JP2003266451A - Manufacturing method for article having predetermined surface shape - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a manufacturing method for an optical element excellent in the adhesion with a substrate and having high accuracy and a wide composition region and an article having a predetermined surface shape. <P>SOLUTION: A substrate material has a pattern surface, wherein an area with a high wettability and an area with a low wettability are regularly arranged, as a molding surface. A film forming liquid composition is bonded to the molding surface of the substrate material and subsequently cured to manufacture the article having the predetermined surface shape wherein cured matter is formed on the area with a high wettability. The area with a high wettability of the substrate material has a fine uneven surface and the area with a low wettability thereof has a smooth surface. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for manufacturing an optical element or other article having a predetermined surface shape, and more particularly to an optical element such as a microlens array (microlens array), a cylindrical lens array or a Fresnel lens and other predetermined surfaces. The present invention relates to a method of manufacturing an article having a shape.

[0002]

2. Description of the Related Art Micro lens array (micro lens array)
Such optical elements have been widely used in the field of micro optics. With the recent increase in demand for optical components for communication, the necessity thereof is increasing more and more.

As a method of manufacturing such a microlens array, a base material having a pattern in which a large wettability area and a small wettability area are regularly arranged on a surface of the base material is used, and an optical property is provided in the high wettability area. A method is known in which a device forming composition is attached to form convex portions. (JP 20
00-199805)

[0004]

However, in this method, since the lens is formed by the movement of the droplets which depends only on the difference in the surface energy due to the difference in the wettability of the substrate surface, the accuracy of the obtained lens is deteriorated. It is easy and requires higher precision. Further, since a resin such as a photocurable resin or a thermosetting resin is used as the liquid composition for forming an optical element, there is a problem that the selection range of the composition of the optical element is narrow. An object of the present invention is to solve the above-mentioned problems and to provide a method for producing an optical element having a high accuracy and a wide composition range and other articles having a predetermined surface shape.

[0005]

DISCLOSURE OF THE INVENTION The present invention is directed to forming a film on a molding surface of a base material having a pattern surface having a pattern surface in which high wettability areas and low wettability areas are regularly arranged. In a method for producing an article having a predetermined surface shape in which a liquid composition is applied and then the composition is cured to form a cured product in the wettable area, the wettable area of the substrate is fine. A method for manufacturing an article having a predetermined surface shape, which has an uneven surface and the small wettability area has a smooth surface.

First, a method for forming a pattern in which areas having high wettability and areas having low wettability are regularly arranged on the molding surface of the substrate will be described. The areas of high wettability and areas of low wettability of the base material surface in the present invention refer to the areas where the liquid composition for film formation is relatively easy to attach and the areas where it is relatively difficult to attach to the surface of the base material, respectively. .
The liquid composition for film formation has a contact angle A of 90 degrees or less with respect to the surface of the area having a large wettability at any stage after the liquid composition for forming a film is attached to the formed surface and becomes a cured product in the area having a large wettability. And a contact angle B larger than the contact angle A by 5 degrees or more with respect to the surface of the area having a small wettability.

In the present invention, the highly wettable area of the molding surface of the base material has a fine uneven surface. It is preferable that the fine uneven surface has a surface roughness Ra of 10 nm or more and a specific surface area SR of 1.2 or more. And the areas of low wettability have a smooth surface. 5n as a smooth surface
It is preferable to have a surface roughness Ra of m or less and a specific surface area SR of 1.0. More preferably, the highly wettable area has a surface roughness Ra of 10 nm to 50 nm and 1.2 to 20.
It has a specific surface area SR of. And the area of low wettability more preferably has a surface roughness Ra of 2 nm or less.

Here, the surface roughness Ra represents the arithmetic mean roughness Ra defined in JIS B 0601. Specific surface area (S _R ) is S _R =
S / S ₀ [S ₀ : Area when the measurement surface is ideally flat. S: Actual surface area of the measurement surface. ] Is required. The actual surface area (S) of the measuring surface is calculated by dividing the measuring surface into a large number of minute triangles and summing the areas of the respective minute triangles.

This pattern is preferably obtained as follows, for example. A photosensitive solution containing a metal compound capable of being hydrolyzed and polycondensed was used, and the surface roughness R was 5 nm or less.
a and 1.0 are applied to the surface of a base substrate having a specific surface area SR to form a film, and the coating film is irradiated with light in a pattern, for example, via a photomask or by an interference exposure method, After the non-exposed portion of is dissolved and removed with a solvent, the exposed portion of the coating film is brought into contact with warm water. By this, 10 nm
A metal oxide film having the above surface roughness Ra and the specific surface area SR of 1.2 or more is formed on the exposed portion surface of the base substrate,
A pattern is formed because the unexposed partial surface of the base substrate has a surface roughness Ra of 5 nm or less and a specific surface area SR of 1.0. Then, the wettability of the exposed surface (metal oxide film) of the base substrate is increased and the wettability of the unexposed portion is decreased by selecting the materials of the base substrate, the photosensitive solution and the liquid composition for film formation. To do.

As a photosensitive solution containing a hydrolyzable and polycondensable metal compound, a solution containing a compound such as an aluminum alkoxide chelate compound, a titanium alkoxide chelate compound and a zirconium chelate compound is preferably used.

As the photomask, one having a pattern in which light transmitting areas and light shielding areas are regularly arranged is preferably used. The light transmitting area has a diameter of 10 to 500
It can have a shape such as a square, a circle, an ellipse, and a regular hexagon of μm, and it is preferable to match the shape of the bottom surface of an article having a predetermined surface shape to be formed.

The pattern of surface fine irregularities is more preferably formed as follows. A solution containing an aluminum alkoxide chelate compound (hereinafter referred to as "aluminum chelate compound") is applied onto a base substrate having a smooth surface, for example, a glass substrate having a soda-lime silicate glass composition to form a coating film on the substrate, The film is irradiated with light in a pattern through a photomask or by an interference exposure method. The exposed portion of the coating film cleaves and decomposes the chelate bond of the aluminum chelate compound by irradiation light to become a solvent-insoluble alumina. Then, the unexposed portion is dissolved and removed with a solvent to expose the underlying substrate, and then the exposed portion is immersed in warm water to form a large number of squares and other shapes corresponding to the light-transmitting areas of the photomask on the glass substrate. Alumina film is formed, and the surface of the film is 10-5
It has a surface roughness Ra of 0 nm and a specific surface area SR of 1.2 to 20. This alumina film forms an area of the substrate having high wettability, and a film-forming liquid composition such as 2
It has a contact angle A of 90 ° or less with respect to a gelled product (polycondensation product) of phenyltriethoxysilane at 00 ° C., for example, 5 °. The glass substrate exposed by dissolving and removing with a solvent has a surface roughness Ra of 5 nm or less and a specific surface area SR of 1.0.
And has a small wettability, and has a contact angle B with respect to the film-forming liquid composition that is 5 degrees or more larger than the contact angle A, for example, 15 degrees.

The underlying substrate used may have the same composition as the exposed film portion or may have a different composition. As an example of the same composition, the alumina coating layer is partially formed on the surface of the alumina substrate having a smooth surface so that the surface has a surface roughness Ra of 10 to 50 nm and a specific surface area SR of 1.2 to 20. When provided, the film-forming liquid composition, for example, 200 ° C.
The phenylsilsesquioxane sol has a contact angle A of 90 degrees or less with respect to the alumina coating layer and a contact angle of 5 degrees or more with respect to A with respect to the alumina substrate. Therefore, for the phenylsilsesquioxane sol, the alumina coating layer corresponds to the high wettability area and the alumina substrate corresponds to the low wettability area.

Other methods include mechanical methods such as sandblasting and fine polishing, electrical methods such as discharge, plasma, electron beam and ion processing, photochemical methods such as photoetching, optical methods such as laser processing and fluorine. The unevenness may be formed directly on the surface of the base substrate having a smooth surface by a chemical method such as etching with hydrofluoric acid. In this case, as the base substrate having a smooth surface, a material having a contact angle of 90 degrees or less with the applied film-forming liquid composition is used. Further, a method of forming a thin film having fine surface irregularities on the surface of the base substrate by a vapor phase method or a liquid phase method may be used.

Below, a photosensitive solution containing an aluminum alkoxide which is a metal compound capable of being hydrolyzed and polycondensed is applied to the surface of a surface-smooth underlying substrate to form a film,
This coating film is irradiated with light in a pattern, the unexposed portion of the coating film is dissolved and removed with a solvent, and then the exposed portion of the coating film is brought into contact with warm water to give fine irregularities to the surface of the exposed portion. .

