JP5182365B2 - Positive radiation-sensitive resin composition, microlens and method for forming microlens - Google Patents

Description

  The present invention relates to a positive radiation sensitive resin composition, a microlens, and a method for forming a microlens.

  A microlens having a lens diameter of about 0.3 to 50 μm or an optical system material for an on-chip color filter such as a facsimile machine, an electronic copying machine, a solid-state image sensor, or an optical fiber connector, or those microlenses are defined. An array of microlenses is used.

  To form a microlens or microlens array, a resist pattern corresponding to the lens is formed and then melt-flowed by heat treatment and used as it is as a lens, or by using the melt-flowed lens pattern as a mask and drying. A method of transferring a lens shape to a base by etching is known. A positive radiation sensitive resin composition is widely used for the formation of the lens pattern (see Patent Document 1 and Patent Document 2).

  In this case, the conditions for the lens forming material include high transparency in the visible light region, excellent heat resistance after lens formation, and further excellent lens forming ability. Can be mentioned.

A cured product obtained from a conventionally known photosensitive siloxane composition is unsatisfactory in terms of heat resistance and melt flow property (hereinafter referred to as “melt property”). For example, if the cured product is not excellent in heat resistance, there is a problem that when the microlens pattern is cured after forming the microlens, the microlens pattern is remelted by heating. On the other hand, when the heat resistance is excellent, it is very difficult to form a lens because the meltability is low (see Patent Document 3).
JP-A-6-18702 JP-A-6-136239 JP 2006-178436 A

  This invention is made | formed based on the above situations, and the objective of this invention is providing the photosensitive resin composition excellent in melt property and heat resistance. A further object of the present invention is to provide a solid-state imaging device represented by a charge coupled device (CCD) or a complementary metal oxide semiconductor (CMOS), particularly a solid-state imaging device using a microlens, and a method for manufacturing the microlens. is there.

To achieve the above object, the present invention provides (A) a hydrolyzate of organosilane represented by the following formula (1) and / or a condensate thereof.

(In the formula, R ¹ is an alkoxyl group having 1 to 6 carbon atoms or an aryloxy group having 6 to 18 carbon atoms, provided that part or all of the hydrogen atoms of the aryloxy group are halogen atoms, cyano groups, nitro groups or R ² may be substituted by an alkyl group having 1 to 6 carbon atoms, and R ² is an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an aryl group having 6 to 18 carbon atoms, or an allyl group. Provided that a part or all of the hydrogen atoms of the aryl group may be substituted by a halogen atom, a cyano group, a nitro group or an alkyl group having 1 to 6 carbon atoms, and a is an integer of 1 to 4, b is an integer of 0 to 3, provided that a + b = 4.)
(B) Cycloaliphatic polyamide, aromatic polyamide, polyamideimide, polyacrylamide, polymethacrylamide, poly (N-methylacrylamide), poly (N-methylmethacrylamide), poly (N, N-dimethylacrylamide), poly (N, N-dimethylmethacrylamide), poly (N-ethylacrylamide), poly (N-ethylmethacrylamide), poly (N, N-diethylacrylamide), poly (N, N-diethylmethacrylamide), poly ( N-isopropylpolyacrylamide), poly (diacetone acrylamide), poly (N-methylolacrylamide), poly (N-methylolmethacrylamide), polyoxazoline, 2-methylpolyoxazoline, 2-ethylpolyoxazoline and poly (N- Vinylpyrrolidone Is at least one resin, and (C) The positive-tone radiation-sensitive resin composition characterized by containing a quinonediazide compound selected from the group consisting of.

As a preferred embodiment of the positive radiation sensitive resin composition, the resin (B) is at least one resin selected from the group consisting of polyacrylamide, poly (N-vinylpyrrolidone) and polyoxazoline,
0.1 to 20 parts by weight of the component (B) with respect to 100 parts by weight of the component (A),
Containing 15 to 40 parts by weight of the component (C) with respect to 100 parts by weight of the component (A),
Furthermore, (D) contains a crosslinking agent,
And (g) a phenol compound,
The positive radiation sensitive resin composition is for forming a microlens,
The positive radiation sensitive resin composition is for forming an interlayer insulating film.

  Another invention is a microlens comprising the positive radiation-sensitive resin composition for forming the microlens.

  Another invention is a method for forming a microlens comprising the following steps in the order described below.

(1) A step of forming a film of the positive radiation sensitive resin composition according to claim 7 on a substrate,
(2) A step of irradiating at least a part of the coating with radiation,
(3) A step of developing the film after irradiation and heating it to obtain a cured product.

  Another invention is a microlens formed by the method described above.

  The cured product obtained from the positive-type radiation-sensitive resin composition of the present invention is excellent in melt property and heat resistance, so that a microlens can be produced satisfactorily, and a solid-state imaging device represented by CCD and CMOS. In particular, a solid-state imaging device using a microlens can be formed.

FIG. 1 is a schematic diagram for evaluating the meltability of a lens using the cross-sectional area of the lens.

[Positive radiation sensitive resin composition]
The positive radiation sensitive resin composition according to the present invention is:
(A) Hydrolyzate and / or condensate of organosilane represented by the following formula (1)

(In the formula, R ¹ is an alkoxyl group having 1 to 6 carbon atoms or an aryloxy group having 6 to 18 carbon atoms, provided that part or all of the hydrogen atoms of the aryloxy group are halogen atoms, cyano groups, nitro groups or R ² may be substituted by an alkyl group having 1 to 6 carbon atoms, and R ² is an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an aryl group having 6 to 18 carbon atoms, or an allyl group. Provided that a part or all of the hydrogen atoms of the aryl group may be substituted by a halogen atom, a cyano group, a nitro group or an alkyl group having 1 to 6 carbon atoms, and a is an integer of 1 to 4, b is an integer of 0 to 3, provided that a + b = 4.)
(B) Cycloaliphatic polyamide, aromatic polyamide, polyamideimide, polyacrylamide, polymethacrylamide, poly (N-methylacrylamide), poly (N-methylmethacrylamide), poly (N, N-dimethylacrylamide), poly (N, N-dimethylmethacrylamide), poly (N-ethylacrylamide), poly (N-ethylmethacrylamide), poly (N, N-diethylacrylamide), poly (N, N-diethylmethacrylamide), poly ( N-isopropylpolyacrylamide), poly (diacetone acrylamide), poly (N-methylolacrylamide), poly (N-methylolmethacrylamide), polyoxazoline, 2-methylpolyoxazoline, 2-ethylpolyoxazoline and poly (N- Vinylpyrrolidone At least one resin selected from the group consisting of, and (C) containing a quinonediazide compound.

<(A) Hydrolyzate of organosilane and / or condensate thereof>
The component (A) contained in the positive radiation sensitive resin composition according to the present invention is a hydrolyzate of organosilane represented by the above formula (1), a condensate of hydrolyzate of organosilane, or the above An organosilane hydrolyzate and a condensate of the organosilane hydrolyzate.

