JP2012106893A - Micro ring-like inorganic oxide particle in which fibrous bacterial cellulose penetrates through hole - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a specific macro ring-like inorganic oxide particle used for obtaining a base material to which a transparent coating film, which is superior in flexibility, film strength, scratch resistance and ductility and further contains inorganic oxide particles while uniformly dispersed, is stuck.SOLUTION: A composite includes: the micro ring-like inorganic oxide particles having a through hole; and a fibrous bacterial cellulose penetrating the through hole.

Description

  The present invention relates to microring-shaped inorganic oxide particles in which fibrous bacterial cellulose has penetrated through holes.

  Conventionally, in order to improve the scratch resistance on the surface of a substrate such as glass, a plastic sheet, and a plastic lens, a transparent film having a hard coat function may be formed on the surface of the substrate. Further, by including inorganic particles such as silica in such a transparent film, the scratch resistance may be further improved.

  For example, Patent Document 1 describes a microring-shaped inorganic oxide particle of a specific aspect, a coating liquid containing the same, and a substrate with a transparent coating formed using the same. Since such microring-like inorganic oxide particles have through-holes inside, the matrix component penetrates into the through-holes to form a transparent film, and even when stress is applied, the particles and matrix It is described that it can be suitably used for improving scratch resistance, film strength, adhesion to a substrate, and the like.

JP 2010-168268 A

  However, the transparent oxide film formed on the surface of the substrate has a problem that the inorganic oxide particles are unevenly distributed and the transparency is easily impaired. Moreover, the transparent film containing inorganic oxide particles tended to be easily broken. In particular, when the content of the inorganic oxide particles was high, it was easily broken easily.

  An object of the present invention is to obtain a substrate having a transparent coating film which is excellent in flexibility in addition to flexibility, film strength and scratch resistance, and further contains inorganic oxide particles dispersed uniformly. An object of the present invention is to provide a coating liquid for forming a transparent film to be used and specific microring-shaped inorganic oxide particles that can be contained in the coating liquid.

The inventor examined the cause of uneven distribution of inorganic oxide particles in the transparent coating. And after apply | coating the coating liquid to the surface of the base material, it was estimated that the convection occurred in the transparent film during the drying, and the inorganic oxide particles moved, so that the uneven distribution of the inorganic oxide particles would occur.
And by connecting the inorganic oxide particles with specific organic fibers and restraining the inorganic oxide particles appropriately, the movement of the inorganic oxide particles can be restricted and uneven distribution can be suppressed. The present invention has been completed by finding that it can be improved.

The present invention includes the following (1) to (13).
(1) A composite comprising microring-shaped inorganic oxide particles having a through hole and fibrous bacterial cellulose penetrating the through hole.
(2) The average outer diameter (D _O ) of the micro-ring-shaped inorganic oxide particles is 10 nm to 20 μm, the average diameter (D _I ) of the through holes is 1 nm to 12 μm, and the ring width (W _R ) The composite according to (1) above, wherein the ratio (W _R / D _O ) to the average outer diameter (D _O ) is 0.2 to 0.45.
(3) The composite according to (1) or (2), wherein the microring-shaped inorganic oxide particles are silica-based.
(4) Furthermore, the composite_body | complex in any one of said (1)-(3) which has on the surface the film which consists of an organosilicon compound represented by following formula (I).
Formula _{(I): R n -SiX 4} -n
However, in formula (I), R is a C1-C10 unsubstituted or substituted hydrocarbon group, and may be the same or different. X is an alkoxy group having 1 to 4 carbon atoms, a hydroxyl group, halogen or hydrogen. N is an integer of 0-3.
(5) A composition comprising the complex according to any one of (1) to (4) above.
(6) A coating solution for forming a transparent film, comprising the composite according to any one of (1) to (4) above, a matrix source, and an organic solvent.
(7) A substrate with a transparent coating comprising a substrate and a transparent coating on the surface of the substrate,
The transparent coating is composed mainly of the composite according to any one of (1) to (4) above and a matrix component,
The base material with a transparent film whose content of the said micro ring-shaped inorganic oxide particle in the said transparent film is 0.01-80 mass%.
(8) The substrate with a transparent coating according to (7), wherein the thickness (Th) of the transparent coating is 50 nm to 20 μm.
(9) The ratio (D _O / Th) between the average outer diameter (D _O ) of the microring-shaped inorganic oxide particles and the thickness (Th) of the transparent coating is 0.3 to 1.0, The base material with a transparent film as described in (7) or (8).
(10) The substrate with a transparent coating according to any one of (7) to (9), wherein the matrix component is an organic resin.
(11) The method for producing a complex according to any one of (1) to (4) above, comprising a step of culturing bacteria producing cellulose in a medium to which the microring-shaped inorganic oxide particles are added.
(12) Manufacture of the coating liquid for transparent film formation as described in said (6) provided with the process of mixing the composite_body | complex in any one of said (1)-(4), a matrix source, and an organic solvent. Method.
(13) A method for producing a substrate with a transparent coating according to (7), comprising a step of applying the coating liquid for forming a transparent coating according to (6) to the surface of the substrate.

  According to the present invention, in addition to flexibility, film strength, and scratch resistance, the substrate is provided with a soft film that is excellent in flexibility, and further includes a transparent film containing inorganic oxide particles dispersed uniformly. The coating liquid for forming a transparent film to be used, and specific microring-shaped inorganic oxide particles that can be contained in the coating liquid can be provided. Since the transparent film obtained by the present invention is excellent in flexibility, it is difficult to break even if more inorganic oxide particles are contained. And if more inorganic oxide particles are contained, a base material provided with a harder transparent film can be obtained.

It is a schematic model figure of the micro ring-shaped inorganic oxide particle in the composite_body | complex of this invention.

The present invention will be described.
This invention is a composite_body | complex which has the micro ring-shaped inorganic oxide particle which has a through-hole, and the fibrous bacterial cellulose which penetrates the said through-hole.
Hereinafter, such a complex is also referred to as “the complex of the present invention”.

Moreover, this invention is a composition containing the composite_body | complex of this invention. This composition is preferably a composition comprising a matrix source and an organic solvent. That is, it is preferably a coating liquid for forming a transparent film containing the composite of the present invention, a matrix source, and an organic solvent.
Hereinafter, such a coating solution for forming a transparent film is also referred to as “the coating solution of the present invention”.