The aluminum alkoxide is generally represented by Al (OR) ₃ (R is an alkyl group having up to 4 carbon atoms), aluminum ethoxide, aluminum isopropoxide, aluminum-n-butoxide, aluminum-
Examples include sec-butoxide and aluminum-tert-butoxide. Examples of the chelating agent include acetylacetone, β-diketone compounds such as benzoylacetone, methyl acetoacetate, β-ketoester compounds such as ethyl acetoacetate, and alkanolamines.When acetylacetone is used, The aluminum alkoxide may be acetylacetonated with acetylacetone, or commercially available aluminum acetylacetonate may be used. The chelating agent used is preferably 1 to 3 mol, and more preferably 1.0 to 1 mol, per mol of the aluminum alkoxide.
It is 1.2 mol.

The diluting solvent used to stably prepare the photosensitive solution is preferably selected depending on the stability of the solution, more preferably alcohols, particularly isopropyl alcohol.

As the coating method of the photosensitive solution for forming the coating film, dip coating method, spin coating method, gravure coating method, spraying method, flexographic printing method, flow coating method, brush coating method, roll coating method and casting method. For example, the film thickness after drying can be controlled to, for example, 50 to 400 nm by changing the pulling rate in the dip coating method, the substrate rotation speed and the holding time in the spin coating method, and the viscosity of the coating solution.

The photosensitive coating film formed on the surface of the surface-smooth base material by the above-mentioned method is dried, and the solvent is removed by evaporation. The drying temperature is 10 to 100 ° C. for 10 minutes to 5 hours.
Preferably, it may be dried at 40 to 60 ° C. for 20 minutes to 1 hour. It is also possible to dry at a higher temperature if necessary.

Next, a photomask having a pattern in which light transmitting areas and light shielding areas are regularly arranged is arranged on the photosensitive coating film. Then, light is irradiated through this photomask. Due to this light irradiation, the chelate complex is cleaved in the light-irradiated portion of the coating film to change into an alumina film, so that a pattern structure in which regions having different solubilities in the solvent in the light-irradiated portion and the light-unirradiated portion are periodically present Will be formed. As the light beam used for this light irradiation, light having an absorption maximum wavelength of the aluminum chelate compound is desirable. This absorption maximum wavelength differs depending on the combination of the aluminum alkoxide and the chelate compound of the raw material of the coating solution for film formation. For example, for aluminum-sec-butoxide and ethyl acetoacetate, the wavelength is 270 nm, and for aluminum-sec-butoxide and benzoylacetone, the wavelength is 325 nm. It is preferable to irradiate with light.

By washing the aluminum chelate compound coating film after light irradiation through a photomask with a solvent,
The non-irradiated portion where the solubility has not changed is removed and the base material is exposed, while the portion where the solubility in the solvent becomes relatively small due to the change to the alumina film by the light irradiation remains. Examples of the washing solvent include methanol, ethanol, isopropanol, acetone, acid and alkali, and it is preferable to select a solvent containing at least one kind from the viewpoint of the above solubility.

By dipping the alumina pattern coating film in warm water, a pattern in which fine irregularities in which the alumina film portion has changed to a fine irregularity structure (petal-like alumina) is regularly arranged is formed on the substrate. The temperature of hot water is 50 ℃
The temperature is preferably 100 ° C., which is determined in consideration of the heat resistance of the base material, but the lower the temperature, the longer the time required to completely form the fine textured structure.

By dipping the pattern coating film in warm water,
The surface layer surface of the alumina film part has a unique micropore-like void, and the unique petal-like shape has a surface layer surface that is randomly aggregated. Can be formed. The hot water treatment time is about 5 minutes to about 24 hours, and the thickness of this petal-like alumina film can be set arbitrarily, but is 50 nm to 400 n.
m is preferred.

Further, a layer containing a compound having an organic group exhibiting water repellency (hereinafter referred to as a water repellent compound layer) is formed on the entire fine concavo-convex texture pattern film by a method such as sol-gel method, vacuum vapor deposition, vapor phase vapor deposition and the like. You may. The contact angle A (90 degrees or less) of the fine uneven portion and the contact angle B (5 degrees or more larger than the contact angle A) of the smooth portion with respect to the film-forming liquid composition are increased by the coating of the water-repellent compound layer. The contact angles are A ′ and B ′, respectively. But the contact angle B '
Is kept larger than the contact angle A ′ by 5 degrees or more.
When the water-repellent compound layer is coated, the contact angle in the peripheral portion of the film-forming liquid composition gathered on the highly wettable region is increased as compared with the case where it is not coated. The slope of the rising portion of the convex portion cured above can be a steep angle. The thickness of this layer is 1-100
nm, preferably 1 to 50 nm.

As the compound having an organic group exhibiting water repellency, a silane compound having a water repellent group is preferably used. Examples thereof include silane compounds having one or more water-repellent groups, such as alkyl groups and fluoroalkyl groups, in the molecule.

