC 88, EFC 772, EFC 777, EFC Chemicals, etc.; Sarfinol 104, 104E, 420, 440, 465, SE, SE-F, 61, 82, 504, 2502, DF58, DF110D, DF110L, DF37, DF75, DF210, CT111, CT121, CT131, CT136, GA, TG, TGE, E104, PD- 001, PD-002W, PD-004, EXP4 001, EXP4051, Dainol 604, Olfine B, Olfine P, Olfine Y, Olfine A, Olfine STG, Olfine SPC, Olfine E1004, Olfine E1010, Olfine AK-02, above Air Products, Inc.; Florene series (Kyoeisha Chemicals ( Stock system); FC series (Sumitomo 3M (share) system); Fluonal TF series (Toho Chemical Co., Ltd.); BYK company BYK series; Sshmego series (Sshmegmann company); Emalgen, Homogenol or above (Kao (share) ))).

The surfactant may be used singly or in combination of two or more. The amount of the surfactant to be added is preferably 50 parts by weight or less, more preferably 0.01 to 40 parts by weight, most preferably 0.1 to 30 parts by weight, per part by weight of (1) + (2) = 100 parts by weight. When it is more than 50 parts by weight, it is possible to dissolve the radiation-sensitive resin composition for forming a microlens, and when it is less than 0.01 part by weight, the coating property of the radiation-sensitive resin composition for forming a microlens is lowered.

Other additives may be added to the following basic compounds. The acid group can be neutralized by adding a basic compound to the above-mentioned polymer containing an acid group 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. By neutralizing, it is possible to suppress self-decomposition during long-term storage in a room temperature state of the polymer containing the acid group, so that the storage stability of the composition for forming a microlens upper film is further improved, and the processing can be solved. Widely used to deal with problems or corrosion problems.

The purpose of adding a basic compound is to control the pH. The basic compound may, for example, be an alkali metal hydroxide such as sodium hydroxide, potassium hydroxide or lithium hydroxide; sodium methoxide, sodium ethoxide, potassium methoxide, sodium third butoxide, and third An alkoxy alkali metal such as potassium butoxide; a carbonate such as sodium carbonate, potassium carbonate or lithium carbonate; methyl lithium, ethyl lithium, n-butyl lithium, second butyl lithium, lithium pentyl, propyl Organometallic compounds such as sodium, methylmagnesium chloride, ethylmagnesium bromide, propylmagnesium iodide, diethylmagnesium, diethylzinc, triethylaluminum, triisobutylaluminum, etc.; ammonia, top three Base amine, triethylamine, tripropylamine, tributylamine, tripentylamine, trihexylamine, trioctylamine, triethanolamine, diethanolamine, N,N-dimethylaminoethanolamine, 2 An amine such as amino-2-methylpropanol, tetramethylammonium hydroxide, pyridine, aniline or hexahydropyridine; or a metal compound such as sodium, lithium, potassium, calcium or zinc. These basic compounds may be used singly or in combination of two or more. Among these basic compounds, triethylamine, triethanolamine, and tetramethylammonium hydroxide are preferred.

The above basic compounds may be used singly or in combination of two or more kinds. The compounding amount of the basic compound is preferably 1 part by weight or more, more preferably 5 parts by weight or more, based on (1) + (2) = 100 parts by weight. By adding a basic compound in the above-mentioned addition amount, it is possible to neutralize the composition for forming a microlens upper film, and it is possible to suppress self-decomposition during long-term storage in a room temperature state of the polymer containing the acid group, so that the micro-enhancement is further enhanced. The storage stability of the composition for forming a lens upper film can be widely used to solve the problem of processing or corrosion in processing.

