JP4477319B2 - Wetability variable substrate and composition for forming wettability variable layer - Google Patents

Description

[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a wettability variable substrate having a wettability variable layer composed of a cohydrolyzed polycondensation product of an organopolysiloxane precursor such as a fluoroalkylsilane compound and an amorphous silica precursor, and the wettability thereof The present invention relates to a functional element formed by utilizing a difference in wettability generated by exposure in the presence of a photocatalyst using a variable substrate. The present invention also relates to a wettability variable layer forming composition for forming such a wettability variable layer.
[0002]
[Prior art]
As a method for forming a fine pattern, a method of performing pattern exposure and development on a photoresist layer provided on a material that can be etched, and performing etching using the obtained resist pattern, or a photosensitive resin composition A functional material for imparting a necessary function is dissolved or dispersed therein, a layer of the photosensitive resin composition is laminated on the substrate, pattern exposure and development are performed again, and the photosensitive resin composition There are methods such as patterning layers.
[0003]
In any method, since development or etching is performed, it is necessary to treat the waste liquid containing the removed resist and the material that can be etched. When functional materials are included, the alkalis used for the development are included. There is also a problem such as deterioration due to liquid. In addition, although a printing method can be used as a method for forming a fine pattern, there are limitations on accuracy, and it is difficult to form a high-definition pattern.
[0004]
The inventors added a fine pattern using a pattern based on the difference in wettability obtained by changing the wettability of the surface of silicone or the like using a photocatalyst as previously disclosed in Patent Document 1. In particular, a method of using a conventional photoresist or a photosensitive resin composition by using a polysiloxane containing a fluoroalkyl group as a material that causes a change in wettability. It has been found that the disadvantages in the above are eliminated.
[0005]
Generally, polysiloxane containing fluoroalkyl groups is formed on a substrate by adding an acid or alkali catalyst to the fluoroalkylsilane compound coating solution, which is a precursor of fluoroalkylsilane, and hydrolyzing it. The condensation polymerization reaction is promoted to react with the surface of the substrate. When these catalysts are added to the coating solution, the usable time of the coating solution is shortened, or excess fluorine is added to the surface of the wettability changing layer. There are problems such as system components remaining, so the wettability variable layer becomes cloudy, and it is necessary to add a wiping work to remove the cloudiness, and in order to avoid cloudiness, it is necessary to add a catalyst The reactivity with the surface of the substrate decreases, and the resulting wettability changing layer has properties such as sufficient durability (adhesion, etc.), transparency, or liquid repellency. Things can not be obtained.
[0006]
[Patent Document 1]
JP2000-249821
[0007]
[Problems to be solved by the invention]
Therefore, the present invention has a long usable time of the coating liquid used when forming a polysiloxane containing a fluoroalkyl group on a substrate, or the resulting wettability variable layer is not clouded, and the It is an object of the present invention to provide a wettability variable substrate having a wettability variable layer having sufficient durability such as adhesion, transparency, or liquid repellency. Moreover, this invention makes it a subject to provide the board | substrate which has a fine pattern using the above wettability changeable board | substrates. Furthermore, this invention makes it a subject to provide the composition for wettability changeable layer formation suitable for manufacturing the wettability changeable layer of the above wettability changeable substrates.
[0008]
[Means for solving the problems]
By the inventors' investigation, it has been found that by using an amorphous silica precursor in addition to a polysiloxane containing a fluoroalkyl group, all of the above problems can be overcome while securing wettability, The present invention has been reached.
[0009]
1st invention has the wettability changeable layer which wettability changes when exposed in presence of a photocatalyst, and the said wettability changeable layer is (A) Y _n SiX _(4-n) (Y represents an alkyl group or a fluoroalkyl group, or a substituent containing these, X represents an alkoxyl group, an acetyl group, or a halogen, respectively, and n in Y subscript n and X subscript 4-n represents 1 to One or more of the organopolysiloxane precursors represented by (3) and (B) SiX ₄ (X is the same as above.) Co-hydrolysis obtained by using the amorphous silica precursor represented by (A) / (B) = 1 / 0.1 to 1/20 in mass ratio. The present invention relates to a wettability variable substrate characterized by containing an organopolysiloxane which is a condensation polymer.
