JP2001062953A - Photocatalytic transfer material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To easily and simply give photocatalysis to a material to be transferred by transferring by sequentially forming a photocatalyst layer, a primer layer and an adhesive layer on one side surface of a base material having releasability. SOLUTION: A photocatalyst layer 2, a primer layer 3 and an adhesive layer 4 are sequentially formed on one side surface of a base material a having releasability. As the material 1, a plastic, paper or the like having smooth and transparent surface is used, and its thickness of 6 to 100 μm is preferred. The layer 2 is coated with a paint formed of a titanium oxide photocatalytic material such as, for example, an anatase-type titanium oxide, and its thickness is set to 0.05 to 1.5 μm. As the layer 3, various type resins such as thermoplastic, thermosetting, ultraviolet curable resin or the like are used solely or by suitably mixing, and its thickness of 0.5 to 10 μm is preferred. As the layer 4, an acrylic resin, epoxy resin, phenol resin or the like is used, and its thickness of 1 to 50 μm is preferred.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a transfer material, and more particularly to a photocatalytic transfer material capable of imparting a photocatalytic property to a transferred material by transferring a photocatalytic layer to the transferred material. It is.

[0002]

2. Description of the Related Art Conventionally, as a transfer material, various types of transfer materials for transferring a metal deposition layer, a coloring layer, and a printing layer are known.

[0003]

However, conventional transfer materials have been able to impart a metallic luster, coloring, or printing by transferring a metal deposition layer, a coloring layer, or a printing layer to an object to be transferred.
No photocatalytic property could be imparted to the transferred material by the transfer. An object of the present invention is to provide a photocatalytic transfer material which can eliminate the above-mentioned disadvantages and can easily and easily impart photocatalytic properties to an object by transfer.

[0004]

SUMMARY OF THE INVENTION The present invention is a photocatalytic transfer material characterized in that a photocatalytic layer, a primer layer and an adhesive layer are sequentially formed on one surface of a substrate having releasability. The primer layer may be composed of a single layer, or may be composed of two layers, a first primer layer in contact with the photocatalyst layer and a second primer layer in contact with the adhesive layer. The photocatalyst layer preferably has a haze value of 9 or less according to JIS K 7105.

[0005]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described with reference to the drawings. FIG. 1 is a partially enlarged cross-sectional view showing one embodiment of the present invention and an example of a state before the present invention is transferred to an object to be transferred and a base material having releasability is peeled off. FIG. 2 is a partially enlarged cross-sectional view showing one example of the present invention and an example of a state before the present invention is transferred to an object to be transferred and a substrate having releasability is peeled off.

[0006] The substrate 1 having releasability in the present invention is a plastic film having a smooth surface and being transparent, such as polyethylene terephthalate film, polybutylene terephthalate film, polypropylene film, or the like.
Various materials such as polyethylene naphthalate film, polyamide film, polyvinyl chloride film and the like, which are conventionally used as a base material of a transfer material, such as plastic films and papers having a smooth surface and transparent paper can be used. Substrate 1 is 6-1
Thicknesses of 00 μm are preferred. When the substrate 1 is a plastic film substrate in particular, if the thickness of the substrate 1 is less than 6 μm, the substrate 1 is easily wrinkled and the substrate 1 is easily broken. When the thickness of the substrate 1 exceeds 100 μm,
When the surface of the transfer object is a curved surface, the substrate 1 is difficult to follow the curved surface, which is not preferable. In order that the substrate 1 is hardly wrinkled, the substrate 1 is hardly broken, and the substrate 1 sufficiently conforms to the curved surface, the substrate 1 preferably has a thickness of 6 to 100 μm, but has a thickness of 12 to 50 μm. A substrate 1 having a thickness is particularly desirable.

When the releasability of the substrate is not sufficient or when the releasability is weak, a release layer may be formed on the surface of the substrate with an appropriate resin to impart sufficient releasability. The substrate 1 on which the release layer is formed as described above is also included in the substrate 1 having releasability according to the present invention.