Further, the present invention is a substrate with a transparent coating having a substrate and a transparent coating on the surface of the substrate, wherein the transparent coating is composed mainly of the complex of the present invention and a matrix component, It is a base material with a transparent film whose content of the said micro ring-shaped inorganic oxide particle in the said transparent film is 0.01-80 mass%.
Hereinafter, such a substrate with a transparent film is also referred to as “a substrate with a transparent film of the present invention”.

<Composite of the present invention>
First, the composite of the present invention will be described.
The composite of the present invention has an embodiment in which fibrous bacterial cellulose penetrates through the through-holes of the microring-like inorganic oxide particles.

[Microring-shaped inorganic oxide particles (ring-shaped particles)]
The micro ring-shaped inorganic oxide particles (hereinafter also referred to as “ring-shaped particles”) in the composite of the present invention will be described with reference to the drawings.
FIG. 1 shows a planar model of ring-shaped particles. In FIG. 1, D _O represents the outer diameter, D _I represents the diameter of the through hole, and W _R represents the ring width. However, since the outer diameter, the diameter of the through-hole and the ring width vary, take a scanning electron micrograph of the ring-shaped particles, measure the outer diameter and the diameter of the through-hole for 100, the average value, The average outer diameter (D _O ) and the average diameter of the through holes (D _I ) are used respectively. The through-holes are present in the center of the ring-shaped particles, assuming that the ring width is _{uniform, D O = D I + 2} × W a value determined by _R is satisfied, the ring width (W _R) And

The average outer diameter (D _O ) of the ring-shaped particles is not particularly limited, but is preferably 10 nm to 20 μm, and more preferably 15 nm to 10 μm. If the average outer diameter (D _O ) is too small, it is difficult to provide a through hole. In addition, when the composite of the present invention is contained in a coating solution for forming a transparent film, if the average outer diameter (D _O ) is too large, it may be easily settled or separated, and obtained using this. The transparency and haze of the transparent film, film strength, scratch resistance, and adhesion to the substrate may be insufficient. However, depending on the application, even those exceeding the upper limit can be used.

The average diameter (D _I ) of the through-holes of the ring-shaped particles is not particularly limited, but is preferably 1 nm to 12 μm, more preferably 2 nm to 10 μm, and further preferably 5 nm to 5 μm. If the average diameter (D _I ) is too small, the effect of improving the scratch resistance, film strength, adhesion to the substrate and the like may not be obtained when a substrate with a transparent coating is produced. On the other hand, if the average diameter (D _I ) is too large, the strength of the particles will be low and sufficient film strength, scratch resistance, etc. may not be obtained.

The ratio (W _R / D _O ) between the ring width (W _R ) and the average outer diameter (D _O ) of the ring-shaped particles is not particularly limited, but is preferably 0.20 to 0.45, 0.23 More preferably, it is -0.40, and it is further more preferable that it is 0.23-0.33. If W _R / D _O is too small, the ring width is narrow for the average outer diameter (D _O ), so the strength is low, and sufficient film strength, scratch resistance, etc. are obtained when a substrate with a transparent coating is produced. It may not be possible. On the other hand, if W _R / D _O is too large, the through hole is too small depending on the average outer diameter (D _O ), and voids are generated when stress is applied to the transparent coating on the substrate with the transparent coating. There is a case.

  Note that FIG. 1 is a model diagram of ring-shaped particles. Actually, there may be a case where the through-hole is not at the center of the ring-shaped particle, or there may be a plurality of through-holes. The ring-shaped particle may have a plurality of through holes.

In the composite of the present invention, the primary particles may be in a ring shape, and the secondary particles (that is, an aggregate of a plurality of particles) may form a ring shape.
In the case of the ring-shaped particles from the primary particles, it is preferred that the average outer diameter (D _O) is 10 to 500 nm, more preferably 10 to 300 nm. In the case of the ring-shaped particles from the secondary particles, it is preferable that the average outer diameter of the primary particles constituting the secondary particles (D _O) is 3 to 100 nm, more preferably 5~50nm .

The material of the ring-shaped particles is not particularly limited as long as it is an inorganic oxide. For example, oxides such as silica, alumina, titania, zirconia, silica-alumina, silica-zirconia, silica-boria (SiO ₂ · B ₂ O ₃ ), etc. And complex oxides. Among these, silica or a composite oxide composed of silica and an oxide other than silica is preferable. That is, the microring-like inorganic oxide particles are preferably silica-based (more specifically, those containing 50% by mass or more of silica are silica-based). Examples thereof include zirconia and silica-boria (SiO ₂ .B ₂ O ₃ ).

[Method for producing micro-ring-shaped inorganic oxide particles (ring-shaped particles)]
A method for producing ring-shaped particles will be described.
Although the manufacturing method of the above ring-shaped particle | grains is not specifically limited, It is preferable that it is the 1st or 2nd method demonstrated below.

[First method]
A first method for producing ring-shaped particles will be described.
First, a conventionally known inorganic oxide sol having an average particle size of approximately 3 to 100 nm is spray-dried to prepare particles having at least a depression (concave portion) on the surface. The spray drying method is not particularly limited, and may be a conventionally known method. For example, an atomizer method or a nozzle method may be used. Further, for example, it can be produced according to the method disclosed in JP-A-61-174103. That is, after the slurry is made into fine droplets with a high-speed gas of Mach 1 or higher such as air or nitrogen, this is used as an opposing flow of Mach 1 or higher to generate ultrasonic waves by colliding the droplets. In this method, the droplets are made smaller and dried. The droplet size can be controlled by adjusting the gas / liquid ratio of the nozzle and / or the gas flow rate. When the droplets are of the same diameter, the particle size of the powder is increased when the solid content concentration of the slurry is high. The diameter increases. In the case of the same concentration, if the droplet diameter is reduced, the particle size of the obtained powder is reduced. Further, if the droplet diameter and the solid content concentration are constant, if the drying speed is decreased, the droplets are densely packed and the particle size is reduced. Therefore, in order to obtain a powder having a target particle size, it is necessary to adjust the gas / liquid ratio of the nozzle, the gas flow rate, the solid content concentration of the raw material liquid, or the drying speed.

