JP2001141906A - Microlens substrate and method of manufacturing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a microlens substrate which is advantageous in terms of cost due to a simple manufacturing process and which has good quality because it is manufactured with high accuracy, and a method for manufacturing such a microlens substrate. The purpose is to provide. A substrate is provided on a surface of the substrate,
The above object is achieved by providing a microlens substrate having a variable wettability layer capable of changing wettability and a plurality of microlenses provided on the variable wettability layer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a microlens substrate having a plurality of microlenses arranged on a substrate,
In particular, the present invention relates to a microlens substrate which is advantageous in cost because it is manufactured by a simple manufacturing method and has good quality, and a manufacturing method thereof.

[0002]

2. Description of the Related Art In recent years, demand for a microlens substrate in which a microlens is arranged on a transparent substrate has been increasing. For example, a color liquid crystal display (LCD) uses a color filter to form constituent pixel portions into three primary colors (R, G,
B) is to perform color display by controlling the transmission of each of the three primary colors by electrical switching of the liquid crystal, and has the advantage of lower power consumption than a plasma display or the like. In such a liquid crystal display, in order to make the display bright and clear, a so-called backlight system having a light source for illumination behind has been widely used in recent years. However, when using a light source for illumination, power consumption increases,
The advantage of the liquid crystal display that the above power consumption is small is spoiled. For this reason, it is required that the light from the illumination light source be efficiently condensed on the pixel portion of the color filter to reduce the power required for the illumination light source. As a means, micro lenses are arranged on a transparent substrate. A liquid crystal display using a microlens substrate has been proposed (Japanese Patent Application Laid-Open No. 60-165623 and the like).

A color image sensor using a CCD or the like has been developed in which a microlens substrate having a microlens corresponding to each light receiving cell is provided on the light receiving surface in order to increase the effective aperture ratio (see, for example, Japanese Patent Application Laid-Open No. H11-157556). Kaisho 61-
67003).

[0004] Further, even in an optical fiber, which has been increasingly used in optical communication and the like in recent years, a microlens is used in combination for coupling light (Japanese Patent Application Laid-Open No. Sho 6 (1988)).
1-153602).

As described above, a microlens substrate having a microlens disposed on one surface of a transparent substrate is used for various purposes. This microlens manufacturing method includes (1) a method of forming a gradient index lens using the distribution of ion concentration diffused in glass (Electronics Le
tters Vol.17, No.13, PP452 (1981)), (2) a method in which the surface of plastic or glass is molded into lens-like irregularities using a mold, and (3) a planar shape of the lens using a thermoplastic resin. A method of forming a convex lens by patterning, and then heating and flowing above the softening point of the thermoplastic resin to cause sagging at the pattern edge (Japanese Patent Laid-Open No.
(4) Proximity exposure of a photosensitive resin to cause blur at a pattern edge, and a distribution of the amount of a photoreaction product according to the blur to obtain a convex lens shape ( JP-A-61-153602),
(5) a method of irradiating a photosensitive resin with light having an intensity distribution and exposing the same to form a refractive index distribution pattern corresponding to the light intensity to form a microlens (JP-A-60-72927, etc.);
(6) A method of forming a convex lens using shrinkage accompanying crystallization caused by light irradiation on photosensitive glass (Ap
plied Optics Vol.24, No.16, PP2520 (1985)), (7) When the photosensitive resin is exposed to a desired pattern using an aligner, unreacted monomers move from the non-exposed area to the exposed area. Convex lens formation method using the phenomenon that the exposed part rises (Applied Physics Society of Japan, Optical Society, Micro-optics Research Group, Journal Vol.5, No.2, PP118 (1987), Vol.6, No.2, PP87
(1988)).

However, in any of the above-described manufacturing methods, it is not possible to more easily manufacture a microlens having desired characteristics, and thus there is a problem in cost and a problem in quality. Was.

The present invention has been made in view of the above circumstances, and is advantageous in terms of cost because the manufacturing process is simple, and has a good quality microlens substrate because it is manufactured with high accuracy. It is a main object to provide a method for manufacturing such a microlens substrate.

[0008]

In order to achieve the above object, according to the present invention, there is provided a semiconductor device comprising: a substrate; and a wettability variable layer provided on a surface of the substrate and capable of changing wettability. And a plurality of microlenses provided on the variable wettability layer.

As described above, since the present invention has a configuration in which a plurality of microlenses are provided on the variable wettability layer, the wettability of the variable wettability layer at the portion where the microlens is provided in advance is determined by contact with the liquid. The lyophilic region having a small angle can be used, and the wettability variable layer in other portions can be used as a lyophobic region having a large contact angle with a liquid. Therefore, by attaching the microlens-forming paint to the portion of the lyophilic region where the microlens is provided, the microlens-forming paint adheres only to the lyophilic region having a small contact angle with the liquid. A microlens can be formed with high precision. Also, the focal length of the microlens is determined by the relationship between the amount of the microlens forming paint and the area of the lyophilic region (microlens forming portion) to which the microlens forming paint is applied. The focal length can be easily controlled.

In the present invention, it is preferable that the substrate is a transparent substrate. Microlenses are used in liquid crystal displays, etc., to increase the luminance in the direction of the viewer or to increase the light sensitivity of imaging devices such as CCD devices. In many cases, it is necessary to be configured to do so. Therefore,
The substrate used for the microlens substrate is preferably a transparent substrate.

[0011] In the first or second aspect of the invention, as described in the third aspect, the variable wettability layer is a photocatalyst-containing layer comprising at least a photocatalyst and a binder, and has a low energy consumption. The layer is preferably a layer whose wettability changes so that the contact angle with the liquid is reduced by irradiation.

As described above, if a photocatalyst-containing layer whose wettability changes so that the contact angle with a liquid is reduced by energy irradiation is formed, the wettability of this layer can be easily determined by performing energy pattern irradiation or the like. Can be changed to form a lyophilic region having a small contact angle with the liquid, and only a portion where a microlens is formed can be easily formed as a lyophilic region. Therefore, since the lyophilic region can be formed more easily and more accurately,
By forming a microlens in this lyophilic region, a more accurate microlens substrate can be obtained in a simpler process.

In the microlens substrate according to the third aspect, as described in the fourth aspect, the photocatalyst containing layer contains fluorine, and when the photocatalyst containing layer is irradiated with energy, the photocatalyst containing layer contains fluorine. It is preferable that the photocatalyst-containing layer is formed so that the fluorine content on the surface of the photocatalyst-containing layer is reduced by the action as compared with before the irradiation with energy.

As described above, since the microlens substrate of the present invention is configured so that the fluorine content of the energy-irradiated portion on the photocatalyst-containing layer formed on the substrate is reduced, pattern irradiation with energy is performed. Thereby, it is possible to form a pattern composed of a portion having a reduced fluorine content. When the fluorine content is reduced, the portion becomes a region having higher lyophilicity as compared with other portions, so that only the portion where the microlens is formed can be easily set as the lyophilic region, and A microlens substrate can be manufactured.

In the microlens substrate according to the third or fourth aspect, as described in the fifth aspect, the photocatalyst comprises titanium oxide (TiO ₂ ), zinc oxide (Z
nO), tin oxide (SnO _2), strontium titanate (SrTiO _3), tungsten oxide (WO _3), bismuth oxide (Bi ₂ O _3), and one kind selected from iron oxide (Fe ₂ O ₃₎ or It is preferable to use two or more substances. In particular, as described in claim 6, the photocatalyst is preferably titanium oxide (TiO ₂ ). This is because titanium oxide has a high band gap energy and is effective as a photocatalyst, and is chemically stable, has no toxicity, and is easily available.

In the microlens substrate according to any one of the third to sixth aspects, the binder as another component constituting the photocatalyst-containing layer may be as follows. _{Y n SiX (4-n)} ( where, Y is an alkyl group, fluoroalkyl group, vinyl group, amino group, a phenyl group or an epoxy group, X until .n 0-3 showing an alkoxyl group or a halogen Is preferably an organopolysiloxane which is one or more hydrolytic condensates or co-hydrolytic condensates of the silicon compound represented by the formula (I). This is because it is easy to introduce a fluoroalkyl group or the like that has a binding energy that opposes the catalytic action of the photocatalyst and exhibits liquid repellency, and can increase lyophilicity when irradiated with energy.

In the microlens substrate according to the seventh aspect, as described in the eighth aspect, among the silicon compounds constituting the organopolysiloxane,
0.01 mol% of a silicon compound containing a fluoroalkyl group
It is preferable that the above is included.

As described above, when the silicon compound containing a fluoroalkyl group is contained in an amount of 0.01 mol% or more, the surface of the photocatalyst-containing layer contains a sufficient amount of elemental fluorine. Since the difference in wettability between the lyophilic region on the photocatalyst-containing layer in which the content of the element has been reduced and the lyophobic region on the surface of the photocatalyst-containing layer where energy has not been irradiated can be increased, the lyophilic region This is because when forming microlenses, the microlens forming coating can be accurately adhered without protruding into the liquid-repellent region, and a high-quality microlens substrate can be manufactured.

In the invention described in any one of claims 3 to 8, as described in claim 9 (in the invention described in claim 10 or 11 described below, The contact angle with the liquid having a surface tension of 40 mN / m on the photocatalyst-containing layer is 10 degrees or more in a portion where no energy is applied, and in a portion where the energy is applied. Preferably it is less than 10 degrees.

Since the portion not irradiated with energy is a portion requiring liquid repellency, a surface tension of 40 m
If the contact angle with the liquid of N / m is less than 10 degrees, the liquid repellency is not sufficient, and there is a possibility that the coating material for forming microlenses remains, which is not preferable. When the contact angle with the liquid having a surface tension of 40 mN / m is 10 degrees or more, the spread of the microlens-forming paint in this portion may be inferior, and the uniform curvature may be obtained. This is because there is a possibility that a problem such as the inability to form a pattern may occur.

A liquid crystal display (Claim 13) and an image pickup device (Claim 1) using the microlens substrate according to any one of the first to ninth aspects.
The method 4) uses a high-quality microlens substrate obtained in a simple process, so that it is advantageous in terms of cost and can have good quality.

Further, according to the present invention, in order to achieve the above object, as described in claim 10, (1) the wettability of the irradiated portion is changed in the direction in which the contact angle with the liquid is reduced by irradiating the substrate with energy. Providing a photocatalyst-containing layer,
(2) a step of pattern-irradiating energy to a microlens forming portion, which is a portion for forming a microlens on the photocatalyst-containing layer provided on the substrate, to form a microlens exposure portion; Applying a coating material for forming a microlens to an exposure unit for a microlens to form a microlens.

As described above, in the method for manufacturing a microlens substrate according to the present invention, the photocatalyst containing layer is provided on the substrate,
By irradiating the photocatalyst-containing layer with a pattern of energy, it is possible to form a microlens exposure portion having a reduced contact angle with a liquid. The microlens can be easily formed by applying the microlens forming paint to the microlens exposure section. Therefore, a microlens substrate in which the positional accuracy of the microlens is accurate can be manufactured by a simple manufacturing method.

