JP4541810B2 - Method for producing photocatalyst layer transfer body - Google Patents

Description

The present invention relates to a photocatalyst layer transfer body provided with a photocatalyst layer containing a photocatalyst and a substrate with a photocatalyst obtained by laminating such photocatalyst layer transfer bodies.

  When photocatalyst is irradiated with light, it exhibits photocatalytic activity and exhibits an oxidizing action, and oxidizes and decomposes organic substances, air pollutants, and bacteria. In addition, the surface is made highly hydrophilic based on the photoreaction, and exhibits various functions such as deodorization, antifouling, antibacterial, sterilization, harmful substance removal, and antifogging. For this reason, photocatalytic technology is used in various fields such as building outer walls, hospital inner walls, mirrors, window glass, sanitary ware, kitchen knives, and cutting boards.

  As such a substance having a photocatalytic function, in addition to metal oxides such as titanium dioxide and zinc oxide, metal sulfides such as CdS, metal chalcogenides such as CdSe, and the like are known. Among these, titanium dioxide is evaluated as a photocatalytic substance having a particularly high utility value from the viewpoints of high safety and chemical stability that is not affected by acids, bases, and organic solvents.

  The photocatalytic mechanism will be described taking titanium dioxide as an example. A photocatalytic substance such as titanium dioxide has characteristics as a photo semiconductor, and ultraviolet rays corresponding to band gap energy (band gap of titanium dioxide is 3.2 eV) (rutile type: λ < When irradiated with 400 nm, anatase type: λ <380 nm, electrons in the valence band are excited to generate two carriers of electrons (e−) and holes (h +). In a general substance, both of these recombine quickly, but in the case of titanium dioxide, these electrons and holes survive for a while, and the surviving holes oxidize the adsorbed water on the catalyst surface, resulting in an oxidizing power. Generates high hydroxyl radical (.OH). And because the oxidizing power of this OH is much stronger than the energy of, for example, C—C, C—H, C—N, C—O, O—H, N—H, etc. in the molecules constituting the organic matter. These bonds are broken and broken down. Thus, it is considered that the redox power due to electrons (e−) and holes (h +) generated by light irradiation is responsible for various photocatalytic actions.

  As one of the methods for fixing the photocatalyst to the substrate surface, a transfer method is known. For example, after applying a coating liquid containing photocatalyst particles to a release film or sheet and drying, an adhesive layer is applied thereon, and a photocatalyst layer and an adhesive layer are sequentially laminated on the release film or sheet. The photocatalyst layer transfer body (sheet used for the transfer method) is disclosed. According to such a photocatalyst layer transfer body, a photocatalyst layer can be fixed to a base material simply and inexpensively by transferring and laminating to a base material with an adhesive layer.

  In such a base material with a photocatalyst layer, it has been pointed out that the base material deteriorates due to the action of the photocatalyst depending on the type of base material to be transferred. Therefore, in order to protect the substrate from the action of the photocatalyst, for example, the adhesive layer is formed from a silicon-based adhesive having both adhesiveness and a protective function, or as disclosed in Patent Document 1, on the base film. Proposals have been made to form a transfer film by sequentially laminating a photocatalyst layer, an inorganic protective layer, and an adhesive layer.

JP 2001-260587 A

  By the way, when an inorganic protective layer is interposed between the photocatalyst layer and the adhesive layer, there is a problem in that the adhesion force at the interface between the adhesive layer and the inorganic protective layer or the interface between the inorganic protective layer and the adhesive layer is reduced. was there. In addition, regarding the invention according to the above-mentioned Patent Document 1, although an effort has been made to increase the adhesion at each interface, since the adhesive layer is made of an organic adhesive, the inorganic protective layer and the adhesive layer There was a problem that the adhesion at the interface of the film becomes insufficient.

  Accordingly, the present invention provides a photocatalyst layer transfer body having a structure in which a photocatalyst layer, a protective layer (primer layer), and an adhesive layer are sequentially laminated, and has a sufficiently high adhesion at each interface, yet can be easily manufactured. It is an object of the present invention to provide a photocatalyst layer transfer body capable of producing

In the present invention, a coating liquid containing a photocatalyst and a component having a Si—O bond is applied onto a peelable film, and a coating liquid containing acrylic modified silicone or acrylic modified titanate and a solvent is formed thereon. By coating, a photocatalyst layer and a primer layer are sequentially formed on the peelable film, and a Si-O bond of a component constituting the photocatalyst layer and an acrylic modified silicone or acrylic modified titanate Si constituting the primer layer Suggest manufacturing method of the photocatalyst layer transfer member for causing the Ti is a siloxane bond crosslinked.