Examples of the silane compound having an alkyl group include CH ₃ (CH ₂ ) ₃₀ SiCl ₃ and CH ₃ (CH ₂ ) ₂₀ Si.
Cl ₃ , CH ₃ (CH ₂ ) ₁₈ SiCl ₃ , CH ₃ (CH ₂ ) ₁₆
SiCl ₃ , CH ₃ (CH ₂ ) ₁₄ SiCl ₃ , CH ₃ (CH ₂ )
₁₂ SiCl ₃ , CH ₃ (CH ₂ ) ₁₀ SiCl ₃ , CH ₃ (C
H ₂ ) ₉ SiCl ₃ , CH ₃ (CH ₂ ) ₈ SiCl ₃ , CH ₃ (C
H ₂ ) ₇ SiCl ₃ , CH ₃ (CH ₂ ) ₆ SiCl ₃ , CH ₃ (C
H ₂ ) ₅ SiCl ₃ , CH ₃ (CH ₂ ) ₄ SiCl ₃ , CH ₃ (C
H ₂ ) ₃ SiCl ₃ , CH ₃ (CH ₂ ) ₂ SiCl ₃ , CH ₃ CH
_{2 SiCl 3, (CH 3 CH} 2) 2 SiCl 2, (CH 3 CH 2)
_{3 SiCl, CH 3 SiCl 3,} (CH 3) 2 SiCl 2, (C
H ₃ ) ₃ SiCl-containing alkyl group-containing chlorosilanes;
_{CH 3 (CH 2) 30 Si} (OCH 3) 3, CH3 (CH 2) 20
Si (OCH ₃ ) ₃ , CH ₃ (CH ₂ ) ₁₈ Si (OCH ₃ ) ₃ ,
_{CH 3 (CH 2) 16 Si} (OCH 3) 3, CH 3 (CH 2) 14
Si (OCH ₃ ) ₃ , CH ₃ (CH ₂ ) ₁₂ Si (OCH ₃ ) ₃ ,
_{CH 3 (CH 2) 10 Si} (OCH 3) 3, CH 3 (CH 2) 9 S
i (OCH ₃ ) ₃ , CH ₃ (CH ₂ ) ₈ Si (OCH ₃ ) ₃ , C
_{H 3 (CH 2) 7 Si} (OCH 3) 3, CH 3 (CH 2) 6 Si
(OCH ₃ ) ₃ , CH ₃ (CH ₂ ) ₅ Si (OCH ₃ ) ₃ , CH
_{3 (CH 2) 4 Si (} OCH 3) 3, CH 3 (CH 2) 3 Si (O
CH ₃ ) ₃ , CH ₃ (CH ₂ ) ₂ Si (OCH ₃ ) ₃ , CH ₃ C
H ₂ Si (OCH ₃ ) ₃ , (CH ₃ CH ₂ ) ₂ Si (OC
_{H 3) 2, (CH 3} CH 2) 3 SiOCH 3, CH 3 Si (OC
_{H 3) 3, (CH 3} ) 2 Si (OCH 3) 2, (CH 3) 3 SiO
CH ₃ , CH ₃ (CH ₂ ) ₃₀ Si (OC ₂ H ₅ ) ₃ , CH ₃ (C
H ₂ ) ₂₀ Si (OC ₂ H ₅ ) ₃ , CH ₃ (CH ₂ ) ₁₈ Si (OC
₂ H ₅ ) ₃ , CH ₃ (CH ₂ ) ₁₆ Si (OC ₂ H ₅ ) ₃ , CH
_{3 (CH 2) 14 Si (} OC 2 H 5) 3, CH 3 (CH 2) 12 Si
(OC ₂ H ₅ ) ₃ , CH ₃ (CH ₂ ) ₁₀ Si (OC ₂ H ₅ ) ₃ ,
_{CH 3 (CH 2) 9 Si} (OC 2 H 5) 3, CH 3 (CH 2) 8 S
i (OC ₂ H ₅ ) ₃ , CH ₃ (CH ₂ ) ₇ Si (OC ₂ H ₅ ) ₃ ,
_{CH 3 (CH 2) 6 Si} (OC 2 H 5) 3, CH 3 (CH 2) 5 S
i (OC ₂ H ₅ ) ₃ , CH ₃ (CH ₂ ) ₄ Si (OC ₂ H ₅ ) ₃ ,
_{CH 3 (CH 2) 3 Si} (OC 2 H 5) 3, CH 3 (CH 2) 2 S
i (OC ₂ H ₅ ) ₃ , CH ₃ CH ₂ Si (OC ₂ H ₅ ) ₃ , (CH
_{3 CH 2) 2 Si (OC} 2 H 5) 2, (CH 3 CH 2) 3 SiOC 2
_{H 5, CH 3 Si (OC} 2 H 5) 3, (CH 3) 2 Si (OC 2 H
₅ ) ₂ , an alkyl group-containing alkoxysilane such as (CH ₃ ) ₃ SiOC ₂ H ₅ ; CH ₃ (CH ₂ ) ₃₀ Si (OCOC)
H ₃ ) ₃ , CH ₃ (CH ₂ ) ₂₀ Si (OCOCH ₃ ) ₃ , CH ₃
(CH ₂ ) ₁₈ Si (OCOCH ₃ ) ₃ , CH ₃ (CH ₂ ) ₁₆ S
i (OCOCH ₃ ) ₃ , CH ₃ (CH ₂ ) ₁₄ Si (OCOCH
₃ ) ₃ , CH ₃ (CH ₂ ) ₁₂ Si (OCOCH ₃ ) ₃ , CH
_{3 (CH 2) 10 Si (} OCOCH 3) 3, CH 3 (CH 2) 9 S
i (OCOCH ₃ ) ₃ , CH ₃ (CH ₂ ) ₈ Si (OCOC
H ₃ ) ₃ , CH ₃ (CH ₂ ) ₇ Si (OCOCH ₃ ) ₃ , CH ₃
(CH ₂ ) ₆ Si (OCOCH ₃ ) ₃ , CH ₃ (CH ₂ ) ₅ Si
(OCOCH ₃ ) ₃ , CH ₃ (CH ₂ ) ₄ Si (OCOC
_{H 3) 3, CH 3 (} CH 2) 3 Si (OCOCH 3) 3, CH 3
(CH ₂ ) ₂ Si (OCOCH ₃ ) ₃ , CH ₃ CH ₂ Si (OC
OCH ₃ ) ₃ , (CH ₃ CH ₂ ) ₂ Si (OCOCH ₃ ) ₂ ,
(CH ₃ CH ₂ ) ₃ SiOCOCH ₃ , CH ₃ Si (OCOC
_{H 3) 3, (CH 3} ) 2 Si (OCOCH 3) 2, (CH 3) 3
An alkyl group-containing acyloxysilane such as SiOCOCH ₃ ; CH ₃ (CH ₂ ) ₃₀ Si (NCO) ₃ , CH ₃ (C
H ₂ ) ₂₀ Si (NCO) ₃ , CH ₃ (CH ₂ ) ₁₈ Si (NC
O) ₃ , CH ₃ (CH ₂ ) ₁₆ Si (NCO) ₃ , CH ₃ (CH
₂ ) ₁₄ Si (NCO) ₃ , CH ₃ (CH ₂ ) ₁₂ Si (NCO)
₃ , CH ₃ (CH ₂ ) ₁₀ Si (NCO) ₃ , CH ₃ (CH ₂ ) ₉
Si (NCO) ₃ , CH ₃ (CH ₂ ) ₈ Si (NCO) ₃ , C
H ₃ (CH ₂ ) ₇ Si (NCO) ₃ , CH ₃ (CH ₂ ) ₆ Si
(NCO) ₃ , CH ₃ (CH ₂ ) ₅ Si (NCO) ₃ , CH ₃
(CH ₂ ) ₄ Si (NCO) ₃ , CH ₃ (CH ₂ ) ₃ Si (NC
O) ₃ , CH ₃ (CH ₂ ) ₂ Si (NCO) ₃ , CH ₃ CH ₂ S
i (NCO) ₃ , (CH ₃ CH ₂ ) ₂ Si (NCO) ₂ , (C
_{H 3 CH 2) 3 SiNCO,} CH 3 Si (NCO) 3, (C
Examples thereof include alkyl group-containing isocyanate silanes such as H ₃ ) ₂ Si (NCO) ₂ and (CH ₃ ) ₃ SiNCO.

