JP3241399B2 - Radiation-sensitive resin composition for microlenses - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a radiation-sensitive resin composition for microlenses. More specifically, the present invention relates to a radiation-sensitive resin composition for microlenses that can be used for a micro optical lens body and a lens array body in which lens bodies are regularly arranged.

[0002]

2. Description of the Related Art A microlens having a lens diameter of about 20 to 200 .mu.m or a microlens array formed by regularly arranging those microlenses is used for an imaging optical system such as a facsimile or an electronic copying machine, or the like. It is applied to the optical system of optical fiber connectors and the like.

[0003] Practical microlenses (microlens arrays) having the above-mentioned lens diameter include a distributed refractive index type flat microlens produced by an ion exchange method and a convex microlens produced by using photosensitive glass. Lenses.

[0004] However, the microlenses currently put into practical use all have complicated manufacturing methods and are therefore high in manufacturing cost, and are limited by other parts in the lens manufacturing stage due to restrictions due to the manufacturing method. There is a problem that it cannot be integrated. In addition, the distributed index flat microlens by the ion exchange method has a problem that the surface must be polished after the lens is formed, and the convex microlens using the photosensitive glass can be formed only into a predetermined shape. are doing. Therefore, in recent years, a method of forming a microlens by forming a resist pattern using a photosensitive resin composition and then subjecting the resist pattern to melt flow by heat treatment has been attempted.

[0005] However, the shape of the microlens obtained in this way depends on the conditions at the time of heat treatment of the resist pattern, and it is difficult to form a microlens of an arbitrary shape. However, there still remain problems to be solved with respect to heat deformation resistance and transparency.

[0006]

An object of the present invention is to provide a radiation-sensitive resin composition for microlenses. Another object of the present invention is to provide a resin composition for a microlens which has a small dependence on conditions of heat treatment when producing a microlens of an arbitrary shape and which gives a lens excellent in heat deformation resistance and transparency. It is in.

[0007] Still other objects and advantages of the present invention will become apparent from the following description.

[0008]

According to the present invention, in order to solve the problems], the above objects and advantages of the present invention, with (A) an alkali-soluble resin
A copolymer of α, β-unsaturated carboxylic acid , (B) a radiation-sensitive acid-generating compound (hereinafter referred to as “acid-generating compound”)
And (C) a compound having at least two epoxy groups in a molecule (hereinafter, referred to as an “epoxy compound”), which is achieved by a radiation-sensitive resin composition for microlenses.

Hereinafter, the components of the present invention will be described. (A) an alkali-soluble resin used in the alkali-soluble resin present invention, alpha, beta - copolymers of unsaturated carboxylic acid (hereinafter, referred to as "copolymer I") it is.

[0010]

[0011]

[0012]

[0013]

[0014]

[0015]

[0016]

[0017]

The copolymer I can be obtained by radical polymerization of an α, β-unsaturated carboxylic acid and another radically polymerizable compound in a solvent. As the α, β-unsaturated carboxylic acid, for example, acrylic acid, methacrylic acid,
Monocarboxylic acids such as crotonic acid; and dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid, and itaconic acid.

Other radically polymerizable compounds include:
For example, acid anhydrides such as maleic anhydride, itaconic anhydride and the like; dicarboxylic acid monoesters such as monoethyl maleate, monoethyl fumarate and monoethyl itaconate; conjugated diolefins such as 1,3-butadiene, isoprene, chloroprene and dimethyl 1,3-butadiene and the like; monoolefinically unsaturated compounds, for example, alkyl methacrylates such as methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate and t-butyl methacrylate, methyl acrylate, isopropyl acrylate and the like Alkyl acrylate, cycloalkyl methacrylate such as cyclohexyl methacrylate, 2-methylcyclohexyl methacrylate, cyclohexyl acrylate, Such acrylic acid cyclic alkyl esters of the methyl cyclohexyl acrylate, phenyl methacrylate, such as methacrylic acid aryl esters of benzyl methacrylate, phenyl acrylate, such as acrylic acid aryl esters of benzyl acrylate,
Styrene, α-methylstyrene, o-methylstyrene,
m-methylstyrene, p-methylstyrene, p-methoxystyrene, acrylonitrile, methacrylonitrile,
Vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, vinyl acetate and the like can be used.