When a coating liquid made of a composition containing acrylic modified silicone or acrylic modified titanate is applied onto a photocatalyst layer made of a composition containing a photocatalyst and a component having a Si-O bond, the acrylic modified silicone in the primer layer Alternatively, Si or Ti in the acrylic modified titanate is attracted to the photocatalyst in the photocatalyst layer, the acrylic modified silicone or acrylic modified titanate is oriented so that the Si or Ti faces the photocatalyst layer side, and the Si or Ti and the photocatalyst layer are inside. Since the Si—O bond forms a siloxane bond (Si—O—Si) and crosslinks, the photocatalyst layer and the primer layer are firmly bonded. At the same time, since the organic group of the acrylic modified silicone or acrylic modified titanate faces the substrate or adhesive layer side, the acrylic modified silicone or acrylic modified titanate and the substrate or adhesive layer, particularly the organic substrate or organic adhesive. The affinity with the layer is increased, and the adhesive force between the primer layer and the base material or the adhesive layer is sufficiently increased.

The photocatalyst layer transfer body of the present invention can form a base material with a photocatalyst provided with a photocatalyst layer on a base material, for example, by transferring (laminating) to various base materials, and can be used for various applications.
Therefore, the present invention also provides a photocatalyst layer, a primer layer, and a substrate with a photocatalyst having a structure obtained by sequentially laminating an organic base material on the peelable film, or the peelable film. The present invention also proposes a photocatalyst layer transfer body having a structure in which the photocatalyst layer, the primer layer, an organic adhesive layer composed of an organic adhesive, and a base material (preferably an organic base material) are sequentially laminated. is there.

  In addition, the meaning expressed as the main component in the present invention includes the meaning that other components may be contained within a range not impeding the function of the component, and preferably 50% by mass or more of the total composition. In particular, a component occupying 70% by mass or more, particularly 90% by mass or more is shown.

BEST MODE FOR CARRYING OUT THE INVENTION

Next, this invention is demonstrated based on embodiment.
However, the embodiment described below is an example of the embodiment of the present invention, and the scope of the present invention is not limited to the following embodiment.

[Photocatalyst layer transfer body 1]
The photocatalyst layer transfer body 1 according to one embodiment of the present invention can be configured by sequentially laminating a photocatalyst layer 3 and a primer layer 4 on a releasable film or sheet 2, for example, as shown in FIG.

[Releasable film or sheet 2]
The releasable film or sheet 2 has an appropriate thickness as a base film, and may be a film or sheet having releasability, and the material, configuration and thickness thereof are not particularly limited. .
As the substrate of the releasable film or sheet 2, a film or sheet composed of a single layer or a plurality of layers composed of polyethylene terephthalate, vinyl chloride resin, acrylic resin, polycarbonate, polyimide, polyethylene, polypropylene or other synthetic resin is suitable. It is also possible to use papers.
If necessary, the surface of the base material may be appropriately subjected to a surface treatment. For example, in order to improve the peelability from the photocatalyst layer 3, a corona treatment or a surface treatment with a release agent such as silicone, fluorine, or the like may be performed.