R ¹ in the above formula (1) is preferably an alkoxyl group having 1 to 4 carbon atoms or an aryloxy group having 6 to 12 carbon atoms, such as a methoxyl group, an ethoxyl group, an n-propyloxy group, or an i-propyloxy group. Phenoxy group, naphthyloxy group, 4-chlorophenoxy group, 4-cyanophenoxy group, 4-nitrophenoxy group, 4-toluyloxy group, and the like. R ² is bonded via an alkyl group having 1 to 3 carbon atoms, an alkenyl group having 2 to 4 carbon atoms, an aryl group having 6 to 12 carbon atoms, or directly or via a methylene group or an alkylene group having 2 to 3 carbon atoms. Specific examples thereof include, for example, methyl group, ethyl group, phenyl group, 4-chlorophenyl group, 4-cyanophenyl group, 4-nitrophenyl group, 4-toluyl group, naphthyl group, vinyl group, An allyl group, 2- (meth) acryloxyethyl group, 3- (meth) acryloxypropyl group and the like can be mentioned.

Specific examples of the organosilane represented by the above formula (1) include, for example, trimethoxysilane, triethoxysilane, tri-n-propoxysilane, tri-iso-propoxysilane, tri-n-butoxysilane, tri-sec. -Butoxysilane, tri-tert-butoxysilane, triphenoxysilane, fluorotrimethoxysilane, fluorotriethoxysilane, fluorotri-n-propoxysilane, fluorotri-iso-propoxysilane, fluorotri-n-butoxysilane, fluoro Tri-sec-butoxysilane, fluorotri-tert-butoxysilane, fluorotriphenoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltri-n-propoxysilane, methyltri-iso-propoxysilane Methyltri-n-butoxysilane, methyltri-sec-butoxysilane, methyltri-tert-butoxysilane, methyltriphenoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltri-n-propoxysilane, ethyltri-iso-propoxysilane, Ethyltri-n-butoxysilane, ethyltri-sec-butoxysilane, ethyltri-tert-butoxysilane, ethyltriphenoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltri-n-propoxysilane, vinyltri-iso-propoxysilane, Vinyltri-n-butoxysilane, vinyltri-sec-butoxysilane, vinyltri-tert-butoxysilane, vinyltriphenoxysilane, n-propylto Methoxysilane, n-propyltriethoxysilane, n-propyltri-n-propoxysilane, n-propyltri-iso-propoxysilane, n-propyltri-n-butoxysilane, n-propyltri-sec-butoxysilane, n-propyltri-tert-butoxysilane, n-propyltriphenoxysilane, i-propyltrimethoxysilane, i-propyltriethoxysilane,
i-propyltri-n-propoxysilane, i-propyltri-iso-propoxysilane, i-propyltri-n-butoxysilane, i-propyltri-sec-butoxysilane, i-propyltri-tert-butoxysilane, i-propyltriphenoxysilane, n-butyltrimethoxysilane, n-butyltriethoxysilane, n-butyltri-n-propoxysilane, n-butyltri-iso-propoxysilane, n-butyltri-n-butoxysilane, n- Butyltri-sec-butoxysilane, n-butyltri-tert-butoxysilane, n-butyltriphenoxysilane, sec-butyltrimethoxysilane, sec-butyl-i-triethoxysilane, sec-butyl-tri-n-propoxysilane , Sec-butyl- Re-iso-propoxysilane, sec-butyl-tri-n-butoxysilane, sec-butyl-tri-sec-butoxysilane, sec-butyl-tri-tert-butoxysilane, sec-butyl-triphenoxysilane, t- Butyltrimethoxysilane, t-butyltriethoxysilane, t-butyltri-n-propoxysilane, t-butyltri-iso-propoxysilane, t-butyltri-n-butoxysilane, t-butyltri-sec-butoxysilane, t- Butyltri-tert-butoxysilane, t-butyltriphenoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltri-n-propoxysilane, phenyltri-iso-propoxysilane, phenyltri-n-butoxysilane, phenol Lutri-sec-butoxysilane, phenyltri-tert-butoxysilane, phenyltriphenoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminoethyl Aminopropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-trifluoropropyltrimethoxysilane, γ-trifluoropropyltriethoxysilane, γ-mercaptopropyltrimethoxy Silane, γ-isocyanatopropyltrimethoxysilane, acryloxypropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, etc. Dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyl-di-n-propoxysilane, dimethyl-di-iso-propoxysilane, dimethyl-di-n-butoxysilane, dimethyl-di-sec-butoxysilane, dimethyl-di- tert-butoxysilane, dimethyldiphenoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, diethyl-di-n-propoxysilane, diethyl-di-iso-propoxysilane,
Diethyl-di-n-butoxysilane, diethyl-di-sec-butoxysilane, diethyl-di-tert-butoxysilane, diethyldiphenoxysilane, di-n-propyldimethoxysilane, di-n-propyldiethoxysilane, di -N-propyl-di-n-propoxysilane, di-n-propyl-di-iso-propoxysilane, di-n-propyl-di-n-butoxysilane, di-n-propyl-di-sec-butoxysilane Di-n-propyl-di-tert-butoxysilane, di-n-propyl-di-phenoxysilane, di-iso-propyldimethoxysilane, di-iso-propyldiethoxysilane, di-iso-propyl-di- n-propoxysilane, di-iso-propyl-di-iso-propoxysilane, di-iso-propyl Pil-di-n-butoxysilane, di-iso-propyl-di-sec-butoxysilane, di-iso-propyl-di-tert-butoxysilane, di-iso-propyl-di-phenoxysilane, di-n- Butyldimethoxysilane, di-n-butyldiethoxysilane, di-n-butyl-di-n-propoxysilane, di-n-butyl-di-iso-propoxysilane, di-n-butyl-di-n-butoxy Silane, di-n-butyl-di-sec-butoxysilane, di-n-butyl-di-tert-butoxysilane, di-n-butyl-di-phenoxysilane, di-sec-butyldimethoxysilane, di-sec -Butyldiethoxysilane, di-sec-butyl-di-n-propoxysilane, di-sec-butyl-di-iso-propoxysilane, -Sec-butyl-di-n-butoxysilane, di-sec-butyl-di-sec-butoxysilane, di-sec-butyl-di-tert-butoxysilane, di-sec-butyl-di-phenoxysilane, di -Tert-butyldimethoxysilane, di-tert-butyldiethoxysilane, di-tert-butyl-di-n-propoxysilane, di-tert-butyl-di-iso-propoxysilane, di-tert-butyl-di- n-butoxysilane, di-tert-butyl-di-sec-butoxysilane, di-tert-butyl-di-tert-butoxysilane, di-tert-butyl-di-phenoxysilane, diphenyldimethoxysilane, diphenyl-di- Ethoxysilane, diphenyl-di-n-propoxysilane, diphenyl-di-i so-propoxysilane, diphenyl-di-n-butoxysilane, diphenyl-di-sec-butoxysilane, diphenyl-di-tert-butoxysilane, diphenyldiphenoxysilane, divinyltrimethoxysilane;
Can be preferably mentioned in terms of reactivity and heat resistance, transparency, and stripping solution resistance of the resulting interlayer insulating film or microlens.

  Specific examples of the component (A) preferably used in the present invention include, for example, methyltrimethoxysilane / phenyltrimethoxysilane cocondensate, methyltrimethoxysilane / γ-glycidoxypropyltrimethoxysilane cocondensate, methyltrimethoxysilane, Examples include methoxysilane / γ-mercaptopropyltrimethoxysilane cocondensate.

  The component (A) is synthesized by hydrolyzing or further condensing the organosilane represented by the above formula (1) in a solvent or without a solvent, preferably in a solvent, preferably in the presence of a catalyst. can do.