Further, in the method of manufacturing a microlens according to the tenth aspect, the step of applying a coating material for forming a microlens to the microlens exposure portion may be performed by an inkjet method. Preferably, it is applied. By applying the ink-jet method, it is possible to apply the microlens-forming paint efficiently, and the application position of the microlens-forming paint is accurate, and the amount of the microlens paint remaining in the liquid-repellent area. This is because it is possible to efficiently manufacture a microlens substrate having higher quality.

[0025]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. First, after describing a microlens substrate,
A method for manufacturing a microlens substrate will be described.

A. First, the microlens substrate of the present invention will be described in detail. The microlens substrate of the present invention comprises a substrate, a variable wettability layer provided on the surface of the substrate and capable of changing wettability, and a plurality of microlenses provided on the variable wettability layer. It is characterized by having.

As described above, in the microlens substrate of the present invention, the microlens is provided on the variable wettability layer capable of changing the wettability. Therefore, the wettability of the portion where the microlens is provided in advance can be a lyophilic region having a small contact angle with the liquid, and the other portion can be a lyophobic region having a large contact angle with the liquid. By applying and adhering the microlens forming paint to the microlens forming portion where the microlenses are provided, the microlens forming paint adheres only to the lyophilic region having a small contact angle with the liquid. The coating for microlens formation spreads evenly over the entire lens formation section,
A microlens having a predetermined angle with respect to the substrate and having a predetermined curvature can be formed. Here,
The microlens substrate is composed of at least a substrate and a plurality of microlenses arranged thereon,
The microlens may be a microlens array in which the microlenses are arranged at predetermined intervals.

An example of such a microlens substrate of the present invention will be described with reference to the drawings.

FIG. 1 shows an example of the microlens substrate of the present invention. The microlens substrate 1 includes a substrate 2, a variable wettability layer 3 provided on the substrate 2,
Further, it comprises a plurality of micro lenses 4 formed on the variable wettability layer 3. The microlens 4 is formed on a microlens forming portion 5 having the wettability variable layer 3 as a lyophilic region, and a portion other than the microlens forming portion 5 is a liquid-repellent wettability variable layer 3. It is. The micro lens 4 is formed on a substrate by utilizing the difference in wettability.

Hereinafter, each part constituting the microlens substrate of the present invention will be described.

(Variable Wettability Layer) The variable wettability layer 3 comprises:
The layer is not particularly limited as long as it can change the wettability of the surface by an external stimulus such as a physical stimulus or a chemical stimulus. For example, it may be a layer whose surface roughness changes due to acid or alkali or the like, and the wettability changes, or a substance in the wettability variable layer changes due to ultraviolet light or visible light to get wet. It may be a layer or the like whose properties change.

Regarding the change in wettability, even if the wettability variable layer has a large contact angle with the liquid before the stimulus is applied and a small contact angle with the liquid after the stimulus is applied. Alternatively, the wettability variable layer may have a small contact angle with the liquid before the stimulus is applied, and a large change in the contact angle with the liquid after the stimulus is applied.

(Photocatalyst-Containing Layer) In the present invention, it is preferable that the variable wettability layer is a photocatalyst-containing layer whose wettability changes so that the contact angle with a liquid is reduced by irradiation of energy. As described above, the wettability is reduced so that the contact angle with the liquid is reduced by the exposure (in the present invention, not only the irradiation of light but also the irradiation of energy). By providing the changing photocatalyst containing layer, it is possible to easily change the wettability by performing energy pattern irradiation and the like, and to form a pattern of a small lyophilic region having a small contact angle with a liquid,
For example, only a region where a microlens is formed can be easily made a lyophilic region. Therefore, the microlens substrate can be manufactured efficiently, which is advantageous in cost. In this case, as the energy in this case, light including ultraviolet light is usually used.

Here, the lyophilic region is a region having a small contact angle with a liquid, and is a region having good wettability with respect to a microlens forming paint or the like. The lyophobic region is a region having a large contact angle with a liquid, and is a region having poor wettability to a microlens forming paint or the like.

The photocatalyst-containing layer has a contact angle of not less than 10 degrees with a liquid having a surface tension of 40 mN / m, preferably a contact angle of not less than 10 degrees with a liquid having a surface tension of 30 mN / m in a portion not exposed. In particular, the contact angle with a liquid having a surface tension of 20 mN / m is preferably 10 degrees or more. This is because the non-exposed portion is a portion requiring liquid repellency in the present invention. Therefore, when the contact angle with the liquid is small, the liquid repellency is not sufficient, and the coating material for forming microlenses is not provided. Is likely to remain in the liquid-repellent region, or it may be difficult to increase the angle of the microlens with respect to the substrate.

In the photocatalyst-containing layer, the contact angle with a liquid is reduced when exposed to light, and the contact angle with a liquid having a surface tension of 40 mN / m is less than 10 degrees, preferably a surface tension of 50 mN / m.
/ M of liquid has a contact angle of 10 degrees or less, especially a surface tension of 60
It is preferable that the layer has a contact angle with the liquid of mN / m of 10 degrees or less. If the contact angle of the exposed portion with the liquid is high, the spread of the ink in this portion may be inferior, and a problem such as the inability to obtain a microlens with an accurate curvature may occur.

Here, the contact angle with a liquid is measured by using a contact angle measuring device (CA-Z type manufactured by Kyowa Interface Science Co., Ltd.) to measure the contact angle with a liquid having various surface tensions (micrometer). 30 seconds after dropping the droplet from the syringe), and the result or the result is graphed. In this measurement, wetting index standard liquid manufactured by Junsei Chemical Co., Ltd. can be used as the liquid having various surface tensions.

The photocatalyst-containing layer of the present invention preferably comprises at least a photocatalyst and a binder. With such a layer, the critical surface tension can be increased by the action of a photocatalyst by energy irradiation, and the contact angle with the liquid can be reduced.

The action mechanism of the photocatalyst represented by titanium oxide as described later in such a photocatalyst containing layer is as follows.
Although it is not always clear, carriers generated by irradiation with light, etc., change the chemical structure of organic matter by direct reaction with nearby compounds or active oxygen species generated in the presence of oxygen and water Is believed to be something.

By using the action of the photocatalyst, oily dirt is decomposed by light irradiation and made hydrophilic so that it can be washed with water, or a hydrophilic film is formed on the surface of glass or the like to provide anti-fogging properties. So-called antibacterial tiles have been proposed that reduce the number of airborne bacteria in the air by forming a layer containing a photocatalyst on the surface of the tile or the like.

In the present invention, when a photocatalyst-containing layer is used as the variable wettability layer, the photocatalyst reduces the wettability of the exposed portion by using the action of oxidation and decomposition of an organic group or an additive which is a part of the binder. It can be changed to make it lyophilic and make a large difference in wettability with non-exposed areas. Therefore, by improving the receptivity (lyophilic property) and repellency (liquid repellency) with the microlens forming paint, a microlens substrate having good quality and advantageous in cost can be obtained.

When such a photocatalyst-containing layer is used in the present invention, the photocatalyst-containing layer contains at least a photocatalyst and fluorine, and the fluorine content on the surface of the photocatalyst-containing layer is more than that of the photocatalyst-containing layer. The photocatalyst-containing layer may be formed such that when the energy is irradiated, the photocatalyst-containing layer is reduced by the action of the photocatalyst as compared with before the energy irradiation.

In a microlens substrate having such characteristics, a pattern composed of a portion having a small fluorine content can be easily formed by pattern irradiation with energy. Here, fluorine has an extremely low surface energy, so that the surface of a substance containing a large amount of fluorine has a smaller critical surface tension. Therefore, the critical surface tension of the portion having a low fluorine content is larger than the critical surface tension of the portion having a high fluorine content. This means that a portion having a low fluorine content is a lyophilic region as compared with a portion having a high fluorine content. Therefore, forming a pattern composed of a portion having a lower fluorine content than the surrounding surface forms a pattern of the lyophilic region in the lyophobic region.

Accordingly, when such a photocatalyst-containing layer is used, the pattern of the lyophilic region can be easily formed in the lyophobic region by pattern irradiation with energy. The microlens can be easily formed only in the active region, and a high-quality microlens substrate can be obtained.

As described above, the content of fluorine contained in the fluorine-containing photocatalyst containing layer is determined by the fact that the fluorine content in the lyophilic region having a low fluorine content formed by irradiation of energy is determined by the energy irradiation. When the fluorine content of the unexposed portion is 100, it is preferably 10 or less, more preferably 5 or less, and particularly preferably 1 or less.

By setting it within such a range, a large difference can be made in the lyophilicity between the energy-irradiated portion and the non-irradiated portion. Therefore, by forming a microlens in such a photocatalyst containing layer, it becomes possible to form a microlens only in the lyophilic region where the fluorine content is reduced, and furthermore, a predetermined angle with respect to the substrate is obtained. This is because a microlens having a predetermined curvature can be formed, and a microlens substrate can be obtained with high accuracy. In addition, this reduction rate is based on weight.

For the measurement of the fluorine content in the photocatalyst-containing layer, various methods generally used can be used, for example, X-ray photoelectron spectroscopy (X-ray Phot spectroscopy).
oelectron Spectroscopy, ESCA (Electron Spectroscop
y for Chemical Analysis). ), Any method capable of quantitatively measuring the amount of fluorine on the surface, such as X-ray fluorescence analysis and mass spectrometry.

The photocatalyst used in the present invention includes, for example, titanium oxide (TiO ₂ ), zinc oxide (ZnO), tin oxide (SnO ₂ ), strontium titanate (SrTiO ₃ ), and tungsten oxide (W) which are known as optical semiconductors.
O ₃ ), bismuth oxide (Bi ₂ O ₃ ), and iron oxide (F
e ₂ O ₃ ), and one or more of them may be used in combination.

In the present invention, titanium oxide is particularly preferably used because it has a high band gap energy, is chemically stable, has no toxicity, and is easily available. Titanium oxide includes anatase type and rutile type, and both can be used in the present invention, but anatase type titanium oxide is preferable. Anatase type titanium oxide has an excitation wavelength of 380 nm or less.

As such anatase type titanium oxide, for example, anatase type titania sol of peptized hydrochloric acid (STS-02 manufactured by Ishihara Sangyo Co., Ltd. (average particle size: 7 nm);
ST-K01 manufactured by Ishihara Sangyo Co., Ltd., anatase titania sol of nitric acid peptization type (TA-15 (average particle size: 12 nm) manufactured by Nissan Chemical Industries, Ltd.) and the like can be mentioned.

The smaller the particle size of the photocatalyst is, the more effective the photocatalytic reaction takes place. The average particle size is preferably 50 nm or less, more preferably 20 nm or less. In addition, the smaller the particle size of the photocatalyst is, the smaller the surface roughness of the formed photocatalyst-containing layer is. It is preferable that the particle size of the photocatalyst exceeds 100 nm. This is not preferred because the lyophobic properties of the non-exposed areas of the containing layer decrease and the lyophilic properties of the exposed areas become insufficient.