The release film or sheet 2 can be provided with a light shielding function to prevent the photocatalyst layer 3 from being decomposed and deteriorated by receiving light until it is used after production.
In order to give the release film or sheet 2 an ultraviolet shielding function, an ultraviolet absorber is kneaded with a resin to form a release film or sheet base material, and then the release film or sheet base material itself has ultraviolet rays. You may make it provide a shielding function, and you may make it form a ultraviolet-ray shielding layer in the upper and lower one surface or both surfaces of a mold release film thru | or a sheet | seat base material. At this time, the ultraviolet shielding layer may be prepared by, for example, adding a UV absorbent to the resin to adjust the coating liquid and applying the coating liquid, or forming a film containing the UV absorbent and laminating it. Alternatively, the ultraviolet absorber may be directly fixed.
The light shielding function imparted to the releasable film or sheet 2 is preferably capable of shielding 80% or more, particularly 85 to 95%, of light in the wavelength region where the photocatalyst can react. For example, when a test for irradiating ultraviolet rays having a wavelength of 365 nm is performed, a release film or sheet 2 is formed using as an index whether or not 80% or more, preferably 85 to 95%, particularly 90 to 95%, can be shielded. Is good. If ultraviolet rays having a wavelength of 365 nm can be sufficiently shielded, ultraviolet rays having a wavelength of 350 to 400 nm can be sufficiently shielded. When anatase-type titanium dioxide is the main component of the photocatalyst, it may be formed using as an index whether or not it is possible to block 80% or more of ultraviolet rays in the 350 to 400 nm region. However, it may be formed using as an index whether or not light in the wavelength region of 200 to 400 nm can be shielded by 80% or more so as to cope with various types of photocatalysts.
Examples of the ultraviolet absorber to be mixed in the release film or sheet base material or the ultraviolet shielding layer include titanium dioxide, zinc oxide, cerium oxide, lead oxide, iron oxide, antimony oxide, panadium oxide, and 2,2′-dihydroxy-4. -Methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2 ', 4,4'-tetrahydroxybenzophenone, 5-chloro-2-hydroxybenzophenone , Phenyl salicylate, 1- (2′-hydroxy-5-methylphenyl) benzotriazole, etc., among which titanium dioxide, zinc oxide, cerium oxide, lead oxide, iron oxide, antimony oxide, panadium oxide Inorganic UV absorbers such as It can be metallized, if any. The ultraviolet absorber is preferably blended in an amount of 0.1 to 10% by mass with respect to the resin.

Moreover, a metal vapor-deposited layer can be formed on one or both sides of the releasable film or sheet 2 to protect the surface of the photocatalyst layer from impacts and wear.
The main component of the metal deposition layer at this time is to deposit a metal composed of any one of aluminum (Al), chromium (Cr), tungsten (W), tin (Sn), etc., or a combination of two or more of these. Preferably formed.
The thickness of the metal vapor deposition layer is preferably 5 nm or more, particularly 10 to 100 nm.

[Photocatalyst layer 3]
The photocatalyst layer 3 should just be formed from the composition containing the component provided with the photocatalyst particle and the Si-O bond, for example, the coating liquid containing the photocatalyst particle and the component provided with the Si-O bond is released. It can form by apply | coating to the surface of an adhesive film thru | or sheet 2, and making it dry.

Examples of the photocatalyst include metal oxides such as titanium dioxide, zinc oxide, tin oxide, lead oxide, ferric oxide, dibismuth trioxide, tungsten trioxide, and strontium titanate. You may add metals, such as Fe, Co, Ni, Cu, Zn, Ru, Rh, Pd, Ag, Pt, Au, to these. Among these, titanium dioxide is preferable because it is harmless, chemically stable, and inexpensive. As titanium dioxide, any of anatase-type titanium dioxide, rutile-type titanium dioxide, and Brooklight-type titanium dioxide can be used, but those mainly composed of anatase-type titanium dioxide having high photocatalytic reaction activity are preferred.
The particle diameter of the photocatalyst particles is not particularly limited, but the average particle diameter determined by the dynamic scattering measurement method is preferably in the range of 10 to 800 nm, particularly 100 to 500 nm.

  As a component provided with a Si—O bond, for example, alkoxysilane, particularly tetraalkoxysilane, among which tetramethoxysilane or tetraethoxysilane can be preferably used. Alkoxysilane also has a binder function that improves the adhesion of the photocatalyst particles and improves the strength of the film by the photocatalyst. However, when tetraalkoxysilane is used, if the alkyl group becomes larger than the butyl group, the affinity with the photocatalyst decreases, and the Si-O bond of tetraalkoxysilane and the acrylic modified silicone or acrylic modified titanate constituting the primer layer. Therefore, it is necessary to use a tetraalkoxysilane having an alkyl group having a carbon number smaller than that of a butyl group.

As described above, the photocatalyst layer 3 can be formed by applying a photocatalyst coating liquid containing photocatalyst particles and a component having a Si—O bond. In this case, the photocatalyst coating liquid is, for example, an organic solvent, It can be prepared by mixing water, a component having a Si—O bond, and photocatalyst particles.