  Examples of the solvent that can be used for the synthesis of the component (A) include alcohol, ether, glycol ether, ethylene glycol monoalkyl ether acetate, diethylene glycol, diethylene glycol monoalkyl ether acetate, propylene glycol monoalkyl ether, propylene glycol alkyl ether acetate. , Propylene glycol alkyl ether propionate, aromatic hydrocarbon, ketone, ester and the like.

Specific examples thereof include alcohols such as methanol, ethanol, benzyl alcohol, 2-phenylethyl alcohol, and 3-phenyl-1-propanol;

Tetrahydrofuran as ether;
Examples of glycol ethers include ethylene glycol monomethyl ether and ethylene glycol monoethyl ether;
Examples of ethylene glycol monoalkyl ether acetate include methyl cellosolve acetate, ethyl cellosolve acetate, ethylene glycol monobutyl ether acetate, and ethylene glycol monoethyl ether acetate;
Examples of diethylene glycol include diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, and diethylene glycol ethyl methyl ether.
Examples of diethylene glycol monoalkyl ether acetate include diethylene glycol monoethyl ether acetate;
Examples of propylene glycol monoalkyl ethers include propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether;
As propylene glycol monoalkyl ether propionate, for example, propylene glycol monomethyl ether propionate, propylene glycol monoethyl ether propionate, propylene glycol monopropyl ether propionate, propylene glycol monobutyl ether propionate, etc .;
As propylene glycol monoalkyl ether acetate, for example, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate and the like;
Aromatic hydrocarbons such as toluene, xylene, etc .;
Examples of ketones include methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, and 4-hydroxy-4-methyl-2-pentanone;
Examples of esters include methyl acetate, ethyl acetate, propyl acetate, butyl acetate, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, methyl hydroxyacetate, hydroxy Ethyl acetate, hydroxybutyl acetate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, methyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, propyl 3-hydroxypropionate, butyl 3-hydroxypropionate, 2-hydroxy -3-methylbutanoate, methyl methoxyacetate, ethyl methoxyacetate, propyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, propyl ethoxyacetate, butyl ethoxyacetate, propoxy Methyl acetate, ethyl propoxyacetate, propyl propoxyacetate, butyl propoxyacetate, methyl butoxyacetate, ethyl butoxyacetate, propyl butoxyacetate, butylbutoxyacetate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, 2-methoxypropionic acid Propyl, butyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, propyl 2-ethoxypropionate, butyl 2-ethoxypropionate, methyl 2-butoxypropionate, ethyl 2-butoxypropionate Propyl 2-butoxypropionate, butyl 2-butoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, 3-methoxypropyl Butyl pionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, propyl 3-ethoxypropionate, butyl 3-ethoxypropionate, methyl 3-propoxypropionate, ethyl 3-propoxypropionate, 3-propoxypropion Examples thereof include propyl acid, butyl 3-propoxypropionate, methyl 3-butoxypropionate, ethyl 3-butoxypropionate, propyl 3-butoxypropionate, butyl 3-butoxypropionate, and the like.

  Of these solvents, ethylene glycol alkyl ether acetate, diethylene glycol, propylene glycol monoalkyl ether or propylene glycol alkyl ether acetate are preferred, and in particular, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol methyl. Ether acetate or methyl 3-methoxypropionate is preferred.

  As a usage-amount of a solvent, it is preferable to set it as the quantity from which the total amount of the organosilane represented by the said Formula (1) in a reaction solution will be 40 to 100 weight%, and it shall be 50 to 100 weight%. It is more preferable.

  The hydrolysis and condensation reaction for synthesizing the component (A) is preferably an acid catalyst (for example, hydrochloric acid, sulfuric acid, nitric acid, formic acid, oxalic acid, acetic acid, trifluoroacetic acid, maleic acid, trifluoromethanesulfonic acid, acidic ion exchange) Resins, various Lewis acids, etc.) or basic catalysts (eg, nitrogen-containing aromatic compounds such as ammonia, primary amines, secondary amines, tertiary amines, pyridine; basic ion exchange resins; water such as sodium hydroxide) Oxides; carbonates such as potassium carbonate; carboxylates such as sodium acetate; various Lewis bases). The amount of the catalyst used is preferably 1 mol or less, more preferably 0.0001 to 0.5 mol, based on 1 mol of the total organosilane represented by the above formula (1).

  The amount of water used, the reaction temperature and the reaction time are appropriately set. For example, the following conditions can be adopted.

The amount of water used is preferably 0.001 to 10 mol, more preferably 0.01 to 8 mol, and still more preferably, relative to 1 mol of the group R ¹ in the organosilane represented by the above formula (1). Is an amount of 0.05 to 6 mol.

  The reaction temperature is preferably 5 to 100 ° C, more preferably 5 to 80 ° C.

  The reaction time is preferably 10 minutes to 10 hours, more preferably 30 to 8 hours.

  The hydrolysis and condensation reaction may be carried out in one step by adding the organosilane represented by the above formula (1) and water at one time, or the organosilane and water represented by the above formula (1) may be performed in stages. The hydrolysis and condensation reaction may be carried out in multiple stages by adding them periodically.

  (A) The polystyrene conversion weight average molecular weight (henceforth "Mw") of a component becomes like this. Preferably it is 300-100000, More preferably, it is 400-80000. If Mw is less than 300, shrinkage due to thermosetting may be large and cracks may easily occur. On the other hand, if Mw exceeds 10,000, control during polymerization may be difficult and gelation may occur.

<(B) Resin>
The resin (B) used in the present invention is a resin having an amide group and / or an oxazoline group, and is an alicyclic polyamide, aromatic polyamide, polyamideimide, polyacrylamide, polymethacrylamide, poly (N-methylacrylamide). ), Poly (N-methylmethacrylamide), poly (N, N-dimethylacrylamide), poly (N, N-dimethylmethacrylamide), poly (N-ethylacrylamide), poly (N-ethylmethacrylamide), poly (N, N-diethylacrylamide), poly (N, N-diethylmethacrylamide), poly (N-isopropylpolyacrylamide), poly (diacetoneacrylamide), poly (N-methylolacrylamide), poly (N-methylolmethacrylate) Amide), polyoxazoline, 2 Methyl polyoxazoline, at least one resin selected from the group consisting of 2-ethyl-polyoxazoline, and poly (N- vinylpyrrolidone). Preferably, it is at least one resin selected from the group consisting of polyacrylamide, poly (N, N-dimethylacrylamide), poly (N-vinylpyrrolidone), and polyoxazoline, particularly preferably polyacrylamide and poly (N-vinyl). Pyrrolidone) and at least one resin selected from the group consisting of polyoxazolines. The weight average molecular weight of the resin (B) used in the present invention by gel permeation column chromatography in terms of polystyrene is 500 to 150,000, preferably 700 to 100,000.

  The use ratio of the resin (B) is preferably 0.1 to 20 parts by weight, more preferably 1 to 10 parts by weight with respect to 100 parts by weight of the component (A). If this ratio is less than 0.1 parts by weight, the melt shape may not be controlled, and if it exceeds 20 parts by weight, the resolution may be lowered.