As described above, the microlens substrate of the present invention contains fluorine on the surface of the photocatalyst-containing layer, and pattern-irradiates the surface of the photocatalyst-containing layer with energy to reduce the fluorine content on the surface of the photocatalyst-containing layer. Thus, a microlens substrate obtained by forming a pattern of a lyophilic region in a lyophobic region and forming a microlens there may be used. Even in this case, it is preferable to use the titanium dioxide as described above as the photocatalyst. However, when titanium dioxide is used in this way, the content of fluorine contained in the photocatalyst containing layer is determined by X-ray photoelectron. Quantitative analysis by spectroscopy shows that when the titanium (Ti) element is 100, the fluorine (F) element is 500 or more,
Preferably, fluorine (F) element is contained on the surface of the photocatalyst-containing layer at a ratio of preferably 800 or more, particularly preferably 1200 or more.

When fluorine (F) is contained in the photocatalyst-containing layer to this extent, the critical surface tension on the photocatalyst-containing layer can be sufficiently reduced, so that the liquid repellency on the surface can be ensured. Pattern, the fluorine content can be reduced and the difference in wettability with the lyophilic region on the surface in the pattern portion can be increased, and the quality of the finally obtained microlens substrate can be improved. Because.

Further, in such a microlens substrate, when the fluorine content in the lyophilic region formed by pattern irradiation of energy is such that the titanium (Ti) element is 100 and the fluorine (F) element is It is preferable that they are contained at a ratio of 50 or less, preferably 20 or less, particularly preferably 10 or less.

If the content of fluorine in the photocatalyst-containing layer can be reduced to this extent, sufficient lyophilicity for forming microlenses and the like can be obtained, and the above-mentioned portion of the energy-unirradiated portion can be obtained. Due to the difference in wettability from the liquid repellency, it is possible to accurately form a microlens or the like, and a microlens substrate with good quality can be obtained.

In the present invention, the binder used in the photocatalyst-containing layer preferably has a high binding energy such that the main skeleton is not decomposed by the photoexcitation of the photocatalyst. For example, (1) chloro or alkoxy by a sol-gel reaction or the like. Examples thereof include organopolysiloxanes that exhibit great strength by hydrolyzing and polycondensing silanes and the like, and (2) organopolysiloxanes obtained by crosslinking reactive silicones having excellent water repellency and oil repellency.

In the case of the above (1), the general formula: Y _n SiX _(4-n) (where Y represents an alkyl group, a fluoroalkyl group, a vinyl group, an amino group, a phenyl group or an epoxy group,
X represents an alkoxyl group, an acetyl group or a halogen. n is an integer from 0 to 3. ) Is preferably an organopolysiloxane that is one or more hydrolytic condensates or cohydrolytic condensates of the silicon compound represented by the formula (1). Here, the carbon number of the group represented by Y is preferably in the range of 1 to 20, and the alkoxy group represented by X is preferably a methoxy group, an ethoxy group, a propoxy group, or a butoxy group. preferable.

Specifically, methyltrichlorosilane, methyltribromosilane, methyltrimethoxysilane, methyltriethoxysilane, methyltriisopropoxysilane, methyltri-t-butoxysilane; ethyltrichlorosilane, ethyltribromosilane, ethyltrichlorosilane Methoxysilane, ethyltriethoxysilane, ethyltriisopropoxysilane, ethyltri-t-butoxysilane; n
-Propyltrichlorosilane, n-propyltribromosilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, n-propyltriisopropoxysilane, n-propyltri-t-butoxysilane; n-
Hexyltrichlorosilane, n-hexyltribromosilane, n-hexyltrimethoxysilane, n-hexyltriethoxysilane, n-hexyltriisopropoxysilane, n-hexyltri-t-butoxysilane; n-decyltrichlorosilane, n-decyltribromosilane,
n-decyltrimethoxysilane, n-decyltriethoxysilane, n-decyltriisopropoxysilane, n-
Decyltri-t-butoxysilane; n-octadecyltrichlorosilane, n-octadecyltribromosilane, n
-Octadecyltrimethoxysilane, n-octadecyltriethoxysilane, n-octadecyltriisopropoxysilane, n-octadecyltri-t-butoxysilane; phenyltrichlorosilane, phenyltribromosilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyl Triisopropoxysilane, phenyltri-t-butoxysilane; tetrachlorosilane, tetrabromosilane, tetramethoxysilane, tetraethoxysilane, tetrabutoxysilane, dimethoxydiethoxysilane; dimethyldichlorosilane, dimethyldibromosilane, dimethyldimethoxysilane , Dimethyldiethoxysilane; diphenyldichlorosilane, diphenyldibromosilane, diphenyldimethoxysilane, diphenyldiethoxysilane Phenyl methyldichlorosilane,
Phenylmethyldibromosilane, phenylmethyldimethoxysilane, phenylmethyldiethoxysilane; trichlorohydrosilane, tribromohydrosilane, trimethoxyhydrosilane, triethoxyhydrosilane, triisopropoxyhydrosilane, tri-t-butoxyhydrosilane; vinyltrichlorosilane, vinyltribromo Silane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriisopropoxysilane, vinyltrit
-Butoxysilane; trifluoropropyltrichlorosilane, trifluoropropyltribromosilane, trifluoropropyltrimethoxysilane, trifluoropropyltriethoxysilane, trifluoropropyltriisopropoxysilane, trifluoropropyltri-t-butoxysilane; γ- Glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ
Glycidoxypropyltriisopropoxysilane, γ
-Glycidoxypropyltri-t-butoxysilane; γ-
Methacryloxypropylmethyldimethoxysilane, γ
-Methacryloxypropylmethyldiethoxysilane,
γ-methacryloxypropyltrimethoxysilane, γ
-Methacryloxypropyltriethoxysilane, γ-
Methacryloxypropyltriisopropoxysilane,
γ-methacryloxypropyltri-t-butoxysilane; γ-aminopropylmethyldimethoxysilane, γ-
Aminopropylmethyldiethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltriisopropoxysilane, γ-aminopropyltri-t-butoxysilane;
γ-mercaptopropylmethyldimethoxysilane, γ-
Mercaptopropylmethyldiethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-mercaptopropyltriisopropoxysilane, γ-mercaptopropyltri-t-butoxysilane; β- (3,4-epoxy Cyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane; and their partial hydrolysates; and mixtures thereof, can be used.

As the binder, a polysiloxane containing a fluoroalkyl group is particularly preferably used. Specifically, one or two or more hydroalkylated condensates or co-hydrolysates of the following fluoroalkylsilanes are preferably used. Decomposition condensates can be used, and those generally known as fluorine-based silane coupling agents can be used.

CF ₃ (CF ₂ ) ₃ CH ₂ CH ₂ Si (OC
H ₃ ) ₃ ; CF ₃ (CF ₂ ) ₅ CH ₂ CH ₂ Si (OC
H ₃ ) ₃ ; CF ₃ (CF ₂ ) ₇ CH ₂ CH ₂ Si (OC
H ₃ ) ₃ ; CF ₃ (CF ₂ ) ₉ CH ₂ CH ₂ Si (OC
_{H 3) 3; (CF 3} ) 2 CF (CF 2) 4 CH 2 CH 2 Si (O
CH ₃ ) ₃ ; (CF ₃ ) ₂ CF (CF ₂ ) ₆ CH ₂ CH ₂ Si
(OCH ₃ ) ₃ ; (CF ₃ ) ₂ CF (CF ₂ ) ₈ CH ₂ CH ₂ S
i (OCH ₃ ) ₃ ; CF ₃ (C ₆ H ₄ ) C ₂ H ₄ Si (OC
_{H 3) 3; CF 3 (} CF 2) 3 (C 6 H 4) C 2 H 4 Si (OC
H ₃ ) ₃ ; CF ₃ (CF ₂ ) ₅ (C ₆ H ₄ ) C ₂ H ₄ Si (OC
_{H 3) 3; CF 3 (} CF 2) 7 (C 6 H 4) C 2 H 4 Si (OC
H ₃ ) ₃ ; CF ₃ (CF ₂ ) ₃ CH ₂ CH ₂ SiCH ₃ (OCH
₃ ) ₂ ; CF ₃ (CF ₂ ) ₅ CH ₂ CH ₂ SiCH ₃ (OC
H ₃ ) ₂ ; CF ₃ (CF ₂ ) ₇ CH ₂ CH ₂ SiCH ₃ (OCH
₃ ) ₂ ; CF ₃ (CF ₂ ) ₉ CH ₂ CH ₂ SiCH ₃ (OC
H ₃ ) ₂ ; (CF ₃ ) ₂ CF (CF ₂ ) ₄ CH ₂ CH ₂ SiCH
₃ (OCH ₃ ) ₂ ; (CF ₃ ) ₂ CF (CF ₂ ) ₆ CH ₂ CH ₂
SiCH ₃ (OCH ₃ ) ₂ ; (CF ₃ ) ₂ CF (CF ₂ ) ₈ C
H ₂ CH ₂ SiCH ₃ (OCH ₃ ) ₂ ; CF ₃ (C ₆ H ₄ ) C ₂
H ₄ SiCH ₃ (OCH ₃ ) ₂ ; CF ₃ (CF ₂ ) ₃ (C
₆ H ₄ ) C ₂ H ₄ SiCH ₃ (OCH ₃ ) ₂ ; CF ₃ (CF ₂ ) ₅
(C ₆ H ₄ ) C ₂ H ₄ SiCH ₃ (OCH ₃ ) ₂ ; CF ₃ (CF
_{2) 7 (C 6 H 4} ) C 2 H 4 SiCH 3 (OCH 3) 2; CF
₃ (CF ₂ ) ₃ CH ₂ CH ₂ Si (OCH ₂ CH ₃ ) ₃ ; CF ₃
(CF ₂ ) ₅ CH ₂ CH ₂ Si (OCH ₂ CH ₃ ) ₃ ; CF
₃ (CF ₂ ) ₇ CH ₂ CH ₂ Si (OCH ₂ CH ₃ ) ₃ ; CF _{3
(CF 2) 9 CH 2 CH} 2 Si (OCH 2 CH 3) 3; and _{CF 3 (CF 2) 7 SO} 2 N (C 2 H 5) C 2 H 4 CH 2 Si
(OCH ₃ ) ₃

By using a polysiloxane containing a fluoroalkyl group as described above as a binder,
The liquid repellency of the non-exposed portion of the photocatalyst-containing layer is greatly improved, and a function of preventing adhesion of the microlens-forming paint and a function of setting the angle of the microlens with respect to the substrate to a predetermined angle or more can be exhibited.

As the reactive silicone of the above (2), compounds having a skeleton represented by the following general formula can be exemplified.

[0063]

Embedded image

Here, n is an integer of 2 or more, and R ¹ ,
R ² is a substituted or unsubstituted alkyl, alkenyl, aryl or cyanoalkyl group having 1 to 10 carbon atoms, and 40% or less of the whole is vinyl, phenyl or halogenated phenyl in a molar ratio. Further, those in which R ¹ and R ² are methyl groups are preferred because the surface energy is minimized, and the molar ratio of the methyl groups is preferably 60% or more. Further, the chain terminal or the side chain has at least one or more reactive group such as a hydroxyl group in the molecular chain.

A stable organosilicon compound which does not undergo a cross-linking reaction such as dimethylpolysiloxane may be mixed with the above-mentioned organopolysiloxane in a binder.