Solvent

In the present invention, a specific amount of the composition for forming a microlens upper film is, for example, 0.1 to 10% by weight of a solid solvent solvent in a solvent, and then, for example, a filter having a pore size of about 0.2 μm can be filtered to prepare a solution. The solvent used for preparing the microlens upper layer film forming composition solution can dissolve the solvent constituting each component of the composition, for example, water or one of the valent alcohols such as methanol, ethanol, or isopropyl alcohol, and can be used. Alcohol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl Ethyl acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, methyl ethyl ketone, cyclohexanone, methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, 2-hydroxy-2- Ethyl methacrylate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, ethyl oxyacetate, methyl 2-hydroxy-3methylbutyrate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutylpropionate, 3-methyl-3-methoxybutylbutyrate, acetate B Ester, butyl acetate, methyl 3-methoxypropionate, ethyl pyruvate, benzyl ethyl ether, dihexyl ether, acetone acetone, isophorone, hexanoic acid, octanoic acid, benzyl acetate ,rest in peace Ethyl oxalate, diethyl maleate, [gamma] -butyrolactone, ethylene carbonate, propylene carbonate, ethylene glycol monophenyl ether acetate.

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

Among the above solvents, it is preferred to contain water and/or monovalent alcohol in an amount of 10% by weight or more.

As described above, according to the present invention, by coating a composition for forming a microlens upper layer film and then heat-treating the lens, a function as a melting control agent for controlling the meltability of the lens can be exhibited, and a desired lens can be formed on the substrate without a gap. . That is, in the present invention, the responder who uses the extreme surface layer of the lens can form the microlens without a gap depending on the size and film thickness of the lens.

Further, the composition for forming a microlens upper film of the present invention is applied only after patterning, and has an advantage that the shape of the lens can be controlled in a simple procedure.

The composition for forming a microlens upper film of the present invention may further contain a basic compound to enhance storage stability.

Example

The invention will be more specifically described by the following examples, but the invention is not limited by the examples.

Further, unless otherwise stated, the parts by weight are expressed in %.

Synthesis Example 1

After the inside of the flask was purged with nitrogen, 500 g of a propylene glycol monomethyl ether solution in which 10 g of 2,2'-azobisisobutyronitrile was dissolved was fed. Then, after feeding 25 g of styrene and 475 g of p-butoxystyrene, stirring was started slowly. The polymerization was started at 70 ° C, and after maintaining this temperature for 12 hours, the solution was slowly returned to room temperature. Thereafter, acetone was added to make a solution concentration of 15% by weight, and then the mixture was dropped in 10 times of methanol to solidify the reactant. The coagulum was sufficiently washed with methanol, and then dissolved in 500 g of a propylene glycol monomethyl ether solution. Re-solidified with a large amount of methanol.

After this re-dissolution-solidification operation was carried out 3 times, the obtained coagulum was vacuum dried at 60 ° C for 48 hours to obtain a desired polymer.

Thereafter, 200 g of this copolymer was fed into a flask to obtain a 15% by weight solution in a solution of 1133 g of propylene glycol monomethyl ether. Thereafter, the flask was placed in an oil bath at 120 ° C, and the solution was stirred under nitrogen bubbles while refluxing. While using a dropping funnel, while taking care to prevent the polymer from being precipitated, 200 g of a 7.2% hydrochloric acid aqueous solution was slowly dropped for 60 minutes, and then the reflux was further continued for 5 hours.

After confirming complete hydrolysis by infrared spectroscopic spectroscopy (IR), the solution was slowly returned to room temperature, diluted with acetone, and dripped in 10 times of ultrapure water to solidify. Thereafter, the mixture was sufficiently washed with ultrapure water until the filtrate was neutral, and the obtained white polymer was dried at 60 ° C for 48 hours to obtain a polymer.

Synthesis Example 2

After 100 g of the aqueous alkali polymer obtained in Synthesis Example 1 was dissolved in 400 g of carbon tetrachloride in a nitrogen-substituted flask, 50 g of bromine was dropped using a dropping funnel while keeping the reaction temperature from exceeding 30 °C. Thereafter, stirring was continued for 3 hours. The precipitated product was filtered, dissolved in 400 g of acetone, and slowly added to 10 times the amount of ultrapure water to precipitate a polymer. After washing with water, the mixture was dissolved in acetone and added to 10 liters of a 4% aqueous NaHCO ₃ solution to precipitate a polymer. After filtration, the polymer was sufficiently washed with water to completely remove NaHCO ₃ , and then dried under vacuum at 40 ° C for 24 hours.

The bromination system measures the infrared absorption spectrum and is confirmed by the reappearance of the absorption of 740 cm ^-1 derived from C-Br.