Examples of the silane compound having a fluoroalkyl group include CF ₃ (CF ₂ ) ₁₁ (CH ₂ ) ₂ SiCl ₃ and CF
₃ (CF ₂ ) ₁₀ (CH ₂ ) ₂ Si (Cl) ₃ , CF ₃ (CF ₂ )
₉ (CH ₂ ) ₂ SiCl ₃ , CF ₃ (CF ₂ ) ₈ (CH ₂ ) ₂ Si
Cl ₃ , CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ SiCl ₃ , CF
₃ (CF ₂ ) ₆ (CH ₂ ) ₂ SiCl ₃ , CF ₃ (CF ₂ ) ₅ (C
H ₂ ) ₂ SiCl ₃ , CF ₃ (CF ₂ ) ₄ (CH ₂ ) ₂ SiC
l ₃ , CF ₃ (CF ₂ ) ₃ (CH ₂ ) ₂ SiCl ₃ , CF ₃ (C
F ₂ ) ₂ (CH ₂ ) ₂ SiCl ₃ , CF ₃ CF ₂ (CH ₂ ) ₂ Si
Fluoroalkyl group-containing trichlorosilane such as Cl ₃ and CF ₃ (CH ₂ ) ₂ SiCl ₃ ; CF ₃ (CF ₂ ) ₁₁ (C
H ₂ ) ₂ Si (OCH ₃ ) ₃ , CF ₃ (CF ₂ ) ₁₀ (CH ₂ ) ₂
Si (OCH ₃ ) ₃ , CF ₃ (CF ₂ ) ₉ (CH ₂ ) ₂ Si (O
CH ₃ ) ₃ , CF ₃ (CF ₂ ) ₈ (CH ₂ ) ₂ Si (OC
_{H 3) 3, CF 3 (} CF 2) 7 (CH 2) 2 Si (OCH 3) 3,
CF ₃ (CF ₂ ) ₆ (CH ₂ ) ₂ Si (OCH ₃ ) ₃ , CF
₃ (CF ₂ ) ₅ (CH ₂ ) ₂ Si (OCH ₃ ) ₃ , CF ₃ (C
F ₂ ) ₄ (CH ₂ ) ₂ Si (OCH ₃ ) ₃ , CF ₃ (CF ₂ )
₃ (CH ₂ ) ₂ Si (OCH ₃ ) ₃ , CF ₃ (CF ₂ ) ₂ (C
H ₂ ) ₂ Si (OCH ₃ ) ₃ , CF ₃ CF ₂ (CH ₂ ) ₂ Si (O
CH ₃ ) ₃ , CF ₃ (CH ₂ ) ₂ Si (OCH ₃ ) ₃ , CF
₃ (CF ₂ ) ₁₁ (CH ₂ ) ₂ Si (OC ₂ H ₅ ) ₃ , CF ₃ (C
F ₂ ) ₁₀ (CH ₂ ) ₂ Si (OC ₂ H ₅ ) ₃ , CF ₃ (CF ₂ ) ₉
(CH ₂ ) ₂ Si (OC ₂ H ₅ ) ₃ , CF ₃ (CF ₂ ) ₈ (C
H ₂ ) ₂ Si (OC ₂ H ₅ ) ₃ , CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂
Si (OC ₂ H ₅ ) ₃ , CF ₃ (CF ₂ ) ₆ (CH ₂ ) ₂ Si (O
C ₂ H ₅ ) ₃ , CF ₃ (CF ₂ ) ₅ (CH ₂ ) ₂ Si (OC
₂ H ₅ ) ₃ , CF ₃ (CF ₂ ) ₄ (CH ₂ ) ₂ Si (OC
₂ H ₅ ) ₃ , CF ₃ (CF ₂ ) ₃ (CH ₂ ) ₂ Si (OC
₂ H ₅ ) ₃ , CF ₃ (CF ₂ ) ₂ (CH ₂ ) ₂ Si (OC
₂ H ₅ ) ₃ , CF ₃ CF ₂ (CH ₂ ) ₂ Si (OC ₂ H ₅ ) ₃ , C
Fluoroalkyl group-containing trialkoxysilanes such as F ₃ (CH ₂ ) ₂ Si (OC ₂ H ₅ ) ₃ ; CF ₃ (CF ₂ )
₁₁ (CH ₂ ) ₂ Si (OCOCH ₃ ) ₃ , CF ₃ (CF ₂ ) ₁₀
(CH ₂ ) ₂ Si (OCOCH ₃ ) ₃ , CF ₃ (CF ₂ ) ₉ (C
H ₂ ) ₂ Si (OCOCH ₃ ) ₃ , CF ₃ (CF ₂ ) ₈ (C
H ₂ ) ₂ Si (OCOCH ₃ ) ₃ , CF ₃ (CF ₂ ) ₇ (C
H ₂ ) ₂ Si (OCOCH ₃ ) ₃ , CF ₃ (CF ₂ ) ₆ (C
H ₂ ) ₂ Si (OCOCH ₃ ) ₃ , CF ₃ (CF ₂ ) ₅ (C
H ₂ ) ₂ Si (OCOCH ₃ ) ₃ , CF ₃ (CF ₂ ) ₄ (C
H ₂ ) ₂ Si (OCOCH ₃ ) ₃ , CF ₃ (CF ₂ ) ₃ (C
H ₂ ) ₂ Si (OCOCH ₃ ) ₃ , CF ₃ (CF ₂ ) ₂ (C
_{H 2) 2 Si (OCOCH 3} ) 3, CF 3 CF 2 (CH 2) 2 Si
(OCOCH ₃ ) ₃ , CF ₃ (CH ₂ ) ₂ Si (OCOC
Fluoroalkyl group-containing triacyloxysilanes such as H ₃ ) ₃ ; CF ₃ (CF ₂ ) ₁₁ (CH ₂ ) ₂ Si (NC
O) ₃ , CF ₃ (CF ₂ ) ₁₀ (CH ₂ ) ₂ Si (NCO) ₃ ,
CF ₃ (CF ₂ ) ₉ (CH ₂ ) ₂ Si (NCO) ₃ , CF ₃ (C
F ₂ ) ₈ (CH ₂ ) ₂ Si (NCO) ₃ , CF ₃ (CF ₂ )
₇ (CH ₂ ) ₂ Si (NCO) ₃ , CF ₃ (CF ₂ ) ₆ (C
H ₂ ) ₂ Si (NCO) ₃ , CF ₃ (CF ₂ ) ₅ (CH ₂ ) ₂ Si
(NCO) ₃ , CF ₃ (CF ₂ ) ₄ (CH ₂ ) ₂ Si (NC
O) ₃ , CF ₃ (CF ₂ ) ₃ (CH ₂ ) ₂ Si (NCO) ₃ , C
F ₃ (CF ₂ ) ₂ (CH ₂ ) ₂ Si (NCO) ₃ , CF ₃ CF ₂
(CH ₂ ) ₂ Si (NCO) ₃ , CF ₃ (CH ₂ ) ₂ Si (NC
O) ₃ such as fluoroalkyl group-containing triisocyanate silane can be exemplified. Of these, fluoroalkyl group-containing trialkoxysilanes, particularly fluoroalkyltrimethoxysilane and fluoroalkyltriethoxysilane having 13 to 22 fluorine atoms, are preferably used.

The water-repellent compound layer may be formed in the following manner only in the area of the smooth surface having low wettability, not in the entire pattern film. For example, a photocatalytically active oxide layer such as a titania anatase layer and a compound layer having a water-repellent group that decomposes by photocatalysis such as a fluoroalkyl group-containing silane compound are formed on the entire pattern film, and then the pattern film is formed. A photomask having the same dimensions as the photomask used for formation is aligned and arranged so that the light-transmitting area of the mask corresponds to the fine concavo-convex area, and light is irradiated through the photomask. The fluoroalkyl group-containing silane compound on the fine concavo-convex area is decomposed by photocatalytic action of the lower titania layer by light irradiation and loses water repellency. As a result, the water-repellent layer is formed only on the smooth underlying substrate portion having no fine texture, the surface of the fine uneven texture exhibits a superhydrophilic state in which the contact angle of water is 4 degrees or less, and the smooth underlying substrate portion has a contact angle of water. Shows a super water repellent state of 150 degrees or more. In this way, the difference between the contact angle A of the fine uneven surface and the contact angle B of the smooth surface with respect to the liquid composition for film formation at room temperature or in the heated state can be further increased.

Then, a liquid containing at least one hydrolyzable compound capable of being hydrolyzed and polycondensed, which is used as a liquid composition for forming a film, a photocurable resin, a thermosetting resin, etc., can be cured after being attached. The resulting solution is coated on the substrate surface having a fine concavo-convex pattern (for example, a petal-like alumina pattern) or on the substrate surface having a compound layer containing a water-repellent group formed thereon. In particular, when forming an optical element, the liquid composition for film formation is preferably highly transparent.

Examples of the hydrolyzable compound capable of being hydrolyzed and polycondensed include metal alkoxides and metal chelates. Specific examples of the metal alkoxide include methoxides such as silicon (Si), aluminum (Al), zirconium (Zr), titanium (Ti), tin (Sn) and antimony (Sb), ethoxides, propoxides, butoxides. It is preferably used as a simple substance or a mixture. For example, examples of silicon alkoxide include tetraethoxysilane, tetramethoxysilane, phenyltriethoxysilane, and methyltriethoxysilane. As the metal chelate, acetylacetonate complexes of silicon, aluminum, zirconium, titanium, tin and antimony, ethyl acetoacetate complexes and benzoylacetonate complexes are preferably used.

Among these, the following formula (1), Y _n SiX _4-n (1) (wherein Y represents an alkyl group, vinyl group, amino group, epoxy group, phenyl group or benzyl group, and X represents Each independently represents an alkoxyl group or halogen, n is 0
Or 1. The silicon compound represented by the formula (1) is more preferably used. As the alkyl group of Y in the above formula (1), a methyl group, an ethyl group, a propyl group, a butyl group, 2-
A linear or branched alkyl group such as an ethylbutyl group and an octyl group, and a cycloalkyl group such as a cyclopentyl group and a cyclohexyl group are preferable. Among the above silicon compounds, Y in the above formula (1) is a phenyl group or a benzyl group, X is a methoxyl group or an ethoxyl group, and n is 1, an organometallic compound, that is, phenyltrimethoxysilane, phenyltri Ethoxysilane, benzyltrimethoxysilane, and benzyltriethoxysilane can (1) increase the maximum thickness of the cured product (for example, the maximum height of the lens), and (2) a liquid composition adhered to the surface of the base material. Because the speed at which the object moves to a highly wettable area is high, and (3) the refractive index of the cured product (for example, the refractive index of the lens) can be increased,
More preferably used. Of these, phenyltriethoxysilane is particularly preferred.

Further, the silicon compound represented by the above formula (1) and the following formula (2), R ₂ SiQ ₂ (2) (wherein each R is independently an alkyl group, a vinyl group, an amino group or an epoxy group). , A phenyl group or a benzyl group, and Q independently represents a halogen or an alkoxyl group) (hereinafter, referred to as “formula (2)”).
Silicon compounds ”)) can be used in combination. Among these, a silicon compound in which R in the above formula (2) is a phenyl group or a methyl group and Q is a methoxyl group or an ethoxyl group is preferably used. This has the effect of improving the fluidity when the film-forming liquid composition is in the form of droplets.

Although the silicon compound of the formula (2) is a hydrolyzable compound capable of being hydrolyzed and polycondensed, it does not form a three-dimensional network structure by itself and is a machine for optical elements and other articles having a predetermined surface shape. Target strength becomes low. Therefore, the silicon compound of the formula (2) is used at 80% or less in terms of the mole fraction of the silicon element based on 100 mol% of the total silicon element of the silicon compound of the formula (1) and the silicon compound of the formula (2). Preferably.