In the microlens substrate of the present invention,
As described above, various binders such as organopolysiloxane can be used for the photocatalyst-containing layer. In the present invention, as described above, the photocatalyst-containing layer containing such a binder and a photocatalyst contains fluorine, and by pattern irradiation with energy, the fluorine on the surface of the photocatalyst-containing layer is reduced, whereby the lyophobic region is formed. You may make it form a lyophilic area | region inside. At this time, it is necessary to contain fluorine in the photocatalyst containing layer, as a method of containing fluorine in the photocatalyst containing layer containing such a binder,
A method of binding a fluorine compound with a binder having a relatively high binding energy with a relatively weak binding energy, a method of mixing a fluorine compound bound with a relatively weak binding energy into a photocatalyst-containing layer, and the like can be given. By introducing fluorine in such a way,
This is because, when energy is applied, first, a fluorine bonding site having a relatively small binding energy is decomposed, whereby fluorine can be removed from the photocatalyst-containing layer.

The first method, that is, a method of binding a fluorine compound with a binder having a high binding energy with a relatively weak binding energy, is a method of introducing a fluoroalkyl group as a substituent into the organopolysiloxane. And the like.

For example, as a method for obtaining an organopolysiloxane, as described in (1) above, chloro or alkoxysilane is hydrolyzed or polycondensed by a sol-gel reaction or the like to obtain an organopolysiloxane exhibiting a large strength. be able to. Here, in this method, as described above, the general formula: Y _n SiX _(4-n) (where Y is an alkyl group, a fluoroalkyl group, a vinyl group,
X represents an amino group, a phenyl group or an epoxy group, and X represents an alkoxyl group, an acetyl group or a halogen. n is an integer from 0 to 3. 1) a silicon compound represented by
The organopolysiloxane is obtained by hydrolyzing or condensing a species or two or more species with a hydrolytic condensate. In this general formula, the organopolysiloxane is synthesized using a silicon compound having a fluoroalkyl group as the substituent Y. Thus, an organopolysiloxane having a fluoroalkyl group as a substituent can be obtained. When an organopolysiloxane having such a fluoroalkyl group as a substituent is used as a binder, when energy is irradiated, the action of the photocatalyst in the photocatalyst containing layer causes
Since the carbon bond portion of the fluoroalkyl group is decomposed, the fluorine content of the portion where the surface of the photocatalyst-containing layer is irradiated with energy can be reduced.

The silicon compound having a fluoroalkyl group used at this time is not particularly limited as long as it has a fluoroalkyl group. However, the silicon compound having at least one fluoroalkyl group may be used. Has a carbon number of 4 to 30, preferably 6 to 20,
Particularly preferably, a silicon compound having 6 to 16 is suitably used. Specific examples of such a silicon compound are as described above, and among them, the silicon compound having a fluoroalkyl group having 6 to 8 carbon atoms, that is, fluoroalkylsilane is preferable.

In the present invention, such a silicon compound having a fluoroalkyl group is mixed with the above-mentioned silicon compound having no fluoroalkyl group, and the cohydrolyzed condensate is used as the organopolysiloxane. Alternatively, one or more silicon compounds having such a fluoroalkyl group may be used, and a hydrolyzed condensate or co-hydrolyzed condensate thereof may be used as the organopolysiloxane.

In the organopolysiloxane having a fluoroalkyl group thus obtained, the silicon compound having the fluoroalkyl group is present in an amount of 0.01 mol% or more, preferably, of the silicon compounds constituting the organopolysiloxane. Preferably, it is contained in an amount of 0.1 mol% or more.

When the fluoroalkyl group is contained to this extent, the lyophobic property on the photocatalyst-containing layer can be enhanced, and the difference in wettability from the lyophilic region when irradiated with energy is increased. Because you can do it.

In the method shown in the above (2), an organopolysiloxane is obtained by crosslinking a reactive silicone having excellent water repellency and oil repellency. By making one or both of R ¹ and R ^{2 in} the compound a fluorine-containing substituent such as a fluoroalkyl group, fluorine can be contained in the photocatalyst-containing layer, and energy irradiation is performed. In this case, the portion of the fluoroalkyl group having a lower binding energy than the siloxane bond is decomposed, so that the content of fluorine on the surface of the photocatalyst-containing layer can be reduced by energy irradiation.

On the other hand, in the latter case, that is, as a method for introducing a fluorine compound bonded with energy lower than the binding energy of the binder, for example, when introducing a low molecular weight fluorine compound, for example, a fluorine-based surfactant is used. And a method of introducing a fluorine compound having a high molecular weight, such as a method of mixing a fluorine resin having high compatibility with the binder resin.

In the present invention, the photocatalyst-containing layer may contain a surfactant in addition to the photocatalyst and the binder. More specifically, NIKK manufactured by Nikko Chemicals Co., Ltd.
Hydrocarbons such as OLBL, BC, BO, and BB series, ZONYL FSN and FSO manufactured by DuPont, Surflon S-141 and 145 manufactured by Asahi Glass Co., Ltd., and Megafax F-141 manufactured by Dainippon Ink and Chemicals, Inc. 144, Neos Co., Ltd. manufactured by Fategent F-200, F251, Daikin Industries, Ltd. Unidyne DS-401, 402,
Examples include fluorine-based or silicone-based nonionic surfactants such as Florad FC-170 and 176 manufactured by 3M Co., Ltd., and a cationic surfactant, an anionic surfactant, and an amphoteric surfactant are used. You can also.

Further, in addition to the above-mentioned surfactants, the photocatalyst-containing layer contains polyvinyl alcohol, unsaturated polyester, acrylic resin, polyethylene, diallyl phthalate, ethylene propylene diene monomer, epoxy resin, phenol resin, polyurethane, melamine resin. Oligomers such as polycarbonate, polyvinyl chloride, polyamide, polyimide, styrene butadiene rubber, chloroprene rubber, polypropylene, polybutylene, polystyrene, polyvinyl acetate, polyester, polybutadiene, polybenzimidazole, polyacrylonitrile, epichlorohydrin, polysulfide, polyisoprene, A polymer or the like can be contained.

The content of the photocatalyst in the photocatalyst containing layer is 5 to 5.
It can be set in the range of 60% by weight, preferably 20 to 40% by weight. Further, the thickness of the photocatalyst-containing layer is 0.1 mm.
It is preferably in the range of 05 to 10 μm, particularly preferably,
It is 0.1 to 0.2 μm.

The photocatalyst-containing layer can be formed by dispersing a photocatalyst and a binder, if necessary, in a solvent together with other additives to prepare a coating solution, and applying the coating solution. As the solvent to be used, alcohol-based organic solvents such as ethanol and isopropanol are preferable. The coating can be performed by a known coating method such as spin coating, spray coating, dip coating, roll coating, and bead coating. When an ultraviolet-curable component is contained as a binder, the photocatalyst-containing layer can be formed by irradiating ultraviolet rays and performing a curing treatment.

(Microlens) The present invention is characterized in that a plurality of microlenses 4 are provided on the variable wettability layer 3, especially the above-mentioned photocatalyst containing layer, as shown in FIG. In the present invention, a microlens is formed in a predetermined pattern by a microlens-forming paint in the lyophilic region exposed to light in the photocatalyst-containing layer and having a low contact angle with a liquid.

In the present invention, it is preferable that the microlenses formed on the substrate be a microlens array in which the microlenses are regularly arranged. This is because, in a liquid crystal display, an image sensor, or the like, which is a main use of a micro lens, it is often used as a micro lens array. This regular arrangement pattern is determined according to the mode of the elements used and the like.

The shape of the bottom surface of each microlens, that is, the shape of the contact surface with the substrate is not particularly limited.
The shape may be not only a circle but also a polygon. In this case, by making the shape of the bottom surface of the microlens a polygon, the area of the region where the microlens is not formed can be made smaller than that of a circular shape.
A microlens with a high aperture ratio can be easily obtained.

On the microlens substrate of the present invention,
The area ratio between the part where the microlens is arranged and the part where the microlens is not arranged varies greatly depending on the functional element used and the required characteristics, but is generally 10,000: 1 to 1: 1. It can be in the range of 10,000. The focal length of the microlens is generally in the range of 100 to 2500 μm, and the pitch of the microlens is 10 to 1000 μm, although it varies greatly depending on the use of the microlens substrate.
It is in the range of μm.

Further, the microlens substrate of the present invention can be a microlens substrate in which the focal length of the microlens is variously changed. That is, in the microlens substrate of the present invention, by adjusting the amount of coating of the microlens forming paint on the substrate, a microlens having a changed focal length can be easily obtained. The lens can be easily formed. Hereinafter, this point will be described with reference to FIG.
This will be specifically described with reference to FIG.

FIG. 2A shows a case where a small amount of a microlens forming paint is applied. That is, in the variable wettability layer 3 formed on the substrate 2, a small amount of a microlens forming paint was applied on the microlens forming portion 5, which was a lyophilic region, to form a microlens 4 having a small curvature. Things. In the microlens substrate of the present invention, since the microlenses 4 are formed on the lyophilic microlens forming section 5, FIG.
Even when a small amount of the microlens forming paint as shown in (a) is applied, the applied microlens forming paint spreads over the entire microlens forming section 5. Therefore, a microlens with a small curvature and a long focal length can be easily formed by reducing the amount of application.

FIG. 2B shows a microlens 4 having a larger curvature and a shorter focal length than that of FIG. In the present invention, since the area of the microlens forming portion 5 serving as the bottom surface of the microlens 4 is fixed, the curvature of the microlens 4 is determined by the amount of the microlens forming paint applied in the microlens forming portion 5. And the focal length can be determined. FIG.
FIG. 3 shows an example in which a larger amount of a microlens forming paint is applied. Thus, in the present invention, by adjusting the amount of the microlens forming paint, a microlens having various curvatures and focal lengths is adjusted. Can be easily obtained.

FIG. 2C shows a microlens 4 having a larger curvature and a shorter focal length. In this case, if the difference in wettability between the microlens forming portion 5 that is the lyophilic region and the wettability variable layer 3 that is the lyophobic region is large, even if the microlens forming paint is applied in a relatively large amount, The microlens can be formed without the microlens-forming paint protruding from portions other than the microlens forming portion 5. Thus, in the present invention,
The lyophilic region and the lyophobic region of the wettability variable layer, that is, FIG.
In (c), a microlens having a large curvature and a short focal length can be easily formed by increasing the difference in wettability between the microlens forming portion 5 which is a lyophilic region and the other wettability variable layer 3. Can be formed.

The microlens on the microlens substrate of the present invention can be a colored microlens. By making the microlenses colored in this way, it is possible to have both functions as a color filter and a function as a microlens that are usually used in a color liquid crystal display or the like. Therefore, there is an advantage that the obtained functional element can be reduced in size and cost.

The material constituting the microlens used in the present invention is liquid at the time of formation,
It is a material that can be applied on the wettability variable layer and can be cured thereafter, and is not particularly limited as long as it is a material having transparency to energy rays such as electromagnetic waves that can have a function as a lens after curing. Absent. Examples of such a resin include those obtained by applying a solution obtained by dissolving the above-mentioned permeable resin in a solvent and then removing the solvent, thermoplastic resins, thermosetting resins, and various resins such as photocurable resins. Although it can be mentioned, a photocurable resin is preferable in that curing is easy and quick, and further, the lens molding material and the base material do not reach a high temperature during curing.