<(C) Quinonediazide compound>
The component (C) used in the present invention is a 1,2-quinonediazide compound that generates a carboxylic acid upon irradiation with radiation, and is a phenolic compound or an alcoholic compound (hereinafter referred to as “base having a hydroxyl group”) or. A condensate of a mother nucleus having an amino group and 1,2-naphthoquinonediazidesulfonic acid halide can be used.

  Examples of the mother nucleus having a hydroxyl group include trihydroxybenzophenone, tetrahydroxybenzophenone, pentahydroxybenzophenone, hexahydroxybenzophenone, (polyhydroxyphenyl) alkane, and other mother nucleus having a hydroxyl group.

Specific examples thereof include trihydroxybenzophenone such as 2,3,4-trihydroxybenzophenone and 2,4,6-trihydroxybenzophenone;
As tetrahydroxybenzophenone, 2,2 ′, 4,4′-tetrahydroxybenzophenone, 2,3,4,3′-tetrahydroxybenzophenone, 2,3,4,4′-tetrahydroxybenzophenone, 2,3,4 2,2'-tetrahydroxy-4'-methylbenzophenone, 2,3,4,4'-tetrahydroxy-3'-methoxybenzophenone, etc .;
Examples of pentahydroxybenzophenone include 2,3,4,2 ′, 6′-pentahydroxybenzophenone;
Examples of hexahydroxybenzophenone include 2,4,6,3 ′, 4 ′, 5′-hexahydroxybenzophenone, 3,4,5,3 ′, 4 ′, 5′-hexahydroxybenzophenone and the like;
Examples of (polyhydroxyphenyl) alkanes include bis (2,4-dihydroxyphenyl) methane, bis (p-hydroxyphenyl) methane, tri (p-hydroxyphenyl) methane, and 1,1,1-tri (p-hydroxyphenyl). ) Ethane, bis (2,3,4-trihydroxyphenyl) methane, 2,2-bis (2,3,4-trihydroxyphenyl) propane, 1,1,3-tris (2,5-dimethyl-4) -Hydroxyphenyl) -3-phenylpropane, 4,4 '-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol, bis (2,5-dimethyl- 4-hydroxyphenyl) -2-hydroxyphenylmethane, 3,3,3 ′, 3′-tetramethyl-1,1′-spirobiindene-5 6,7,5 ′, 6 ′, 7′-hexanol, 2,2,4-trimethyl-7,2 ′, 4′-trihydroxyflavan and the like;
Examples of other mother nucleus having a hydroxyl group include 2-methyl-2- (2,4-dihydroxyphenyl) -4- (4-hydroxyphenyl) -7-hydroxychroman, 2- [bis {(5-isopropyl-4 -Hydroxy-2-methyl) phenyl} methyl], 1- [1- (3- {1- (4-hydroxyphenyl) -1-methylethyl} -4,6-dihydroxyphenyl) -1-methylethyl]- 3- (1- (3- {1- (4-hydroxyphenyl) -1-methylethyl} -4,6-dihydroxyphenyl) -1-methylethyl) benzene, 4,6-bis {1- (4- And hydroxyphenyl) -1-methylethyl} -1,3-dihydroxybenzene.

  Examples of the mother nucleus having an amino group include compounds in which the hydroxyl group of the mother nucleus having the hydroxyl group is substituted with an amino group.

  Among these mother nuclei, 2,3,4,4′-tetrahydroxybenzophenone, 4,4 ′-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] Bisphenol is preferred.

  As the 1,2-naphthoquinone diazide sulfonic acid halide, 1,2-naphthoquinone diazide sulfonic acid chloride is preferable, and specific examples thereof include 1,2-naphthoquinone diazide-4-sulfonic acid chloride and 1,2-naphthoquinone diazide- 5-sulfonic acid chloride can be mentioned, and among these, 1,2-naphthoquinonediazide-5-sulfonic acid chloride is preferably used.

  In the condensation reaction, 1 corresponds to preferably 30 to 85 mol%, more preferably 50 to 70 mol%, based on the number of hydroxyl groups in the phenolic compound or alcoholic compound or the number of amino groups in the mother nucleus having an amino group. , 2-Naphthoquinonediazide sulfonic acid halide can be used.

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

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

  (C) The usage-amount of a component becomes like this. Preferably it is 15-40 weight part with respect to 100 weight part of (A) component, More preferably, it is 25-35 weight part. When this ratio is less than 15 parts by weight, the difference in solubility between the irradiated part and the unirradiated part in the alkaline aqueous solution that is the developer is small, and patterning may be difficult. Alternatively, the heat resistance and solvent resistance of the microlens may be insufficient. On the other hand, when this ratio exceeds 40 parts by weight, the solubility in the alkaline aqueous solution becomes excessive in the radiation-irradiated part, and the development speed may not be controlled, or the sensitivity may be too fast and difficult to control.

  In addition, it is known that the light transmittance of the cured film obtained by adding a 1,2-quinonediazide compound is impaired. In the composition for forming an interlayer insulating film or microlens using a conventionally known acrylic resin or phenol resin, a desired radiation sensitivity cannot be obtained unless a large amount of this 1,2-quinonediazide compound is added. There was a limit in improving the light transmittance of the resulting cured film. However, the radiation-sensitive resin composition of the present invention can achieve high radiation sensitivity with a small amount of (B) 1,2-quinonediazide compound as compared with the conventional one as described above, and thus has a high light transmittance. An advantage is that the film can be formed with high radiation sensitivity. The amount of the (B) 1,2-quinonediazide compound used in the radiation sensitive resin composition of the present invention can be further 30 parts by weight or less with respect to 100 parts by weight of the component (A).

Other components The positive-type radiation-sensitive resin composition of the present invention contains the above-mentioned component (A), component (B) and component (C) as essential components. (E) Adhesion aid, (F) solvent, (G) additive, etc. can be contained.

<(D) Crosslinking agent>
The crosslinking agent for component (D) is preferably at least one selected from the group consisting of (d1) a compound having an alkyl etherified amino group, (d2) an epoxy resin, and (d3) an oxetane resin.

[(D1) Compound having alkyl etherified amino group]
The compound (d1) having an alkyl etherified amino group is preferably a compound having at least two alkyl etherified amino groups in the molecule. In particular,
Nitrogen-containing compounds obtained by alkyl etherifying all or part of active methylol groups such as (poly) methylolated melamine, (poly) methylolated glycoluril, (poly) methylolated benzoguanamine, (poly) methylolated urea, and more specifically Examples include hexamethoxymethylated melamine, hexabutoxymethylated melamine, tetramethoxymethylated glycoluril, and tetrabutoxymethylated glycoluril.

  These alkyl etherified amino group-containing compounds (d1) can be used alone or in combination of two or more.

  In the composition of the present invention, the compounding amount of the compound (d1) having an alkyl etherified amino group is preferably 1 to 30 parts by weight, more preferably 100 parts by weight of the component (A). 2 to 20 parts by weight. When the blending amount is in the above range, crosslinking can be promoted while maintaining the resolution.

[(D2) Epoxy resin]
Examples of the epoxy resin (d2) used in the present invention include bisphenol A type epoxy, bisphenol F type epoxy, hydrogenated bisphenol A type epoxy, hydrogenated bisphenol F type epoxy, bisphenol S type epoxy, brominated bisphenol A type epoxy, biphenyl. Type epoxy, naphthalene type epoxy, fluorene type epoxy, spiro ring type epoxy, bisphenol alkane epoxy, phenol novolac type epoxy, orthocresol novolak type epoxy, brominated cresol novolak type epoxy, trishydroxymethane type epoxy, tetraphenylolethane type Examples thereof include epoxy, alicyclic epoxy, alcohol type epoxy, and aliphatic-aromatic type epoxy.