Further, a silicon compound represented by the above formulas (1) and (2) is used in combination with at least one compound selected from the group consisting of titanium alkoxide, zirconium alkoxide, aluminum alkoxide and chelate compounds thereof. can do. For example titanium butoxide, aluminum butoxide,
Alkoxide compounds such as zirconium butoxide,
Optical formed by using a metal compound such as titanium acetylacetonate complex having a higher refractive index of oxide than silicon oxide in combination with the silicon compound represented by the above formula (1). Not only can the refractive index of elements and other articles having a predetermined surface shape be controlled, but various characteristics such as hardness and shrinkage can also be controlled. These metal compounds are represented by the mole fraction of the metal element with respect to the silicon compound represented by the formula (1) and the formula (2) and the sum of silicon and the metal element of the compound, and are represented by a mole fraction of 30.
% Or less, more preferably 3 to 20%.

As described above, by using two or more kinds of metal compounds in combination, for example, when phenyltriethoxysilane is used alone, the optical element obtained has a refractive index of about 1.53. By combining ethoxysilane and methyltriethoxysilane, an optical element having a refractive index of 1.48 to 1.53 can be obtained,
By adjusting the mixing ratio of phenyltriethoxysilane and methyltriethoxysilane, the refractive index of the optical element and other predetermined surface shapes can be precisely controlled.

The film-forming liquid composition contains a hydrolyzable compound capable of being hydrolyzed and polycondensed, water, an acid catalyst and a solvent. As the catalyst used at this time, inorganic acids such as hydrochloric acid, nitric acid, sulfuric acid, acetic acid, oxalic acid, formic acid, propionic acid,
Organic acids such as p-toluenesulfonic acid are used.
The amount of the acid catalyst used is expressed as a molar ratio and the metal compound 1
The amount is preferably 3 mmol to 200 mmol, and more preferably 10 mmol to 100 mmol.

Water is preferably added in a stoichiometric ratio or more necessary for hydrolysis. If the amount of water added is less than the stoichiometric ratio, unreacted metal compounds are likely to volatilize during drying for gelation, which is not preferable. Usually, the amount of water added is 1.1 to 3 of the required stoichiometric ratio, including the water of the catalyst aqueous solution.
It is 0 times, and in terms of molar ratio, it is 1.
It is preferably 5 to 20 times, more preferably 2 to 10 times.

The solvent in the film-forming liquid composition varies depending on the coating method and the characteristics of the coating liquid, and a plurality of solvents may be mixed and used. The amount of solvent used is expressed as a molar ratio and is 0.
It is preferably 3 to 5 times, more preferably 0.5 to 3 times.

When the spray coating method is used as a method for coating the film-forming liquid composition on the surface of the substrate on which the pattern structure in which the fine surface irregularity areas are regularly arranged is formed, the film-forming liquid composition is a liquid. Since it adheres to the substrate in the form of drops, it is easy to move to the fine concavo-convex area, which is preferable. It is advantageous in that the thickness (height) of the finally obtained cured product can be adjusted by changing the overall spray deposition amount.

The dip coating method is also preferably used. By immersing the substrate with a patterned film in a bath of the liquid composition for film formation and pulling it up at a predetermined pulling rate, the liquid composition adheres in a droplet state only to the fine irregular areas of the substrate surface. However, in some cases, the liquid composition may be coated with a substantially uniform thickness over the entire surface of the substrate. At this time, vibration of the substrate or the coating liquid layer, ultrasonic vibration, etc. may be applied, or the coating liquid layer may be applied. The liquid composition can be gathered in the fine irregular areas on the surface of the substrate by blowing air. However, some liquid forming liquid compositions, for example, phenyltrimethoxysilane, phenyltriethoxysilane, benzyltrimethoxysilane, trialkoxysilanes such as benzyltriethoxysilane, acid catalysts, water,
When a liquid composition comprising a solvent is used, and particularly when the amount of the solvent and water is relatively small or the area ratio of the fine uneven areas on the substrate surface is large, the fine uneven areas on the substrate surface immediately after coating Aggregation may not occur.
However, after coating and drying for several hours, the substrate was maintained with its coated surface facing upwards and substantially horizontal.
When heated at 0 to 300 ° C., the coating film which has been in a solid state until then has a reduced viscosity and is softened to be in a melted state, and aggregates in the fine uneven areas on the substrate surface. When the heating is further continued, it is completely cured, and the protrusions of phenylpolysiloxane or benzylpolysiloxane firmly adhered to the substrate are formed in the fine surface irregularity areas. By applying the liquid composition and applying vibration thereafter as necessary, the liquid composition gathers in the fine irregular areas of the substrate surface to form a droplet, and then a film containing a hydrolyzable compound is formed. In the case of a liquid composition, 10 minutes to 3 at 10 to 300 ° C
By heating for 100 minutes, the hydrolysis and polycondensation reaction proceed, and the transparent fine solid convex portions are firmly attached to the fine irregular areas on the substrate.

As the above, a liquid composition for forming a film containing a hydrolyzable compound capable of being hydrolyzed and polycondensed, a compound containing at least one compound selected from the group consisting of a hydrolyzate and a polycondensate thereof is used. If you want to. In addition to the above, examples of the film-forming liquid composition also include raw materials of a photocurable resin and a thermosetting resin. Photocurable resin,
Resins such as thermosetting resins are preferably used when high heat resistance is not required. When using the above hydrolyzable compound, excellent heat resistance is obtained.

The photocurable resin has at least one functional group and is a monomer or oligomer which is cured by irradiation of a curing energy ray to cause ionic polymerization and radical polymerization to increase the molecular weight and form a crosslinked structure. Is. The functional group is an atomic group or a binding mode that causes a reaction such as a vinyl group, a carboxyl group, an epoxy group, an acrylate group, and a hydroxyl group. Examples of the photo-curable resin include transparent resins such as epoxy resin such as fluorinated epoxy resin, acrylic resin, unsaturated polyester resin and the like. The thermosetting resin is not particularly limited as long as it is a resin that can be cured by heat energy. Examples of the thermosetting resin include transparent resins such as epoxy resin and polyimide.

Even when the above-mentioned liquid composition made of a photo-curable resin material or a thermosetting resin material is used, the viscosity of the liquid composition is so high that immediately after the application, the liquid composition is not gathered in the fine uneven areas on the substrate surface. It may not occur. However, when heated at 50 to 150 ° C. after coating, the liquid composition collects in the fine uneven areas. Then, by irradiating with light or heating, the resin is hardened and the transparent fine solid convex portions are firmly attached to the fine irregular areas on the substrate. In the case of the photocurable resin raw material, the light irradiation is, for example, 20 to 200 mW / cm from a mercury lamp.
It is performed by irradiating with ultraviolet light at an illuminance of ² for 5 seconds to 10 minutes, and heating in the case of a thermosetting resin raw material is, for example, 80
It is carried out at ˜130 ° C. for 1 minute to 1 hour.

In this way, the liquid composition for film formation is adhered and then cured to form a cured product in the area having a large wettability, and microlenses, microlens arrays, cylindrical lens arrays or Fresnel lenses are formed on the substrate. Optical elements such as and other predetermined surface shapes can be obtained.

In the present invention, the convex portions are formed due to the difference in surface energy in the pattern in which the fine surface irregularities having high wettability and the surface smooth areas having low wettability are regularly arranged and the capillary phenomenon in the fine irregularities. It is also possible to control the optical element and other predetermined surface shapes obtained by controlling the surface energy difference and the degree of fine irregularities. In the conventional method utilizing only the difference in wettability, when the liquid composition for forming a film containing titanium alkoxide has high viscosity and low fluidity, the liquid composition moves to a region with large wettability. Although it is difficult to do so, in the present invention, since the suction force due to the capillary action works, it is possible to move the liquid composition for film formation having high viscosity and low fluidity, so that the composition range that can be used as the liquid composition for film formation is Will be expanded. Further, in the present invention, the suction force due to the capillary action works, so that the stability of the shape of the film-forming liquid composition gathered in an area having greater wettability becomes better than in the past, and as a result, the dimensional accuracy of a cured product such as a lens is improved. Becomes higher.

As the base substrate used in the present invention, a flat substrate is preferably used. The material of the base substrate is not particularly limited, but in consideration of wettability with the liquid composition for film formation to be used, expansion coefficient of the cured product of the liquid composition for film formation, and adhesiveness with this cured product. Therefore, it is preferable to select the material, size, and shape of the base material that does not cause peeling or cracking.
As an example of a preferable material for the base substrate, silicate glass,
Examples thereof include oxide glass such as borosilicate glass and other inorganic glass, quartz, transparent ceramics, light or thermosetting resin, thermoplastic resin, metal and the like. Of these, materials having excellent heat resistance and transparency, such as inorganic glass, quartz, and transparent ceramics, are particularly preferably used for optical element applications.