The photocatalytic layer 2 can be formed by converting a photocatalytic material into a paint to form a photocatalytic paint, and applying the photocatalytic paint to one surface of the substrate 1 having releasability. As the photocatalytic material, a titanium oxide-based photocatalytic material such as a photocatalytic material made of anatase-type titanium oxide can be used, and a commercially available photocatalytic material can be used.
The photocatalytic material may contain a small amount of rutile type titanium oxide, silicon oxide, zinc oxide, tungsten oxide, niobium oxide, iron oxide, cadmium sulfide, strontium titanate, or the like.

The coating of the photocatalytic material can be obtained by using a suitable resin as a binder and mixing the photocatalytic material into the resin. As the binder, various resins such as thermoplastic, thermosetting, and ultraviolet curable resins can be used alone or in a suitable mixture. However, those that are hardly subjected to the photocatalytic action as much as possible can increase the cohesive force of the photocatalytic material. Those are preferable, among which, silicone modified acrylic resin, fluorine modified acrylic resin, silicone resin, fluororesin,
It is particularly preferable to use an acrylic resin, a silicon-modified polycarbonate resin, or the like as a main component.

The photocatalyst layer 2 preferably has a thickness of 0.05 to 1.5 μm. The thickness of the photocatalyst layer 2 is 0.05 μm
If less than the above, the catalytic action of the photocatalyst layer as a whole is too weak to be weak. When the thickness exceeds 1.5 μm, the photocatalyst layer 2
Is easily broken, and the optical properties are also affected, so that the transparency is easily damaged. The most desirable thickness is 0.1-
When the thickness is within this range, the photocatalytic action is stabilized, cracks do not occur, and the haze value of the photocatalytic layer 2 is optimally 9 or less.

The photocatalyst layer 2 is formed by a gravure coating method, a reverse coating method, a microgravure method, a screen printing method,
Can be formed by a conventionally known coating method.

The photocatalyst layer 2 is formed according to the measuring method JIS K 710.
The haze value according to 5 (Testing method for optical properties of plastic) is preferably 9 or less. When the haze value of the photocatalyst layer 2 exceeds 9, the transparency of the photocatalyst layer 2 tends to deteriorate,
In addition, the photocatalyst layer 2 is easily peeled off due to deterioration over time,
Further, the surface of the transferred material 5 after the transfer becomes dull and the sharpness is easily impaired.

If necessary, various additives such as an antifoaming agent, a coagulation auxiliary agent such as a titanium coupling agent, and a fine particle type slip agent may be added to the photocatalyst layer 2. Further, a silane coupling agent, a silica-forming agent to be mineralized (for example,
Polysilazane manufactured by Tonen Corporation, Glasca manufactured by JSR Corporation, etc. can also be used as additives.

The primer layer 3 is formed on the photocatalyst layer 2 to fix the photocatalyst layer 2, physically protect the transferred material 5 after transfer, and protect it from ultraviolet rays.

The primer layer 3 has a resin which can be used as a binder of the photocatalyst layer 2, that is, a thermoplastic resin, a thermosetting resin, or the like.
Various resins such as ultraviolet curability can be used alone or in appropriate mixture, but as described above, silicone modified acrylic resin, fluorine modified acrylic resin, silicone resin, fluorine resin,
It is particularly preferable to use an acrylic resin, a silicon-modified polycarbonate resin, or the like as a main component.

The primer layer 3 preferably has a thickness of 0.5 to 10 μm. The thickness of the primer layer 3 is 0.5μ
If less than m, the fixing of the photocatalyst layer 2 will not be sufficient.
If it exceeds 10 μm, it is sufficient for fixing the photocatalyst layer 2 and protecting the transferred object 5 after the transfer, but the photocatalyst layer 2 looks colored or has reduced transparency after the transfer. So less preferred. The most desirable thickness of the primer layer 3 is 1 to 5 μm from the viewpoints of fixing the photocatalyst layer 2, protecting the transferred material 5 after transfer, and maintaining transparency.

The primer layer 3 can be formed by a conventionally known coating method such as a gravure coating method, a reverse coating method, a microgravure method, and a screen printing method.