Such a photocurable resin usually has at least one functional group, and performs ion polymerization and radical polymerization by ions or radicals generated by irradiating a photopolymerization initiator with a curing energy ray. It is obtained by curing a resin composition having at least a monomer or oligomer for increasing the molecular weight and forming a crosslinked structure if necessary and a photopolymerization initiator. The term "functional group" as used herein means an atomic group or a bonding mode that causes a reaction such as a vinyl group, a carboxyl group, and a hydroxyl group.

Examples of such monomers and oligomers include unsaturated polyester type, thiol type, and acrylic type. Among them, acrylic type is preferable from the viewpoint of curing speed and a wide range of choice of physical properties. Among such acrylic monomers and oligomers, those having a monofunctional group include 2
-Ethylhexyl acrylate, 2-ethylhexyl E
O adduct acrylate, ethoxydiethylene glycol acrylate, 2-hydroxyethyl acrylate, 2
-Hydroxypropyl acrylate, caprolactone adduct of 2-hydroxyethyl acrylate, 2-phenoxyethyl acrylate, phenoxydiethylene glycol acrylate, nonylphenol EO adduct, acrylate of caprolactone added to nonylphenol EO adduct, 2-hydroxy-3-phenoxypropyl acrylate , Tetrahydrofurfuryl acrylate, caprolactone adduct of furfuryl alcohol, acryloylmorpholine, dicyclopentenyl acrylate, dicyclopentanyl acrylate, dicyclopentenyloxyethyl acrylate, isobonyl acrylate, 4,4-dimethyl-1,3- Acrylate of caprolactone adduct of dioxolane, 3
And acrylate of caprolactone adduct of -methyl-5,5-dimethyl-1,3-dioxolan.

Among the acrylic monomers and oligomers, polyfunctional ones include hexanediol acrylate, neopentyl glycol diacrylate, polyethylene glycol diacrylate, tripropylene glycol diacrylate, and neopentyl glycol ester hydroxypivalate. Acrylate, diacrylate of caprolactone adduct of hydroxypivalic acid neopentyl glycol ester, acrylic acid adduct of diglycidyl ether of 1,6-hexanediol, diacrylate of acetal compound of hydroxypivalaldehyde and trimethylolpropane, 2,2 -Bis [4-
(Acryloyloxydiethoxy) phenyl] propane,
2,2-bis [4- (acryloyloxydiethoxy) phenyl] methane, diacrylate of hydrogenated bisphenol ethylene oxide adduct, tricyclodecane dimethanol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, triacrylate Methylolpropane propylene oxide adduct triacrylate, glycerin propylene oxide adduct triacrylate, mixture of dipentaerythritol hexaacrylate pentaacrylate, dipentaerythritol caprolactone adduct acrylate, tris (acryloyloxyethyl) isocyanurate, 2-acryloyloxy Ethyl phosphate and the like can be mentioned.

Further, examples of the photopolymerization initiator include acetophenone, benzophenone, Michler's ketone, and the like.
Carbonyl compounds such as benzyl, benzoin, benzoin ether, benzyldimethyl ketal, benzoin benzoate, α-acyloxime ester, sulfur compounds such as tetramethylthiuram monosulfide, thioxanthone, and 2,4,6-trimethyl Phosphorus compounds such as benzoyldiphenylphosphinoxide can be mentioned.

In addition, if necessary, a photoinitiating auxiliary such as an aliphatic amine or an aromatic amine, or a photosensitizer such as thioxanthone may be added.

As the thermoplastic resin, those having high transparency, particularly in the visible light region, and excellent in optical characteristics such as a refractive index, a dispersion characteristic and a birefringence are preferable. Specifically, polycarbonate, polymethyl methacrylate, methyl phthalate homopolymer or copolymer, polyethylene terephthalate, polystyrene, diethylene glycol, bisallyl carbonate, acrylonitrile / styrene copolymer, methyl methacrylate / styrene copolymer, poly (- 4-methylpentene-1) and the like.

Further, as described above, it is possible to color the microlens on the microlens substrate of the present invention, but the coloring agent used for the coloration may be a dye, an inorganic pigment, an organic pigment, or the like. Can be mentioned,
The colorant is not particularly limited as long as it is a colorant usually used for a color filter. In the present invention, a material that can give a high concentration among them and that does not easily discolor at the time of curing the lens or when used as a microlens substrate is preferable.

As specific coloring agents, dyes include
Azo dyes, anthraquinone dyes, indigoid dyes, phthalocyanine dyes, carbonium dyes, quinone imine dyes, methine dyes, quinoline dyes, nitro dyes, benzoquinone dyes, naphthoquinone dyes,
Examples include naphthalimide dyes, perinone dyes, pyrylium dyes, thiapyrylium dyes, azurenium dyes, and squarylium salt dyes. Also,
Pigments include dianthraquinone, halogenated copper phthalocyanine, copper phthalocyanine, other phthalocyanine pigments, perylene pigments, polycyclic quinone pigments such as pyranthrone pigments, indigo pigments, quinacridone pigments, pyrrole pigments, and pyrrolopyrrole pigments Organic pigments such as pigments and azo pigments can be mentioned.

(Substrate) The material of the substrate used for the microlens substrate of the present invention varies greatly depending on the use of the microlens substrate. For example, when used for a liquid crystal display or an image sensor, the substrate is required to be transparent to visible light and the like, like the microphone lens.
It must be a transparent substrate. On the other hand, when the microlens substrate is used as a mold, or when the microlens substrate is used by reflecting light instead of transmitting light or the like, the transparent substrate does not need to be used.

As described above, the substrate used in the present invention is:
Various materials such as a metal material, a semiconductor material, and an organic material can be used depending on the application. However,
At present, the most common use of a microlens substrate is to use a microlens substrate such as a liquid crystal display and an image pickup device by transmitting light to the microlens substrate in many cases. Is preferred.

Such a transparent substrate is not particularly limited, and may be an inorganic material or an organic material as long as it can transmit visible light. Among them, preferred materials include soda glass, quartz glass, and optical glass (for example, BSC7 (trade name) manufactured by HOYA Corporation).
Etc.), glass for electronics (eg, non-alkali glass), translucent ceramics, plastic films such as polycarbonate, methyl methacrylate homopolymer or copolymer, polyethylene terephthalate, and polystyrene, and plastic sheets.

The thickness of the substrate in the present invention is not particularly limited, and may be a thickness according to the use of the microlens substrate.

(Light-shielding part) The microlens substrate of the present invention may be provided with a light-shielding part if necessary. The light-shielding portion is usually provided so that unnecessary light beams around the lens do not enter the lens. FIG.
This will be described with reference to FIG.

FIG. 3 shows an example in which a light-shielding portion is provided on the surface of the microlens substrate of the present invention opposite to the surface on which the microlenses are provided. The microlens substrate 1 shown in FIG. 3 is similar to the microlens substrate shown in FIG.
A variable wettability layer 3 is provided thereon, a microlens forming section 5 serving as a lyophilic region is formed in the variable wettability layer 3, and a microlens 4 is provided here. In the microlens substrate 1 shown in FIG. 3, a light shielding portion 6 is further formed on a surface opposite to the surface on which the microlenses 4 are formed.
In the example shown in FIG. 3, the light-shielding portion 6 is provided with the wettability variable layer 3 similarly to the surface on which the microlenses 4 are formed, and the light-shielding portion forming portion 7 in the wettability variable layer 3 is formed as a lyophilic region. Is formed, and a light shielding portion 6 is provided here.

The light-shielding portion 4 may be formed so that only the transmitting portion of the light converged by the microlens 4 is opened as shown in FIG. 4. In this example, the central portion of the microlens 4 is used. Is defined as an opening 8.

In the microlens substrate of the present invention, the position where the light-shielding portion is formed is not particularly limited.
As shown in FIGS. 3 and 4, it is preferable that the substrate is formed on the surface opposite to the surface on which the microlenses are formed.

The light-shielding portion in the present invention may be provided by a conventional method such as a method of forming a metal thin film of chromium or the like by a sputtering method and patterning the same, for example, as shown in FIG. A variable wettability layer, preferably a photocatalyst-containing layer, may be provided on a transparent substrate, and may be formed by utilizing the change in wettability.

As the material for forming the light shielding portion of the present invention,
Examples of the material include metals such as chromium as described above, and organic materials in which light-shielding particles such as carbon fine particles, metal oxides, inorganic pigments, and organic pigments are contained in a resin binder.
Examples of such a resin binder include polyimide resin, acrylic resin, epoxy resin, polyacrylamide, polyvinyl alcohol, gelatin, casein, cellulose, or a mixture of two or more resins, a photosensitive resin, and a photosensitive resin. / W emulsion-type resin compositions, for example, those obtained by emulsifying a reactive silicone can be used.

B. About the manufacturing method of the micro lens substrate
Te next be described in detail the preparation of the micro lens substrate of the present invention. The method for manufacturing a microlens substrate according to the present invention includes: (1) providing a photocatalyst-containing layer on the substrate, the wettability of an irradiated portion being changed by energy irradiation in a direction in which a contact angle with a liquid is reduced; A step of irradiating a pattern with energy to form a microlens exposure section on a microlens formation section, which is a section for forming a microlens on a photocatalyst containing layer provided on a substrate, and (3) this microlens exposure section Applying a microlens-forming paint to the portion to form a microlens.

First, the first step of providing a photocatalyst-containing layer will be described. This photocatalyst containing layer is formed by dispersing a photocatalyst and a binder as described above in a solvent together with other additives as necessary to prepare a coating solution,
After the application of the coating solution, the photocatalyst is firmly fixed in a binder by advancing hydrolysis and polycondensation reactions, thereby forming a coating. The solvent used is preferably an alcoholic organic solvent such as ethanol or isopropyl alcohol, and the coating can be performed by a known coating method such as spin coating, spray coating, dip coating, roll coating, or bead coating. When an ultraviolet-curable component is contained as a binder, a photocatalyst-containing layer can be formed on a substrate by irradiating ultraviolet rays to perform a curing treatment.

Next, a description will be given of a second step, that is, a step of forming a microlens exposure portion. The photocatalyst-containing layer is formed on the base material by the first step, and the photocatalyst-containing layer is irradiated with energy to form an exposure portion for microlenses. The arrangement and the like are the same as the above-described parts and arrangements where the microlenses are formed, and thus description thereof will be omitted.

In the present invention, light including ultraviolet light can be used as the irradiation energy. As a light source including such ultraviolet light, for example, a mercury lamp, a metal halide lamp, a xenon lamp, and the like can be given. The wavelength of light used for this exposure can be set within a range of 400 nm or less, preferably 380 nm or less, and the irradiation amount of light at the time of exposure is such that the exposed portion becomes lyophilic by the action of a photocatalyst. The irradiation dose required for expression can be set.