[0010]
In a second invention, the wettability variable layer surface of the wettability variable substrate described in the first invention is exposed in a pattern in the presence of a photocatalyst and has a surface tension of 40 mN / m. A pattern forming body comprising a wettability pattern comprising an unexposed region having a contact angle with a liquid of 10 ° or more and an exposed region having a contact angle with a liquid having a surface tension of 40 mN / m of 9 ° or less. It is about.
[0011]
3rd invention is a material different from the material which comprises the said wettability changeable layer on the said wettability changeable layer surface so that the said wettability pattern of the pattern formation body described in 2nd invention may be followed The present invention relates to a functional element characterized in that a functional layer made of is laminated.
[0012]
The fourth invention is (A) Y _n SiX _(4-n) (Y represents an alkyl group or a fluoroalkyl group, or a substituent containing these, X represents an alkoxyl group, an acetyl group, or a halogen, respectively, and n in Y subscript n and X subscript 4-n represents 1 to An organopolysiloxane precursor represented by (B) SiX ₄ (X is the same as described above) and (C) the acid concentration is 0.0005N-0.05N Each component of an aqueous solution containing an acid Consist of , A wettability variable layer forming composition used for forming a wettability variable layer whose wettability changes by exposure in the presence of a photocatalyst, wherein each of the components (A) to (C) The mass ratio of (A) / (B) = 1 / 0.1 to 1/20 and (C) / ((A) + (B)) = 1 / 0.25 to 1/30 The present invention relates to a composition for forming a wettability-changing layer.
[0013]
The fifth invention is (A) Y _n SiX _(4-n) (Y represents an alkyl group or a fluoroalkyl group, or a substituent containing these, X represents an alkoxyl group, an acetyl group, or a halogen, respectively, and n in Y subscript n and X subscript 4-n represents 1 to An organopolysiloxane precursor represented by the following formula:
(B) SiX ₄ (X is the same as described above), and an amorphous silica precursor represented by
(C) An aqueous solution containing an acid having an acid concentration of 0.0005N to 0.05N
A composition for forming a wettability changing layer obtained by a co-hydrolysis condensation polymerization reaction using at least these components as starting materials,
The mass ratio of each component (A) to (C) is (A) / (B) = 1 / 0.1 to 1/20, and (C) / ((A) + (B)) = It is related with the composition for wettability change layer formation characterized by being 1 / 0.25-1/30.
[0014]
DETAILED DESCRIPTION OF THE INVENTION
Component (A) for forming the wettability variable layer is Y _n SiX _(4-n) (Y represents an alkyl group or a fluoroalkyl group, or a substituent containing these, X represents an alkoxyl group, an acetyl group, or a halogen, respectively, and n in Y subscript n and X subscript 4-n represents 1 to It is an organopolysiloxane precursor represented by the general formula: The total number of carbon atoms of the substituent represented by Y is preferably in the range of 1-20, and more preferably in the range of 5-10. The alkoxyl group represented by X is preferably a methoxy group, an ethoxy group, a propoxy group, or a butoxy group. Thus, a polysiloxane containing a fluoroalkyl group can be preferably used, and those generally known as fluorine-based silane coupling agents can be used.
[0015]
Examples of the fluoroalkylsilane compound used in the present invention include tri-fluoropropyl-tris- (methoxy) silane, tri-fluoropropyl-tri-chlorosilane, trideca-fluorooctyl-tri-chlorosilane, and trideca-fluorooctyl. -Tris- (methoxy) silane, heptadeca-fluorodecyl-tri-chlorosilane, heptadeca-fluorodecyl-tris- (methoxy) silane, heptadeca-fluorodecylmethyl-di-chlorosilane, heptadeca-fluorodecylmethyl-bis- (methoxy) Silane, henicosa-fluorododecyl-tris- (methoxy) silane, heptadeca-fluorodecyl-tris- ( Butoxy) silane, Henicosa- fluoro dodecyl-tris-(ethoxy) silane.
[0016]
Y above _n SiX _(4-n) The fluoroalkylsilane represented by the formula (1) preferably has a fluorine-substituted alkyl group in which 3 or more atoms are substituted with fluorine atoms, but among them, a fluoroalkylsilane having a fluorine-substituted alkyl group in which 9 or more atoms are substituted with fluorine atoms is more preferred. A fluoroalkylsilane having a fluorine-substituted alkyl group in which 17 atoms or more are substituted with fluorine atoms is particularly preferable because a high contact angle of 105 ° or more can be obtained.