  In the composition of the present invention, the amount of the epoxy resin (d2) is preferably 1 to 30 parts by weight, more preferably 2 to 20 parts by weight with respect to 100 parts by weight of the component (A). If the blending amount is less than 1 part by weight, the crosslinking effect is not observed, and if the blending amount exceeds 30 parts by weight, the resolution may be lowered.

[(D3) Oxetanyl group-containing compound]
The oxetanyl group-containing compound has one or more oxetanyl groups in the molecule. Specific examples include compounds represented by the following formulas (A) to (C).

[In each of the formulas (A), (B) and (C), R ⁵ is an alkyl group such as a methyl group, an ethyl group or a propyl group, and R ⁶ is an alkylene such as a methylene group, an ethylene group or a propylene group. R ⁷ is an alkyl group such as a methyl group, an ethyl group, a propyl group or a hexyl group; an aryl group such as a phenyl group or a xylyl group; a dimethylsiloxane residue represented by the following formula (i); a methylene group; An alkylene group such as an ethylene group or a propylene group; a phenylene group; or a group represented by the following formulas (ii) to (vi): i is an integer of 1 to 4, which is equal to the valence of R ⁷ . ]

In the formula, x and y are integers of 0 to 50, and Z is a single bond or —CH ₂ —, —C (CH ₃ ) ₂ —, —C (CF ₃ ) ₂ —, or —SO ₂ —. It is a divalent group.

  Examples of the compounds represented by the above formulas (A) to (C) include bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene (trade name “XDO” manufactured by Toagosei Co., Ltd.), bis [(3-ethyl -3-Oxetanylmethoxy) methyl-phenyl] methane, bis [(3-ethyl-3-oxetanylmethoxy) methyl-phenyl] ether, bis [(3-ethyl-3-oxetanylmethoxy) methyl-phenyl] propane, bis [ (3-ethyl-3-oxetanylmethoxy) methyl-phenyl] sulfone, bis [(3-ethyl-3-oxetanylmethoxy) methyl-phenyl] ketone, bis [(3-ethyl-3-oxetanylmethoxy) methyl-phenyl] Hexafluoropropane, tri [(3-ethyl-3-oxetanylmethoxy) methyl] benzene, teto [(3-ethyl-3-oxetanylmethoxy) methyl] benzene, and there can be mentioned the compounds represented by the following chemical formula (D) ~ (H).

  In addition to these compounds, compounds having a high molecular weight polyvalent oxetane ring can also be used. Specific examples include oxetane oligomers (trade name “Oligo-OXT” manufactured by Toagosei Co., Ltd.) and compounds represented by the following chemical formulas (I) to (K).

  In the formula, p, q and s are each independently an integer of 0 to 10,000.

  Among the above, 1,4-bis {[(3-ethyloxetane-3-yl) methoxy] methyl} benzene (manufactured by Toagosei Co., Ltd., trade name: OXT-121), 3-ethyl-3-{[ (3-Ethyloxetane-3-yl) methoxy] methyl} oxetane (manufactured by Toagosei Co., Ltd., trade name: OXT-221) is preferred.

  In the composition of the present invention, the amount of the oxetanyl group-containing compound (d3) is preferably 1 to 30 parts by weight, more preferably 2 to 20 parts by weight, based on 100 parts by weight of the component (A). is there. When the blending amount is in the above range, crosslinking can be promoted while maintaining the resolution.

<(E) Adhesion aid>
In the positive radiation sensitive resin composition of the present invention, (E) an adhesion assistant can be used to improve the adhesion to the substrate.

  As such (E) adhesion assistant, a functional silane coupling agent is preferably used. For example, a silane coupling agent or isocyanurate having a reactive substituent such as a carboxyl group, a methacryloyl group, an isocyanate group or an epoxy group. Examples include a silane coupling agent having a ring. Specifically, trimethoxysilylbenzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, tris (3- (trimethoxysilyl) propyl) isocyanurate and the like. Such (E) adhesion assistant is preferably used in an amount of 20 parts by weight or less, more preferably 10 parts by weight or less, relative to 100 parts by weight of component (A). In the case where the amount of the adhesion assistant exceeds 20 parts by weight, there may be a case where development residue is likely to occur in the development process.

<(F) Solvent>
Examples of the solvent (F) used in the present invention include those that can uniformly dissolve the component (A) and each component and that do not react with each component. As such a solvent, the solvent similar to the solvent used when manufacturing (A) component can be used. Also, N-methylformamide, N, N-dimethylformamide, N-methylformanilide, N-methylacetamide, N, N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, benzylethyl ether, dihexyl ether, acetonylacetone , Isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, phenyl cellosolve acetate, etc. High boiling solvents can also be used.

  Among these, from the viewpoint of solubility, reactivity with each component, and ease of resin film formation, alkyl ethers of polyhydric alcohols such as ethylene glycol monoethyl ether and diethylene glycol monomethyl ether; ethylene glycol monoethyl ether acetate, Alkyl ether acetates of polyhydric alcohols such as propylene glycol monomethyl ether acetate; esters such as ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, ethyl 2-hydroxypropionate and ethyl lactate; ketones such as diacetone alcohol Are preferred.

  The said solvent can be used individually by 1 type or in mixture of 2 or more types. Moreover, the usage-amount of a solvent can be suitably determined according to a use, a coating method, etc.

<(G) Additive>
Examples of the additive that can be added to the positive radiation-sensitive resin composition of the present invention include (g) a phenol compound, a surfactant, and a thermal acid generator.

<Phenol compound (g)>
The phenol compound (g) that can be used in the photosensitive insulating resin composition of the present invention is a low molecular weight compound having a phenolic hydroxyl group, and can improve the sensitivity of the positive radiation sensitive resin composition.

  Examples of the phenol compound (g) include 4,4′-dihydroxydiphenylmethane, 4,4′-dihydroxydiphenyl ether, tris (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane. , Tris (4-hydroxyphenyl) ethane, 1,3-bis [1- (4-hydroxyphenyl) -1-methylethyl] benzene, 1,4-bis [1- (4-hydroxyphenyl) -1-methyl Ethyl] 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, 1,1,2,2-tetra (4-hydroxyphenyl) Such as ethane.

  The phenol compound (g) is preferably used in an amount of 1 to 200 parts by weight, more preferably 2 to 100 parts by weight, and particularly preferably 5 to 50 parts by weight with respect to 100 parts by weight of the resin (A). Can do. By containing a phenol compound (g) in the said range, the composition which expresses sufficient resolution is obtained.

<Surfactant>
Surfactants are used to improve coatability. As the surfactant, a fluorine-based surfactant, a silicone-based surfactant, and a nonionic surfactant can be suitably used.