When preparing the photocatalyst coating liquid, the photocatalyst can be mixed in a powder state, but can also be prepared and mixed in a slurry or sol form as described below.
That is, the photocatalyst can be prepared in a slurry or sol state with less sedimentation and added and mixed. Commercially available titanium dioxide slurry or sol may be used as long as necessary physical properties are satisfied.
Further, it is preferable that a dispersion stabilizer is allowed to coexist in order to prevent a change in particle diameter due to particle aggregation and sedimentation. These dispersion stabilizers can coexist from the time of preparing the particles, or may be added when preparing the photocatalyst coating liquid.
As the dispersion stabilizer, various chemicals can be used. However, since titanium dioxide tends to aggregate near neutrality, an acidic or alkaline dispersion stabilizer is preferable. Examples of the acidic dispersion stabilizer include mineral acids such as nitric acid and hydrochloric acid, and organic acids such as carboxylic acid, oxycarboxylic acid and polycarboxylic acid. Examples of the alkaline dispersion stabilizer include one or more compounds selected from carboxylic acids, alkali metal salts of polycarboxylic acids and ammonia, primary to quaternary amines, and alkanolamines having a hydroxy group added thereto. As mentioned. In particular, the use of an organic acid is preferable because it has good miscibility with the organic solvent described later, and the pH does not become extremely low and the equipment used during production is hardly corroded. As the organic acid, acetic acid, oxalic acid, glycolic acid, lactic acid, tartaric acid, malic acid, citric acid and the like can be preferably used, and the dispersion can be stabilized with one or more kinds of acids selected from these.

Examples of the organic solvent include monohydric lower alcohols such as methyl alcohol, ethyl alcohol, and isopropyl alcohol, polyhydric alcohols such as ethylene glycol and propylene glycol, and their esters, cellsolve, ethyl acetate, methyl isobutyl ketone, isobutanol, Methyl ethyl ketone, toluene, xylene and the like can be suitably used. Monovalent lower alcohols, particularly isopropyl alcohol and ethanol are preferably used.

  The composition of the coating liquid containing the photocatalyst particles is not particularly limited, but the photocatalyst particles preferably contain 5 to 20% by mass, particularly 5 to 10% by mass in terms of solid content. If it is less than 5%, the effect of the photocatalyst after coating is small, and it is difficult to expect the effect of preventing contamination. If it exceeds 20%, the stability of the coating solution is lowered and the pot life is lowered. Moreover, it is preferable that the component provided with the Si-O bond contains 0.04 to 40% by mass, particularly 1 to 2% by mass in the coating liquid, and is 10% by mass or more and less than 25% by mass with respect to the photocatalyst. It is preferable to contain.

The means for applying the coating liquid containing photocatalyst particles is not particularly limited. For example, various coating methods such as gravure coating, spray coating, dip coating and the like can be selected, and it is preferable to apply using a gravure roll coater. The formation of the photocatalyst layer on the releasable film or sheet is preferably carried out by applying the coating liquid and heating and drying.
Heat drying is preferably performed at a heating temperature of 80 to 150 ° C. Furthermore, it is good to carry out on the conditions of drying hot air wind speed 10-30 m / sec and drying time 20-180 seconds.

The coating film thickness of the photocatalyst coating solution, that is, the thickness of the photocatalyst layer is preferably 5 to 50 g / m ^{2 in} the WET state before drying, and 0.1 to 1 μm in terms of the thickness of the coating film after drying. If the thickness is less than this, the activity of the photocatalytic reaction is low. On the other hand, if the thickness is more than this, the adhesion strength and the surface hardness are lowered, and the coating is easily peeled off.
In addition, you may perform the application | coating of the coating liquid containing a photocatalyst particle not only once but multiple times. You may comprise a photocatalyst layer by the multiple layer comprised by the photocatalyst particle of a different average particle diameter.

  Further, after the drying of the photocatalyst layer 3 is completed, it may be aged for a required time. Thereby, the peeling strength of the coated film can be improved. Aging is preferably performed at 30 to 60 ° C. for 30 hours or more.

[Primer layer 4]
The primer layer 4 is a layer having a function of blocking the action of the photocatalyst so as not to affect the photocatalytic action on the substrate side. The primer layer 4 is formed from a composition containing acrylic modified silicone or acrylic modified titanate, and is acrylic modified. The coating liquid containing silicone or acrylic modified titanate can be formed by applying on the photocatalyst layer 3 and drying.