The temperature of the spray-drying atmosphere is preferably 20 to 150 ° C, more preferably 30 to 120 ° C, although it varies depending on the concentration of the inorganic oxide sol to be sprayed. If the temperature of the spray-drying atmosphere is too low, the desired through-holes or recesses may not be formed. Conversely, if the temperature is too high, the ring may become too thin, or broken crumb-like particles may be formed. .
Moreover, although the density | concentration of inorganic oxide sol changes also with the kind of inorganic oxide sol and the magnitude | size of particle | grains, it is preferable that it exists in the range of 0.1-50 mass%, Furthermore, 1-20 mass%. If the concentration of the inorganic oxide sol is too low or too high, particles having depressions (recesses) cannot be obtained by spray drying, and simple particles may be obtained.

  Moreover, the humidity of the spray drying atmosphere can be adjusted as needed. The humidity at this time is to adjust the drying speed supplementarily and generate a desired through hole. The humidity is preferably 3 to 13 vol%, more preferably 5 to 9 vol%.

Next, the particles obtained as described above are treated with an acid or a base. Examples of the acid include hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, organic acid and the like, and examples of the base include NaOH, KOH, ammonia, quaternary ammonium hydroxide, etc. It is done.
When treated with an acid or a base, the recesses are eroded to form through holes, and the size of the through holes, the ring width, etc. can be adjusted to the desired size.

Specific examples of the first method include the following methods.
Silica sol (manufactured by JGC Catalysts & Chemicals Co., Ltd .: Cataloid (registered trademark), SI-30, average particle size 12 nm, SiO ₂ concentration 30% by mass) is supplied to the opposed two-fluid nozzle of the spray drying device, and the amount of processing liquid 120L / Hr, nozzle pressure 0.40 MPa, drying atmosphere temperature 50 ° C., humidity 7.2% by volume to prepare inorganic oxide particles having concave portions on the surface. Then, 1 g of inorganic oxide particles having recesses on the surface is added to 10 g of an aqueous tetraethylammonium hydroxide solution having a concentration of 25% by mass, stirred at 25 ° C. for 12 hours, filtered, washed thoroughly, and then at 120 ° C. By drying for 10 hours, ring-shaped particles can be obtained.

The average outer diameter (D _O ) of the ring-shaped particles obtained by such a first method is approximately 0.5 to 20 μm.

[Second method]
A second method for producing ring-shaped particles will be described.
The second method can be produced in accordance with, for example, the method for producing hollow silica-based fine particles disclosed in JP-A Nos. 2001-233611, 2004-203683, and the like.

Specifically, composite oxide fine particles composed of silica and an inorganic oxide other than silica are used as nuclei. At this time, a silica coating layer of 10 nm or less may be formed as necessary. Then, inorganic oxides other than silica are removed from the core particles with an acid.
When an inorganic oxide other than silica is removed with an acid, it becomes a squirted particle such as a sponge, which becomes a precursor. You may form a silica coating layer in this precursor further as needed.

The ring-shaped particles can be obtained by treating the precursor of the obtained ring-shaped particles with an acid or a base, or by hydrothermal treatment.
In the above, particles having concave portions on the surface are obtained at the stage where inorganic oxides other than silica are removed with an acid, and then ring-shaped particles having through-holes are obtained by treatment with acid or base or hydrothermal treatment. It is done. In addition, it will become a hollow particle only by forming a silica coating layer, without processing in this way.
The kind of acid (one that dissolves the inorganic oxide and one used in the subsequent treatment) and alkali are not particularly limited, and for example, the same ones as exemplified in the first method can be used. .

Specific examples of the second method include the following methods.
3900 g of pure water was added to 100 g of silica sol (manufactured by JGC Catalysts & Chemicals Co., Ltd .: Cataloid (registered trademark), SI-550, average particle diameter 5 nm, SiO ₂ concentration 20% by mass) and heated to 98 ° C. While holding, 13345 g of a sodium silicate aqueous solution having a concentration of 1.5% by mass as SiO ₂ and 13345 g of a sodium aluminate aqueous solution having a concentration of 0.5% by mass as Al ₂ O ₃ were added, and SiO ₂ · Al ₂ O _{A three-} particle dispersion (average particle size 35 nm) is obtained.

Next, 109830 g of a sodium silicate aqueous solution having a concentration of 1.5% by mass as SiO ₂ and 36610 g of a sodium aluminate aqueous solution having a concentration of 0.5% by mass as Al ₂ O ₃ were added to form composite oxide fine particles (average particle diameter 60 nm). ) Dispersion.

  Next, 1125 g of pure water is added to 500 g of the dispersion of fine composite oxide particles having a solid content of 13% by mass washed with an ultrafiltration membrane, and concentrated hydrochloric acid (concentration 35.5% by mass) is further added dropwise. The pH is adjusted to 1.0 and dealumination is performed. Next, while adding 10 L of hydrochloric acid aqueous solution of pH 3 and 5 L of pure water, the aluminum salt dissolved in the ultrafiltration membrane is separated and washed to obtain an aqueous dispersion of silica-based hollow fine particles having a solid content concentration of 20% by mass.

Next, a mixture of 150 g of silica-based hollow fine particle aqueous dispersion, 500 g of pure water, 1750 g of ethanol, and 626 g of ammonia water having a concentration of 28% by mass was heated to 35 ° C., and then this mixture was mixed with ethyl silicate (SiO ₂ concentration). (28% by mass) 47 g was added to form a silica coating layer, which was washed with an ultrafiltration membrane while adding 5 L of pure water to form a silica coating layer having a solid content concentration of 20% by mass. Obtain a liquid.

  Next, ammonia water is added to the silica-based hollow fine particle dispersion having the silica coating layer to adjust the pH of the dispersion to 10.5, and then aged at 200 ° C. for 11 hours, and then cooled to room temperature. And after adding sodium hydroxide and adjusting pH to 12, stirring at 80 degreeC for 12 hours, if it wash | cleans sufficiently, the aqueous dispersion of the ring-shaped particle | grain with a solid content concentration of 20 mass% will be obtained.

The average outer diameter (D _O ) of the ring-shaped particles obtained by the second method is about 10 to 500 nm.