  Specific examples of the fluorosurfactant include 1,1,2,2-tetrafluorooctyl (1,1,2,2-tetrafluoropropyl) ether, 1,1,2,2-tetrafluorooctylhexyl ether. , Octaethylene glycol di (1,1,2,2-tetrafluorobutyl) ether, hexaethylene glycol (1,1,2,2,3,3-hexafluoropentyl) ether, octapropylene glycol di (1,1 , 2,2-tetrafluorobutyl) ether, hexapropylene glycol di (1,1,2,2,3,3-hexafluoropentyl) ether, sodium perfluorododecyl sulfonate, 1,1,2,2,3 , 3,9,9,10,10-decafluorododecane, 1,1,2,2,3,3-hexafluorodecane, etc., and fluoroalkyl Sodium Nzensuruhon acid; fluoroalkyl polyoxyethylene ethers; fluoroalkyl ammonium iodide, fluoroalkyl polyoxyethylene ethers, perfluoroalkyl polyoxyethylene ethanol; perfluoroalkyl alkoxylate; fluorine-based alkyl ester, and the like.

  These commercial products include BM-1000, BM-1100 (manufactured by BM Chemie), MegaFuck F142D, F172, F173, F183, F178, F191, F191 (and above, Dainippon Ink). Chemical Industries, Ltd.), Fluorad FC-170C, FC-171, FC-430, FC-431 (above, manufactured by Sumitomo 3M), Surflon S-112, S-113, S-131, S-141, S-145, S-382, SC-101, SC-102, SC-103, SC-104, SC-105, SC-106 (manufactured by Asahi Glass Co., Ltd.) ), F-top EF301, 303, and 352 (manufactured by Shin-Akita Kasei Co., Ltd.).

  Examples of the silicone surfactant include DC3PA, DC7PA, FS-1265, SF-8428, SH11PA, SH21PA, SH28PA, SH29PA, SH30PA, SH-190, SH-193, SZ-6032 (above, Toray Dow Corning)・ Silicon Co., Ltd.), TSF-4440, TSF-4300, TSF-4445, TSF-4446, TSF-4460, TSF-4442 (above, GE Toshiba Silicone Co., Ltd.) are commercially available. You can list what you have.

  Examples of the nonionic surfactant include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, and polyoxyethylene oleyl ether; polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether Polyoxyethylene aryl ethers such as polyoxyethylene dilaurate, polyoxyethylene dialkyl esters such as polyoxyethylene distearate, etc .; (meth) acrylic acid copolymer polyflow Nos. 57 and 95 (Kyoeisha Chemical Co., Ltd.) ))) Can be used.

  These surfactants can be used alone or in combination of two or more.

  These surfactants are preferably used in an amount of 5 parts by weight or less, more preferably 2 parts by weight or less based on 100 parts by weight of component (A). When the usage-amount of surfactant exceeds 5 weight part, when forming a coating film on a board | substrate, the film peeling of a coating film may arise easily.

<Heat acid generator>
The thermal acid generator is used to promote crosslinking of the hydrolyzate of (A) organosilane and / or its condensate by heat. Although it does not specifically limit as a thermal acid generator, The aromatic sulfonium type | system | group thermal acid generator shown to following formula (L) can be used suitably. Moreover, the decomposition temperature of a thermal acid generator becomes like this. Preferably it is 100-250 degreeC, More preferably, it is 120-230 degreeC, More preferably, it is 130-200 degreeC.

(In the formula, R represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a group represented by the following formula (M). X represents an anionic species selected from hexafluorophosphate, triflate, and bis (trifluoromethanesulfonyl) imide. Is shown.)

<Preparation of positive radiation sensitive resin composition>
The positive-type radiation-sensitive resin composition of the present invention is prepared by uniformly mixing the above-mentioned component (A), component (B) and component (C) and other components optionally added. The positive radiation-sensitive resin composition of the present invention is preferably used in a solution state after being dissolved in the appropriate solvent. For example, a positive radiation-sensitive resin composition in a solution state is prepared by mixing the component (A), the component (B) and the component (C) and other components optionally added at a predetermined ratio. be able to.

  When preparing the positive radiation sensitive resin composition of the present invention in a solution state, components other than the solvent in the solution (that is, (A) component, (B) component and (C) component and optionally added) The ratio (solid content concentration) of the total amount of other components can be arbitrarily set according to the purpose of use, the desired film thickness, etc., but is preferably 5 to 50% by weight, more preferably 10%. -40% by weight, more preferably 15-35% by weight.

  The composition solution thus prepared may be used after being filtered using a Millipore filter having a pore size of about 0.2 μm.

[Method of forming microlenses]
Next, a method for forming the microlens of the present invention using the radiation sensitive resin composition of the present invention will be described. The method for forming a microlens of the present invention includes the following steps in the order described below.

(1) forming a film of the positive radiation sensitive resin composition on a substrate;
(2) A step of irradiating at least a part of the coating with radiation,
(3) A step of developing the film after irradiation and heating it to obtain a cured product.

  Hereinafter, each step of the method for forming a microlens of the present invention will be described in detail.

(1) In the step (1) of forming a film of the positive radiation sensitive resin composition of the present invention on a substrate, the composition solution of the present invention is applied to the substrate surface, preferably by pre-baking. The solvent is removed to form a film of the radiation sensitive resin composition.

  Examples of the substrate that can be used include a glass substrate, a silicon substrate, and a substrate on which various metals are formed.

  The method of applying the composition solution is not particularly limited, and an appropriate method such as a spray method, a roll coating method, a spin coating method (spin coating method), a slit die coating method, a bar coating method, an ink jet method, or the like is employed. In particular, a spin coating method or a slit die coating method is preferable. Prebaking conditions vary depending on the type of each component, the proportion of use, and the like. For example, it can be set at 60 to 110 ° C. for about 30 seconds to 15 minutes.

  As a film thickness of the film formed, for example, 0.5 to 3 μm is preferable as a value after pre-baking.

(2) In the step (2) of irradiating at least a part of the coating, at least a part of the coating formed as described above is irradiated with radiation. In order to irradiate a part of the film with radiation, for example, a method of irradiating radiation through a mask having a predetermined pattern can be used.

  Thereafter, patterning is performed by developing with a developer to remove the irradiated portion. Examples of the radiation used at this time include ultraviolet rays, far ultraviolet rays, X-rays, and charged particle beams.

  Examples of the ultraviolet rays include radiation containing g-line (wavelength 436 nm), i-line (wavelength 365 nm), and the like. Examples of the far ultraviolet light include KrF excimer laser. Examples of X-rays include synchrotron radiation. Examples of the charged particle beam include an electron beam.

  Among these, ultraviolet rays are preferable, and radiation containing g-line and / or i-line is particularly preferable.

The dose of radiation as (exposure amount), 50~1,500J / m ² In the case of forming an interlayer insulating film, in the case of forming the microlenses and 50~2,000J / m ² It is preferable to do.

(3) Developing the film after irradiation and heating it to obtain a cured product Step (3) The developer used in the development treatment is, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, silica. Sodium acid, sodium metasilicate, ammonia, ethylamine, n-propylamine, diethylamine, diethylaminoethanol, di-n-propylamine, triethylamine, methyldiethylamine, dimethylethanolamine, triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxy An aqueous solution of an alkali (basic compound) such as pyrrole, pyrrole, piperidine, 1,8-diazabicyclo [5.4.0] -7-undecene, 1,5-diazabicyclo [4.3.0] -5-nonane. Can be used In addition, an aqueous solution obtained by adding an appropriate amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant to the above aqueous alkali solution, or various organic solvents that dissolve the composition of the present invention can be used as a developing solution.