[0017]
Particularly preferred fluoroalkylsilanes in the present invention have a sufficiently large perfluoroalkyl group, and also have three leaving groups (halogen, alkoxy, etc. that can be eliminated from the silicon atom and cause a condensation reaction with silanol on the glass surface). heptadeca-fluorodecyl-tris- (methoxy) silane, heptadeca-fluorodecyl-tris- (ethoxy) silane, henicosa-fluorododecyl-tris- (methoxy) silane, henicosa-fluorododecyl-tris- (ethoxy) silane, and the like. .
[0018]
Note that the above Y _n SiX _(4-n) The organopolysiloxane precursor shown by can be used 1 type or in mixture of 2 or more types.
[0019]
The amorphous silica precursor of the component (B) for forming the wettability variable layer is to contribute to improving the adhesion between the wettability variable layer and the substrate. In particular, when the substrate is glass, the organopolysiloxane precursor of component (A) contains a fluoroalkyl group, which inhibits hydrolysis condensation polymerization reaction with hydroxyl groups on the glass surface, Since it is difficult to obtain sufficient adhesion to the surface of the glass, the wettability variable layer and the surface of the glass can be obtained by subjecting the amorphous silica precursor (B) rich in reactivity with the surface of the glass to a cohydrolytic condensation polymerization reaction. Adhesiveness can be improved.
[0020]
Component (B) is SiX ₄ (X is Y _n SiX _(4-n) Are the same as those described in the above, and represent a halogen, an alkoxyl group such as a methoxy group or an ethoxy group, or an acetyl group. ), An amorphous silica precursor represented by the general formula, silanol which is a hydrolyzate thereof, or a polysiloxane having an average molecular weight of 3000 or less. Specific examples include tetraethoxysilane, tetraisopropoxysilane, tetra-n-propoxysilane, tetrabutoxysilane, and tetramethoxysilane.
[0021]
The above components (A) and (B) are used in a ratio (mass ratio) of (A) / (B) = 1 / 0.1 to 1/20, and are subjected to cohydrolytic condensation polymerization to form organopolysiloxane. As described above, a wettability variable layer can be obtained by applying the composition onto a suitable substrate and drying it. In the present invention, the mass ratio (A) / (B) of the above components (A) and (B) is in the range of 1 / 0.2 to 1/15, particularly 1/1 to 1/10. It is preferable to be within the range.
[0022]
When the mass ratio of the component (A) is less than the lower limit of the above mass ratio, sufficient liquid repellency on the surface, such as ink repellency, cannot be obtained. Even if an attempt is made to pattern the functional layer forming composition by causing the above difference, there is a possibility that the functional layer forming composition may remain in the unexposed area, which is not preferable. Further, when the mass ratio of the component (A) exceeds the upper limit in the above mass ratio, the liquid repellency of the wettability variable layer is improved originally, but the unreacted component (A) and its hydrolysis Since the residue on the surface of the object also increases, the surface becomes cloudy, and if it is severe, the liquid repellency may be lowered, and the lyophilicity by photocatalytic action on the wettability variable layer, for example, This is not preferable because the ink affinity may be significantly inhibited. In addition, since the component (A) is generally expensive, an increase in the content increases the cost.
[0023]
When the mass ratio of the amorphous silica precursor as the component (B) is less than the lower limit in the mass ratio, sufficient adhesion to the substrate, particularly the surface of the glass cannot be obtained, and the component (B) When the mass ratio exceeds the upper limit in the above mass ratio, the content of the component (A) is relatively lowered, and when a fluoroalkylsilane that is a preferred organopolysiloxane precursor is used, the surface of the wettability changing layer Since the fluoroalkyl group content is less, the liquid repellency is lowered, which is not preferable.
[0024]
In order to form the wettability variable layer, in addition to the components (A) and (B), the component (C) is added as follows to prepare a wettability variable layer forming composition. And preferably used.
[0025]
That is, the wettability variable layer forming composition of the present invention is
(A) Y _n SiX _(4-n) (Y represents an alkyl group or a fluoroalkyl group, or a substituent containing these, X represents an alkoxyl group, an acetyl group, or a halogen, respectively, and n in Y subscript n and X subscript 4-n represents 1 to An organopolysiloxane precursor represented by the following formula:
(B) SiX ₄ (X is the same as described above), and an amorphous silica precursor represented by
(C) An aqueous solution containing an acid having an acid concentration of 0.0005N to 0.05N
Each component at least,
The mass ratio of each component (A) to (C) is (A) / (B) = 1 / 0.1 to 1/20, and (C) / ((A) + (B)) = 1 / 0.25 to 1/30.