The coating liquid containing the composition containing acrylic modified silicone or acrylic modified titanate is not particularly limited in composition, but can be prepared from, for example, acrylic modified silicone or acrylic modified titanate and an organic solvent. What is necessary is just to prepare the density | concentration of an acrylic modified silicone or an acrylic modified titanate suitably.
It is also possible to add a dispersant such as colloidal silica and other additives.

The means for forming the primer layer 4 is not particularly limited, as is the case with the means for applying a coating liquid containing photocatalyst particles to a release film or sheet. For example, various coating methods such as gravure coating, spray coating, and dip coating can be selected. It is preferable to use a gravure roll coater. What is necessary is just to heat-dry after laminating | stacking a primer layer on a photocatalyst layer.
The coating liquid containing the photocatalyst particles may be applied not only once but a plurality of times, but the primer layer is preferably coated only once.

When a coating liquid containing a composition containing acrylic-modified silicone or acrylic-modified titanate is applied onto the photocatalyst layer 3, Si or Ti of the acrylic-modified silicone or acrylic-modified titanate is a photocatalyst in the drying process (solidification process). The acryl-modified silicone or acryl-modified titanate is naturally oriented so that the Si or Ti is attracted to the photocatalyst in the layer 3 and the Si or Ti faces the photocatalyst layer 3 side. The O bond forms a siloxane bond (Si—O—Si) and crosslinks. Therefore, the photocatalyst layer 3 and the primer layer 4 are firmly bonded.

The thickness of the primer layer 4 is preferably 1 to 50 g / m ^{2 in} the WET state before drying, 0.1 μm or more, and particularly preferably 0.2 μm to 10 μm in thickness after drying. If it is thinner than 0.1 μm, the orientation of the acrylic modified silicone or acrylic modified titanate is not sufficiently promoted, and in the primer layer 4, the Si or Ti side and the organic group side are not sufficiently separated, and the photocatalyst layer 3 and the primer layer 4. Adhesion between the primer layer 4 and the base material or adhesive layer cannot be sufficiently obtained.

[Adhesive layer 5]
As shown in FIG. 3, the photocatalyst layer transfer body 1 according to an aspect of the present invention can be configured by further forming an adhesive layer 5 on the primer layer 4.
For example, even if the base material, which is an object on which the photocatalyst layer transfer body 1 is laminated (transferred), is an inorganic material such as a metal or glass material, or a synthetic resin, it is laminated (transferred) at a low temperature of 100 ° C. or less. If the primer layer 4 is required, the adhesive strength may not be sufficient with the primer layer 4 alone. Therefore, when used in such applications, the adhesive layer 5 is formed and laminated on the substrate via the adhesive layer 5 ( It is preferable that the image forming apparatus can be transferred).

The adhesive layer 5 is preferably selected from organic adhesives in consideration of the composition of the primer layer 4 and the material of the base material (transfer object) on which the primer layer 4 is laminated. For example, when the base material is composed of a synthetic resin material, the adhesive layer preferably contains an acrylic resin, an acrylic-modified silicone resin compound or a silicon-modified acrylic resin compound as a main component, and the primer layer 4 is mainly composed of acrylic. In the case of a modified silicone resin compound, it is particularly preferable to select an acrylic resin. Specifically, it is preferable to form the adhesive layer 5 by applying a coating solution obtained by dissolving an acrylic resin in an organic solvent.

The means for applying the adhesive layer 5 is not particularly limited, as is the case with the means for applying a coating liquid containing photocatalyst particles to a release film or sheet. For example, various coating methods such as gravure coating, spray coating, and dip coating can be selected. It is preferable to use a gravure roll coater.
In addition, since the case where a transfer body is hot-melted can also be assumed, an adhesive layer is not necessarily required.

The thickness of the adhesive layer 13 is not particularly limited, but is preferably 0.1 μm or more, particularly preferably 0.2 μm to 10 μm.

[Substrate with photocatalyst layer 10]
As shown in FIG. 2, the photocatalyst layer transfer body 1 of the present invention can form a base material 10 with a photocatalyst layer by laminating the base material 11 via a primer layer 4 or an adhesive layer 5.
When using the base material 10 with a photocatalyst layer having such a configuration, the photocatalytic action can be exhibited by peeling the release film or sheet 2 and exposing the photocatalyst layer 3.