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. If it is less than 5% by weight,
Since the obtained copolymer is difficult to dissolve in an aqueous alkaline solution, it is difficult to form a sufficient resist pattern due to easy development residue. On the other hand, if it exceeds 40% by weight, the solubility of the obtained copolymer in an aqueous alkali solution becomes too large, and it becomes difficult to prevent dissolution of the unexposed portion, that is, film development. As the other radical polymerizable compound, a conjugated diolefin or a monoolefin-based unsaturated compound is preferable in view of the properties of the obtained copolymer.

When this conjugated diolefin is used, the flexibility unique to rubber can be imparted to the copolymer, so that the copolymer has flexibility, and the copolymer is free from cracking and the product yield is remarkably improved. Can be done. Further, the adhesion of the copolymer to the substrate is increased. Further, when the copolymerization amount of the conjugated diolefin is increased, the melting temperature of the obtained copolymer shifts to a lower temperature side.

Further, by incorporating a monoolefinic unsaturated compound into the copolymer, the mechanical properties of the copolymer can be appropriately controlled, and the alkali aqueous solution can be controlled in relation to the components soluble in the alkaline aqueous solution described above. It is possible to finely adjust the solubility of the powder.

The monoolefinically unsaturated compounds include:
For example, methyl methacrylate, ethyl methacrylate,
alkyl methacrylates such as n-butyl methacrylate, sec-butyl methacrylate, and t-butyl methacrylate; alkyl acrylates such as methyl acrylate and isopropyl acrylate; cyclic alkyl methacrylates such as cyclohexyl methacrylate and 2-methylcyclohexyl methacrylate; cyclohexyl Acrylic acid cyclic alkyl esters such as acrylate and 2-methylcyclohexyl acrylate; methacrylic acid aryl esters such as phenyl methacrylate and benzyl methacrylate; acrylic acid aryl esters such as phenyl acrylate and benzyl acrylate;
Diesters of dicarboxylic acids such as diethyl maleate, diethyl fumarate and diethyl itaconate; hydroxyalkyl esters such as 2-hydroxyethyl methacrylate and 2-hydroxypropyl methacrylate; styrene, α-methylstyrene, o-methylstyrene, m -Methylstyrene, p-methylstyrene, vinyltoluene,
p-Methoxystyrene, 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. In consideration of the influence of the monoolefinic unsaturated compound on various properties, the preferable copolymerization amount is 25 to 90% by weight, particularly preferably 30 to 90% by weight.
80% by weight. When the content of the monoolefin-based unsaturated compound is less than 25% by weight, the content of other components in the resin, that is, the content of α, β-unsaturated carboxylic acid, which is a component soluble in a conjugated diolefin-based compound or an aqueous alkali solution, is reduced. Since it increases, it is difficult to control the mechanical properties and alkali developability of the resin. On the other hand, if it exceeds 90% by weight, the solubility of the resin in the aqueous alkali solution relatively decreases, which is not preferable.

Solvents used for producing the 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 cellosolve acetate. And aromatic hydrocarbons, ketones, esters and the like.

As a polymerization catalyst in the radical polymerization, a usual radical polymerization initiator can be used. For example, 2,2'-
Azobisisobutyronitrile, 2,2'-azobis-
Azo compounds such as (2,4-dimethylvaleronitrile), 2,2'-azobis- (4-methoxy-2,4-dimethylvaleronitrile); benzoyl peroxide, lauroyl peroxide, t-butylperoxypivalate,
Organic peroxides such as 1,1-bis- (t-butylperoxy) cyclohexane and hydrogen peroxide can be exemplified. When a peroxide is used as the radical polymerization initiator, a redox initiator may be used in combination with a reducing agent.

The molecular weight of the above alkali-soluble resin is not particularly limited as long as the solution of the composition of the present invention can be applied uniformly. Incidentally, the copolymer I, which is the above-mentioned alkali-soluble resin is preferably the importance or we especially during heat treatment in manufacturing the microlens.