When an object transparent to light of a desired wavelength, for example, light in the visible range, ultraviolet range, or infrared range, such as a glass substrate, is used as the base substrate in the present invention, in the present invention, a lens or a conductive film is used. It is possible to exert the function of further combining transmissive optical elements such as a waveguide, a diffraction grating, and a prism.

In the method for producing an optical element or other article having a predetermined shape according to the present invention, the liquid composition for film formation is applied to the surface of a substrate on which surface fine irregular areas are regularly arranged, and then the temperature is set to 100 ° C. or higher. It is possible to form a desired article with high accuracy by inducing the liquid composition for film formation into the surface fine irregularities of the pattern portion by heat treatment in step 1, or by irradiating with ultraviolet light after the heat treatment.

[0049]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be specifically described below. However, these examples are for helping understanding of the present invention and do not limit the scope of the claims. [Example 1] (1) Preparation and film formation of aluminum chelate compound solution 0.5 mol of benzoylacetone was added to a product prepared by diluting 1.0 mol of aluminum sec-butoxide with 20 mol of isopropanol and stirring for about 3 hours. To give an aluminum chelate compound solution.

A glass substrate having a thickness of 2.0 mm and a size of 25 mm × 25 mm was dipped in the above solution and pulled up at a pulling rate of 1.11 mm / sec to dip coat the surface of the glass substrate to form a coating film. Then 50
The coating was dried at 30 ° C. for 30 minutes and coated with an amorphous alumina chelate compound film.

(2) Light irradiation and solvent dissolution Circular openings (light transmitting portions) having a diameter of 150 μm are spaced apart (between the centers of circles) at 175 μm and are approximately 20,000 in a grid pattern.
The individually arranged photomask is placed on the glass substrate coated with the above aluminum chelate compound film, and 220 to 310 nm from an ultra-high pressure mercury lamp (“UIS-25102” manufactured by Ushio Electric Co., Ltd. 250 W, light wavelength 250 nm to 450 nm)
23.0 mW / cm ² , 310-39 with light in the wavelength range
It was irradiated with light having a wavelength in the range of 0 nm at an illuminance of 73.0 mW / cm ² for 20 minutes. In the exposed portion of the aluminum chelate compound film, the benzoylacetone complex coordinated with the aluminum alkoxide was cleaved by absorbing light, and the aluminum chelate compound film was changed to an amorphous alumina film.

Next, this light irradiation film was washed with an acetone solution containing 1.2% by volume of nitric acid as a solvent for 1 minute. As a result, only the non-exposed portion, which is the unreacted portion, was dissolved and removed in the solvent, and it was possible to form an amorphous alumina pattern in which only the exposed portion having a diameter of 150 μm remained at 175 μm intervals.

(3) Hot Water Treatment Subsequently, the alumina patterned substrate was immersed in warm water of about 100 ° C. for 20 minutes to perform hot water treatment, and then dried at room temperature. The obtained substrate with a patterned film shows high transparency, and an atomic force microscope (AFM) observation was performed on the alumina film portions having a diameter of 150 μm formed at intervals of 175 μm, and the average roughness Ra value was 24 nm. Surface area SR
Fine concavo-convex structure with a value of 1.8 (petal-like alumina structure)
It was found that the alumina pattern changed to a petal-like alumina pattern.

(4) Preparation of FAS sol and film formation: 0.01 mol of heptadecafluorodecyltrimethoxysilane (FAS) diluted with 2.0 mol of isopropanol was dissolved in 0.06% by weight of nitric acid to prepare water. 02 mol was added and stirred to obtain FAS sol.

The substrate with the petal-like alumina pattern film and the FAS sol in the flask were placed in a closed electric furnace and heated at 240 ° C. for 20 minutes to form a film of several nm on the petal-like alumina pattern film. A thick FAS film was vapor deposited.

(5) Preparation of phenylsilsesquioxane sol and formation of film and formation of lens array 1 mol of phenyltriethoxysilane was dissolved in 1.5 parts of ethanol.
After diluting with mol and adding 4 mol of water in which hydrochloric acid is dissolved at 1.44% by weight and stirring for about 2 hours, phenyltriethoxysilane is hydrolyzed and polycondensed to phenylsilsesquioxane (PhSiO _3/2 ). I got a sol.

With the above-mentioned petal-like alumina pattern film (F
(Without AS layer) The substrate is dipped in the bath of the above phenylsilsesquioxane sol and pulled up at a pulling rate of 1.11 mm / sec to dip the phenylsilsesquioxane sol on the surface of the petal-like alumina pattern film on the glass substrate. Coated. This was dried at room temperature for about 15 hours to form a gel film. This gel film spreads on the surface of the substrate with a petal-shaped alumina pattern film with a substantially uniform thickness, and the film thickness was about 1 μm, and the sol lost fluidity due to the evaporation of the solvent and gelled into a solid state. . Next, when this gelled film was kept at 200 ° C., after about 10 minutes, the gel became fluid and became liquid, and the gel on the glass substrate exposed by the solvent removal in the non-exposed area moved. To form a lens shape by gathering on a petal-like alumina portion (circle having a diameter of 150 μm). When this heating was continued for another 20 minutes, the convex parts of the petal-like alumina part were completely gelled to form a hardened lens having a diameter of 120 μm, and about 2 μm on the surface of the substrate.
A microlens array having 10,000 lenses adhered was obtained. The thickness between the top and bottom of the lens was about 3 μm. A three-dimensional surface profile of the formed lens array measured by using an atomic force microscope (AFM) is shown in FIG. The cross-sectional profile of one lens of this lens array is shown in FIG. The above 200
The gel having fluidity when kept at 0 ° C. had a contact angle of about 3 degrees at the petal-like alumina portion and a contact angle of about 10 degrees at the glass substrate.

When the variation in the thickness of the molded lens was evaluated at 5 points, it was 3 ± 0.1 μm, and the error was about ± 3.3.
%Met. When the focal length is measured, it is 761 ± 20μ
The error was ± 2.6%. Furthermore, when the transmittance of light of wavelength 400 to 2500 nm of this material was evaluated, it was confirmed that there was no problematic absorption in the wavelength range of the communication band. Further, the adhesion to the substrate was good, and the lens was not peeled from the substrate even when the peripheral portion of the substrate was cut or washed.

For the above microlens array, 3
After carrying out a heat resistance test of holding at 00 ° C. for 2 hours, the temperature was returned to room temperature and the presence or absence of cracks was observed to evaluate the heat resistance. As a result, the lens and the substrate were not cracked or peeled off, and the focal lengths of all the lenses were the same as before the heat resistance test.

[Example 2] Preparation of phenylsilsesquioxane sol containing titanium and formation of film and formation of lens array 0.95 mol of phenyltriethoxysilane was diluted with 1 mol of ethanol to obtain 1.44% by weight. 4 mol of water in which hydrogen chloride was dissolved was added, and the mixture was stirred for about 30 minutes. 0.05 for this
A mole of titanium acetoacetate ethyl complex was added, and the mixture was further stirred for about 30 minutes to obtain a titanium-containing phenylsilsesquioxane sol.

In the same manner as in Example 1, a substrate with a petal-like alumina pattern film (without FAS layer) was coated with the above-mentioned titanium-containing phenylsilsesquioxane sol, dried, and treated at 200 ° C. to form a lens array. Formed. The refractive index of the obtained lens part was 1.55. The refractive index of the lens manufactured in Example 1 was 1.53, which shows that the refractive index can be controlled. In addition,
The gel having fluidity generated by keeping it at 200 ° C. had a contact angle of 2 degrees at the petal-like alumina portion and a contact angle of 9 degrees at the glass substrate.

[Example 3] Preparation of phenylsilsesquioxane sol containing titanium and the like, film formation and lens array formation Phenyltriethoxysilane 0.45 mol, diphenyldiethoxysilane 0.45 mol and ethanol 1 mol Was diluted with, and 4 mol of water in which hydrogen chloride was dissolved at 1.44% by weight was added, and the mixture was stirred for about 30 minutes. To this, 0.10 mol of titanium acetoacetate ethyl complex was added and further stirred for about 30 minutes to obtain a phenylsilsesquioxane sol containing titanium and the like.