When pattern irradiation is necessary for energy irradiation, pattern irradiation through a photomask can be performed using the above-described light source. Alternatively, a laser such as excimer or YAG is used. It is also possible to use a method of drawing and irradiating in a pattern shape. However, such a method may have a problem that the apparatus is expensive, difficult to handle, and that continuous output cannot be performed.

Therefore, in the present invention, the photocatalytic reaction initiation energy is applied to the photocatalyst-containing layer, and the reaction rate increasing energy is applied in a pattern to the region to which the photocatalytic reaction initiation energy has been applied, thereby forming a lyophilic region. May be formed. By forming a pattern using such an energy irradiation method, it is possible to use a relatively inexpensive and easy-to-handle reaction speed increasing energy such as an infrared laser when forming a pattern, and thereby, as described above. This is because no problem occurs.

The reason that the pattern of the lyophilic region having changed wettability can be formed by applying such energy is as follows. That is, first, the photocatalytic reaction of the photocatalyst with the photocatalyst containing layer is started by applying the photocatalytic reaction start energy to the region where the pattern is formed. Then, the reaction rate increasing energy is added to the region where the photocatalytic reaction start energy is added.
By adding the reaction rate increasing energy in this manner, the photocatalytic reaction start energy is already added, and the reaction in the photocatalyst-containing layer in which the reaction is started by the catalytic action of the photocatalyst is rapidly promoted. Then, by applying the reaction rate increasing energy for a predetermined period of time, the change of the property in the property changing layer is changed to a desired range, and the pattern to which the reaction rate increasing energy is added is converted into the lyophilic region where the wettability has changed. It can be a pattern.

Here, the photocatalytic reaction initiation energy will be described first. The photocatalytic reaction initiation energy used in this energy irradiation method refers to the energy at which the photocatalyst initiates a catalytic reaction for changing the characteristics of the compound in the photocatalyst-containing layer.

The amount of the photocatalytic reaction initiation energy added here is such that the wettability in the photocatalyst-containing layer does not suddenly change. If the amount of photocatalytic reaction initiation energy added is small, it is not preferable because the sensitivity in forming a pattern by adding the reaction rate increasing energy is unfavorable. The degree of change in the properties of the containing layer becomes too large, and the difference from the region to which the reaction rate increasing energy is added becomes unclear, which is not preferable. The amount of energy to be added is determined by performing preliminary experiments and the like on the amount of energy to be added and the amount of change in wettability in the photocatalyst-containing layer in advance.

The photocatalytic reaction initiation energy in this method is not particularly limited as long as it is an energy capable of initiating the photocatalytic reaction, but light is particularly preferred.

The photocatalyst used in the present invention has a different wavelength of light for initiating a catalytic reaction depending on its band gap. For example, if cadmium sulfide is 496 nm,
In the case of iron oxide, visible light of 539 nm is used, and in the case of titanium dioxide, ultraviolet light of 388 nm is used. Therefore, any light, whether visible light or ultraviolet light, can be used in the present invention. However, as described above, since the bandgap energy is high, it is effective as a photocatalyst, and titanium dioxide is preferably used as a photocatalyst because it is chemically stable, has no toxicity, and is easily available. It is preferable that the light includes ultraviolet light that initiates a catalytic reaction of titanium. In particular,
It is preferable that ultraviolet light in a range of 400 nm or less, preferably 380 nm or less is included.

Examples of the light source of light containing such ultraviolet light include various ultraviolet light sources such as a mercury lamp, a metal halide lamp, a xenon lamp and an excimer lamp.

In the present invention, the range to which the photocatalytic reaction initiation energy is applied may be a part of the photocatalyst containing layer. For example, the photocatalytic reaction initiation energy is applied in a pattern, and the reaction rate increasing energy described later is also increased. It is also possible to form a pattern of the lyophilic region having changed wettability by adding it in a pattern form, but for reasons such as simplification and simplification of the process, the photocatalytic reaction initiation energy is used to form the pattern. It is preferable to add the reaction speed increasing energy in a pattern to the region where the photocatalytic reaction initiation energy is applied over the entire surface, so that a pattern of the lyophilic region is formed on the photocatalyst containing layer. Is preferable.

Next, the reaction rate increasing energy used in this method will be described. The reaction rate increasing energy used in this method refers to energy for increasing the reaction rate of a reaction that changes the wettability of the photocatalyst-containing layer initiated by the photocatalytic reaction initiation energy. In the present invention, any energy can be used as long as it has such an effect, but it is particularly preferable to use thermal energy.

The method of applying such heat energy to the photocatalyst-containing layer in a pattern is not particularly limited as long as it can form a pattern by heat on the photocatalyst-containing layer. A method using a heat-sensitive head can be used. As such an infrared laser, for example, an infrared YAG laser (1064n) having an advantage of having high directivity and a long irradiation distance is used.
m) and a diode laser (LED; 830 nm, 1064 nm, 110) having an advantage of being relatively inexpensive.
0 nm), a semiconductor laser, a He-Ne laser, a carbon dioxide laser, and the like.

In this method, by applying the above-described photocatalytic reaction initiation energy, the photocatalyst is activated to start the change in wettability due to the catalytic reaction in the photocatalyst-containing layer, and the portion where the change in wettability occurs is generated. The reaction rate increase energy is added to the reaction to accelerate the catalytic reaction in that part, and the pattern of the lyophilic area is changed by the difference in the reaction rate between the area where the reaction rate increase energy is added and the area where the reaction rate increase energy is not added. Can be formed.

Finally, the third step of forming a micro lens on a substrate will be described. The microlens forming paint used in this step is a paint containing the above-described microlens material, and can be applied to the microlens exposure section (microlens forming section) and then cured. By doing so, there is no particular limitation as long as it has a function as a microlens. When the microlens is made of a photocurable resin, the form of the microlens-forming coating may be a liquid in which a monomer and a photopolymerization initiator are dissolved or dispersed, and a solution in which an oligomer and a photopolymerization initiator are dissolved. Alternatively, a liquid in which a monomer or oligomer and a photopolymerization initiator are dissolved or dispersed, or a liquid in which a monomer or oligomer is dissolved or dispersed can be used. When the microlens is a colored microlens as described above, a material obtained by mixing the above-mentioned coloring agent with the above-mentioned microlens forming paint is used.

The method of applying such a microlens-forming paint to the microlens-exposed portion (microlens-forming portion) is not particularly limited, but specific examples include dip coating, roll coating, and bead coating. Methods such as coating, spin coating, air doctor coating, blade coating, knife coating, rod coating, gravure coating, rotary screen coating, kiss coating, slot orifice coating, spray coating, cast coating, and extrusion coating can be used. Is preferable in that a large amount of microlenses can be formed in a short time.

Further, in the present invention, when applying the microlens-forming paint to the microlens exposure section, a method using nozzle discharge may be used. As such a nozzle discharge method, for example, a micro syringe,
Dispenser, ink jet, method to fly paint for microlens formation from external tip such as electric field from needle point, method to fly paint for microlens formation from element using vibrating element such as piezo element vibrated by external stimulus, A method of attaching the attached microlens-forming coating material to the surface of the substrate can be used. These are suitable for forming a lens-shaped object having a large contact angle and a high height.

In the present invention, among the above-mentioned coating methods,
It is preferable that the paint for microlenses is applied by an inkjet method from the viewpoint of accuracy and speed of application. In this case, the inkjet device used includes:
Although not particularly limited, a method in which charged ink is continuously ejected and controlled by a magnetic field, a method in which ink is ejected intermittently using a piezoelectric element, an intermittent method in which ink is heated and foaming is utilized. An ink jet apparatus using various methods such as a method of ejecting ink to a liquid can be used.

The application of the microlens forming paint by the ink jet method is also effective for a colored microlens forming paint in which a coloring agent is mixed with the microlens forming paint.

The microlens is formed on the substrate by curing the microlens forming coating applied in the microlens exposure section in this manner, and the microlens substrate is formed. In the present invention, the curing of the coating material for forming microlenses is performed by various methods depending on the type of the raw material used. For example, in the case of a coating dissolved in a solvent, the solvent is removed by heating or the like, and solidification is performed.

Considering the curing process of the coating material for forming microlenses, the type of the material of the microlenses used in the present invention is preferably a photocurable resin. This is because if a microlens forming paint using a photocurable resin is used, the microlens forming paint can be quickly cured by irradiating light, thereby shortening the manufacturing time of the microlens substrate. Because it can be.

As described above, since the microlens-forming paint applied in the microlens-exposed portion spreads evenly, the microlens is formed by curing such a microlens-forming paint. A microlens substrate having a constant lens curvature and good positional accuracy can be formed.

C. C. Regarding Liquid Crystal Display The microlens substrate of the present invention can be used as a component adjacent to or in close contact with a display such as a liquid crystal display in order to increase the luminance in the direction of the viewer. In this case, a light-shielding portion may be provided in order to suppress the influence of ambient external light such as indoor lighting or sunlight and to improve display image quality. It is preferable to reduce the thickness of the wettability variable layer, preferably the photocatalyst-containing layer, for the purpose of enhancing light transmittance or preventing color formation due to light interference. Specifically, it is 1 μm or less, more preferably 0.1 μm.
2 μm or less.

FIG. 5 shows an example of a liquid crystal display using the microlens substrate of the present invention. In this liquid crystal display, a microlens substrate 1 is arranged on a side surface of a color filter 11 of a liquid crystal display section 12 including an array side substrate 9, a liquid crystal section 10, and a color filter 11. This microlens substrate 1
Each micro lens 4 is formed on the substrate 2 so that the position of the pixel portion of the color filter 11 coincides with the pixel portion, and these micro lenses 4 are arranged on the color filter 11 side. This microlens substrate 1
As described above, the light shielding portion 6 is formed to suppress the influence of external light and improve the display image quality. In such a liquid crystal display, light generated in the liquid crystal display section 12 is emitted to the outside as light emission 13 through the microlens substrate 1 of the present invention, and the brightness of the viewer is increased by the action of the microlens.

Since the liquid crystal display using the microlens substrate of the present invention uses the microlens substrate which is good in quality and advantageous in cost, the liquid crystal display having good quality as the liquid crystal display and low cost is used. It has the advantage that it can be.

D. Regarding the image pickup device The microlens substrate of the present invention can be used as a component adjacent to or in close contact with the image pickup device such as a CCD in order to increase the light sensitivity of the image pickup device. in this case,
It is preferable to provide a light-shielding portion for reasons such as avoiding adverse effects on characteristics such as a decrease in contrast due to stray light. Further, as in the case of the liquid crystal display, it is preferable to reduce the thickness of the wettability variable layer, preferably the photocatalyst containing layer, and the specific thickness is 1 μm.
m or less, more preferably 0.2 μm or less.

FIG. 6 shows an example of an image sensor using the microlens substrate of the present invention. This image sensor has a configuration in which the microlens substrate 1 is arranged on the side surface of the color filter 14 of the image sensor unit 16 including the color filter 14 and the photoelectric conversion element 15. The microlens substrate 1 has a light-shielding portion 6 disposed on the colored filter 14 side, and a microlens 4 formed on a surface opposite to the substrate 2 on which the light-shielding portion 6 is formed. The incident light 17 enters the image sensor 16 via the microlens 4 of the microlens substrate 1, so that the light sensitivity of the image sensor can be increased.