[0026]
(C) component added in order to comprise the composition for wettability changeable layer formation is the aqueous solution containing the acid which acts as a catalyst. The acid works effectively as a catalyst for the reaction between the fluoroalkylsilane and the surface of an inorganic material such as glass, and functions to increase the reactivity with the surface and increase the liquid repellency. In the present invention, such an acid is added as an aqueous solution containing an acid. The acid concentration in the aqueous solution at this time is in the range of 0.0005N to 0.05N as described above, preferably in the range of 0.001N to 0.04N, and particularly in the range of 0.002N to 0.02N. The inside is preferable.
[0027]
When the acid concentration is higher than the above range, the pot life as a composition is shortened, which is disadvantageous in the process, and the decomposition rate may be lowered, which is not preferable. On the other hand, when the acid concentration is lower than the above range, it may be difficult to effectively act as a catalyst, and there is a possibility that an unreacted portion remains.
[0028]
The acid used in the aqueous solution containing such an acid is not particularly limited, and can be selected from, for example, hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, formic acid, oxalic acid, or acetic acid. In the present invention, it is preferable to use hydrochloric acid or nitric acid. This is because the catalytic effect is high and the possibility of occurrence of problems when used is low.
[0029]
In the present invention, the component (C) is (C) / ((A) + (B)) = 1 / 0.25-1 in terms of mass ratio with respect to the component (A) and component (B) described above. / 30, preferably within the range of 1 / 0.5 to 1/20, particularly preferably within the range of 1/1 to 1/10.
[0030]
When the mass ratio of the aqueous solution containing the acid of component (C) is less than the lower limit in the above mass ratio, it does not act effectively as a catalyst. This is not preferable because the usable time of the composition for use is shortened.
[0031]
In addition, for the purpose of obtaining a desired viscosity of the composition for forming a wettability variable layer, for the purpose of obtaining a desired film thickness during coating, or for extending the usable time of the composition for forming a wettability variable layer. For the purpose, the composition for forming a wettability-modifying layer comprising the above (A) to (C) may be further diluted appropriately with a hydrophilic organic solvent.
[0032]
The hydrophilic organic solvent used for the above purpose is an organic solvent capable of dissolving water at least 20% or more, preferably 40% or more, more preferably 60% or more. More preferably, the hydrophilic organic solvent is capable of dissolving 80% or more of water, and is particularly preferably an organic solvent that can be mixed with water at an arbitrary ratio. These percentages are based on mass.
[0033]
Specific examples of the hydrophilic organic solvent include alcohols such as methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, sec-butyl alcohol, diethylene glycol dimethyl ether, acetone, dimethylformamide (DMF), or dimethyl sulfoxide (DMSO). ) And the like, but alcohols are preferable from the viewpoint of good solubility of fluoroalkylsilanes and appropriate volatility. When alcohols are used as the hydrophilic organic solvent, those having a boiling point of 110 ° C. or less are preferably used. The hydrophilic organic solvent is preferably one that forms an azeotropic mixture with water, and when such an organic solvent is used, the water repellent treatment agent is dried well. From such a viewpoint, it is particularly preferable to use alcohols that form an azeotropic mixture with water, such as ethyl alcohol and isopropyl alcohol.
[0034]
The composition for forming a wettability variable layer of the present invention has the same components (A) to (C) as described above in the same mass ratio as described above, and uses these as starting materials for the cohydrolytic condensation polymerization reaction. The composition for forming a wettability changing layer obtained by the above may be used. That is, the composition for forming a wettability variable layer of the present invention also includes a composition for forming a wettability variable layer in a state in which a part of the component (A) and the component (B) has undergone a cohydrolytic condensation polymerization reaction. It is a waste. This is because when the composition for forming a wettability changing layer is used, better physical properties may be obtained by using a composition in which cohydrolysis condensation polymerization reaction has progressed to some extent.