By adding an appropriate amount of an additive such as a silane coupling agent to the primer layer 3, for example, 2 to 5% by weight, the function of the primer layer 3 for fixing the photocatalyst layer 2 can be further improved. Can be. In addition, by appropriately adding an anti-blocking agent, a lubricant and the like to the primer layer 3, the function of the primer layer 3 to physically protect the transferred material 5 after transfer and to protect it from ultraviolet rays is further improved. Can be done.

The primer layer 3 may be composed of one layer as shown in FIG. 1, or may be composed of two layers as shown in FIG. When the primer layer 3 is composed of two layers, the layer in contact with the photocatalyst layer 2, that is, the first primer layer has a function of fixing the photocatalyst layer 2, and the side in contact with the adhesive layer 4 described later. This layer, that is, the second primer layer, may have a function of physically protecting the transferred material 5 after transfer and protecting the transferred material 5 from ultraviolet rays. When the primer layer 3 is composed of two layers, the above-mentioned resin can be used for the first primer layer. Further, the above-mentioned resin can be preferably used for the second primer layer, and further, a vinyl alcohol resin, a urethane resin, a melamine resin, an alkyd resin, a phenol resin,
It is particularly preferable to use a commonly used coating resin or a vehicle such as a cellulose resin as the main agent. This is because the second primer layer is not in contact with the photocatalyst layer 2 and thus is not easily affected by the photocatalysis, and the function of fixing the photocatalyst layer 2 does not need to be considered. In addition, various metal thin film layers or metal oxide thin film layers may be formed in the second primer layer instead of the resin layer. Examples of the metal thin film layer and the metal oxide thin film layer include an aluminum thin film layer such as an aluminum vapor deposition layer, a metal thin film layer such as a zinc thin film layer, a tin thin film layer, and a silver thin film layer, or a silicon oxide thin film layer and a tin oxide thin film layer. And the like which can be formed by conventionally known various thin film forming methods, such as a metal oxide thin film layer.

When the primer layer 3 is composed of two layers, when both layers are layers using a resin, the thickness of each layer is 0.5 to 10 μm, preferably 1 to 10 μm, respectively.
3 μm. When the second primer layer of the two-layered primer layer is a metal thin film layer or a metal oxide thin film layer, the thickness thereof is preferably 50 to 2000 °. In this case, the thickness of the first primer layer is 0.5
10 to 10 μm, preferably 1 to 3 μm.

The adhesive layer 4 can be formed on the primer layer 3 using a resin used for an adhesive layer of a conventional transfer material such as an acrylic resin, an epoxy resin, or a phenol resin.

The adhesive layer 4 preferably has a thickness of 1 to 50 μm. If the thickness of the adhesive layer 4 is less than 1 μm, a sufficient adhesive force to the transfer object 5 cannot be obtained. Also, 50 μm
If it exceeds, the transparency of the adhesive layer 4 deteriorates. The most desirable thickness is 2 to 10 μm, and in this range, both the adhesive strength and the transparency are sufficient.

The adhesive layer 4 can be formed by a conventionally known coating method such as a gravure coating method, a reverse coating method, a microgravure method, and a screen printing method.

Various additives such as an anti-blocking agent can be appropriately added to the adhesive layer 4.

[0025]

EXAMPLES (Measurement of Haze) The measurement of haze of the photocatalyst layer in the following Examples 1 to 3 was conducted in accordance with JIS K71.
05, using a haze meter 300A (manufactured by Nippon Denshoku Industries Co., Ltd.) to form a haze of a peelable substrate before forming a photocatalytic layer and to form a photocatalytic layer on a peelable substrate. After that, the haze was measured, and the value obtained by subtracting the former measured value from the latter measured value was defined as the haze value of the photocatalytic layer. Example 1 A transparent and smooth substrate having a thickness of 12 as a peelable substrate
μm polyethylene terephthalate film (manufactured by Mitsubishi Chemical Polyester Film Co., Ltd.) was used and a photocatalytic material made of anatase-type titanium oxide (photocatalyst agent PC-C2-T manufactured by Titanium Industry Co., Ltd.) was added to one surface of the film using an acrylic resin as a binder An antifoaming agent and a titanium coupling agent as an agglomeration aid were added as a material to form a coating, and a photocatalytic layer having a thickness of 0.5 μm was formed by a gravure coating method. The haze value of the formed photocatalyst layer was 4.5. Next, a first primer layer having a thickness of 1.5 μm is formed on the photocatalyst layer by a gravure coating method using the acrylic resin emulsion for photocatalyst agent PC-C2-T (manufactured by Titanium Industry Co., Ltd.). did. Then, on the first primer layer, a silicon-modified acrylic resin-based varnish (SC3 manufactured by Yamanan Synthetic Chemical Co., Ltd.)
95) using a gravure coating method to obtain a thickness of 1.5
A μm second primer layer was formed. Further, on the second primer layer, an acrylic resin-based adhesive (manufactured by Dainichi Seika Co., Ltd.) was used as a heat-sensitive adhesive, and a blocking inhibitor was added to the acrylic resin-based adhesive. An adhesive layer having a thickness of 4 μm was formed to obtain a photocatalytic transfer material of the present invention having two primer layers as shown in FIG.