(1) Preparation Example of Sensitive Radiation Linear Resin Composition

10.0 g of the aqueous alkali polymer obtained in Synthesis Example 2 was dissolved in 13.0 g of diethylene glycol dimethyl ether, and then 4'-hydroxy 2,3,4-trihydroxybenzophenone 0.4 g and 1, 1-bis(4-hydroxyphenyl)-[4-[1-(4-hydroxyphenyl)-1-methylethyl]phenyl]ethane and 1,2-naphthoquinonediazide-5- 2,5 mole condensate of sulfonic acid 3.0 g, glycidoxypropyl trimethoxy decane 0.2 g, hexamethoxy melamine 1 g, Epicote 152 (made by Japan Epoxy Resin Co., Ltd.) 0.5 g, ethyl lactate 120.0 g, modulating the radiation sensitive linear resin composition (1) by filtering with a millipore filter membrane having a pore size of 0.2 μm.

Similarly, it was changed to 10 g of the hydroxystyrene (Marukalyncur-M, manufactured by Maruzen Petrochemical Co., Ltd.), which was changed to an alkali aqueous solution, and the others were prepared in exactly the same composition to obtain a radiation-sensitive linear resin composition (2).

Similarly, 10.0 g of Marukalyncur-PHM-C was dissolved in 13.0 g of diethylene glycol dimethyl ether to give 4'-hydroxy 2,3,4-trihydroxybenzophenone 0.4 g, 1,1-double ( 4-hydroxyphenyl)-[4-[1-(4-hydroxyphenyl)-1-methylethyl]phenyl]ethane and 1,2-naphthoquinonediazide-5-sulfonic acid 2 5 g condensate 3.0 g, glycidoxypropyl trimethoxy decane 0.2 g, hexamethoxy melamine 1 g, Epicote 152 (made by Japan Epoxy Resin Co., Ltd.) 1.0 g, ethyl lactate 120.0 g, with pore diameter A 0.2 μm millipere filter membrane was filtered to modulate the radiation sensitive linear resin composition (3).

Similarly, after dissolving 10.0 g of Marukalyncur-M in diethylene glycol dimethyl ether, 4'-hydroxy 2,3,4-trihydroxybenzophenone 0.4 g, 1,1-bis (4- Hydroxyphenyl)-1-[4-[1-(4-hydroxyphenyl)-1-methylethyl]phenyl]ethane and 1,2-naphthoquinonediazide-5-sulfonic acid 2 5 g condensate 3.0 g, glycidoxypropyl trimethoxy decane 0.2 g, hexamethoxy melamine 1 g, Epicote 152 (made by Japan Epoxy Resin Co., Ltd.) 1.5 g, ethyl lactate 120.0 g, with pore diameter A 0.2 μm millipere filter membrane was filtered to modulate the radiation sensitive linear resin composition (4).

Synthesis Example 3

After the inside of the flask was purged with nitrogen, 250.0 g of a diethylene glycol dimethyl ether solution in which 7.0 g of 2,2'-azobis(2,4-dimethylvaleronitrile) was dissolved was fed. Then, after adding 5.0 g of styrene, 22.0 g of methacrylic acid, 28.2 g of dicyclopentyl methacrylate, and 45.0 g of glycidyl methacrylate, stirring was started slowly. The polymerization was started at 70 ° C, and after maintaining this temperature for 6 hours, the polymerization was terminated to obtain a polymerization liquid having a solid concentration of 30% by weight.

(1) Preparation Example of Sensitive Radiation Linear Resin Composition

33.3 g (copolymer 10 g) of the copolymer solution obtained in Synthesis Example 3 was diluted with 162.0 g of diethylene glycol dimethyl ether to give 1,1-bis(4-hydroxyphenyl)-[4-[ 2.0 mol condensate of 1-(4-hydroxyphenyl)-1-methylethyl]phenyl]ethane and 1,2-naphthoquinonediazide-5-sulfonic acid 3.0 g, propylene oxide Propyltrimethoxydecane 0.5 g, SH-28PA (0.005 g of Toray Dow Corning Silicone Co., Ltd.) was dissolved, and filtered with a milliipore filter membrane having a pore size of 0.2 μm to prepare a radiation sensitive linear resin composition (5).