[0035]
Here, the state in which a part of the component (A) and the component (B) is subjected to cohydrolytic condensation polymerization reaction means that the substituent X in the component (A) and the component (B) is 10 moles compared to the input amount. The state decreased within the range of% to 90 mol% is preferable, and the state decreased particularly within the range of 25 mol% to 75 mol% is preferable. If it is less than the above range, there may be a problem in the physical properties of the finally obtained film, and if it exceeds the above range, the composition may be gelled.
[0036]
The composition for forming a wettability changing layer as described above is a composition for forming a wettability changing layer in which each component is dissolved or dispersed by stirring or kneading with a hydrophilic organic solvent or other additives as necessary. The wettability variable layer can be formed by preparing a product, applying the wettability variable layer forming composition on an appropriate substrate, and drying the composition. The thickness is preferably 0.001 μm to 1 μm, and more preferably 0.01 μm to 0.1 μm so that the change in wettability upon exposure in the presence of a photocatalyst is performed at a preferable rate.
[0037]
The contact angle of the surface of the wettability variable layer obtained by the above-described composition and production method with a liquid having a surface tension of 40 mN / m is 10 ° or more in an unexposed state, and exposure in the presence of a photocatalyst is possible. In the state after application, it is preferably 9 ° or less. If the angle is less than 10 ° in the unexposed state, the liquid repellency is not sufficient, and there is a possibility that the composition for forming a functional layer may remain thereon, and the state after exposure is 9 °. If it exceeds the above range, the functional layer-forming composition thereon is not sufficiently spread, and there is a possibility that an uncoated portion may be formed in the area to be coated with the functional layer-forming composition. . If the contact angle has a difference of 1 ° or more between the unexposed state and the state after the exposure in the presence of the photocatalyst as described above, the difference in wettability is used. Thus, the composition for forming a functional layer can be selectively applied onto a portion in a state after being exposed in the presence of a photocatalyst.
[0038]
The surface of the wettability variable layer 3 in the wettability variable substrate 1 of the present invention preferably has a contact angle with a liquid having a surface tension of 40 mN / m of 10 ° or more in the unexposed area, but is not exposed. In the region, the contact angle with a liquid having a surface tension of 30 mN / m is more preferably 10 ° or more, and in the unexposed region, the contact angle with a liquid having a surface tension of 20 mN / m is 10 ° or more. It is particularly preferred that This is because the unexposed area, which is in an unexposed state, is a part that requires liquid repellency to repel the composition for forming a functional layer when forming a fine pattern. This is because the liquid repellency is not sufficient and the functional layer forming composition may remain, which is not preferable. The unexposed area of the wettability variable layer 3 has a critical surface tension of 50 mN / m or less, preferably 30 mN / m or less.
[0039]
In addition, the surface of the wettability variable layer 3 in the wettability variable substrate 1 of the present invention has a contact angle with a liquid having a surface tension of 40 mN / m after exposure in the presence of a photocatalyst. In the portion (hereinafter referred to simply as “exposure region”), it is preferably 9 ° or less, but in the exposure region, the contact angle with a liquid having a surface tension of 40 mN / m is preferably 9 ° or less. Is preferably a layer having a contact angle with a liquid having a surface tension of 50 mN / m of 10 ° or less, and particularly a contact angle with a liquid having a surface tension of 60 mN / m of 10 ° or less. This is because if the contact angle with the liquid in the exposure region is high, the composition for forming a functional layer attached to this portion is not sufficiently spread and may not reach the exposure region.
[0040]
The measurement of the contact angle with the liquid was performed using a contact angle measuring device (manufactured by Kyowa Interface Science Co., Ltd., product name: CA-Z type), and the measurement was performed 30 seconds after the droplet was dropped from the microsyringe. Or the result was obtained in a graph. In this measurement, a commercially available wetness index standard solution (manufactured by Junsei Co., Ltd.) was used as the liquid having various surface tensions.
[0041]
The wettability-changing substrate of the present invention, as previously disclosed in Japanese Patent Application Laid-Open No. 2000-249821, is subjected to pattern exposure, whereby a liquid-repellent region that is an unexposed region and a lyophilic region that is an exposed region. Is formed on the surface of the wettability changing layer, and a pattern forming body having such a wettability pattern can be obtained. And the functional element which has a functional layer of a fine pattern is obtained by making the functional layer formation composition adhere on the lyophilic area | region of such a pattern formation body, and forming a functional layer. Can do. FIG. 1 and FIG. 2 are diagrams showing steps for forming the above-described pattern forming body and functional element using the wettability variable substrate of the present invention.