In the same manner as in Example 1, a substrate having a petal-like alumina pattern film (no FAS layer) was coated with phenylsilsesquioxane sol containing titanium and the like, dried, and treated at 200 ° C. to form a lens array. Was formed. The refractive index of the lens portion formed at this time was 1.58. The refractive index of the lens manufactured in Example 1 is 1.53.
It is shown that the refractive index can be controlled. The gel having fluidity generated by keeping it at 200 ° C. had a contact angle of 4 degrees at the petal-like alumina portion and a contact angle of 11 degrees at the glass substrate.

Example 4 Preparation of phenylsilsesquioxane sol containing methylsilsesquioxane, formation of film and formation of lens array Phenyltriethoxysilane (0.60 mol) and methyltriethoxysilane (0.40 mol) were prepared. The mixture was diluted with 1.5 mol of ethanol, 4 mol of water in which hydrogen chloride was dissolved at 1.44% by weight was added, and the mixture was stirred for about 30 minutes to obtain a phenylsilsesquioxane sol containing methylsilsesquioxane.

In the same manner as in Example 1, a substrate with a petal-like alumina pattern film (without FAS layer) was coated with the phenylsilsesquioxane sol containing methylsilsesquioxane, dried, and treated at 200 ° C. To form a lens array. The refractive index of the lens portion formed at this time was 1.50. The refractive index of the lens manufactured in Example 1 was 1.53, which shows that the refractive index can be controlled. The gel having fluidity generated by keeping it at 200 ° C. had a contact angle of 2 degrees at the petal-like alumina portion and a contact angle of 9 degrees at the glass substrate.

[Example 5] The phenylsilsesquioxane sol used in Example 1 was used for the substrate with a petal-shaped alumina pattern film coated with the FAS layer obtained in Example 1, and the pulling rate was 3.03 mm / A film was formed by dip coating in seconds, and then dried at room temperature for about 15 hours. Next, when the gelled film was heated at 200 ° C. for 30 minutes,
As in Example 3, after the gel film was softened and gathered on the petal-like alumina portion (circle having a diameter of 150 μm) coated with FAS to form a convex portion, the gel film was completely gelled and cured to a diameter of 120 μm. A hemispherical lens was formed, and a microlens array having about 20,000 lenses fixed on the surface of the substrate was obtained. The thickness between the apex and the bottom of the lens was about 8 μm. A three-dimensional surface profile of the formed lens array measured by using an atomic force microscope (AFM) is shown in FIG. The cross-sectional profile of one lens of this lens array is shown in FIG. FIG. 4 in the case where the FAS layer is coated has a steeper slope at the rising portion of the convex portion as compared with FIG. 3 in the case where the FAS layer is not coated (Example 1), and the phenyls gathered on the petal-like alumina. It can be seen that the contact angle at the periphery of the silsesquioxane sol is increased due to the presence of FAS. In addition, the above-mentioned gel having fluidity generated by keeping it at 200 ° C. has a contact angle of about 40 degrees in the petal-like alumina portion with FAS.
The contact angle on the attached glass substrate was about 75 degrees.

The variation in the thickness of the formed lens is 5
The point evaluation was 8 ± 0.3 μm, and the error was about ± 3.
8%, the radius of curvature is 253 ± 8 μm, and the error is about ± 3.
It was 2%. When the focal length is measured, it is 333 ± 22
The error was ± 6.5%. Furthermore, when the transmittance of light of wavelength 400 to 2500 nm of this material was evaluated, it was confirmed that there was no problematic absorption in the wavelength range of the communication band. Also, the adhesion to the substrate was good, and the lens did not peel off from the substrate during cutting or washing.

Regarding the above microlens array, 3
After carrying out a heat resistance test of holding at 00 ° C. for 2 hours, the temperature was returned to room temperature and the presence or absence of cracks was observed to evaluate the heat resistance. As a result, the lens and the substrate were not cracked or peeled off, and the focal lengths of all the lenses were the same as before the heat resistance test.

[Example 6] The phenylsilsesquioxane sol containing titanium used in Example 2 was used as a lens-forming material on the substrate with a petal-like alumina pattern film coated with the FAS layer obtained in Example 1. Coated, dried and processed at 200 ° C. to form a lens array.

[Example 7] The phenylsilsesquioxane sol containing titanium used in Example 3 was used as a lens-forming material on the substrate with a petal-like alumina pattern film coated with the FAS layer obtained in Example 1. The lenses were coated, dried and processed at 200 ° C to form lenses.

Example 8 The methylsilsesquioxane-containing phenylsilsesquioxane sol used in Example 4 was applied to the substrate with a petal-shaped alumina pattern film coated with the FAS layer obtained in Example 1. A lens array was formed by coating as a lens forming material, drying, and processing at 200 ° C.

[Example 9] Preparation of silica sol, film formation, and formation of lens array Polyethylene glycol (average molecular weight 200) was added to 20% by weight of colloidal silica dispersed in water to a concentration of 20% by weight, and the mixture was stirred for about 1 hour. Then, silica sol was obtained.

When the silica sol was spin-coated on the substrate with a petal-shaped alumina pattern film coated with the FAS layer obtained in Example 1 at a substrate rotation speed of 3000 rpm and a holding time of 5 seconds, it adhered only to the petal-shaped alumina portion. did. This was dried at 150 ° C. for 30 minutes to obtain a microlens array.

[Example 10] FAS obtained in Example 1
On the surface of the substrate with a petal-like alumina pattern film coated with a layer, 0.01 g of a UV curable resin (fluorinated epoxy resin: UV-3200 manufactured by Daikin Industries, Ltd.) is used with a liquid precision quantitative discharge device (dispenser manufactured by Musashi Engineering Co., Ltd.). After the ejection, dry air was blown onto the surface of the substrate with a petal-shaped alumina pattern film to spread it to a substantially uniform thickness. Next, when the temperature was kept at 100 ° C., after about 10 minutes, the resin on the glass substrate exposed by the solvent removal in the non-exposed portion was moved and the petal-like alumina portion (diameter 15
0 μm circle). After that, by irradiating light from a high pressure mercury lamp (240W manufactured by Ushio Inc.) with a wavelength in the range of 365 nm at an illuminance of 88.9 mW / cm ² for 2.5 minutes, the resin collected in the petal-like alumina part with a diameter of 120 μm was It was cured and a lens was obtained. The thickness of the apex and the bottom of the lens was about 4 μm.

Wavelength of the formed lens material is 400 nm
When the transmittance of light having a wavelength of 2,500 nm was evaluated, there was no problematic absorption in the wavelength band of the communication band, and the refractive index of the lens part was 1.48.

[Embodiment 11] Size of about 25 mm × 25 m
m, a polycarbonate substrate with a thickness of about 1 mm, a neutral detergent,
It was rinsed with water and washed successively with alcohol, dried, and then used as a coating substrate. 0.5 mol of benzoylacetone was added to a product obtained by diluting 1.0 mol of aluminum-sec-butoxide (Al (O-sec-Bu) ₃ ) with 20 mol of isopropanol. This was stirred for about 3 hours at room temperature to obtain an aluminum chelate compound solution.

Then, the polycarbonate substrate was dipped in the coating solution, and then a coating film was formed on the surface of the substrate by a dipping method (withdrawing speed of about 1 mm / sec).
Then, it was dried at room temperature for 30 minutes to coat a transparent amorphous alumina film.

Using the same photomask and light source as those used in Example 1, light irradiation was performed under the same conditions and dissolution with a solvent was performed. As a result, the diameter of 1
Amorphous alumina with 50 μm and 175 μm intervals formed a pattern. Next, a hot water treatment of immersing in warm water of about 60 ° C. for a predetermined time was performed, and it was dried again at room temperature. The obtained alumina thin film had a high transmittance in the visible region, and the film thickness was about 200 nm. The polycarbonate substrate coated with this transparent alumina thin film (having a diameter of 150 μm and covered at intervals of 175 μm) has a thickness of 19 at the alumina thin film portion.
It had a fine uneven surface (petal-like alumina structure) with a surface roughness Ra of nm and a specific surface area SR of 1.7. The exposed polycarbonate part has a surface roughness R of 1 nm.
a and had a smooth surface with a specific surface area SR of 1.0.

A phenylsilsesquioxane sol containing titanium was coated on the polycarbonate substrate with a petal-shaped alumina pattern film by the same method as in Example 1, dried and treated at 200 ° C. to form a lens. The refractive index of the obtained lens part was 1.55.