(B) Acid-generating compound The acid-generating compound is a compound that generates a carboxylic acid upon irradiation with radiation, for example, 1,2-benzoquinonediazidesulfonic acid ester, 1,2-naphthoquinonediazidesulfonic acid ester, 1,2 -Benzoquinonediazidosulfonic acid amide, 1,2-naphthoquinonediazidosulfonic acid amide, and the like. Specifically, J.I. K
Osar, "Light-Sensitive Sys."
tems "339-352, (1965), John
Wiley & Sons (New York) and W.S. S. “Photoresis” by De Forest
t "50, (1975), McGraw-Hill,
Inc. 1, 2 described in (New York)
-Quinonediazide compounds.

Among them, after irradiation,
Compounds that minimize absorption in the visible light region from 0 to 800 nm, for example, 2,3,4-trihydroxybenzophenone, 2,3,4,4'-tetrahydroxybenzophenone, 3'-methoxy-2,3,4, 4'-tetrahydroxybenzophenone, 2,2 ', 5,5'-tetramethyl-2 ", 4,4'-trihydroxytriphenylmethane, 4,4'-[1- [4- (1- (4 -Hydroxyphenyl) -1-methylethyl) phenyl] ethylidene]
Diphenol and 2,4,4-trimethyl-2 ', 4',
1,2- of 7-trihydroxy-2-phenylflavan
Benzoquinonediazide-4-sulfonic acid ester, 1,
2-naphthoquinonediazide-4-sulfonic acid ester,
Preferred are 1,2-naphthoquinonediazide-5-sulfonic acid ester and the like.

The amount of the acid-forming compound to be added is preferably 5 to 100 parts by weight, particularly preferably 10 to 50 parts by weight, per 100 parts by weight of the alkali-soluble resin. When the amount is less than 5 parts by weight, the amount of the carboxylic acid generated by absorbing the radiation becomes small, so that it is not possible to make a difference in the solubility in the aqueous alkali solution before and after the irradiation, and it becomes difficult to perform patterning. Also in the reaction with the compound, since the amount of the involved carboxylic acid is small, there is a possibility that a problem may occur in the heat deformation resistance of the formed microlens. On the other hand, if the amount exceeds 100 parts by weight, most of the added acid-generating compound remains in the form as it is by short-time irradiation, so that the effect of insolubilizing in an aqueous alkaline solution is too high to make development difficult.

(C) Epoxy compound An epoxy compound is a compound that reacts with carboxylic acid generated by irradiation of radiation during heat treatment of the microlens, and is thermally cured by the reaction with the carboxylic acid to impart heat resistance to the microlens. Is what you do. Therefore, the epoxy compound needs to contain two or more epoxy groups in the molecule, and examples thereof include the following. Commercially available bisphenol A type epoxy resins include, for example, Epicoat 1001, 1002, 1003, 100
4, 1007, 1009, and 1010 (manufactured by Yuka Shell Epoxy Co., Ltd.); commercial products of bisphenol F type epoxy resin include, for example, Epicoat 807 (manufactured by Yuka Shell Epoxy Co., Ltd.) bisphenol AD epoxy resin; Commercially available phenol novolak type epoxy resins include, for example, Epicoat 152 and 154 (manufactured by Yuka Shell Epoxy Co., Ltd.), EPPN-201 and EPPN-202 (manufactured by Nippon Kayaku Co., Ltd.); For example, EOCN-102S, 103
S, 104S, 1020, 1025, 1027
(Nippon Kayaku Co., Ltd.); Epikote 180S75 (Yuoka Shell Epoxy Co., Ltd.); Commercially available cycloaliphatic epoxy resins include, for example, CY-175, 177, and 17
9 (manufactured by CIBA-GEIGY), ERL-4234,
4299, 4221, and 4206 (manufactured by UCC); commercial products of glycidyl ester-based epoxy resins include, for example, Shodyne 508 (manufactured by Showa Denko KK);
Araldite CY-182, 192, 184 (CI
BA-GEIGY), Epicron 200, 400
(Dai Nippon Ink Co., Ltd.), Epicoat 871, 87
2 (manufactured by Yuka Shell Epoxy Co., Ltd.), ED-5661,
5662 (Celanese Coatings Co., Ltd.);

Commercially available glycidylamine epoxy resins include, for example, tetraglycidyldiaminodiphenylmethane, triglycidyl-para-aminophenol, triglycidyl-meta-aminophenol, diglycidylaniline, diglycidyltoluidine, tetraglycidylmetaxylylenediamine, Diglycidyltribromoaniline, tetraglycidylbisaminomethylcyclohexane; commercially available heterocyclic epoxy resins include, for example, Araldite PT810 (manufactured by CIBA-GEIGY), Epicoat RXE-15 (Yukaka Epoxy Co., Ltd.)
And EPITEC (manufactured by Nissan Chemical Industries, Ltd.).