Since the imaging device using the microlens substrate of the present invention uses a microlens substrate having good quality and being advantageous in cost, the imaging device having good quality and low cost as the imaging device is used. It can be.

Note that the present invention is not limited to the above embodiment. The above embodiment is an exemplification, and has substantially the same configuration as the technical idea described in the scope of the claims of the present invention. It is included in the technical scope of the invention.

[0138]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to Examples.

(Example 1 / Formation of Photocatalyst-Containing Layer) 3 g of isopropyl alcohol, 0.4 g of organosilane (Toshiba Silicone TSL8113), 0.3 g of fluoroalkoxysilane MF-160E (Tochem Products), and photocatalytic inorganic coating agent ST- K01 (Ishihara Sangyo) 2g
Was mixed. This solution is applied by spin coating.
It was applied on a transparent substrate made of quartz glass. Then, by drying at a temperature of 150 ° C. for 10 minutes, the hydrolysis and the polycondensation reaction proceeded, and a transparent layer having a thickness of 0.2 μm in which the photocatalyst was firmly fixed in the organopolysiloxane was obtained. . On this photocatalyst containing layer, 70
Pattern exposure was performed through a mask for 50 seconds at an illuminance of mW / cm ² .

As a result of measuring the contact angle between the unexposed portion and the liquid in the exposed portion, the surface tension was 30 mN /
The contact angle with a liquid (ethylene glycol monoethyl ether manufactured by Junsei Chemical Co., Ltd.) is measured using a contact angle measuring device (CA-Z type manufactured by Kyowa Interface Science Co., Ltd.). 30 seconds later) as a result,
The contact angle with a liquid having a surface tension of 50 mN / m (wetting standard reagent liquid No. 50 manufactured by Junsei Chemical Co., Ltd.) was similarly measured at the exposed portion, and was 7 degrees. Exposure unit,
A pattern having different wettability was formed in the non-exposed area.

(Example 2 / Formation by coating of microlens) Example 1 was formed on a transparent substrate made of quartz glass.
The photocatalyst containing layer was formed by the spin coating method using the photocatalyst containing layer forming material described in 1). Through a negative photomask in which a plurality of circular patterns having an opening diameter of 50 μm are arranged at an interval of 2 μm, a mercury lamp is used to form a 7-inch photomask.
Exposure was performed for 90 seconds at an illuminance of 0 mW / cm ² to obtain a transparent substrate having a circular pattern composed of lyophilic regions formed on the surface.

1000 g of an ultraviolet-curable monomer (PO-modified glycerin triacrylate: manufactured by Arakawa Chemical Industry Co., Ltd., trade name: Beam Set 720), a curing initiator (manufactured by Ciba Specialty Chemicals, trade name: Irgacure 18)
4) 50 g was mixed and stirred for 3 minutes. The resulting mixed solution (coating material for forming microlenses) was applied to a transparent substrate on which a circular pattern having a different wettability as described above was applied by a bead coating method (slide coating method) to a thickness of 12 μm.
As a result, the mixed solution adhered only to the exposed portion (circular pattern portion). 70m with a mercury lamp
Exposure for 5 seconds at an illuminance of W / cm ² results in a diameter of 5
A microlens substrate having a microlens array of 0 μm and a focal length of 1 mm was obtained.

(Example 3 / Formation by Microlens Discharge Method) A photocatalyst-containing layer was formed on a transparent substrate made of quartz glass by the spin coating method using the photocatalyst-containing layer forming material described in Example 1. did. This has an opening diameter of 20
Through a negative photomask in which a plurality of 0 μm circular patterns are arranged at 100 μm intervals, a mercury lamp is used.
Exposure was performed for 90 seconds at an illuminance of 0 mW / cm ² to obtain a transparent substrate having a circular pattern of lyophilic regions formed on the surface.

UV-curable monomers (PO-modified glycerol)
Triacrylate: Arakawa Chemical Industry Co., Ltd., product name: B
Musset 720) 1000g, curing initiator UV curing type
Monomer (PO-modified glycerin triacrylate: Arakawa
Product name: Beam Set 720) 1000, manufactured by Chemical Industry Co., Ltd.
g, photopolymerization initiator (Ciba Specialty Chemicals, Inc.)
Irgacure 184) 50 g
Stirred for minutes. The resulting mixture (for microlens formation)
Dispenser for liquid precision dispensing (paint)
Sir, 1500XL-15).
Circular pattern on a transparent substrate with a circular pattern
0.0001 ml was discharged at the center of the minute. At this time
(Microlens forming paint) is only for the circular pattern part
It did not spread, it did not spread to other parts. this
70mW / cm by mercury lamp ^Two10 seconds at an illuminance of
By exposure, the diameter is 200 μm and the focal length is 500
Microlens base with micrometer microlens array
A board was obtained.

(Example 4 / Formation of Colored Microlens by Discharge Method) A photocatalyst-containing layer was formed on a transparent substrate made of quartz glass by the spin coating method using the photocatalyst-containing layer forming material described in Example 1. . This has an opening diameter of 20
70 mW using a mercury lamp through a negative photomask in which a plurality of 0 μm circular patterns are arranged at intervals of 100 μm.
/ Cm ² for 90 seconds to obtain a transparent substrate having a surface on which a circular pattern composed of a lyophilic region was formed.

Next, an ultraviolet-curable monomer (bifunctional acrylate monomer, manufactured by Nippon Kayaku Co., Ltd., trade name: KAYA
500 g of RADPEG 400DA), 25 g of a photopolymerization initiator (manufactured by Ciba Specialty Chemicals, trade name: Darocur 1173), and 0.5 g of a red dye (Rose Bengal, manufactured by Tokyo Chemical Industry Co., Ltd.) were mixed and stirred for 3 minutes, and the mixture was stirred for 3 minutes. A paint for forming a lens was obtained.

Further, an ultraviolet curable monomer (bifunctional acrylate monomer, manufactured by Nippon Kayaku Co., Ltd., trade name: KAYAR
ADPEG400DA) 500 g, photopolymerization initiator (manufactured by Ciba Specialty Chemicals, trade name: Darocure 1)
173) and 0.5 g of a green dye (Villiant Green, manufactured by Tokyo Kasei Co., Ltd.) were mixed and stirred for 3 minutes to obtain a green microlens forming paint.

Further, an ultraviolet-curable monomer (bifunctional acrylate monomer, manufactured by Nippon Kayaku Co., Ltd., trade name: KAYA
500 g of RADPEG400DA), 25 g of a photopolymerization initiator (manufactured by Ciba Specialty Chemicals, trade name: Darocur 1173), and 0.5 g of a blue dye (Victoria Blue, manufactured by Tokyo Chemical Industry Co., Ltd.) are mixed, and stirred for 3 minutes. A paint for forming a lens was obtained.

The obtained paint for forming a microlens was applied to a liquid precision discharge device (EFD dispenser, 1500XL
-15), the center of the circular pattern portion on the transparent substrate on which the circular pattern having the different wettability is applied is 0.00
01 ml was discharged. At this time, the discharge liquid (coating material for forming microlenses) spread only in the circular pattern portion, and did not spread in other portions. This was exposed to an illuminance of 70 mW / cm ² for 10 seconds using a mercury lamp to obtain a microlens substrate having a colored microlens array having a diameter of 200 μm and a focal length of 500 μm.

Example 5 / Formation by Coating of Colored Microlens Example 1 on a quartz glass transparent substrate
The photocatalyst containing layer was formed by spin coating using the photocatalyst containing layer forming material described above. In addition, a circular pattern having an opening diameter of 200 μm is vertically spaced at 100 μm intervals.
Exposure was performed for 90 seconds with a mercury lamp at an illuminance of 70 mW / cm ² through a plurality of negative photomasks arranged at intervals of 700 μm in the horizontal direction. Obtained.

Next, an ultraviolet curable monomer (bifunctional acrylate monomer: manufactured by Nippon Kayaku Co., Ltd., trade name: KAYA
RADPEG400DA) 400 g, ultraviolet curable monomer (1,6 hexanediol diacrylate, manufactured by Nippon Kayaku Co., Ltd., trade name: KS-HDDA) 100 g, photopolymerization initiator (Ciba Specialty Chemicals Co., trade name: Darocure 1173) 25 g , Red dye (Tokyo Kasei Co., Ltd.,
(0.5 g of Rose Bengal) and stirred for 3 minutes to obtain a red microlens forming paint.

An ultraviolet-curable monomer (bifunctional acrylate monomer: manufactured by Nippon Kayaku Co., Ltd., trade name: KAYAR
ADPEG400DA) 400 g, UV curable monomer (1,6 hexanediol diacrylate, manufactured by Nippon Kayaku Co., Ltd., trade name: KS-HDDA) 100 g, photopolymerization initiator (Ciba Specialty Chemicals Co., trade name: Darocure 1173) 25 g , 0.5 g of green dyeing department (Villiant Green manufactured by Tokyo Chemical Industry Co., Ltd.) and stirred for 3 minutes,
A green microlens forming paint was obtained.

Further, an ultraviolet-curable monomer (bifunctional acrylate monomer: manufactured by Nippon Kayaku Co., Ltd., trade name: KAYA
RADPEG400DA) 400 g, ultraviolet curable monomer (1,6 hexanediol diacrylate, manufactured by Nippon Kayaku Co., Ltd., trade name: KS-HDDA) 100 g, photopolymerization initiator (Ciba Specialty Chemicals Co., trade name: Darocure 1173) 25 g , Blue dye (manufactured by Tokyo Chemical Industry,
(Victoria Blue) was mixed and stirred for 3 minutes to obtain a blue microlens forming paint.

The resulting red microlens forming paint was applied by a dip coating method on a transparent substrate having a circular pattern having the above-mentioned different wettability at a thickness of 12 μm. , Lyophilic area). This is done with a mercury lamp 7
The resin was cured by exposing to light of 0 mW / cm ² for 10 seconds.

A photocatalyst-containing layer is formed on the transparent substrate on which the red microlens is formed in the same manner as described above, and a lyophilic region is formed at a distance of 100 μm from the vertical line of the red lens under the same conditions as above. Was formed. A green microlens was formed by performing the same operation as for the red color using the green microlens forming paint.

The same operation was performed using the blue microlens forming coating material. A blue microlens was formed at a distance of 100 μm between vertical rows of red and green microlenses, and had a diameter of 200 μm and a focal length of 200 μm. A microlens substrate having a 1 mm colored microlens array was obtained.

(Example 6 / Formation of Coating of Light-Shielding Part) Example 1 was formed on the back surface of a microlens substrate (substrate: quartz glass) of the present invention having a microlens array having a diameter of 100 μm and arranged at intervals of 10 μm. A photocatalyst containing layer was formed using the photocatalyst containing layer forming material described above. Then, the opening diameter is 10 μm, and 100 μm
After the alignment of the photomask and the lens arranged at the intervals of, pattern exposure was performed using a mercury lamp.