[0042]
As shown in FIGS. 1A and 1B, a wettability variable substrate 1 and a photocatalyst substrate 4 used for controlling the wettability of the wettability variable substrate 1 are prepared.
[0043]
The wettability variable substrate 1 is usually configured by laminating the wettability variable layer 3 on the substrate 2 (first substrate), but is configured by the wettability variable layer 3 alone. May be. The wettability changing layer 3 may be accompanied by a protective layer, but at least a portion to be used is not accompanied by a protective layer and needs to be exposed. Further, the wettability changing layer 3 may be laminated on the entire surface of the substrate 2 or may be formed on a part thereof.
[0044]
When the wettability variable substrate 1 is accompanied by the substrate 2, examples of the material constituting the substrate 2 include metals such as glass, aluminum, and alloys thereof, plastics, woven fabrics, nonwoven fabrics, and the like. Can be selected according to the use of the substrate having the fine pattern obtained. The substrate 2 includes a flexible film.
[0045]
The photocatalyst substrate 4 is configured by laminating a photocatalyst layer 6 on a substrate 5 (second substrate) different from the substrate 1. Since the substrate 5 is usually on the exposure side during exposure in the presence of a photocatalyst, it is preferably made of a transparent material such as a plastic film or glass, and the photocatalyst layer 6 is made of, for example, titanium dioxide. It is a dry coating film of the inorganic type paint to contain.
[0046]
As shown in FIG. 1C, the wettability variable substrate 1 and the photocatalyst substrate 4 are overlapped with each other so that the wettability variable layer 3 and the photocatalyst layer 6 are in contact with each other. Exposure is performed through the mask 7 from the substrate 5 side.
[0047]
As shown in FIG. 2A, the exposed surface of the wettability variable layer 3 has high wettability (in other words, it is lyophilic) caused by the change in surface energy in the exposure region. ) Wetting consisting of areas having different wettability consisting of the area 3A and the area 3B which is left untouched in the unexposed area and is relatively low in wettability (in other words, liquid repellent). As a result, a pattern forming body on which a sexual pattern is formed is obtained. The reason why a wettability pattern is formed when exposed to light in the presence of a photocatalyst in this way is that the action of the photocatalyst causes oxidation, decomposition, etc. of organic groups that are part of the components of the wettability variable layer 3. It is done.
[0048]
As shown in FIG. 2B, in the highly wettable region 3A, the functional layer forming composition and the like are better wetted than the other regions. When the attached coating is selectively adhered and solidified by drying, heating, or the like, the solid content contained in the aqueous solution or aqueous dispersion is solidified as shown in FIG. 2 (c). A functional element having a fine pattern of the functional layer in which the solidified film 10 ′ is formed on the highly wettable region 3A can be obtained.
[0049]
There may be several variations in how to wet the wettability changing substrate 1 and the photocatalyst substrate 4 and in exposure. First, during exposure, the wettability variable substrate 1 and the photocatalyst substrate 4 may be in close contact with each other, but may not be in close contact with each other, and may be in a state of facing each other at a very close distance, The wettability changing layer 3 and the photocatalyst layer 6 may be 200 μm or less which is the working distance between them.
[0050]
In the above description, the exposure is performed through a different mask from the wettability variable substrate 1 and the photocatalyst substrate 4, but the mask pattern 9 is either the wettability variable substrate 1 or the photocatalyst substrate 4. You may use what was formed in a cramp, or it may be not the exposure performed through a mask, but the method of scanning an exposure beam as in manufacturing a photomask for manufacturing a semiconductor. Any method can be used as long as pattern exposure can be performed as a result.
[0051]
If the photocatalyst is anatase-type titanium dioxide, the excitation wavelength is 380 nm or less. Therefore, the exposure light only needs to have a peak at 380 nm or less. Therefore, exposure can be performed using an ultraviolet light source used for exposure. The exposure can be performed using various kinds of mercury lamps, metal halide lamps, xenon lamps, excimer lamps or other ultraviolet lamps, or laser light sources such as excimers or YAG for scanning.
[0052]
By using the wettability variable substrate of the present invention and selecting and using various functional layer forming compositions prepared using a material different from the material constituting the wettability variable layer according to the application. Various functional elements can be obtained.