Examples 1 to 9

(1) In a stainless steel pressure cooker equipped with a stirrer, a thermometer, a heater, a pump for adding a monomer, and a nitrogen gas introduction device, 140 parts by weight of ethylene glycol monobutyl ether was fed, and the gas phase was replaced with nitrogen for 15 minutes. The internal temperature is raised to 80 °C. Thereafter, while maintaining the internal temperature at 80 ° C, 10 parts by weight of 2-propenylamine-2-methylpropanesulfonic acid and 50 parts by weight of perfluorooctylethyl acrylate were continuously added for 3 hours. A mixture of 40 parts by weight of perfluoromethylethyl acrylate and 2 parts by weight of benzoyl peroxide was added, and after further addition, the mixture was further reacted at 85 to 95 ° C for 2 hours, and then cooled to 25 ° C. Thereafter, the reaction solution was dried under vacuum to remove the solvent to obtain an aqueous solution resin having a solid content of 10% by weight.

This aqueous resin has a Mw of 3.0×10 ⁴ and a copolymerization of 2-propenylamine-2-methylpropanesulfonic acid/2-(perfluoro-n-octyl)ethyl acrylate/perfluoromethylethyl acrylate. The ratio is 10/70/10 (%). This aqueous solution resin is referred to as "water-soluble resin (A-1)".

(2) 1 part by weight of a surfactant, Sarfinol 465, manufactured by Air Products Co., Ltd., was added to 100 parts by weight of the water-soluble resin (A-1), and further added with water to form a solid content concentration of 1% by weight, and then filtered at a pore size of 0.2 μm. The membrane was filtered to obtain a composition (B-1) for the microlens upper layer film.

Similarly, a composition (B-2) for a microlens upper layer film having a solid content concentration of 0.5% by weight was obtained.

In the same manner, 100 parts by weight of (A-1) was added to Surffin 465, a surfactant of Air Products Co., Ltd., 10 parts by weight of triethylamine, and further water was added to form a solid content concentration of 1% by weight to obtain a composition for a microlens upper film. (B-3).

(3) The above-mentioned radiation-sensitive linear resin composition (1) or (2) is spin-coated on a ruthenium wafer having a transparent resin layer of 6 inches, and pre-baked on a hot plate at 100 ° C. Bake for 90 seconds to form a desired thick photoresist film. Thereafter, exposure was performed for a specific time using a Nikon stepper NSR 2205 i12 D (365 nm). Thereafter, it was developed using a 1% by weight aqueous solution of tetramethylammonium hydroxide at 25 ° C for 1 minute, and washed with water to form a photoresist pattern. In Examples 1 to 4 and 7 to 9 having a film thickness of 0.3 μm, the irradiation amount was 190 mJ/cm ² , and in Example 5 (film thickness 0.45 μm), it was 220 mJ/cm ² , and in Example 6 (film thickness) In the 0.73 μm), it is 250 mJ/cm ² .

Thereafter, the composition for the above-mentioned microlens upper film was spin-coated, then washed with water, dried, and then re-used with a Nikon stepper NSR 2205 i12 D (365 nm) at NA 0.63, δ 0.6. Full exposure for a specific time. Thereafter, it was baked at 200 ° C for 4 minutes to form a microlens.

In the present process, in order to confirm the residual film of the microlens, the photosensitive resin composition (2) was spin-coated on a ruthenium wafer having a diameter of 6 inches with a transparent resin layer, and then at 100 ° C. The hot plate was prebaked for 90 seconds to form a desired thickness of the photoresist film. Thereafter, the film was developed for 1 minute at 25 ° C using a 1% by weight aqueous solution of tetramethylammonium hydroxide without exposure (not shown), and the same process as that for forming a photoresist pattern was carried out. Then, a person who does not apply the composition for forming a microlens upper layer film to perform total exposure (a), spin-coats the composition for forming a microlens upper film, and performs full exposure (b), and the aforementioned microlens The composition for forming an upper layer film was spin-coated, washed with water, dried, and then exposed to a full exposure (c), and baked at 200 ° C for 4 minutes to prepare a β film. (a) The surface contact angle is 72 degrees, the surface contact angle of (b) is 99 degrees, the surface contact angle of (c) is 100 degrees, and the film thickness difference between (b) and (a) is 36 nm, (c) The difference in film thickness from (a) is 15 nm, and it can be confirmed that the upper film remains.