[Fibrous bacterial cellulose]
The composite of the present invention has a mode in which fibrous bacterial cellulose penetrates through the through-holes of the ring-shaped particles as described above.
Here, fibrous bacterial cellulose means cellulose having a fine fiber structure produced by bacteria.
When a transparent film is formed on the surface of a substrate using a coating liquid for forming a transparent film containing ring-shaped particles in which fibrous bacterial cellulose penetrates through holes, flexibility, film strength, and scratch resistance are improved. In addition, the present inventor has found that a substrate having a transparent film having flexibility and further containing ring-shaped particles uniformly dispersed can be obtained. In this regard, the present inventor connects the ring-shaped particles with fibrous bacterial cellulose and restricts the ring-shaped particles by restraining the ring-shaped particles appropriately, during drying after applying the coating liquid, etc. It is believed that even if convection occurs in the transparent film, it can be made unevenly distributed, and at the same time, the flexibility of the transparent film itself can be improved.
Further, since the transparent film has flexibility, it is difficult to break even when it is dried, even if more inorganic particles are contained. And if more ring-shaped particles are contained, a base material provided with a harder transparent film can be obtained.

  The bacteria to be used are not particularly limited as long as they can produce cellulose in the medium, and examples include bacteria belonging to the genus Acetobacter, Gluconobacter, Agrobacterium, Pseudomonas, and the like. Among these, bacteria belonging to the genus Acetobacter are preferable, and Acetobacter xylinum is more preferable.

The composite of the present invention contains ring-shaped particles and bacterial cellulose, and may contain others, but is preferably composed of ring-shaped particles and bacterial cellulose.
Although the content rate of the ring-shaped particle | grain in the composite_body | complex of this invention is not specifically limited, It is preferable that it is 1-80 mass%, It is more preferable that it is 3-60 mass%, It is that it is 5-50 mass%. Further preferred.
The content of bacterial cellulose in the complex of the present invention is not particularly limited, but is preferably 20 to 99% by mass, more preferably 40 to 97% by mass, and further preferably 50 to 95% by mass. preferable.

[Method for producing composite of the present invention]
Next, the manufacturing method of the composite_body | complex of this invention is demonstrated.
Although the manufacturing method of the composite_body | complex of this invention is not specifically limited, It is preferable that it is a manufacturing method provided with the process of culture | cultivating the bacteria which produce a cellulose in the culture medium which added the ring-shaped particle | grain. Among them, the production method of culturing bacteria that produce fibrous cellulose in a medium to which animal serum or a serum-containing component and ring-shaped particles are added is more preferable. The through-holes of the ring-shaped particles are small, but with this method, fibrous bacterial cellulose is formed so as to penetrate the through-holes. When the ring-shaped particles are made of silica (or when silica is the main component), the surface of the through-holes in the ring-shaped particles is hydrophobic, so that fibrous cellulose is easily formed so as to penetrate the through-holes.

The medium to be used is not particularly limited as long as animal serum or a component containing serum is added to the basic medium.
Further, the basic medium is not particularly limited as long as it can produce the cellulose by culturing the above-mentioned bacteria. For example, Hestrin-Schramm medium (Schramm et al., J. General Biology, 11, 123-129, 1954).
Examples of animal serum include serum from calves, fetal bovines, adult cattle, horses, rabbits, humans, etc. or those obtained by fractionating serum according to desired criteria such as molecular weight and solubility by salting-out treatment. Among these, calf serum or a fraction thereof is preferable. As calf serum, serum collected from a newborn within 24 hours of birth without colostrum (precolostrum new born calf serum), newborn calf serum (newborn calf serum; calf serum within one week of birth), calf serum ( calf serum; calf serum within 3 months of life) and the like. In addition, the “component containing serum” means the one containing the blood serum, blood coagulation factor, etc. in an amount that does not impair the object of the present invention together with the serum.

  The content of the animal serum or serum-containing component added to the basic medium (however, the amount as serum, the fraction itself) is preferably 1 to 40% by volume, and 5 to 30% in the medium. % Is more preferable, 5 to 20% by volume is more preferable, and 5 to 15% by volume is more preferable.

  Moreover, it is not specifically limited to culture conditions, The culture conditions in normal bacteria can be applied. For example, the pH is preferably 5 to 9, and more preferably 6 to 7. Moreover, 20-40 degreeC is preferable and 25-35 degreeC is more preferable. The culture period is usually preferably about 3 to 10 days.

[Coating made of organosilicon compound]
It is preferable that the composite of the present invention further has a film made of an organosilicon compound represented by the following formula (I) on the surface.

Formula _{(I): R n -SiX 4} -n

  However, in formula (I), R is a C1-C10 unsubstituted or substituted hydrocarbon group, and may be the same or different. X is an alkoxy group having 1 to 4 carbon atoms, a hydroxyl group, halogen or hydrogen. Moreover, n means the number of R couple | bonded with Si, is an integer of 0-3, and it is preferable that it is an integer of 1-3. Therefore, at least one X is bonded to Si.

When a coating composed of an organosilicon compound is provided on the surface, the composite of the present invention is easily dispersed in the coating liquid of the present invention, and as a result, in the matrix component in the transparent coating of the substrate with the transparent coating of the present invention. Easy to disperse uniformly. And it is easy to obtain a transparent film excellent in film strength, scratch resistance and the like. This is because the organosilicon compound has at least one hydrocarbon group, so the affinity with hydrophobic matrix components that are difficult to mix with each other is increased, and the ring-shaped particles can be dispersed without being unevenly distributed in the matrix. This is probably because of this.
In addition, it is expected that the film strength, scratch resistance, and adhesion of the formed coating film will be increased by surface treatment with an organosilicon compound having a functional group that undergoes a polymerization reaction during matrix preparation and substrate preparation. The
In addition, after apply | coating an organosilicon compound to ring-shaped particle | grains, it is comparatively difficult to form so that fibrous cellulose may be penetrated to a through-hole. In this regard, the present inventors presume that this is because the surface of the through-hole in the ring-shaped particle is no longer hydrophobic. Therefore, it is preferable to form the coating film made of the organosilicon compound after forming the fibrous cellulose so as to penetrate the through hole.