Example 2 A second primer layer having a thickness of 45 formed by a vacuum evaporation method
A photocatalytic transfer material of the present invention comprising two primer layers was obtained in the same manner as in Example 1 except that the aluminum metal thin film of 0 ° was used. The haze value of the formed photocatalyst layer is 3.5.
Met.

Example 3 A transparent base material having a smooth surface and a thickness of 25 was used as a peelable substrate.
Using a μm polyethylene terephthalate film (Lumirror T60 manufactured by Toray Industries, Inc.), on one surface thereof, a photocatalytic material composed of anatase-type titanium oxide (photocatalyst agent PC-C2-T manufactured by Titanium Industry Co., Ltd.) as an acrylic resin binder,
An antifoaming agent as an additive and a titanium coupling agent as an agglomeration aid were added to form a coating, and a photocatalyst layer having a thickness of 1.0 μm was formed by a gravure coating method. The haze value of the formed photocatalyst layer was 6.3. Next, on the photocatalyst layer,
Using the acrylic resin emulsion for photocatalyst agent PC-C2-T (manufactured by Titanium Co., Ltd.), a primer layer having a thickness of 3.0 μm was formed by a reverse coating method. Further, on the primer layer, an acrylic resin-based adhesive (manufactured by Dainichi Seika Co., Ltd.) was used, an anti-blocking agent was added to the acrylic resin-based adhesive, and a thickness of 7 was applied by a reverse coating method.
An adhesive layer having a thickness of μm was formed to obtain a photocatalytic transfer material of the present invention having a single primer layer as shown in FIG.

Comparative Example 1 A 0.5 μm thick polyethylene terephthalate film (manufactured by Mitsubishi Chemical Polyester Film Co., Ltd.) having a smooth surface and a transparent thickness of 0.5 μm was coated by a gravure coating method using an acrylic resin varnish. A mold layer was formed to obtain a substrate having releasability. Next, an acrylic resin-based varnish (Almatex L1043 manufactured by Mitsui Chemicals, Inc.) and an isocyanate group-containing curing agent (Coronate 2030 manufactured by Nippon Polyurethane Industry Co., Ltd.) were mixed with the release layer surface of the base material having releasability. A transparent cured transparent resin layer was formed to a thickness of 3.0 μm by a gravure coating method. Next, on the transparent resin layer, using an acrylic resin-based adhesive (manufactured by Dainichi Seika), an anti-blocking agent (manufactured by Nippon Aerosil Co., Ltd.) was added to the acrylic resin-based adhesive, and the thickness was determined by a reverse coating method. A transfer material was obtained by forming a 7 μm adhesive layer.

Comparative Example 2 Instead of the transparent resin layer, a thickness of 450 ° was formed by a vacuum evaporation method.
A transfer material was obtained in the same manner as in Comparative Example 1, except that the aluminum metal thin film was formed.

The photocatalytic transfer material obtained in each of the examples and the transfer material obtained in each of the comparative examples were transferred to a 2 mm
Each of the base materials having a releasability was peeled off by roll transfer onto a thick white polystyrene plate. In this way, when using the photocatalytic transfer material obtained in each example, a photocatalytic layer is formed on the surface, and when using the transfer material obtained in each comparative example, a transparent resin layer or a metal thin film is formed on the surface. Each of the transferred materials was obtained on the surface, and the transferred material was used as a test piece to test the photocatalytic property. The photocatalytic properties were tested for decolorization (water purification) and decolorization (decomposition of tobacco fat).