As described above, in this example, the aluminum chelate compound coating film was irradiated with light and washed with a solvent to form an alumina pattern, and then the alumina portion was dipped in warm water to form a petal-like pattern having fine irregularities on the surface. By changing to an alumina pattern, the surface energy difference in the surface fine uneven pattern and the capillary phenomenon of the fine uneven structure form a convex portion in the fine uneven area of the film forming liquid composition. At this time, when a specific film-forming liquid composition was used, a film-forming liquid that was once solid was formed by forming a film with a uniform film thickness on the entire surface of the petal-shaped alumina pattern at the coating step, and drying and heating. The composition becomes a droplet state and a convex portion is formed in the fine uneven area due to the difference in surface energy and the capillary phenomenon. Since the liquid composition for film formation enters the surface of fine irregularities and cures, excellent adhesion is obtained.

[0081]

As described above, according to the present invention,
An optical element having excellent adhesion to a substrate in a simple process, high precision, and a wide composition range by utilizing a surface energy difference and a capillary phenomenon by using a pattern in which fine irregular areas are regularly arranged. It enables the manufacture of articles having other predetermined surface shapes. When the hydrolyzable compound is used as the film-forming liquid composition, an article having a predetermined surface shape with excellent heat resistance can be obtained.

[Brief description of drawings]

FIG. 1 is a perspective view showing a three-dimensional surface profile of a microlens array obtained according to Example 1 of the present invention.

FIG. 2 is a perspective view showing a three-dimensional surface profile of a microlens array obtained according to Example 5 of the present invention.

FIG. 3 is a graph showing a cross-sectional profile of one lens of the microlens array obtained according to Example 1 of the present invention.

FIG. 4 is a graph showing a cross-sectional profile of one lens of the microlens array obtained according to Example 5 of the present invention.

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Seiji Tadanaga             256-1 Fone, Nagasone-machi, Sakai City, Osaka Prefecture             O 401 (72) Inventor Atsunori Matsuda             12-5 Midorigaoka Nakamachi, Kawachinagano City, Osaka Prefecture (72) Inventor Teruyuki Sasaki             4-7-28 Kitahama, Chuo-ku, Osaka, Japan Plate             Glass Co., Ltd. (72) Inventor Koichiro Nakamura             4-7-28 Kitahama, Chuo-ku, Osaka, Japan Plate             Glass Co., Ltd. (72) Inventor Hiroaki Yamamoto             4-7-28 Kitahama, Chuo-ku, Osaka, Japan Plate             Glass Co., Ltd. F-term (reference) 4F204 AA36 AA44 AA49 AD03 AD04                       AD05 AF01 AH74 AH75

Claims (20)

[Claims] 1. A liquid composition for forming a film is adhered to a molding surface of a substrate having as a molding surface a pattern surface in which areas of high wettability and areas of low wettability are regularly arranged. In the method for producing an article having a predetermined surface shape, wherein the composition is cured to form a cured product in the high wettability area, the high wettability area of the substrate has a fine uneven surface and the wettability is high. A method for producing an article having a predetermined surface shape, characterized in that an area having a small property has a smooth surface. 2. The area of high wettability of the substrate is 10 n
smooth surface having a surface roughness Ra of m or more and a specific surface area SR of 1.2 or more, and the small wettability area having a surface roughness Ra of 5 nm or less and a specific surface area SR of 1.0. The method for producing an article having a predetermined surface shape according to claim 1, which has a surface. 3. The area of high wettability of the substrate is 50 n
3. The predetermined according to claim 2, which has a fine textured surface having a surface roughness Ra of m or less and a specific surface area SR of 20 or less, and the small wettability area has a smooth surface having a surface roughness Ra of 2 nm or less. A method for manufacturing an article having a surface shape. 4. The liquid composition has a contact angle A of 90 degrees or less with respect to the surface of a region having a large wettability at any stage from the time when the liquid composition is attached to the forming surface to the cured product. And the contact angle A with respect to the surface of the area having small wettability
The method for producing an article having a predetermined surface shape according to any one of claims 1 to 3, which has a contact angle B larger than that by 5 degrees or more. 5. The liquid composition contains at least one compound selected from the group consisting of a hydrolyzable compound capable of undergoing hydrolysis and polycondensation, its hydrolyzate and its polycondensation product. A method for manufacturing an article having a predetermined surface shape according to any one of 1. 6. The liquid composition has a contact angle A of 90 degrees or less with respect to the surface of a highly wettable area in the state of a heated polycondensate, and with respect to the surface of a less wettable area. The contact angle B is larger than the contact angle A by 5 degrees or more, the liquid composition is attached to the entire surface of the molding surface, and the liquid composition is heated to the state of the polycondensation product to perform the condensation. The method for producing an article having a predetermined surface shape according to claim 5, wherein the polymer is collected in an area having high wettability. 7. The method for producing an article having a predetermined surface shape according to claim 1, wherein the liquid composition contains a raw material of light or thermosetting resin. 8. The liquid composition has a contact angle A of 90 degrees or less with respect to the surface of a highly wettable area in a heated state, and the contact angle A with respect to a surface of a less wettable area. Having a contact angle B larger than that by 5 degrees or more,
The method for producing an article having a predetermined surface shape according to claim 7, wherein the liquid composition is attached to the entire surface of the molding surface, and the liquid composition is heated to collect the heated material in an area having a high wettability. 9. The substrate having the patterned surface as a molding surface is prepared by using a photosensitive solution containing a metal compound capable of being hydrolyzed and polycondensed, and having a surface roughness Ra of 5 nm or less and a specific surface area SR of 1.0. A film is formed by coating on the surface of a base substrate having a film, the coating film is irradiated with light in a pattern, the unexposed portion of the coating film is dissolved and removed with a solvent, and then the exposed portion of the coating film is contacted with warm water. 9. A metal oxide film having a surface roughness Ra of 10 nm or more and a specific surface area SR of 1.2 or more is formed on the surface of the exposed portion of the base substrate, thereby obtaining a metal oxide film according to claim 1. A method for producing an article having the prescribed surface shape described. 10. The metal compound in the photosensitive solution is a chelate compound of aluminum alkoxide.
A method for producing an article having a predetermined surface shape according to item 1. 11. The method for producing an article having a predetermined surface shape according to claim 9, wherein the base substrate is made of inorganic glass, light or thermosetting resin, thermoplastic resin or metal. 12. The article having a predetermined surface shape according to claim 1, wherein the molding surface is provided with a thin layer of a compound having a water-repellent group on the entire pattern surface. Manufacturing method. 13. The method for producing an article having a predetermined surface shape according to claim 12, wherein the compound having a water-repellent group is an alkyl group-containing silane compound or a fluoroalkyl group-containing silane compound. 14. The hydrolyzable compound in the liquid composition is at least one selected from the group consisting of silicon, aluminum, zirconium, titanium, tin and antimony.
The method for producing an article having a predetermined surface shape according to claim 5 or 6, which is an alkoxide or a chelate compound of a seed element. 15. The hydrolyzable compound in the liquid composition is represented by the following formula (1): Y _n SiX _4-n. (1) where Y is an alkyl group, a vinyl group, an amino group, an epoxy group, 6. A silicon compound represented by the formula: phenyl group or benzyl group, X each independently represents an alkoxyl group or halogen, and n is 0 or 1.
Or the manufacture of an article having a predetermined surface shape according to item 6. 16. The production of an article having a predetermined surface shape according to claim 15, wherein Y in the formula (1) is an alkyl group or a phenyl group, X is a methoxyl group or an ethoxyl group, and n is 1. Method. 17. The liquid composition further comprises, in addition to the silicon compound, a compound represented by the following formula (2), R ₂ SiQ ₂ ··· (2), wherein each R independently represents an alkyl group, a vinyl group, an amino group, 16. A silicon compound represented by: an epoxy group, a phenyl group or a benzyl group, and Qs each independently representing an alkoxyl group or a halogen.
Or a method for producing an article having a predetermined surface shape according to item 16. 18. The liquid composition further comprises, as the hydrolyzable compound, at least one metal selected from the group consisting of titanium alkoxide, zirconium alkoxide, aluminum alkoxide and chelate compounds thereof, in addition to the silicon compound. The method for producing an article having a predetermined surface shape according to any one of claims 14 to 17, which comprises a compound, a hydrolyzate thereof, or a polycondensate thereof. 19. The heating temperature of the polycondensation product is 100.
The method for producing an article having a predetermined surface shape according to claim 6, wherein the temperature is from 300C to 300C. 20. The method for producing an article having a predetermined surface shape according to claim 1, wherein the article having the predetermined surface shape is a microlens array, a cylindrical lens array or a Fresnel lens.