  R in the formula (I) is an alkyl group, alkenyl group, alkynyl group, cycloalkyl group, cycloalkenyl group, amino group, amide group, alkoxy group, epoxy group, carboxyl group, which may be halogen-substituted, It preferably contains at least one organic functional group selected from the group consisting of a ketone group, an ether group, an aryl group, a heteroaryl group, a phosphate group, a halogen group, a thiol group, and a sulfonyl group. By having such an organic functional group, particularly when combined with an organic functional group as a matrix component, it has excellent scratch resistance, film strength, adhesion, etc., and even when stress is applied, it does not easily generate voids. For this reason, the transparency and haze of the substrate with a transparent coating do not deteriorate. Further, by combining in this way, the effect of using the complex of the present invention is highly expressed even in a very small amount.

  Examples of the organosilicon compound represented by the formula (I) include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, diphenyldimethoxysilane, methyltrimethylsilane. Ethoxysilane, dimethyldiethoxysilane, phenyltriethoxysilane, diphenyldiethoxysilane, isobutyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (βmethoxyethoxy) silane, 3,3,3-trifluoropropyl Trimethoxysilane, methyl-3,3,3-trifluoropropyldimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxymethyltrimethoxy Sisilane, γ-glycidoxymethyltriexylsilane, γ-glycidoxyethyltrimethoxysilane, γ-glycidoxyethyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxy Silane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltriethoxysilane, γ- (β-glycidoxyethoxy) propyltrimethoxysilane, γ- (meth) acrylooxymethyltrimethoxysilane, γ- (meth) acrylooxymethyltriethoxysilane, γ- (meth) acrylooxyethyltrimethoxysilane, γ- (meth) acryloxyethyltriethoxysilane, γ- (meth) acryloxypropyltrimethoxy Silane, γ- (meth) acrylooxypropyltrimethoxysilane, -(Meth) acrylooxypropyltriethoxysilane, γ- (meth) acryloxypropyltriethoxysilane, butyltrimethoxysilane, isobutyltriethoxysilane, hexyltriethoxysilaoctyltriethoxysilane, decyltriethoxysilane, Butyltriethoxysilane, isobutyltriethoxysilane, hexyltriethoxysilane, octyltriethoxysilane, decyltriethoxysilane, 3-ureidoisopropylpropyltriethoxysilane, perfluorooctylethyltrimethoxysilane, perfluorooctylethyltriethoxysilane, Perfluorooctylethyltriisopropoxysilane, trifluoropropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldimethoxy Partial hydrolysates such as silane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, trimethylsilanol, methyltrichlorosilane, etc. It may be. Furthermore, two or more kinds of condensates or modified products of these organosilicon compounds may be used.

  These organosilicon compounds are appropriately selected in view of the reactivity with the matrix component. As a method for treating with an organosilicon compound, a conventionally known method can be employed. For example, a necessary amount of an organosilicon compound is added to a liquid in which the complex of the present invention is dispersed in alcohol, and water is added thereto. The surface treatment can be performed by adding an acid or alkali as a hydrolysis catalyst to hydrolyze the organosilicon compound.

  The amount of the organosilicon compound used is preferably 2 to 50 parts by mass and more preferably 5 to 20 parts by mass with respect to 100 parts by mass in the composite of the present invention.

<Coating liquid of the present invention>
Next, the coating solution of the present invention will be described.
The coating liquid of the present invention contains the composite of the present invention, a matrix source, and an organic solvent.

[Matrix source]
The matrix source contained in the coating liquid of the present invention is a matrix component in the transparent film, and is preferably an organic resin. As the organic resin, a known ultraviolet curable resin, thermosetting resin, thermoplastic resin, or the like can be used as a coating resin. Specifically, (meth) acrylic acid resins, γ-glycyloxy resins, urethane resins, vinyl resins and other UV curable resins, polyester resins, polycarbonate resins, polyamide resins, polyphenylene oxide resins, thermoplastics Acrylic resin, vinyl chloride resin, fluororesin, vinyl acetate resin, thermoplastic resin such as silicone rubber, urethane resin, melamine resin, silicon resin, butyral resin, reactive silicone resin, phenol resin, epoxy resin, unsaturated polyester resin, Examples thereof include thermosetting resins such as thermosetting acrylic resins. Further, it may be a copolymer or modified body of two or more of these resins.
In addition, these resins may be emulsion resins, water-soluble resins, and hydrophilic resins.
Further, it may be a thermosetting resin or an electron beam curable type such as an ultraviolet ray, and in the case of a thermosetting resin, a curing catalyst may be included. In the case of a curable resin such as a thermosetting type or an electron beam curable type, the matrix source may be a monomer before the reaction. In this case, the matrix component is a polymer obtained by polymerization reaction of the monomer.
Moreover, the said organosilicon compound can also be used as a matrix source.

[Organic solvent]
The organic solvent contained in the coating solution of the present invention is particularly limited as long as it can dissolve or disperse the matrix source and the polymerization initiator used as necessary, and can disperse the ring-shaped particles uniformly. For example, a conventionally known solvent can be used. Specifically, alcohols such as methanol, ethanol, propanol, 2-propanol (IPA), butanol, diacetone alcohol, furfuryl alcohol, tetrahydrofurfuryl alcohol, ethylene glycol, hexylene glycol, isopropyl glycol; methyl acetate, acetic acid Esters such as ethyl and butyl acetate; diethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol isopropyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol mono Ethers such as ethyl ether; acetone, methyl Ethyl ketone, methyl isobutyl ketone, butyl methyl ketone, cyclohexanone, methyl cyclohexanone, dipropyl ketone, methyl pentyl ketone, diisobutyl ketone, isophorone, acetylacetone, ketones such as acetoacetate, toluene, xylene and the like. These may be used alone or in combination of two or more.

[Polymerization initiator]
Further, the coating agent of the present invention may contain a polymerization initiator, and for example, conventionally known ones can be used. For example, bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, bis (2,6-dimethoxybenzoyl) 2,4,4-trimethyl-pentylphosphine oxide, 2-hydroxymethyl-2-methylphenyl- Propane-1-ketone, 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane -1-one etc. are mentioned.