The substrate 11, that is, the object on which the photocatalyst layer transfer body 1 is laminated is a sheet, a film, a rod-like body, a cylindrical body, a box-like body, a bottle body, various laminated bodies and other shapes depending on the purpose and application. It is also a feature that there is no limitation on the thickness of the base material.
However, organic materials such as synthetic resins are suitable for the material. For example, those composed of a single layer or a plurality of layers of polycarbonate, polyethylene terephthalate, vinyl chloride resin, acrylic resin, polyimide, polyethylene, polypropylene and other synthetic resins are preferably used.
Although a composite material including paper may be used, it is not preferable that a material made of a metal such as aluminum or iron or a material such as glass is directly laminated with the primer layer 4 in terms of adhesive strength. In the case of these non-organic base materials, it is preferable to laminate them through the adhesive layer 5, so that they can be suitably used as the base material.
In addition, even when a synthetic resin is required to be bonded at a low temperature of about 100 ° C., it is difficult to directly bond to the primer layer 4 without using the adhesive layer 5. It is preferable to laminate via the agent layer 5.

Here, the specific example of the manufacturing method of the base material 10 with a photocatalyst layer is demonstrated.
The photocatalyst layer transfer body 1 is fed out from the supply roll and guided to the cast roll (cooling roll) through the press roll, while the synthetic resin to be the base material 11 is melt-extruded from the die through the extruder. And if the primer layer 4 or the adhesive bond layer 5 of the photocatalyst layer transfer body 1 and the base material 11 are laminated | stacked by the extrusion lamination method, the base material 10 with a photocatalyst layer can be obtained.

In the case of using the extrusion lamination method, when a crystalline polymer material (crystalline resin) is used as the base material 11, it is preferably performed at a temperature equal to or higher than the crystallization temperature of the synthetic resin used as the base material 11. In the case of an amorphous resin, it is preferable to laminate at the melting point. For example, when polycarbonate is used as the substrate, it is necessary to perform lamination at about 165 ° C.
By using an acrylic-modified silicone resin compound as the main component of the primer layer 4 and an acrylic resin as the main component of the adhesive layer 5, it is possible to transfer at a temperature of 100 ° C. or higher and 180 ° C. or lower.

It can also be produced by a reheating (thermal) lamination method. For example, while the photocatalyst layer transfer body 1 is guided from the supply roll to the cast roll (cooling roll), the synthetic resin to be the base material 11 is melt-extruded from the die through the extruder, and then temporarily passed through the cast roll (cooling roll). Or after forming the sheet-like base material 11 and passing through a roll, it is reheated by a heater to raise the temperature of the base material, and the primer layer 4 or the adhesive layer 5 of the photocatalyst layer transfer body and the base are heated by a thermal lamination method. If the material 11 is laminated | stacked, the base material 10 with a photocatalyst layer can be obtained.
In the case of using the reheating lamination method, when a crystalline polymer material is used as the substrate 11, it is preferably performed at a temperature that is equal to or higher than the crystallization temperature of the synthetic resin that will be the substrate 11. In the case of a crystalline resin, it is broad from the start of crystallization to melting, and all of this range is the melting point, so that lamination can be performed within such a range of crystallization temperature. In the case of an amorphous resin, the melting point is sharp, so that lamination can be performed only at the melting point.

Moreover, the base material with a photocatalyst layer of this invention can coat | cover and use the surfaces, such as a steel plate and other metal plates, with the form as it is.
It can be used for building materials (particularly interior decoration materials), office equipment materials, agricultural materials, packaging materials, fishery materials, and other various industrial materials such as terraces, balconies, cars, etc. It is particularly effective as an exterior material used outdoors such as a roof such as a port or a side wall material.

As mentioned above, although the example of embodiment of this invention was demonstrated, this invention is not limited to what was demonstrated above, In the range of the summary of this invention, it can change and add suitably. Specifically, in the photocatalyst layer transfer body of the present invention, a layer having other functions, for example, a hard coat layer on which inorganic particles such as silica are deposited, an infrared absorber such as a sulfur compound or a copper compound is provided. It may further include a layer such as an infrared shielding layer.
In addition, even if the upper limit and lower limit of the numerical range in the present invention are outside the numerical range specified by the present invention, as long as the same effects as those in the numerical range are provided, they are within the equivalent range of the present invention. Including intention to include.