  As a developing method, for example, an appropriate method such as a liquid filling method, a dipping method, a rocking dipping method, a shower method, or the like can be used. The development time at this time varies depending on the composition of the composition, but can be, for example, 30 to 120 seconds.

The patterned thin film is preferably subjected to a rinsing process by, for example, washing with running water, and further preferably irradiated with a high-pressure mercury lamp or the like on the entire surface (post-exposure), thereby remaining 1,2- After performing the decomposition treatment of the quinone diazide compound, the thin film is subjected to a heat treatment (post-bake treatment) with a heating device such as a hot plate or an oven, whereby the thin film is cured. Exposure at the later exposure step is preferably 2,000~5,000J / m ^2. Moreover, the baking temperature in this hardening process is 120 degreeC or more and less than 250 degreeC, for example. Although heating time changes with kinds of heating apparatus, for example, when performing heat processing on a hotplate, it can be set to 30 to 90 minutes when performing heat processing in oven, for example. At this time, a step baking method or the like in which a heating process is performed twice or more can also be used. In this way, a patterned thin film corresponding to the target microlens can be formed on the surface of the substrate.

[Microlens]
The microlens of the present invention formed as described above is excellent in heat resistance and has a good melt shape, as will be apparent from examples described later, and is used as a microlens for a solid-state imaging device. It can be suitably used.

[Solid-state imaging device]
A solid-state imaging device can be manufactured by a known method using the microlens of the present invention formed as described above.

[Synthesis Example 1]
[Synthesis of Polysiloxane A1]
In a separable flask equipped with a condenser, 100 g of methyltrimethoxysilane and 230 g of phenyltrimethoxysilane were dissolved and then stirred with a three-one motor to stabilize the solution temperature at 60 ° C. Next, 80 g of ion-exchanged water in which 1.5 g of maleic acid was dissolved was added to the solution over 30 minutes. Then, after making it react at 60 degreeC for 3 hours, the reaction liquid was cooled to room temperature. Add 200 g of propylene glycol monopropyl ether and remove the water that was not used in the reaction in the evaporator and the process of removing methanol generated from the reaction three times to obtain a polysiloxane A1 resin solution (solid content concentration 40 wt%). Obtained. Polysiloxane A1 had a polystyrene equivalent weight average molecular weight Mw of 3,100.

[Synthesis Example 2]
[Synthesis of Polysiloxane A2]
In a separable flask equipped with a condenser, 100 g of methyltrimethoxysilane and 100 g of phenyltrimethoxysilane were dissolved and then stirred with a three-one motor to stabilize the solution temperature at 60 ° C. Next, 50 g of ion-exchanged water in which 0.4 g of maleic acid was dissolved was added to the solution over 30 minutes. Then, after making it react at 60 degreeC for 3 hours, the reaction liquid was cooled to room temperature. Add 250 g of propylene glycol monopropyl ether and remove the water not used for the reaction in the evaporator and the methanol generated from the reaction three times to obtain a polysiloxane A2 resin solution (solid content concentration 40 wt%). Obtained. Polysiloxane A2 had a weight average molecular weight Mw in terms of polystyrene of 4500.

[Comparative Synthesis Example 1]
[Adjustment of a1]
Marcalinker M (manufactured by Maruzen Petrochemical Co., Ltd.) was dissolved in diethylene glycol dimethyl ether to obtain a resin solution of a1 (solid content concentration: 43%).

[Adjustment Example 1]
[Adjustment of B1]
A step of adding 100 g of isopropyl alcohol to 100 g of polyoxazoline (trade name “Epocross WS-500”, 40% solid solution by Nippon Shokubai Co., Ltd.) and removing water with an evaporator three times to obtain a resin solution of B1 (solid A partial concentration of 40%).

[Adjustment Example 2]
[Adjustment of B2]
The process of adding 100 g of isopropyl alcohol to 100 g of polyacrylamide (manufactured by Wako Pure Chemical Industries, Ltd., solid content concentration 50%) and removing water with an evaporator is performed three times to obtain a resin solution of B2 (solid content concentration 40%). It was.

[Example 1]
The amount of A1 resin solution corresponding to 16 g (solid content) of A1, 4,4 ′-[1- [4- [1- (4-hydroxyphenyl) -1-methylethyl] phenyl] as phenol compound g1 Ethylidene] bisphenol 4 g, B1 resin solution 2.5 g (solid content 1.0 g), adhesion assistant E1 β- (3,4 epoxycyclohexyl) ethyltrimethoxysilane 1 g, additive G1 trimethyl orthoformate 1 g, 1,1-bis (4-hydroxyphenyl) -1- [4- [1- (4-hydroxyphenyl) -1-methylethyl] phenyl] ethane and 1,2-naphthoquinonediazide-5-sulfone as quinonediazide compound C1 2.5 g condensate with acid, 1 g of methylated melamine resin MW-100 manufactured by Sanwa Chemical Co., Ltd. as crosslinker D1, and 0.2 g of SH-28PA manufactured by Toray Dow Corning Silicone Co., Ltd. diluted to 1% solid content with lenglycol monomethyl ether, and 0.6 g of thermal acid generator as additive G2 were dissolved in 88.8 g of ethyl lactate as solvent F1. The mixture was filtered through a Teflon (registered trademark) filter having a pore diameter of 0.2 μm to obtain a radiation-sensitive composition of Example 1. About this radiation sensitive composition, the resolution, melt property, heat resistance, and glass transition temperature (TGA) were evaluated by the following method. The results are shown in Table 3.

[Examples 2 to 7 and Comparative Examples 1 and 2]
In the same manner as in Example 1, with the compounding ratios shown in Tables 1 and 2, (A) siloxane resin, (a) phenol resin, (B) resin, (C) quinonediazide compound, (D) crosslinking agent, (E) Each radiation-sensitive composition was prepared by dissolving the adhesion assistant, (G) additive and (g) phenolic compound in (F) solvent. About these radiation sensitive compositions, the resolution, melt property, heat resistance, and glass transition temperature (TGA) were evaluated by the following method. The results are shown in Table 3.