[0053]
For example, by forming a wettability changing layer on a glass substrate or the like and exposing in the presence of a photocatalyst to a highly patterned region 3A having high wettability, red, green, By applying a coating composition for forming a colored layer such as blue and a coating composition for forming a light shielding layer, a color filter (functional element) used in a liquid crystal display device or the like can be obtained. For example, the color filter layer forming ink composition is attached to the wettability changing layer in which the fine pattern-like region 3A having high wettability is formed by an ink jet apparatus or the like, and cured, thereby easily forming a colored layer (function In addition, since the pattern shape itself is determined by the shape of the highly wettable region, the number of steps is small and a simple method can be obtained while obtaining a high-definition color filter. it can.
[0054]
In addition, the formation of a microlens (functional element) using a transparent resin coating composition as the functional layer forming composition, or the fine electric power using the conductive coating composition as the functional layer forming composition. The above method can also be used for manufacturing a circuit board (functional element). In addition, instead of selectively attaching the functional layer forming composition to the wettability variable layer in which the finely patterned region 3A having high wettability is formed, a thin film of metal or the like is deposited or sputtered. Thus, a functional element having a fine pattern made of a thin film is formed by using the fact that the adhesion is low except in the region 3A having high wettability after being formed on one surface, and peeling the thin film other than the region 3A having high wettability. It can also be formed.
[0055]
【Example】
Example 1
Tetramethoxysilane (GE Toshiba Silicone Co., Ltd., product name: TSL8114) 5 g, fluoroalkylsilane (GE Toshiba Silicone Co., Ltd., product name: TSL8223) 1.5 g, and 0.005 N HCl (aqueous solution) 2.36 g Then, the solution was stirred at a temperature of 20 ° C. for 24 hours, and then the solution was diluted 100 times with isopropyl alcohol (on a mass basis, the same applies to comparative examples) to obtain a composition for forming a wettability variable layer. Using this wettability variable layer forming composition, a glass substrate is spin-coated and dried at a temperature of 150 ° C. for 10 minutes to obtain a wettability variable substrate having a transparent and uniform wettability variable layer. It was.
[0056]
An aqueous dispersion of titanium dioxide (product name; manufactured by Ishihara Sangyo Co., Ltd.) on the mask pattern side of a photomask having a mask pattern in which a Cr thin film is formed in a stripe shape having a width of 50 μm and a pitch of 100 μm on a glass substrate; “ST-K03”) is spin-coated and heat-dried so that the photocatalyst layer side of the photocatalyst layer is the wettability variable layer side of the wettability variable substrate. Then, UV light with a wavelength of 365 nm is applied at 20 mW / cm from the photomask side with an ultrahigh pressure mercury lamp. ² The film was exposed by irradiating at an illuminance of 5 to form a wettability pattern on the surface of the wettability variable layer. The obtained wettability pattern has a contact angle with water in the unexposed area of 115 °, a contact angle with liquid with a surface tension of 40 mN / m is 83 °, and a contact angle with water in the exposed area of 10 °. It took 120 seconds for the angle of contact with a liquid having a surface tension of 40 mN / m or less to be 9 ° or less. Further, the width of the unexposed portion was 49 μm, and the width of the exposed portion was 51 μm.
[0057]
(Example 2)
The blending ratio of each component was set to 0.59 g of tetramethoxysilane (GE Toshiba Silicone Co., Ltd., product name: TSL8114), 5.91 g of fluoroalkylsilane (GE Toshiba Silicone Co., Ltd., product name: TSL8223), and 0.81 g. A wettability pattern was formed in the same manner as in Example 1 except that 2.36 g of 005N HCl (aqueous solution) was used. The obtained wettability pattern has a contact angle with water in an unexposed area of 120 °, a contact angle with a liquid having a surface tension of 40 mN / m is 89 °, and a contact angle with water in an exposed area of 10 °. It took 230 seconds for the contact angle with a liquid having a surface tension of 40 mN / m or less to be 9 ° or less. Further, the width of the unexposed portion was 49 μm, and the width of the exposed portion was 51 μm.