  Examples of the present invention will be described below, but the present invention is not limited to these examples. In addition, unless otherwise indicated, all% shows the mass%.

Example 1
On one side of a PET (polyethylene terephthalate; H100C12 manufactured by Mitsubishi Chemical Polyester Film) film as a peelable protective film, 8 parts by mass of anatase-type titanium dioxide having a particle size of 100 to 300 nm, 2 parts by mass of tetraethoxysilane, and 40 parts by mass of water Then, 5 g / m ^{2 of a} coating liquid consisting of 50 parts by mass of ethanol was applied by gravure coating and dried at 135 ° C. for 2 minutes to form a photocatalyst layer.

Next, 5 g / m ^{2 of the following} primer coating liquid A was applied on the photocatalyst layer by gravure coating, and dried at 135 ° C. for 2 minutes to form a primer layer. Furthermore, a coating solution prepared by dissolving an acrylic resin in methyl ethyl ketone (MEK) at a solid content concentration of 25% is applied, and 8 g / m ^{2 is} applied and dried at 135 ° C. for 2 minutes. A layer was formed to obtain a photocatalyst transfer body.

  Primer coating liquid A: A coating liquid in which 5 parts by mass of an acrylic-modified silicone resin as a solid content and 40 parts by mass of isobutyl alcohol, 40 parts by mass of 2-propanol and 15 parts by mass of methyl ethyl ketone (MEK) as a solvent are mixed and suspended.

(Example 2)
A photocatalyst transfer body was formed in the same manner as in Example 1 by using a primer coating solution containing an acrylic modified titanate resin instead of the acrylic modified silicone resin of Example 1.

(Comparative Example 1)
Similarly to Example 1, 8 parts by mass of anatase-type titanium dioxide having a particle diameter of 100 to 300 nm and 2 parts by mass of tetraethoxysilane are formed on one side of a PET (polyethylene terephthalate; H100C12 manufactured by Mitsubishi Chemical Polyester Film) as a peelable protective film. Then, 5 g / m ^{2 of a} coating solution composed of 40 parts by mass of water and 50 parts by mass of ethanol was applied by gravure coating and dried at 135 ° C. for 2 minutes to form a photocatalyst layer.

Next, on the photocatalyst layer, the following primer coating solution B 5 g / m ² coated by gravure coating, the remaining points were formed in the same manner as in Example 1 photocatalyst transcript.

  Primer coating liquid B: A coating liquid in which 5 parts by mass of a silicon resin as a solid content, 40 parts by mass of isobutyl alcohol, 40 parts by mass of 2-propanol, and 15 parts by mass of methyl ethyl ketone (MEK) as a solvent are mixed and suspended.

(Comparative Example 2)
On one side of a PET (polyethylene terephthalate; H100C12 manufactured by Mitsubishi Chemical Polyester Film) film as a peelable protective film, 8 parts by mass of anatase-type titanium dioxide having a particle size of 100 to 300 nm, 2 parts by mass of tetrabutoxysilane, and 40 parts by mass of water Then, 5 g / m ^{2 of a} coating liquid consisting of 50 parts by mass of ethanol was applied by gravure coating and dried at 135 ° C. for 2 minutes to form a photocatalyst layer.
Next, a photocatalyst transfer body was formed on the photocatalyst layer in the same manner as in Example 1 using the primer coat liquid A.

<Transfer result>
The photocatalyst transfer bodies obtained in Example 1-2 and Comparative Example 1-2 were extruded at a pressure of 50 kg / cm ² at 180 ° C., which is higher than the crystallization temperature (about 150 ° C.) of the polycarbonate (PC) plate. Then, a photocatalyst transfer body was heated and pressed on a PC plate through an adhesive layer by a lamination method and laminated (transferred) to try to form a substrate with a photocatalyst.

As a result, using the photocatalyst transfer bodies obtained in Example 1-2 and Comparative Example 1, the film thickness of the photocatalyst layer was about 0.3 μm, the film thickness of the primer layer was about 0.6 μm, and the film of the adhesive layer A substrate with a photocatalyst having a thickness of about 2 μm was obtained.
However, the photocatalyst transfer body obtained in Comparative Example 2 was peeled off at the interface between the primer layer and the photocatalyst layer, and could not be transferred.