Although many of the epoxy compounds mentioned here are high molecular weight compounds, the epoxy compounds used in the present invention are not limited by the molecular weight. For example, bisphenol A or diglycidyl ether of bisphenol F may be used. Such low molecular weight compounds can also be used.

Among them, phenol novolak type epoxy resin, crusol novolak type epoxy resin, cycloaliphatic epoxy resin,
Glycidyl ester epoxy resins are preferred. The amount of the epoxy compound to be used is preferably 1 to 100 parts by weight, more preferably 2 to 2 parts by weight, based on the acid generating compound (B).
0 parts by weight.

When the amount is less than 1 part by weight, the reaction with the carboxylic acid generated by irradiating the acid-generating compound with radiation hardly proceeds sufficiently, and the heat resistance of the formed microlens hardly becomes sufficient. If it exceeds 100 parts by weight, the melting point of the composition as a whole will decrease,
It becomes difficult to increase the temperature range of the heat treatment performed when manufacturing the microlens.

(D) Other Compounding Agents The composition of the present invention may contain a surfactant. As the surfactant, for example, BM-100
0, BM-1100 (manufactured by BM Chemie), MegaFac F142D, F172, F173, F1
83 (manufactured by Dainippon Ink and Chemicals, Inc.), Florard F
C-135, FC-170C, FC-430, F
C-431 (manufactured by Sumitomo 3M Limited), Surflon S
-112, S-113, S-131, S-14
1. A fluorine-based surfactant commercially available under the name of S-145 (produced by Asahi Glass Co., Ltd.) or the like can be used.
The amount of these surfactants to be used is preferably 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).

(Preparation of Radiation-Sensitive Resin Composition) The composition of the present invention can be easily prepared by uniformly mixing the above-mentioned components. Further, it is used in the form of a solution after being dissolved in an appropriate solvent. As a solvent to be used, a solvent that can uniformly dissolve components such as an alkali-soluble resin, an acid generating compound, and an epoxy compound and does not react with each component is used. Examples of such a solvent include alcohols such as methanol and ethanol;
Ethers such as tetrahydrofuran; glycol ethers such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether; ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate; diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether and the like Diethylene glycols; 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 ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone Ketones; 2 Hydroxypropionic acid ethyl, 2
Ethyl-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, 2-hydroxy-3
Esters such as methyl-methylbutanoate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, ethyl acetate and butyl acetate can be used.

Further, N-methylformamide, N, N
-Dimethylformamide, N-methylformanilide,
N-methylacetamide, N, N-dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, benzylethylether, dihexylether, acetonylacetone, isophorone, caproic acid, caprylic acid, 1
High-boiling solvents such as -octanol, 1-nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, and phenyl cellosolve acetate can also be added.

Among these solvents, glycol ethers such as ethylene glycol monoethyl ether; ethylene glycol alkyl ether acetates such as ethyl cellosolve acetate; 2 Esters such as ethyl hydroxypropionate; diethylene glycols such as diethylene glycol monomethyl ether are preferred.

In preparing the solution of the composition, three kinds of solutions, for example, a solution of an alkali-soluble resin, a solution of an acid-generating compound and a solution of an epoxy compound are prepared, and these solutions are prepared immediately before use. They can be mixed in proportions. The composition prepared as described above is used after being filtered using, for example, a millipore filter having a pore size of 0.2 μm.

(Method for Preparing Microlens) In the present invention, a desired coating film can be formed by applying a solution of the composition described above to a predetermined substrate surface and removing the solvent by heating. The method of coating the substrate surface is not particularly limited, and various methods such as a spray method, a roll coating method, and a spin coating method can be employed.