[0058]
(Example 3)
The compounding ratio of each component was 6.19 g of tetramethoxysilane (manufactured by GE Toshiba Silicone Co., Ltd., product name: TSL8114), 0.31 g of fluoroalkylsilane (manufactured by GE Toshiba Silicone Co., Ltd., product name: TSL8223), and 0.81 g. A wettability pattern was formed in the same manner as in Example 1 except that 2.36 g of 005N HCl (aqueous solution) was used. The obtained wettability pattern has a contact angle with water in the unexposed area of 105 °, a contact angle with liquid with a surface tension of 40 mN / m is 72 °, and a contact angle with water in the exposed area of 10 °. It took 90 seconds for the angle of contact with the liquid having a surface tension of 40 mN / m or less to be 9 ° or less. Further, the width of the unexposed portion was 49 μm, and the width of the exposed portion was 51 μm.
[0059]
(Comparative Example 1)
The blending ratio of each component is 5 g of tetramethoxysilane (GE Toshiba Silicone Co., Ltd., product name: TSL8114), 1.5 g of fluoroalkylsilane (GE Toshiba Silicone Co., Ltd., product name: TSL8223), and 0.005 N. A composition for forming a wettability variable layer was obtained in the same manner as in Example 1 except that 0.2 g of HCl (aqueous solution) was used. The resulting wettability variable layer-forming composition was coated on a glass substrate, but due to insufficient adhesion to the glass substrate surface, repelling occurred on the glass substrate, resulting in a change in wettability. The formation of the protective layer was not possible.
[0060]
(Comparative Example 2)
The compounding ratio of each component is 5 g of tetramethoxysilane (GE Toshiba Silicone Co., Ltd., product name: TSL8114), 1.5 g of fluoroalkylsilane (GE Toshiba Silicone Co., Ltd., product name: TSL8223), and 0.1N. A wettability variable substrate was formed in the same manner as in Example 1 except that 2.36 g of HCl (aqueous solution) was used. The wettability variable layer of the obtained wettability variable substrate was cloudy because of the excess fluorine component remaining on the surface.
[0061]
(Comparative Example 3)
In addition to the tetramethoxysilane blended in the compounding ratio of each component, 6.5 g of fluoroalkylsilane (manufactured by GE Toshiba Silicone Co., Ltd., product name: TSL8223) and 2.36 g of 0.005 N HCl (aqueous solution) were used. Was carried out in the same manner as in Example 1 to obtain a wettability variable layer forming composition. The resulting wettability variable layer-forming composition was coated on a glass substrate, but due to insufficient adhesion to the glass substrate surface, repelling occurred on the glass substrate, resulting in a change in wettability. The formation of the protective layer was not possible.
[0062]
【The invention's effect】
According to the present invention, since it is configured using a cohydrolyzed polycondensation product of an organopolysiloxane precursor such as fluoroalkylsilane and an amorphous silica precursor, it has sufficient liquid repellency and is present in the presence of a photocatalyst. It is possible to provide a wettability variable substrate having a wettability variable layer that is capable of producing a wettability pattern and having no white turbidity and excellent adhesion to the substrate. .
[Brief description of the drawings]
FIG. 1 is a schematic cross-sectional view showing a wettability variable substrate, a photocatalyst substrate, and a state in which they are exposed by overlapping.
FIG. 2 is a schematic cross-sectional view showing a state after exposure of a wettability variable substrate, a state where a paint is adhered, and a state where the substrate is solidified.
[Explanation of symbols]
1 wettability variable substrate (2; substrate, 3; wettability variable layer)
4 Photocatalyst substrate (5; substrate, 6; photocatalyst layer)
7 Mask
10 Paint (10 '; solidified film)

Claims (3)

(A) Y _n SiX _(4-n) (Y represents an alkyl group or a fluoroalkyl group, or a substituent containing these, X represents an alkoxyl group, an acetyl group, or a halogen, respectively; N in the subscript 4-n is an integer of 1 to 3.)
(B) Each component of an amorphous silica precursor represented by SiX ₄ (X is the same as above), and (C) an aqueous solution containing an acid having an acid concentration of 0.0005N to 0.05N, A composition for forming a wettability variable layer used for forming a wettability variable layer whose wettability is changed by exposure in the presence of a photocatalyst,
The mass ratio of the components (A) to (C) is (A) / (B) = 1 / 0.1 to 1/20, and (C) / ((A) + (B)) = A composition for forming a wettability variable layer, wherein the composition is 1 / 0.25 to 1/30. Further characterized in that it is diluted with the parent water-soluble organic solvent, the wettability changeable layer forming composition of claim 1. The parent water-soluble organic solvent, wherein the water is an organic solvent which can dissolve more than 20 wt%, the wettability changeable layer forming composition according to claim 2.

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