[Composition of coating liquid of the present invention]
The coating liquid of the present invention contains the ring-shaped particles of the present invention, a matrix source, and an organic solvent, and may contain others, but the ring-shaped particles of the present invention, the matrix source, the organic solvent, Preferably it consists of.

  Although the total concentration of the ring-shaped particles and the matrix source in the coating liquid of the present invention is not particularly limited, the solid content is preferably 1 to 60% by mass, and more preferably 2 to 50% by mass. If the total concentration is too small, a predetermined film thickness may not be obtained by a single application, and if application and drying are repeated, adhesion and the like become insufficient, which is disadvantageous in terms of economy. On the other hand, if the total concentration is too high, the viscosity increases, and the thickness of the resulting transparent coating may become non-uniform.

Moreover, although the density | concentration of the ring-shaped particle | grain in the coating liquid of this invention is not specifically limited, It is preferable that it is 0.05-48 mass% as solid content, and it is more preferable that it is 0.1-30 mass%.
The concentration of the ring-shaped particles in the coating liquid of the present invention is such that when the transparent film is formed using the coating liquid of the present invention, the content of the ring-shaped particles in the obtained transparent film is 0.01 to 80 mass. %, And it is more preferable that the concentration be 0.05 to 75% by mass.

Moreover, although the density | concentration of the matrix source in the coating liquid of this invention is not specifically limited, It is preferable that it is 0.2-57 mass% as solid content, and it is more preferable that it is 0.5-54 mass%.
The concentration of the matrix source in the coating liquid of the present invention is such that when the transparent film is formed using the coating liquid of the present invention, the content of the matrix component in the obtained transparent film is 20 to 99.99% by mass. The concentration is preferably such that the concentration is 25 to 99.95% by mass.

  The coating liquid of the present invention can be obtained by mixing the complex of the present invention, the matrix source and the organic solvent so that the concentrations of the complex and matrix source of the present invention are as described above. Moreover, a polymerization initiator can also be added as needed. When using a polymerization initiator, the concentration of the polymerization initiator in the coating solution of the present invention is preferably 0.5 to 20% by mass, and more preferably 1 to 10% by mass.

<Substrate with Transparent Film of the Present Invention>
Next, the base material with a transparent film of the present invention will be described.
The base material with a transparent film of the present invention can be formed by applying the paint of the present invention to the surface of a base material.

[Base material]
A conventionally well-known thing can be especially used for the base material with which the base material with a transparent film of this invention is equipped without a restriction | limiting. Examples include glass, polycarbonate (PC), acrylic resin, polyethylene terephthalate (PET), triacetyl cellulose (TAC), plastic sheets such as cyclopolyolefin and norbornene, plastic films, and plastic panels. Among these, a resin base material can be preferably used. Moreover, the base material with a film in which another film was formed on such a base material can also be used. Examples of other coatings include conventionally known primer films, hard coat films, high refractive index films, and conductive films.

[Matrix component]
The transparent film with which the base material with a transparent film of this invention is provided contains a matrix component other than the composite_body | complex of this invention.
The matrix component may be the same as the matrix source contained in the coating solution of the present invention, and is preferably an organic resin.

[Composition of transparent film]
The transparent film with which the base material with a transparent film of the present invention is provided is composed mainly of the composite of the present invention and a matrix component. Here, the main component means 50% by mass or more. The total content of the complex of the present invention and the matrix component in the transparent film provided in the substrate with a transparent film of the present invention is preferably 60% by mass or more, more preferably 70% by mass or more, and 80 More preferably, it is 90% by weight or more, more preferably 95% by weight or more, and 100% by weight, that is, the transparent film is substantially composed of the composite of the present invention. It preferably consists of a matrix component.

  Moreover, content of the ring-shaped particle | grains in the transparent film with which the base material with a transparent film of this invention is provided is 0.01-80 mass%, and it is more preferable that it is 0.05-75 mass%. If the content of the ring-shaped particles in the transparent film is too small, the scratch resistance, film strength, etc. may be insufficient. Conversely, if the content is too large, there are few matrix components, adhesion to the substrate, transparency, Haze, scratch resistance, etc. may be insufficient.

  Moreover, it is preferable that it is 20-99.99 mass%, and, as for content of the matrix component in the transparent film with which the base material with a transparent film of this invention is provided, it is more preferable that it is 25-99.95 mass%. If the content of the matrix component is too small, adhesion to the substrate, transparency, haze, scratch resistance, etc. may be insufficient. On the other hand, if the content of the matrix component is too large, the amount of ring-shaped particles decreases, and the scratch resistance, film strength, etc. may be insufficient. However, when using particles that have been surface-treated with an organosilicon compound that has a functional group that undergoes a polymerization reaction during matrix preparation and base material preparation, the coating film formed has a high film strength and scratch resistance even if the content is small. , Adhesion may increase.

  The substrate with a transparent coating of the present invention can contain conventionally known particles in addition to the ring-shaped particles in the transparent coating depending on the purpose. For example, it can further contain low refractive index inorganic oxide particles, high refractive index inorganic oxide particles, conductive inorganic oxide particles and the like.

[Thickness of transparent film]
The thickness (Th) of the transparent film provided in the substrate with a transparent film of the present invention is preferably 50 nm to 20 μm, and more preferably 100 nm to 20 μm. If the thickness of the transparent film is too thin, the scratch resistance and film strength may be insufficient. On the other hand, if the thickness is too thick, the thickness of the film becomes non-uniform, cracks and voids occur in the transparent film, and the film strength is insufficient. Alternatively, warping may occur.

  The thickness (Th) of the transparent coating is a value obtained by measurement by a stylus method.

Further, it is preferable that the ratio of the average outer diameter and (D _O) and the thickness _{(Th) (D O) /} (Th) is 0.3 to 1.0, which is 0.5 to 0.9 Is more preferable. Furthermore, it is such (D _O ) / (Th), the thickness (Th) of the transparent coating is 50 nm to 20 μm, and the average outer diameter (D _O ) of the ring-shaped particles is 10 nm to More preferably, it is 20 μm. This is because it is possible to obtain a substrate with a transparent coating that is more excellent in adhesion to the substrate, hardness, scratch resistance, and the like. If this ratio (D _O ) / (Th) is too small, the effect of improving adhesion to the substrate, the effect of improving hardness, scratch resistance, etc. will be insufficient, and conversely (D _O ) / (Th If it is large, irregularities may be formed on the surface of the transparent coating, and scratch resistance, pencil hardness, etc. may be reduced.