The heating conditions for the coating film of the composition of the present invention vary depending on the specific types and blending ratios of the components, but are usually at 70 to 90 ° C. for about 5 to 15 minutes. Next, through a mask of a predetermined pattern on the obtained coating film,
For example, after irradiation with ultraviolet rays, development is performed using an alkaline aqueous solution to form a resist pattern. Examples of the developer in the present invention include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, ethylamine, n-propylamine, diethylamine, di-n-propylamine,
Triethylamine, methyldiethylamine, dimethylethanolamine, triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, pyrrole, piperidine, 1,8-diazabicyclo (5,4,0) -7-undecene, 1,5-diazabicyclo An aqueous solution of an alkali such as (4,3,0) -5-nonane can be used. Further, an aqueous solution obtained by adding an appropriate amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant to an aqueous solution of the above alkalis can be used as the developer.

The developing time is preferably from 30 to 180 seconds, and the developing method may be any of a puddle method and a dipping method. After the development, washing with running water is performed for 30 to 90 seconds, and by air drying with compressed air or compressed nitrogen,
A resist pattern can be formed. afterwards,
For example, the acid generating compound remaining in the resist pattern is changed to a carboxylic acid compound by irradiating ultraviolet rays. Then, using a heating device such as a hot plate or an oven, at a predetermined temperature, for example, 100 to 170 ° C.
For a predetermined time, for example, 2 to 10 minutes on a hot plate,
The microlens can be obtained by performing a heat treatment for 15 to 45 minutes in an oven.

[0044]

Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited by these examples. Also, unless otherwise noted
% Indicates% by weight.

Synthesis Example 1 After the atmosphere in the flask was replaced with nitrogen, 459.0 g of a diethylene glycol dimethyl ether solution in which 9.0 g of 2,2'-azobisisobutyronitrile was dissolved was charged. Subsequently, styrene (37.5 g) and methyl methacrylate (75.0) were used.
After charging 37.5 g of methacrylic acid, gentle stirring was started. The polymerization was started at 80 ° C.
After holding for a period of time, the mixture was heated at 90 ° C. for 1 hour to terminate the polymerization.

Thereafter, the reaction product solution was dropped into a large amount of water to coagulate the reaction product. This coagulated product was washed with water, redissolved in 200 g of tetrahydrofuran, and coagulated again with a large amount of water. After performing the re-dissolution-coagulation operation a total of three times, the obtained coagulated product was vacuum-dried at 60 ° C. for 48 hours to obtain a target copolymer. Thereafter, a copolymer solution was prepared using diethylene glycol so that the solid content concentration became 25% by weight.

Synthesis Example 2 After the inside of a pressure-resistant glass bottle was replaced with nitrogen, 229.5 g of a diethylene glycol dimethyl ether solution in which 4.5 g of 2,2'-azobisisobutyronitrile was dissolved was charged. Subsequently, 13.05 g of styrene, 27.08 g of methyl methacrylate, and 13.50 g of methacrylic acid were charged, and 8.03 g of 1,3-butadiene was charged. The polymerization was started at 70 ° C., and after maintaining this temperature for 8 hours, the mixture was heated at 90 ° C. for 1 hour to terminate the polymerization. Then, Synthesis Example 1
A copolymer solution was obtained in the same manner as described above.

Synthesis Example 3 After the inside of the flask was replaced with nitrogen, a diethylene glycol dimethyl ether solution 50 containing 4.5 g of 2,2'-azobisisobutyronitrile and 45.0 g of maleic anhydride was dissolved.
8.5 g was charged. Followed by α-methylstyrene 13
5.0 g was charged and stirring was started slowly. The polymerization was started at 70 ° C., and the temperature was maintained for 5 hours.
The polymerization was terminated by heating for an hour. Thereafter, a copolymer solution was obtained in the same manner as in Synthesis Example 1.