<(A) Siloxane resin>
A1: Methyltrimethoxysilane / phenyltrimethoxysilane = 100 g / 2300 g
A2: Methyltrimethoxysilane / phenyltrimethoxysilane = 100 g / 1000 g
<(A) Phenolic resin>
a1: Polyhydroxystyrene (manufactured by Maruzen Petrochemical Co., Ltd., trade name “Marcalinker M”)
<(B) Resin>
B1: Polyoxazoline B2: Polyacrylamide B3: Poly (N-vinylpyrrolidone) [trade name “K-30” manufactured by Wako Pure Chemical Industries, Ltd.]
B4: Poly (N-vinylpyrrolidone) [trade name “K-25” manufactured by Wako Pure Chemical Industries, Ltd.]
<(C) Quinonediazide compound>
C1: 1,1-bis (4-hydroxyrenyl) -1- [4- [1- (4-hydroxyphenyl) -1-methylethyl] phenyl] ethane and 1,2-naphthoquinonediazide-5-sulfonic acid 2.5-Mole Condensate with (D) Crosslinking Agent
D1: Methylated melamine resin [manufactured by Sanwa Chemical Co., Ltd., trade name “Nicarac MW-100”]
D2: Epoxy crosslinking agent [trade name “Epicoat 152” manufactured by Japan Epoxy Resin Co., Ltd.]
<(E) Adhesion aid>
E1: β- (3,4-Epoxycyclohexyl) ethyltrimethoxysilane E2: 4′-hydroxy 2,3,4-trihydroxybenzophenone E3: γ-glycidoxypropyltrimethoxysilane <(F) solvent>
F-1: Ethyl lactate <(G) additive>
G1: methyl orthoformate G2: hexafluorophosphate thermal acid generator [manufactured by Sanshin Chemical Industry Co., Ltd., decomposition temperature 155.5 ° C.]
G3: Surfactant [Toray Dow Corning Silicone Co., Ltd., trade name “SH-28PA”]
<(G) Phenol compound>
g1: 4,4 '-[1- [4- [1- (4-hydroxyrenyl) -1-methylethyl] phenyl] ethylidene] bisphenol [2] Evaluation of radiation-sensitive composition (1) Resolution 6 inches The silicon wafer was spin-coated with the radiation-sensitive composition and heated at 110 ° C. for 3 minutes using a hot plate to produce a uniform resin film having a thickness of 0.35 μm. Thereafter, from a high pressure mercury lamp through a pattern mask (line: 2 μm, space: 0.35 μm, 0.45 μm, 0.55 μm) using a stepper (Nikon Corporation, “NSR2205i12D”, irradiation amount = 180 mJ / cm ² ). Were exposed so that the exposure amount at a wavelength of 365 nm was 500 mJ / cm ² . Next, immersion development was performed at 23 ° C. for 30 seconds using a 2.38 wt% tetramethylammonium hydroxide aqueous solution. And the minimum dimension of the obtained pattern was made into resolution (micrometer).

(2) Melt property A 6-inch silicon wafer was spin-coated with the radiation-sensitive composition and heated at 110 ° C. for 3 minutes using a hot plate to produce a 1.3 μm thick uniform resin coating film. Thereafter, using a stepper (Nikon Corporation, “NSR2205i12D”, irradiation amount = 260 mJ / cm ² ), UV light from a high-pressure mercury lamp through a pattern mask (4 μm square, space 2 μm) has an exposure amount of 500 mJ / cm at a wavelength of 365 nm. It exposed so that it might become ² . Immersion development was performed at 23 ° C. for 30 seconds using a 2.38 wt% tetramethylammonium hydroxide aqueous solution to obtain a pattern of 4 μm square and 2 μm space. Subsequently, each was heated at 100 ° C., 130 ° C., 170 ° C. for 2 minutes with a hot plate, and the melt property of the lens was evaluated using the cross-sectional area of the lens as shown in the schematic diagram of FIG.

  Of the cross-sectional area (A) of the lens, the area of the portion having an independent radius of curvature (B) was determined. 80% or more of (B / A) × 100 (%) can be used as a lens, and less than 80% cannot be used as a lens.

(3) Heat resistance A radiation sensitive composition was spin-coated on a glass substrate. Examples 1 to 5 and Comparative Example 1 were heated on a hot plate at 110 ° C. for 180 seconds, and Comparative Example 2 was heated at 100 ° C. for 90 seconds. A 1.3 μm thick radiation sensitive composition film was formed. Thereafter, Examples 1 to 5 and Comparative Example 1 were developed with a 2.38% aqueous solution of tetramethylammonium hydroxide for 30 seconds, and Comparative Example 2 was developed with a 1% aqueous solution for 30 seconds, washed with water, and then washed with a stepper (manufactured by Nikon Corporation, “ NSR2205i12D ”, irradiation amount = 300 mJ / cm ² ), followed by baking at 170 ° C. for 2 minutes. Thereafter, a heat test was conducted at 150 ° C. for 200 hours. The transmittance at 400 nm before and after the heating test was compared. Similarly, after baking at 170 ° C. for 2 minutes, a heating test was performed at 280 ° C. for 10 minutes, and the transmittance at 400 nm before and after the heating test was compared.

(4) Glass transition temperature (TGA)
The glass transition temperature was measured using a device name TG / DTA300 (manufactured by SEIKO Instruments). A photosensitive silicon composition was spin-coated on a wafer substrate. Examples 1 to 5 and Comparative Example 1 were heated on a hot plate at 110 ° C. for 180 seconds, and Comparative Example 2 was heated at 100 ° C. for 90 seconds to have a thickness of 2 μm. An adhesive composition film was formed. Thereafter, Examples 1 to 5 and Comparative Example were developed with a tetramethylammonium hydroxide 2.38% aqueous solution for 30 seconds, and Comparative Example 2 was developed with a 1% aqueous solution for 30 seconds, washed with water, and then washed with a stepper (“NSR2205i12D, manufactured by Nikon Corporation). ”, Irradiation amount = 300 mJ / cm ² ), followed by baking at 170 ° C. for 2 minutes. 10 μg was taken out from these membranes, and the temperature at which the weight decreased by 5% was measured on a dedicated aluminum pan at a heating rate of 10 ° C./min.

Claims (10)

(A) Hydrolyzate and / or condensate of organosilane represented by the following formula (1)

(In the formula, R ¹ is an alkoxyl group having 1 to 6 carbon atoms or an aryloxy group having 6 to 18 carbon atoms, provided that part or all of the hydrogen atoms of the aryloxy group are halogen atoms, cyano groups, nitro groups or R ² may be substituted by an alkyl group having 1 to 6 carbon atoms, and R ² is an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an aryl group having 6 to 18 carbon atoms, or an allyl group. Provided that a part or all of the hydrogen atoms of the aryl group may be substituted by a halogen atom, a cyano group, a nitro group or an alkyl group having 1 to 6 carbon atoms, and a is an integer of 1 to 4, b is an integer of 0 to 3, provided that a + b = 4.)
(B) polyacrylamide, poly (N- vinylpyrrolidone) and Poriokisazori at least one resin selected from the group consisting of down, and (C) The positive-tone radiation-sensitive resin composition characterized by containing a quinonediazide compound . Wherein (A) relative to 100 parts by weight of component (B) the positive-tone radiation-sensitive resin composition according to claim 1, wherein the component is characterized in that it contains 0.1 to 20 parts by weight. The positive radiation-sensitive resin composition according to claim 1 or 2 , wherein the component (C) is contained in an amount of 15 to 40 parts by weight with respect to 100 parts by weight of the component (A). Furthermore, (D) A crosslinking agent is contained, The positive radiation sensitive resin composition in any one of Claims 1-3 characterized by the above-mentioned. Furthermore, (g) a phenolic compound is contained, The positive radiation sensitive resin composition in any one of Claims 1-4 characterized by the above-mentioned. A microlens formation, the positive-tone radiation-sensitive resin composition according to any of claims 1-5. A interlayer insulating film formed, the positive-tone radiation-sensitive resin composition according to any of claims 1-5. A microlens comprising the positive radiation-sensitive resin composition according to claim 6 . A method for forming a microlens, comprising the following steps in the order described below.
(1) A step of forming a film of the positive radiation sensitive resin composition according to claim 6 on a substrate,
(2) A step of irradiating at least a part of the coating with radiation,
(3) A step of developing the film after irradiation and heating it to obtain a cured product. A microlens formed by the method according to claim 9 .

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