Lens evaluation

1. The gap between the lenses was patterned by the above method with a mask size of 2 μm ² and a gap of 0.3 μm, and the distance (μm) between the microlenses was measured by SEM observation.

2. Meltability The meltability of the lens was evaluated using the cross-sectional area of the lens as shown in the schematic diagram in Fig. 1.

Among the cross-sectional areas (A) of the lenses, the area of the portion having the independent radius of curvature (B) was obtained.

(B/A) × 100 (%) of 80% or more can be used as a lens, and less than 80% cannot be used as a lens.

3. The improvement of the storage stability is stored by the gel permeation chromatography (GPC) (device; HLC-8220 GPC (manufactured by Tosoh), tube) after storage for a specific number of days as shown in Table 1 below. In the column, one of TSKgel GMPW and TSKgel G3000 PW, the weight average molecular weight (Mw) of the composition for forming a microlens upper film which adjusted the solid content concentration to 0.2% was calculated. The weight average molecular weight is determined by the above GPC, using ultrapure water/sodium sulfate/acetonitrile=2100/15/900 as the dissolution solvent, and the monodisperse polymerization is measured at a column temperature of 25 ° C and a flow rate of 1.2 ml/min. The value calculated by styrene as a standard.

The results are shown in Table 2.

Comparative example 1~4

The microlenses used in the examples (Comparative Examples 1 and 2) were formed in the same manner as the lensless upper film. Further, in Comparative Example 1, the lens forming temperature was changed to 160 ° C for 4 minutes, and the baked one was used as Comparative Example 3. Further, the same procedure as in Example 1 was carried out, except that a 1% by weight aqueous solution of polyvinyl alcohol (manufactured by Wako Pure Chemical Industries, Ltd.; alkalinity: 78 to 82%, average polymerization degree: 1500) was used. As Comparative Example 4.

The results are shown in Table 3.

Figure 1 is a schematic cross-sectional view of a contiguous microlens.

Claims (9)

A method for manufacturing a microlens, comprising the steps of: (a) applying a photosensitive radiation resin composition for forming a microlens on a substrate; (b) performing patterning by exposure and development; a step of: (c) coating a microlens upper layer film forming composition on the pattern on the substrate; and (d) performing a heat treatment step; and the microlens upper layer film forming composition in the step (c) is containing a polymer which is a unit containing a structure represented by the following formula (IV); In the formula (IV), R ³ represents a hydrogen atom or a monovalent organic group, and R ⁴ represents a divalent organic group. The method for producing a microlens according to the first aspect of the invention, wherein the photosensitive resin composition in the step (a) comprises (A) an alkali-soluble resin, (B) 1,2-naphthoquinonediazide compound, and (C) a compound having at least one epoxy group in the molecule. The method for producing a microlens according to item 2 of the patent application, wherein the 1,2-naphthoquinonediazide compound (B) is the following formula (I): Here, the three Ds are the same or different and represent 1,2-naphthoquinonediazide-4-sulfonyl or 1,2-naphthoquinonediazide-5-sulfonyl. The method for producing a microlens according to the first aspect of the invention, wherein the polymer is water-soluble. The method for producing a microlens according to the first aspect of the invention, wherein the gap between the adjacent microlenses produced is 0.1 μm or less. a composition comprising a polymer and used to form a microlens upper film; the polymer comprising a unit having a structure represented by the following formula (IV); In the formula (IV), R ³ represents a hydrogen atom or a monovalent organic group, and R ⁴ represents a divalent organic group. The composition of claim 6, wherein the polymer is water soluble. The composition of claim 6 further comprising a basic compound. The use of a polymer for forming a microlens upper film, characterized in that the polymer contains a unit having a structure represented by the following formula (IV); In the formula (IV), R ³ represents a hydrogen atom or a monovalent organic group, and R ⁴ represents a divalent organic group.