[0049]

Example 1 (1) Preparation of Radiation Sensitive Solution 100 g of the copolymer solution obtained in Synthesis Example 1 (Copolymer 2
5 g) with diethylene glycol dimethyl ether 13.
After dilution with 64 g, 4,4 '-[1- [4- (1-
10.0 g of 1,4-naphthoquinonediazide-5-sulfonic acid ester of (4-hydroxyphenyl) -1-methylethyl) phenyl] ethylidene] diphenol (average esterification rate: 66.7 mol%) and o-cresol novolak 1.25 g of a type epoxy resin EOCN-1020 (manufactured by Nippon Kayaku Co., Ltd.) was dissolved, and the solution was filtered through a millipore filter having a pore size of 0.22 μm to prepare a radiation-sensitive liquid (1).

(2) Formation of Coating Film The above radiation-sensitive solution (1) is applied on a wafer having a silicon oxide film treated with hexamethyldisilazane by a spinner, and then prebaked in an oven at 80 ° C. for 10 minutes. Thus, a resist film having a thickness of 2.0 μm was formed.

(3) Preparation of microlens A predetermined pattern mask is closely attached to the resist film obtained in (2) above, and the light intensity at 365 nm is 10 m.
An ultraviolet ray of J / cm ² was irradiated for 30 seconds. Then, after developing with a 0.12% aqueous solution of tetramethylammonium hydroxide at 25 ° C. for 2 minutes and rinsing with ultrapure water for 1 minute, a space having a line width of 0.8 μm could be resolved. Thereafter, the entire surface was exposed using the same exposure apparatus for 50 seconds, and heated in a clean oven at a lens-forming temperature shown in Table 1 for 30 minutes. As a result, a microlens having a width of 5.0 μm could be formed. The heat deformation resistance was evaluated using this lens, and the results are shown in Table 1 (the same applies to Examples 2 to 10).

The heat deformation resistance was evaluated as follows. Heat deformation resistance: After heating the obtained microlens at 170 ° C. for 3 hours, ○ when the line width of the space exceeds 80% of the line width before heating, Δ when 50 to 80%, and 50% The case of less than was evaluated as x.

(4) Evaluation of Transparency In (2) above, a transparent substrate (Corning 7059: manufactured by Corning Incorporated) was used instead of the wafer having a silicon oxide film treated with hexamethyldisilazane. A resist film was formed in the same manner as in (1). Then
After developing with an aqueous solution of tetramethylammonium hydroxide, the substrate was rinsed with ultrapure water for 1 minute. The whole surface was further exposed for 50 seconds, heated using a clean oven at a temperature capable of forming a pattern having a line width of 5.0 μm on the lens, and further heated at 200 ° C. for 1 hour. The transparent substrate having the obtained microlens was placed on a spectrophotometer (150-20).
Mold double beam; manufactured by Hitachi, Ltd.)
The transmittance at ８００800 nm was measured, and the case where the minimum transmittance exceeded 95% was rated as ○, the case where the minimum transmittance was 90 to 95% as Δ, and the case where less than 90% was less than 90%. The results are shown in Table 1 (hereinafter the same in Examples 2 to 10).

Example 2 The copolymer solution obtained in Synthesis Example 2 was used in place of the copolymer solution obtained in Synthesis Example 1 to prepare and evaluate the same procedures as in Example 1. A space with a line width of 1.0 μm could be resolved with a 0.20% aqueous hydroxide solution. Further, similar microlenses could be formed by heating at a temperature of 130 to 140 ° C.

Example 3 The copolymer solution obtained in Synthesis Example 3 was used in place of the copolymer solution obtained in Synthesis Example 1 to prepare and evaluate it according to Example 1. After irradiation for 10 seconds, a space having a line width of 0.8 μm could be resolved with a 2.0% aqueous solution of tetramethylammonium hydroxide. Also, 150
A similar microlens could be formed by heating at a temperature of １６０160 ° C.

[0057]

[0058]

Example 4 4,4 '-[1- [4- (1- (4
M-cresol / p-cresol = 6/4 (weight ratio) instead of 1,2-naphthoquinonediazide-5-sulfonic acid ester of -hydroxyphenyl) -1-methylethyl) phenyl] ethylidene] diphenol Example 1 using novolak resin having an average number of nuclei of 3.9 and 10.0 g of 1,2-naphthoquinonediazide-5-sulfonic acid ester (average esterification rate: 58.0 mol%)
When prepared and evaluated according to the following, after irradiation with ultraviolet rays for 30 seconds, 0.16% of tetramethylammonium hydroxide was used.
A space having a line width of 1.0 μm could be resolved with the aqueous solution. Further, by heating at a temperature of 150 to 170 ° C., a similar microlens could be formed.