[Method for Producing Substrate with Transparent Film of the Present Invention]
The substrate with a transparent coating of the present invention is prepared by applying the coating solution of the present invention to a substrate by a known method such as a dipping method, a spray method, a spinner method, a roll coating method, a bar coating method, a gravure printing method, a micro gravure printing method, or the like. A transparent film can be formed by applying, drying, and curing by an ordinary method such as ultraviolet irradiation or heat treatment.

<Example 1>
Hestrin-Schram's medium (glucose 2.0%, peptone 0.5%, yeast extract 0.5%, disodium phosphate 0.15%, citric acid 0.27% and sterile water; pH = 6.0) Was used as a basic medium, and calf serum (calf serum; manufactured by Wako Pure Chemical Industries, Ltd.) was added thereto to prepare a liquid medium A having a calf serum content of 10% by volume.
Next, 20 ml of this liquid medium A and 2 g of ring-shaped particles were placed in a 50 ml Erlenmeyer flask, and Acetobacter xylinum (accession number ATCC 10245 was cultured for 1 week in the basic medium (20 ml). 0.5 ml of the bacterial cell solution (deposited) was added, and stationary culture was performed at 29 ° C. for 6 days to culture fibrous cellulose to produce a complex. The pH of the liquid medium A after culture was 3-4.
Here, the ring-shaped particles are made of silica, the average outer diameter (D _O ) is 0.06 μm, the average diameter of the through holes (D _I ) is 20 nm, the ring width (W _R ) and the average outer diameter (D _O ) and a ratio (W _R / D _O ) of 0.33 was used. Table 1 shows the mode of the ring-shaped particles.

  Next, after the composite was separated from the liquid medium A and observed using a scanning electron microscope, it was confirmed that one or more fibrous celluloses penetrated through the through-holes of the ring-shaped particles.

Next, a 1/1 (mass ratio) mixed solvent of isopropanol and ethylene glycol monobutyl ether was prepared. And, this mixed solvent: 25 g, a dispersion having a solid content concentration of 20% by mass in which the composite is dispersed in ethanol: 22.5 g, and an acrylic resin (manufactured by DIC Corporation:
UNIDIC (registered trademark), 17-824-9, solid content concentration of 77% by mass): 17.53 g was mixed to obtain a coating solution for forming a transparent film. Here, the mass ratio of the composite to the matrix source (acrylic resin) is 30:70 as shown in Table 2.

Next, the obtained coating solution was PET film (Toyobo Co., Ltd .: Cosmo Shine A-4300, thickness: 188 μm, refractive index 1.65, base material transmittance 90.0%, haze 0.6%) After coating with a bar coater method (bar # 20) and drying at 80 ° C. for 2 minutes, an ultraviolet irradiation device equipped with a high pressure mercury lamp (120 W / cm) (UV irradiation device manufactured by Nippon Battery Co., Ltd .: CS30L21-3) Was cured by irradiation with 600 mJ / cm ² to obtain a substrate with a transparent coating. The thickness (Th) of the transparent coating at this time was 8 μm.

  Next, the total light transmittance of the obtained transparent film was measured with a haze meter (manufactured by Nippon Denshoku Industries Co., Ltd.). Further, flexibility, pencil hardness, scratch resistance and light resistance were evaluated by the following methods and standards. The results are shown in Table 3.

<Flexibility (void)>
The substrate with a transparent coating was cut out, a section with a width of 1 cm and a length of 5 cm was prepared, one end of the section was fixed, and the other end was bent with a width of 5 cm up and down 20 times. Evaluation based on the criteria.
The transparent film maintained its original transparency: ◎
The transparency of the transparent coating was slightly reduced: ○
Whitening was observed in the transparent film: △
Whitening due to void formation was observed in the transparent film: ×

<Measurement of pencil hardness>
It measured with the pencil hardness tester according to JIS-K-5400.

<Measurement of scratch resistance>
Using # 0000 steel wool, sliding was performed 50 times with a load of 500 g / cm ² , and the surface of the film was visually observed and evaluated according to the following criteria.
Evaluation criteria:
No streak injury is found: ◎
Slightly scratched streak: ○
There are many scratches on the streak: △
Noodles are shaved overall: ×

<Measurement of light resistance>
Water-soluble resin (manufactured by Nippon Synthetic Chemical Co., Ltd .: Polyester 970, resin concentration 20% by mass): 100 parts by mass, complex: 30 parts by mass, and 1/1 (mass ratio) of isopropanol and ethylene glycol monobutyl ether Mixed solvent: 50 parts by mass were mixed to prepare a paint. This paint was applied to a polycarbonate substrate (thickness: 3 mm) with a wire bar and dried at 100 ° C. for 30 minutes to obtain a transparent film having a thickness of 3 μm.
The substrate on which the transparent film was formed was placed in a light resistance tester (Suga Test Instruments Co., Ltd., Sunshine Super Long Life Weather Meter) and irradiated with ultraviolet rays for 250 hours while maintaining the surface temperature of the coated substrate at 60 ° C. The change of the substrate with the transparent coating was observed and evaluated according to the following criteria.
No discoloration was observed. : ◎
Slight discoloration was observed. : ○
Clearly discoloration was observed. : △
A deep discoloration was observed. : ×

<Example 2>
Except for using ring-shaped particles having an average diameter (D _I ) of through-holes of 30 nm and a ratio of the ring width (W _R ) to the average outer diameter (D _O ) (W _R / D _O ) of 0.25. All the same operations and evaluation tests as in Example 1 were performed.
Table 1 shows the mode of the ring-shaped particles. Table 2 shows the mass ratio of the composite to the matrix source (acrylic resin) in the coating liquid for forming the transparent film and the thickness (Th) of the transparent film. Table 3 shows the evaluation results of total light transmittance, flexibility, pencil hardness, scratch resistance and light resistance.

<Example 3>
The average outer diameter (D _O) is 0.5 [mu] m, the average size of the through-hole (D _I) is 200 nm, the ratio of the ring width (W _R) and the average outer diameter _{(D O) (W R /} D O) 0 The same operation and evaluation test as in Example 1 were performed except that 30 ring-shaped particles were used.
Table 1 shows the mode of the ring-shaped particles. Table 2 shows the mass ratio of the composite to the matrix source (acrylic resin) in the coating liquid for forming the transparent film and the thickness (Th) of the transparent film. Table 3 shows the evaluation results of total light transmittance, flexibility, pencil hardness, scratch resistance and light resistance.

<Example 4>
The average outer diameter (D _O) is 10 [mu] m, the average size of the through-hole (D _I) is 5000 nm, the ratio of the ring width (W _R) and the average outer diameter _{(D O) (W R /} D O) 0.25 The same operation and evaluation test as in Example 1 were performed except that the ring-shaped particles were used.
Table 1 shows the mode of the ring-shaped particles. Table 2 shows the mass ratio of the composite to the matrix source (acrylic resin) in the coating liquid for forming the transparent film and the thickness (Th) of the transparent film. Table 3 shows the evaluation results of total light transmittance, flexibility, pencil hardness, scratch resistance and light resistance.

<Example 5>
The same operation and evaluation test as in Example 1 were performed except that the silica was 70% by mass, the balance was alumina, and D _O , D _I and W _R were the same ring-shaped particles.
Table 1 shows the mode of the ring-shaped particles. Table 2 shows the mass ratio of the composite to the matrix source (acrylic resin) in the coating liquid for forming the transparent film and the thickness (Th) of the transparent film. Table 3 shows the evaluation results of total light transmittance, flexibility, pencil hardness, scratch resistance and light resistance.

<Comparative Example 1>
The same operation and evaluation test as in Example 1 were performed except that fibrous cellulose did not pass through the through-holes of the ring-shaped particles.
This is specifically shown below.

  Liquid medium A was prepared in the same manner as in Example 1. Unlike Example 1, fibrous cellulose was cultured without adding ring-shaped particles. That is, 20 ml of liquid medium A was placed in a 50 ml Erlenmeyer flask, and 0.5 ml of Acetobacter xylinum cell culture cultured in a basic medium (20 ml) for 1 week was added thereto, and the mixture was allowed to stand at 29 ° C. for 6 days. After culturing, fibrous cellulose was cultured.

  Next, the obtained fibrous cellulose: 2.5 g and the same ring-shaped particles used in Example 1: 2 g were mixed to obtain a mixture. Moreover, the 1/1 (mass ratio) mixed solvent of isopropanol and ethylene glycol monobutyl ether was prepared. Then, this mixed solvent: 25 g, a dispersion having a solid content of 20% by mass in which the mixture obtained by culturing was dispersed in ethanol: 22.5 g, an acrylic resin (manufactured by DIC Corporation: UNIDIC (registered trademark)) ), 17-824-9, solid content concentration 77 mass%): 17.53 g was mixed to obtain a coating solution for forming a transparent film. Here, the mass ratio of the mixture to the matrix source (acrylic resin) is 30:70 as shown in Table 2.

Next, a substrate with a transparent film was obtained in the same manner as in Example 1 using the obtained coating solution.
And the evaluation test similar to Example 1 was done.
Table 1 shows the mode of the ring-shaped particles. Table 2 shows the mass ratio of the composite to the matrix source (acrylic resin) in the coating liquid for forming the transparent film and the thickness (Th) of the transparent film. Table 3 shows the evaluation results of total light transmittance, flexibility, pencil hardness, scratch resistance and light resistance.

From Tables 1 to 3, although the total light transmittance did not show any difference in the examples and comparative examples, the flexibility, pencil strength, scratch resistance and light resistance were compared with those of the comparative examples. Can be said to be excellent.

Claims (13)

  A composite comprising microring-shaped inorganic oxide particles having a through-hole and fibrous bacterial cellulose penetrating the through-hole. The average diameter (D _O ) of the micro ring-shaped inorganic oxide particles is 10 nm to 20 μm, the average diameter (D _I ) of the through holes is 1 nm to 12 μm, the ring width (W _R ) and the average outer diameter (D _O) and the ratio of (W _R / D _O) is from 0.2 to 0.45, the complex of claim 1.   The composite according to claim 1 or 2, wherein the microring-shaped inorganic oxide particles are silica-based. Furthermore, the composite_body | complex in any one of Claims 1-3 which has the film which consists of an organosilicon compound represented by following formula (I) on the surface.
Formula _{(I): R n -SiX 4} -n
However, in formula (I), R is a C1-C10 unsubstituted or substituted hydrocarbon group, and may be the same or different. X is an alkoxy group having 1 to 4 carbon atoms, a hydroxyl group, halogen or hydrogen. N is an integer of 0-3.   The composition containing the composite_body | complex in any one of Claims 1-4.   The coating liquid for transparent film formation containing the composite_body | complex in any one of Claims 1-4, a matrix source, and an organic solvent. A substrate with a transparent coating having a substrate and a transparent coating on the surface of the substrate,
The said transparent film has as a main component the composite_body | complex in any one of Claims 1-4, and a matrix component,
The base material with a transparent film whose content of the said micro ring-shaped inorganic oxide particle in the said transparent film is 0.01-80 mass%.   The base material with a transparent film of Claim 7 whose thickness (Th) of the said transparent film is 50 nm-20 micrometers. The ratio (D _O / Th) between the average outer diameter (D _O ) of the microring-shaped inorganic oxide particles and the thickness (Th) of the transparent film is 0.3 to 1.0, or 8. A substrate with a transparent coating according to 8.   The base material with a transparent film in any one of Claims 7-9 whose said matrix component is organic resin.   The manufacturing method of the composite_body | complex in any one of Claims 1-4 provided with the process of culture | cultivating the bacteria which produce a cellulose in the culture medium which added the said micro ring-shaped inorganic oxide particle.   The manufacturing method of the coating liquid for transparent film formation of Claim 6 provided with the process of mixing the composite_body | complex in any one of Claims 1-4, a matrix source, and an organic solvent. The manufacturing method of the base material with a transparent film of Claim 7 provided with the process of apply | coating the coating liquid for transparent film formation of Claim 6 to the surface of a base material.

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