<Durability test>
The durability test using a sunshine weather meter was performed on the photocatalyst-equipped substrates obtained in Examples 1 and 2 and Comparative Example 1.
As a result, the substrate with the photocatalyst obtained in Comparative Example 1 showed that the photocatalyst layer was peeled off in the cello tape peeling test in 2000 hours of sunshine weather, whereas the base with the photocatalyst obtained in Examples 1 and 2 was used. No peeling occurred with the material.
In addition, since sunshine weather 2000 hours is equivalent to 5 years in actual outdoors, it is suggested that the durability of Comparative Example 1 is equivalent to 5 years in an actual use environment.

<Measurement of amount of Si or Ti>
About the base material with a photocatalyst obtained in Examples 1 and 2 and Comparative Example 1, the amount of Si or Ti at each depth from the sheet surface was measured using X-ray photoelectron spectroscopy (ESCA). Further, the photocatalyst layer and the primer layer were distinguished by observation with an electron microscope (SEM).

As a result, for the substrate with a photocatalyst obtained in Examples 1 and 2, a significant amount of Si or Ti was confirmed on the boundary side with the photocatalyst layer in the primer layer, and the primer layer in the photocatalyst layer was Many O elements were confirmed on the boundary side. On the other hand, such a tendency was not confirmed for the substrate with a photocatalyst obtained in Comparative Example 1.
From this, in the base material with a photocatalyst obtained in Examples 1 and 2, Si or Ti of acrylic modified silicone or acrylic modified titanate is oriented to the photocatalyst layer side in the primer layer, and the primer layer in the photocatalyst layer It was found that the O element was oriented on the side.
From this, in consideration of the substrate peel strength with the photocatalyst obtained in Examples 1 and 2 in the above-mentioned cello tape peel test, in the substrate with the photocatalyst obtained in Examples 1 and 2, the components constituting the photocatalyst layer It is considered that the Si—O bond of the above and the Si or Ti of the acrylic modified silicone or acrylic modified titanate constituting the primer layer form a siloxane bond and are crosslinked.

It is sectional drawing typically shown in order to demonstrate the structural example of the photocatalyst layer transfer body of this invention. It is sectional drawing typically shown in order to demonstrate the structural example of the transparent base material with a photocatalyst layer of this invention obtained by laminating | stacking the photocatalyst layer transfer body shown in FIG. 1 on a base material. It is sectional drawing typically shown in order to demonstrate the other structural example of the photocatalyst layer transfer body of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Photocatalyst layer transfer body 2 Releaseable film thru | or sheet 3 Photocatalyst layer 4 Primer layer 5 Adhesive layer 10 Base material 11 with a photocatalyst layer Base material

Claims (7)

By applying a coating liquid containing a photocatalyst and a component having a Si-O bond on the peelable film, and applying a coating liquid containing acrylic modified silicone or acrylic modified titanate and a solvent thereon. In addition, a photocatalyst layer and a primer layer are sequentially formed on the peelable film, and Si—O bonds as components constituting the photocatalyst layer and Si or Ti of acrylic modified silicone or acrylic modified titanate constituting the primer layer are siloxane. manufacturing method of the photocatalyst layer transfer member for causing combined crosslinked. The method for producing a photocatalyst layer transfer body according to claim 1, wherein the component having Si-O bonds constituting the photocatalyst layer is alkoxysilane . The method for producing a photocatalyst layer transfer body according to claim 1, wherein the component having a Si-O bond constituting the photocatalyst layer is tetraethoxysilane . The method for producing a photocatalyst layer transfer body according to any one of claims 1 to 3, wherein the primer layer has a thickness of 0.1 µm or more . The method for producing a photocatalyst layer transfer body according to any one of claims 1 to 4, wherein an adhesive layer is further formed on the primer layer . Photocatalyst layer transfer body provided with the structure formed by laminating | stacking the photocatalyst layer transfer body obtained by the manufacturing method in any one of Claims 1-4 on an organic type base material through the primer layer of this photocatalyst layer transfer body Base material. Producing a photocatalyst layer transfer body obtained by the method, photocatalytic layer transfer member photocatalyst layer with a substrate having a structure formed by laminating the organic substrate through a contact Chakuzaiso of claim 5.

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