Next, an ultraviolet curable monomer (bifunctional acrylate monomer, manufactured by Nippon Kayaku Co., Ltd., trade name: KAYA
RADPEG 400DA) and carbon black (100 g) in a mixed solution of 500 g of a photopolymerization initiator (trade name: Darocur 1173, manufactured by Ciba Specialty Chemicals).
g were dispersed to prepare a composition for forming a light-shielding portion. When this composition for forming a light-shielding portion was applied over the entire surface of the photocatalyst-containing layer which had been pattern-exposed by a blade coater, the non-exposed portion selectively adhered to only the exposed portion. Then 150
Heating was performed at 30 ° C. for 30 minutes to form a light-shielding portion, and a microlens substrate having a light-shielding portion was obtained.

(Embodiment 7 / Formation of light-shielding portion by discharge method)
A photocatalyst-containing layer was formed using the photocatalyst-containing layer material described in Example 1 on the back surface of the microlens substrate (substrate: quartz glass) of the present invention having a microlens array having a diameter of 700 μm and arranged at 10 μm intervals. . Next, through a photomask having an opening having a diameter of 10 μm and arranged at intervals of 700 μm, alignment with a lens was performed, followed by pattern exposure using a mercury lamp.

Next, the composition for forming a light-shielding portion described in Example 6 was discharged onto an exposed portion by a dispenser (manufactured by EFD), so that the composition for forming a light-shielding portion was adhered only to the exposed portion. Next, heating was performed at 150 ° C. for 30 minutes to obtain a microlens substrate having a light-shielding portion.

Example 8 Change in Focal Length Due to Microlens Discharge Amount Example 1 on a quartz glass transparent substrate
The photocatalyst containing layer was formed by the spin coating method using the photocatalyst containing layer forming material described in 1). This was exposed to an illuminance of 70 mW / cm ² for 90 seconds with a mercury lamp through a mask having a circular pattern with an opening diameter of 9 mm to obtain a transparent substrate having a circular pattern as a lyophilic region on the surface.

UV-curable monomer (bifunctional acrylate monomer, manufactured by Nippon Kayaku Co., Ltd., trade name: KAYARADP)
EG400DA) 500 g, photopolymerization initiator (manufactured by Ciba Specialty Chemicals, trade name: Darocur 117)
3) 25 g were mixed and stirred for 3 minutes. The obtained microlens-forming paint was discharged with a microsyringe at the center of the circular pattern portion on the transparent substrate on which the above-mentioned circular patterns having different wettabilities were applied, in an amount of 15 to 55 μL. At this time, the discharged liquid (coating material for forming a microlens) spread only to the circular pattern portion and did not spread to the other portions, and the contact angle with the substrate became larger as the amount of dripping was larger. This was exposed to an illuminance of 70 mW / cm ² for 10 seconds using a mercury lamp to obtain a diameter of 9 mm and a focal length of 27-9.
A lens of 0 mm could be designed and created by controlling the discharge amount of the resin mixture (coating material for forming microlenses). Table 1 shows the results.

[0163]

[Table 1]

(Comparative Example) For comparison, the above resin mixture was applied to a quartz glass transparent substrate having no photocatalyst containing layer (substrate having no wettability pattern) by 15 to 55 μm.
L was discharged. At this time, the discharged liquid became wet and spread as the discharge amount increased, and its shape was not stable, but took various shapes. The contact angle with the substrate did not change according to the discharge amount.
This is irradiated with a mercury lamp at an illuminance of 70 mW / cm ² for 10
Exposure for 2 seconds, the resulting lens-shaped object has a shape, diameter,
The focal length was not controlled. Table 2 shows the relationship among the amount of the resin solution (coating material for forming microlenses) dropped, the contact angle with the substrate, the diameter of the formed lens-shaped object, and the focal length.

[0165]

[Table 2]

As is clear from Tables 1 and 2, the contact angle of the microlens of Example 8 with the base material of the macrolens changes depending on the amount of the microlens-forming paint dripped, and the focal length also changes accordingly. Although it changed, the microlens of the comparative example did not have such a tendency, and the radius of the formed lens increased as the amount of the microlens-forming paint dropped increased.

Example 9 A photocatalyst-containing layer was formed on a quartz glass transparent substrate by the spin coating method using the photocatalyst-containing layer forming material described in Example 1.

The photocatalyst-containing layer was irradiated with a high-pressure mercury lamp at an illuminance of 25 mW / cm ² (365 nm) for 40 seconds, and was irradiated in a pattern with a semiconductor laser having an irradiation wavelength of 830 nm. The pattern irradiation of the semiconductor laser was performed using a galvanometer based on the CAD data for forming the microlens array. At this time, the temperature of the semiconductor laser irradiation surface was 50 ° C. The contact angle of the irradiated surface with a liquid having a surface tension of 50 mN / m (manufactured by Junsei Chemical Co., Ltd., wet standard reagent No. 50) was measured using a contact angle measuring instrument (manufactured by Kyowa Interface Science Co., Ltd., CA-Z type). Measurement (30 drops by dropping a droplet from a micro syringe)
Seconds later), the result was 7 degrees.

1000 g of an ultraviolet curable monomer (PO-modified glycerin triacrylate, manufactured by Arakawa Chemical Industries, trade name: Beam Set 720), a photopolymerization initiator (manufactured by Ciba Specialty Chemicals, trade name: Irgacure 18)
4) 50 g of the mixture was mixed and stirred for 3 minutes to prepare a coating material for forming a microlens.

The obtained paint for forming a microlens was applied to a liquid precision discharge device (EFD dispenser, 1500XL
In -15), 0.0001 mL was discharged to a portion having different wettability formed based on the CAD data. At this time, the discharged liquid (paint for forming a microlens) is CA
It spread only to the portions having different wettability formed based on the D data, and did not spread to other portions.

[0171] This was applied to a mercury lamp at 70 mW / cm ²
The microlens substrate having a microlens array having various bottom shapes with a diameter of 30 to 50 μm set by the CAD data was obtained by exposing at an illuminance of 10 seconds.

[0172]

The present invention relates to a substrate, a variable wettability layer provided on the surface of the substrate and capable of changing the wettability, and a plurality of microlenses provided on the variable wettability layer. A microlens substrate comprising: As described above, since the present invention has a configuration in which a plurality of microlenses are formed on the variable wettability layer, the wettability of the variable wettability layer in the portion where the microlens is provided is determined by the contact angle with the liquid. The liquid-repellent region having a small contact angle with the liquid can be used as a small lyophilic region and the wettability variable layer in the other portion can be large. Therefore, by attaching the microlens-forming paint to the portion of the lyophilic region where the microlens is provided, the microlens-forming paint adheres only to the lyophilic region having a small contact angle with the liquid. A microlens can be formed with high precision. In addition, the focal length of the microlens is determined by the relationship between the amount of the microlens forming paint and the area of the lyophilic region to which the microlens forming paint is applied. This has the effect of enabling control.

[Brief description of the drawings]

FIG. 1 is a schematic sectional view showing an example of a microlens substrate of the present invention.

FIG. 2 is a schematic sectional view showing adjustment of a focal length in the microlens substrate of the present invention.

FIG. 3 is a schematic cross-sectional view showing an example in which a light shielding portion is formed on the microlens substrate of the present invention.

FIG. 4 is a schematic plan view showing a surface of the microlens substrate shown in FIG. 3 on which a light shielding portion is formed.

FIG. 5 is a schematic sectional view showing a liquid crystal display using the microlens substrate of the present invention.

FIG. 6 is a schematic cross-sectional view illustrating an imaging device using the microlens substrate of the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 ... Micro lens board 2 ... Substrate 3 ... Variable wettability layer 4 ... Micro lens

Continuation of the front page (72) Inventor Hironori Kobayashi 1-1-1, Ichigaga-cho, Shinjuku-ku, Tokyo Dai Nippon Printing Co., Ltd. F term (reference) 4M118 AA10 AB01 BA10 CB14 EA20 GB11 GC07 GD04 GD07 5C024 CY47 EX43 GZ36

Claims (14)

[Claims] A substrate provided on a surface of the substrate;
A microlens substrate comprising: a wettability variable layer capable of changing wettability; and a plurality of microlenses provided on the wettability variable layer. 2. The microlens substrate according to claim 1, wherein the substrate is a transparent substrate. 3. The variable wettability layer is a photocatalyst-containing layer comprising at least a photocatalyst and a binder, and is a layer whose wettability changes so as to reduce a contact angle with a liquid by irradiation of energy. The microlens substrate according to claim 1, wherein the substrate is a microlens substrate. 4. The photocatalyst-containing layer contains fluorine, and when the photocatalyst-containing layer is irradiated with energy, the action of the photocatalyst lowers the fluorine content on the surface of the photocatalyst-containing layer as compared to before the energy irradiation. 4. The microlens substrate according to claim 3, wherein the photocatalyst-containing layer is formed so as to perform the process. 5. The method according to claim 1, wherein the photocatalyst is titanium oxide (Ti).
O ₂ ), zinc oxide (ZnO), tin oxide (SnO ₂ ), strontium titanate (SrTiO ₃ ), tungsten oxide (WO ₃ ), bismuth oxide (Bi ₂ O ₃ ), and iron oxide (Fe ₂ O ₃ ) The microlens substrate according to claim 3, wherein the substrate is at least one substance selected from the group consisting of: 6. The microlens substrate according to claim 5, wherein said photocatalyst is titanium oxide (TiO ₂ ). 7. The method according to claim 1, wherein the binder is Y _n SiX _(4-n) (where Y is an alkyl group, a fluoroalkyl group, a vinyl group,
X represents an amino group, a phenyl group or an epoxy group, and X represents an alkoxyl group or a halogen. n is an integer from 0 to 3. 7. An organopolysiloxane which is one or more hydrolytic condensates or co-hydrolytic condensates of the silicon compound represented by the formula (7). 3. The microlens substrate according to claim 1. 8. The microlens substrate according to claim 7, wherein, among the silicon compounds constituting the organopolysiloxane, a silicon compound containing a fluoroalkyl group is contained in an amount of 0.01 mol% or more. . 9. A surface tension 4 on the photocatalyst containing layer.
9. A contact angle with a liquid of 0 mN / m is 10 degrees or more in a part where energy is not irradiated and less than 10 degrees in a part where energy is irradiated. The microlens substrate according to claim 1. 10. A step of: (1) providing a photocatalyst-containing layer on the substrate, the wettability of an irradiated portion being changed by energy irradiation in a direction in which the contact angle with a liquid decreases; and (2) providing a photocatalyst-containing layer on the substrate. Forming a microlens exposure portion by irradiating energy to the microlens formation portion which is a portion on the photocatalyst containing layer where the microlens is formed; and (3) forming a microlens formation portion on the microlens exposure portion. Applying a coating material to form a microlens. 11. The method of manufacturing a microlens substrate according to claim 10, wherein the step of applying the microlens forming paint to the microlens exposure unit is performed by an inkjet method. 12. A contact angle with a liquid having a surface tension of 40 mN / m on the photocatalyst-containing layer is 10 degrees or more in a part where energy is not irradiated and is less than 10 degrees in a part where energy is irradiated. The method for manufacturing a microlens substrate according to claim 10, wherein: 13. A liquid crystal display using the microlens substrate according to any one of claims 1 to 9. 14. An imaging device using the microlens substrate according to any one of claims 1 to 9.