(Test Method) Test Method for Decolorization (Water Purification) In the decolorization (water purification), a change in dye concentration was examined as follows. A. Preparation of dye solution A small amount of IPA is added to the dried methylene blue dye to dissolve and wet the dye, adjusted to a dye concentration of 20 ppm with pure water, and left for 24 hours to deaerate and stabilize the color. Was. The dye concentration was determined by measuring the spectral transmittance using an SZ optical system manufactured by Nippon Denshoku Industries Co., Ltd./#80 colorimeter and calculating the optical density from the transmittance obtained by leveling the transmittance from 600 nm to 680 nm. Calibration curve data indicating the relationship between density and dye concentration was prepared in advance, and the concentration was known from this data. B. Measurement of change in dye concentration A 40 × 70 mm square was cut out from a test piece and used as a sample. The sample was submerged in a polypropylene container containing 90 cm ³ of the above dye solution. The container in which the sample was submerged was placed in a container box having a 400 × 600 mm floor with three fluorescent lamps (National FL15BA-37-K) for insect repellent mounted at a distance of 23 cm above the floor. Light was irradiated in this state, and the dye concentration was measured over time with the colorimeter described above, and the change was measured. The results were as shown in Table 1.

[0032]

Test Method for Decolorization (Decomposition of Tobacco Fat) For decolorization (decomposition of tobacco fat), the change in yellowness was examined as follows. A. Preparation of cigarette fat liquid A short piece brand cigarette (20 mg of nicotine) was ignited, and 70% of the leaf length was ashed in about 3 minutes per cigarette using a suction device. Suction is performed at a constant suction flow rate, and the suctioned gas is passed through an IPA solution to remove fat / tar fine particles and vaporized substances in the suction gas.
The solution was dissolved in solution A, and the solution was further concentrated to a cigarette fat solution. B. Measurement of change in yellowness The test piece was coated on the photocatalytic layer surface, the transparent resin layer surface, or the metal thin film surface with the cigarette fat solution with a wire bar (# 6) to form a cigarette fat layer, and placed in the container box described above. installed. Light was irradiated in this state, and the yellowness was measured over time with the above-mentioned colorimeter, and the change was measured. The results were as shown in Table 2.

[0034]

[0035]

According to the present invention, the photocatalytic property can be easily and easily imparted to the transferred material by the transfer. Therefore, the transferred object on which the photocatalytic transfer material according to the present invention has been transferred has various properties such as decomposability of stains such as tobacco fat, deodorant properties, anti-cloud properties, antibacterial properties, and the like by photocatalysis. .

[Brief description of the drawings]

FIG. 1 is a partially enlarged cross-sectional view showing one embodiment of the present invention and an example of a state before the present invention is transferred to an object to be transferred and a substrate is peeled off.

FIG. 2 is a partially enlarged cross-sectional view showing one embodiment of the present invention and an example of a state before the present invention is transferred to an object to be transferred and a substrate is peeled off.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Base material 2 Photocatalyst layer 3 Primer layer 4 Adhesive layer 5 Transfer object

 ──────────────────────────────────────────────────続 き Continued on the front page F-term (reference) 2H113 AA03 BA03 BA22 CA00 DA53 DA57 EA01 EA07 3B005 EB01 FB00 FB21 FB24 FB44 FB53 FB62 4F100 AA21B AK25B AK25C AK25G AK42A AR00B AR00C AT00A BA03BA07B00B10B00B00C JL14A JM01G JN01B YY00B

Claims (3)

[Claims] 1. A photocatalyst layer on one side of a substrate having releasability.
A photocatalytic transfer material, wherein a primer layer and an adhesive layer are sequentially formed. 2. The photocatalytic transfer material according to claim 1, wherein the primer layer comprises two layers, a first primer layer in contact with the photocatalyst layer and a second primer layer in contact with the adhesive layer. 3. The photocatalytic transfer material according to claim 1, wherein the haze value of the photocatalytic layer is 9 or less.