Example 5 4,4 '-[1- [4- (1- (4
Instead of 1,2-naphthoquinonediazide-5-sulfonic acid ester of -hydroxyphenyl) -1-methylethyl) phenyl] ethylidene] diphenol, 2,3,
It was prepared and evaluated according to Example 1 using 10.0 g of 1,2-naphthoquinonediazide-5-sulfonic acid ester of 4,4′-tetrahydroxybenzophenone (average esterification rate: 75 mol%), and it was measured for 30 seconds. 0.14% of tetramethylammonium hydroxide after UV irradiation
A space having a line width of 0.8 μm could be resolved with the aqueous solution. Further, by heating at a temperature of 140 to 150 ° C., a similar microlens could be formed.

Example 6 Instead of the o-cresol novolak type epoxy resin of Example 1, bisphenol A type epoxy resin Epicoat 8
28 (manufactured by Yuka Shell Epoxy Co., Ltd.) and prepared and evaluated according to Example 1. After irradiation with ultraviolet rays for 30 seconds, a line width of 0.18% aqueous solution of tetramethylammonium hydroxide was used. A 0.2 μm space could be resolved. Further, similar microlenses could be formed by heating at a temperature of 140 to 160 ° C.

Example 7 Instead of the o-cresol novolak type epoxy resin of Example 1, bisphenol F type epoxy resin epicoat 8
15 (manufactured by Yuka Shell Epoxy Co., Ltd.) and prepared and evaluated according to Example 1. After irradiation with ultraviolet rays for 30 seconds, a line width of 0.14% aqueous solution of tetramethylammonium hydroxide was used. A space of 0.0 μm could be resolved. Further, similar microlenses could be formed by heating at a temperature of 130 to 140 ° C.

Example 8 The cycloaliphatic epoxy resin CY-179 (CIB) was used instead of the o-cresol novolak type epoxy resin of Example 1.
Example 1 using 1.25 g of A-GEIGY Corporation
When prepared and evaluated according to the following, after irradiation with ultraviolet rays for 30 seconds, tetramethylammonium hydroxide 0.20%
A space having a line width of 0.8 μm could be resolved with the aqueous solution. Further, similar microlenses could be formed by heating at a temperature of 150 to 160 ° C.

Example 9 An oarcrete CY184 (CIBA-GEIG) was used in place of the o-cresol novolak type epoxy resin of Example 1.
Y (manufactured by Y Corp.) was prepared and evaluated according to Example 1. After irradiation with ultraviolet rays for 30 seconds, a space having a line width of 1.0 μm was prepared with a 0.16% aqueous solution of tetramethylammonium hydroxide. It could be resolved. Also,
By heating at a temperature of 120 to 140 ° C., a similar microlens could be formed.

[0065]

[Table 1]

Comparative Examples 1 to 6 Synthesis, preparation and evaluation were carried out in the same manner without adding the epoxy compound as a component of the compositions shown in Examples 1 to 6 . Table 2 summarizes the results.

[0067]

[Table 2]

[0068]

According to the present invention, there is provided a resin composition for a microlens capable of producing a microlens having a desired shape and providing a lens having excellent heat deformation resistance and transparency.

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Masayuki Endo 2--11-24 Tsukiji, Chuo-ku, Tokyo Japan Synthetic Rubber Co., Ltd. (72) Inventor Yasuaki Yokoyama 2-11-24 Tsukiji, Chuo-ku, Tokyo Japan Synthetic Rubber Co., Ltd. (56) Reference JP-A-61-153602 (JP, A) JP-A-64-65509 (JP, A) JP-A-55-129341 (JP, A) JP-A-63-313150 (JP JP, A) JP-A-3-116148 (JP, A) JP-A-3-126708 (JP, A)

Claims (1)

(57) [Claims] (A) An alkali-soluble resin α, β
A copolymer of unsaturated carboxylic acid , (B) a radiation-sensitive acid-forming compound and (C) at least two epoxy groups in the molecule.
A radiation-sensitive resin composition for microlenses, comprising: