JP5538153B2 - Construction method of advertisement / notification media having air purification function and advertisement / notification media having air purification function constructed using the same - Google Patents

Description

  The present invention relates to a method for constructing an advertisement / notification medium having an air purification function, and more particularly, an advertisement in which the air purification function is greatly improved by using a non-vinyl chloride printed layer, a protective layer, and a photocatalyst layer. -It relates to a method for constructing a notification media and an advertisement / notification media having an air purification function constructed using the method.

  Conventionally, it is known that a long-term effect can be obtained by providing a layer of titanium oxide particles as photocatalyst particles on a printed matter.

  For example, in Patent Document 1, in a printed matter that requires weather resistance, at least a printing layer, an active blocking layer made of an inorganic material that blocks light activity, and a protective layer composed of a photoactive antifouling layer are sequentially formed. By laminating, the surface of the printed matter that is installed outdoors for a long period of time while being exposed to wind and rain, or that is displayed or posted for an extremely long period of time, adheres to and accumulates dust, dust, etc. in the atmosphere. It has been reported that weather-resistant printed materials having excellent durability that prevent contamination, discoloration / discoloration of pigments, and associated discoloration of printed materials, and maintain beautiful printed materials.

  In addition, for example, in Patent Document 2, a hydrophilic substrate is provided on one side of a transparent base sheet, and the other side is used as a printing surface. Antifouling printing sheets with self-cleaning properties due to sexual effects, as well as antifouling printing sheets, antifouling prints, and antifouling prints that can be printed by ordinary household and office printers and copiers have been reported. ing.

  On the other hand, with the recent global population growth, industrial development in emerging countries and improvement of living standards, many nitrogen oxides and sulfur oxides are emitted from thermal power plants, factories, automobiles, airplanes, etc. . The acid rain that falls on the ground when the discharged nitrogen oxides and sulfur oxides are taken up by rain, snow, etc. is not only in industrialized countries such as Europe and North America, but also on a global scale such as China and Southeast Asia. It has become an international issue that transcends national borders due to the acidification of forests and the decline of forests, and prompt measures are urgently needed (Non-patent Document 1).

JP 2000-117187 A WO 2006/137446

EIC Secretariat, “Mechanism of Acid Rain”, [online], March 29, 2006, Environmental Information Dissemination Center, [Search June 10, 2010], Internet <URL: http: // www .eic.or.jp / library / ecolife / knowledge / earth01a.html>

  The present invention has been made in view of the above-described background art, and its problem is to provide a method for constructing an advertisement / notification medium having an air purification function in a simple process in an advertisement / notification medium installed outdoors. In particular, there are cases where nitrogen oxides (hereinafter referred to as “NOx”) that cause acid rain, which is currently an international problem, by providing advertisement / notification media using the media. ) To contribute to the removal.

  In addition, the present inventor newly found out that there is a case where the removal efficiency of NOx is lowered depending on the type of material forming each layer constituting the advertisement / notification medium having the photocatalyst layer. It is also an object of the present invention to provide an advertisement / notification medium in which the NOx removal efficiency of the photocatalyst particles in the photocatalyst layer does not decrease.

  Furthermore, the present inventor has newly found that abnormalities such as discoloration may be observed in the printed layer due to ultraviolet irradiation depending on the type of material forming each layer constituting the advertisement / notification medium having the photocatalyst layer. As a result of the finding, it is also an object of the present invention to provide an advertisement / notification medium excellent in weather resistance of printed matter.

  As a result of intensive studies to solve the above problems, the present inventor generally considered that the photocatalyst layer should be provided over a long period of time, but generally compared to the outdoors. Even in advertising / notification media that are installed in a “short term”, the formation of a photocatalyst layer and a protective layer can provide an air purification function such as NOx removal and contribute to the prevention of environmental pollution.・ We found out that the installation of announcement media has the effect of appealing that the installed company is working on environmental issues.

  In addition, by forming the printed material layer, the protective layer and the photocatalyst layer at the outdoor construction site of the above advertisement / notification media, the advertisement / notification media having an air purification function such as NOx removal can be efficiently performed in a simple process. It was found that it can be reliably constructed.

  Furthermore, it has been found that the use of a (meth) acrylic acid ester (co) polymer on the surface of the printing material layer can particularly exhibit the effect of the photocatalytic layer in terms of NOx removal and weather resistance. It came to be completed.

That is, the present invention
On the surface of the printing material layer of the printing medium prepared by laminating the release sheet, the adhesive layer, and the printing material layer having at least the (meth) acrylic acid ester (co) polymer on the surface Print,
At the construction site of the advertisement / notification media having the air purification function, the release sheet of the printing medium is peeled off, and the adhesive layer is applied directly to at least one side surface of the outdoor structure or on the substrate installed on the side surface. Glue to form a printed layer,
Next, at the construction site, a coating liquid containing a reactive silane compound is sprayed on the surface of the printed material layer using a spray gun to form a protective layer having a thickness of 1 μm to 10 μm.
Further, a coating liquid containing titanium oxide particles as photocatalyst particles is sprayed onto the surface of the protective layer formed by polymerization or crosslinking of the reactive silane compound using a spray gun, and the film thickness is 0.03 μm to 1 μm. The present invention provides a method for constructing an advertisement / notification medium having an air purification function characterized by forming a photocatalyst layer.

  In addition, the present invention provides an advertisement / notification medium having an air purification function, which is constructed by using the above-described method for constructing an advertisement / notification medium having an air purification function. .

  According to the present invention, there is provided a method for solving the above-mentioned problems, and in particular, a method for constructing an advertisement / notification medium having an air purification function excellent in both an advertisement / notification effect and an effect of removing nitrogen oxides in a simple process. can do.

That is, according to the present invention,
(1) Installation of advertisement / notification media with air purification function on outdoor structures can be done in a simple process, notify the desired advertisement or notification information, and improve the aesthetics of the city and buildings. Or improve the aesthetics of containers placed in urban areas and harbors.
(2) After printing desired characters and patterns on a printing medium prepared in advance, the release sheet of the printing medium is peeled off at the construction site to form a printed material layer, and then a protective layer and a photocatalytic layer. A protective layer and a photocatalyst layer are laminated at a place that is not already at the construction site, and deterioration such as peeling of the photocatalyst layer that occurs when the protective layer and the photocatalyst layer are carried to the construction site can be prevented.
Specifically, for example, when carrying to the installation site by winding advertisement / notification media etc., if there is nothing to protect the photocatalyst particles, the photocatalyst particles may be rubbed and dropped.・ At the installation site of the announcement media, a protective layer and a photocatalyst layer are formed, which can be prevented.
Further, when carrying the advertisement / notification media to the installation site, it is possible to prevent the surface of the photocatalyst layer from being scratched or soiled.

(3) By providing a photocatalytic function, it is possible to appeal that companies that have installed advertising / notification media are seriously working on environmental issues.
In particular, advertising / notification media are often installed for the purpose of showing notification items, etc. to outdoor structures, etc., but at that time, the outdoor structures under construction may have an adverse effect on the environment. Can be mitigated or offset by advertising / notification media having an air purification function.

(4) By providing a protective layer of a specific material between the printed material layer and the photocatalyst layer, the effects of the photocatalyst of dyes and pigments used in printing can be prevented, and the characters or designs of the advertisement / notification media can be clearly seen. .
(5) The photocatalyst particles of the photocatalyst layer are decomposed and removed from NOx in the atmosphere, and in addition, for example, odorous substances such as aldehydes, mercaptans, ammonia, various amines and the like, decomposition and deodorization of harmful substances, SOx, Recognized by the decomposition and removal of harmful substances such as PCBs, dioxins, organohalogen compounds, organophosphorus compounds, sterilization and algae treatment of various fungi and algae, etc., contributing to environmental protection and purification of the space around outdoor structures can do.

(6) By using a (meth) acrylic acid ester (co) polymer on the surface of the printing material layer, the photocatalyst layer can particularly exhibit the effect of decomposing and removing NOx in the atmosphere, or the printing material layer By using the (meth) acrylic acid ester (co) polymer on the surface, it is possible to prevent the NOx decomposition / removal effect in the atmosphere of the photocatalyst layer from being attenuated as compared with the case of using other materials.
(7) By using a (meth) acrylic acid ester (co) polymer on the surface of the printing material layer, it is possible to prevent abnormalities such as discoloration in the printed layer even by ultraviolet irradiation, and weather resistance of the printed matter. Can provide excellent advertising and announcement media.

(8) The NOx gas decomposition effect of the photocatalyst particles in the photocatalyst layer is remarkably superior to the mitigation effect brought about by trees, so the harmful substances in the atmosphere caused by exhaust gases from urban areas and harbor areas with few trees It is extremely effective for reduction.

It is a schematic sectional drawing which shows the structure of each layer after construction of the advertisement and notification media which have the air purification function of this invention. It is a schematic sectional drawing which shows the structure of each layer of the to-be-printed medium before construction of this invention.

  Hereinafter, the present invention will be described, but the present invention is not limited to the following specific embodiments, and can be arbitrarily modified within the scope of the technical idea.

The construction method of the advertisement / notification media having the air purification function of the present invention is as follows:
On the surface of the printing material layer of the printing medium prepared by laminating the release sheet, the adhesive layer, and the printing material layer having at least the (meth) acrylic acid ester (co) polymer on the surface Print,
At the construction site of the advertisement / notification media having the air purification function, the release sheet of the printing medium is peeled off, and the adhesive layer is applied directly to at least one side surface of the outdoor structure or on the substrate installed on the side surface. Glue to form a printed layer,
Next, at the construction site, a coating liquid containing a reactive silane compound is sprayed on the surface of the printed material layer using a spray gun to form a protective layer having a thickness of 1 μm to 10 μm.
Further, a coating liquid containing titanium oxide particles as photocatalyst particles is sprayed onto the surface of the protective layer formed by polymerization or crosslinking of the reactive silane compound using a spray gun, and the film thickness is 0.03 μm to 1 μm. The photocatalyst layer is formed.

<Printed media>
In the present invention, the printing medium is prepared by laminating a release sheet, an adhesive layer, and a “printing material layer having at least a (meth) acrylic acid ester (co) polymer” on the surface thereof.

  The release sheet is provided in order to prevent the adhesive layer from adhering to other things and sticking to it or from adhering to the dust before the printing medium is installed. At the construction site of advertisement / notification media having a purification function, it is peeled off and used when adhering a printing medium subjected to desired printing to an outdoor structure or the like. Although there is no limitation in particular as a peeling sheet, What consists of synthetic resin sheets, such as paper and polyethylene terephthalate etc. which have a silicone resin coated on the surface, can be used suitably according to the objective.

  The adhesive layer is used when a printing medium subjected to desired printing is adhered to an outdoor structure or the like at a construction site of an advertisement / notification medium having an air purification function. Adhesives used for the adhesive layer include acrylic resin adhesives, urethane resin adhesives, melamine resin adhesives, phenol resin adhesives, epoxy resin adhesives, depending on the combination of the printing material layer and release sheet. Adhesives, modified silicone resin adhesives, and the like can be appropriately selected and used. In addition to the adhesive, a pressure-sensitive adhesive may be appropriately used depending on the purpose.

  The material layer to be printed is not particularly limited as long as it has a (meth) acrylic acid ester (co) polymer at least on the surface thereof; a layer formed of the (meth) acrylic acid ester (co) polymer itself; resin A layer of (meth) acrylic acid ester (co) polymer coated on the surface of film, paper, woven fabric, non-woven fabric, knitted fabric, etc .; yarn or fiber whose surface is coated with (meth) acrylic acid ester (co) polymer And a layer of woven fabric, non-woven fabric, knitted fabric, etc.

  Commercially available products include (meth) acrylic acid ester (co) polymer films sold by Nip Corporation, Inc .; NSG1200GMRT-54, manufactured by Nichiei Kako Co., Ltd .; IJ5381, manufactured by Sumitomo 3M; 055AV50, M-056AV50, G-064AV50, G-073AV30, M-074AV30; Technoloy series manufactured by Sumitomo Chemical Co., Ltd .; Plexiglas film series manufactured by Daicel Evonik Co., Ltd .; Para-Glass series; Kanase Industrial Co., Ltd., Kanaselite series; Asahi Kasei Technoplus Co., Ltd., Delagrass series; Le ester (co) polymer films. In addition, this invention is not limited to a commercial item.

  In the present invention, the material layer to be printed has a (meth) acrylic acid ester (co) polymer on the surface thereof, and the “surface of the material layer to be printed” refers to the surface to be printed and is printed. The surface where no part, specifically, the part where the printing ink is not attached, is in contact with the protective layer. Here, “(meth) acrylic acid ester (co) polymer” means an acrylic acid ester polymer, an acrylic acid ester copolymer, a methacrylic acid ester polymer, or a methacrylic acid ester copolymer. The parentheses may or may not be present, and so on.

  The (meth) acrylic acid ester (co) polymer is not particularly limited, and specifically, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, (meth) acrylic Preferable examples include (co) polymers such as butyl acid, 2-ethylhexyl (meth) acrylate, 2-dimethylaminoethyl (meth) acrylate, and 2-hydroxyethyl (meth) acrylate. These can be polymerized by one kind or copolymerized by two or more kinds.

  Although there is no limitation in particular as a monomer copolymerized with (meth) acrylic acid ester, (meth) acrylic acid, styrene, vinyl acetate, ethylene, propylene, butadiene, etc. are mentioned. In the case of a (meth) acrylic acid ester copolymer, those in which (meth) acrylic acid ester is copolymerized by 50 mol% or more are preferable, 70 mol% or more is more preferable, and 90 mol% or more is particularly preferable.

  Among them, in the construction method of the advertisement / notification media having the air purification function of the present invention, the “(meth) acrylic acid ester (co) polymer having the above-mentioned printing material layer on its surface” Particularly preferred is a coalescence.

  By using the (meth) acrylic acid ester (co) polymer on the surface of the printing material layer (the surface in contact with the protective layer), the effect of decomposing and removing NOx in the atmosphere of the photocatalyst layer can be particularly exhibited. In addition, even when exposed to ultraviolet rays outdoors, abnormalities such as discoloration can be prevented in the printed layer, and an advertisement / notification medium having excellent weather resistance of the printed matter can be provided.

  If the surface of the printing material layer is a (meth) acrylic acid ester (co) polymer, the chemical action with the photocatalyst particles in the photocatalyst layer has achieved the above-described good effects, Furthermore, it is conceivable that the layer forming physical properties such as the coating property of the photocatalyst layer thereon are improved, and the above-described good effects are finally achieved. In addition, when the (meth) acrylic acid ester (co) polymer is present on the surface of the printing material layer, the surface has good mechanical or physical properties, and the protective layer is more uniform than in the case of other materials. Titanium oxide particles that can be formed, and the photocatalyst particles of the photocatalyst layer can form a uniform layer, so that the effect of the protective layer can be sufficiently exerted, or the photocatalyst layer becomes uniform, and thus is irradiated with light. It is conceivable that the substantial surface area of the photocatalyst increases and the NOx removal rate of the photocatalyst layer is remarkably improved.

  On the surface of the printing material layer, desired printing such as characters, figures, symbols, and patterns can be performed. In the present invention, the printing ink layer present on the printing material layer on which the desired printing is performed is used as the printing layer. There is no print layer in the non-image area where printing ink is not attached, or in the halftone area where there is no halftone dot, so the printing material layer and the protective layer are in direct contact. Yes. Therefore, the chemical and physical influence of the (meth) acrylic acid ester (co) polymer of the printing material layer reaches the direct protective layer and the photocatalyst layer directly through the protective layer.

  The printing method for forming the printing layer is not particularly limited and may be appropriately selected according to the purpose from hand drawing, letterpress printing, offset printing, gravure printing, screen printing, inkjet printing, electrostatic printing (electrophotographic printing), and the like. Can do.

  Among them, in the method for constructing the advertisement / notification medium having the air purification function of the present invention, it is particularly preferable that the printing applied to the printing material layer is screen printing or ink jet printing.

  The dye or pigment of the ink paint used in the printing is not particularly limited, and those having excellent weather resistance are appropriately selected and used depending on the purpose. Ink paint dyes or pigments are usually formed as small dots called halftone dots to form a printing layer, so the area occupied by the printing layer on the printing medium is considerably small, and the printing layer is printed. It is considered that the interaction between the material layer and the photocatalyst layer is not affected.

<Printed material layer>
In the present invention, the printed material layer is installed directly on or on at least one side surface of the outdoor structure by peeling the release sheet of the printing medium at the construction site of the advertisement / notification media having an air purification function. The adhesive layer is formed on the substrate by bonding.

  When the printed material layer is formed by directly adhering the adhesive layer to the side surface of the outdoor structure, at least the “advertising / notification medium having an air purification function” of the present invention effectively exhibits the effect of the present invention. A side surface such as a single wall surface, which is irradiated with light such as sunlight, is preferable. The side surface may be a flat surface or a gently curved surface. Moreover, as long as it is a surface which can peel and peel firmly a peeling sheet from a to-be-printed medium, some rough surfaces may be sufficient. When the wall surface is rough, it is also preferable to apply a buffer / filler in advance within a range that does not reduce the adhesive strength of the adhesive layer in order to obtain a smooth flat surface.

  Moreover, the board | substrate which is a plane may be attached to the side surface of an outdoor structure with fasteners, such as a screw, or the frame for attaching a printed matter layer may be provided and affixed. When installing a board | substrate or a frame in order to fix a board | substrate to an outdoor structure, the shape and material are not specifically limited. It can be appropriately selected in consideration of strength, durability, weather resistance and the like. In particular, the aluminum plate is preferable because it is lightweight and easy to install, and does not bend and has a strength to hold a flat surface. In addition, what is necessary is just to use arbitrary fixing methods, such as an adhesive agent and a screw stop, in order to install a board | substrate in a frame.

  The advertisement / notification media of the present invention exerts an air purification function particularly in a position where sunlight can reach, so if it is such a position, it can be applied as necessary not only to the side but also to the ceiling and floor. In addition, the titanium oxide particles that are photocatalyst particles in the present invention are appropriately selected from those that can handle visible light, and the applicable range is not limited to the above range, and the ultraviolet rays are weaker and wider. Applicable even under a range of light irradiation.

An outdoor structure is an outdoor construction, construction or construction, civil engineering, construction, etc .; outdoor signboards, advertising towers, etc .; vehicles or ships operating on land or sea; This refers to a structure to be stored.
For example, a structure itself such as a building; an external structure (for example, a fence, a fence, a panel, an outer wall, etc.) created around the structure; an outdoor signboard; an incidental equipment such as a public facility; a temporary enclosure; Signs for construction; Ventilation towers; Piers; Signs; Kilometer posts; Bridge piers; Bridge girders; Transportation structures such as stations and bus stops; and external structures built around them; Window signs; Car bodies such as buses, vehicles, railway vehicles; Ships; airplanes; containers (transport boxes used for transporting cargo, items used as simple warehouses, etc.); sunshade signs; vending machines; parking signboards;

  Therefore, the construction site of the advertisement / notification media having the air purification function is a place where the outdoor structure or the like exists or a place around it. Specific examples of the “advertisement media” include corporate advertisements. Further, “notification media” specifically includes administrative public relations.

<Protective layer>
In the present invention, when the printed material layer contains an organic material, the protective layer is formed to suppress the deterioration because the organic material may be deteriorated by the photocatalytic function of the photocatalyst layer. Moreover, it forms in order to improve the adhesiveness of a printing layer or to-be-printed material layer, and a photocatalyst layer, and the coating-film characteristic of a photocatalyst layer.

  The coating liquid for the protective layer contains a reactive silane compound. The reactive silane compound is not particularly limited as long as it contains silicon in the molecule and forms a protective layer by polymerization or crosslinking, but an alkoxysilane compound is preferable. Examples of the alkoxysilane compound include organotrialkoxysilanes such as methyltriethoxysilane, methyltrimethoxysilane, and ethyltriethoxysilane; fluoroalkylalkoxysilanes; diorganopolysiloxanes; tetramethoxysilane, tetraethoxysilane, and tetrapropoxysilane. Tetraalkoxysilane; etc. are preferably used. A reactive protective silane compound such as an alkoxysilane compound is polymerized or crosslinked after coating to form a good protective layer.

  In particular, the forming method is characterized in that a coating liquid containing a reactive silane compound is sprayed and formed on the surface of the printed material layer using a spray gun at the construction site. The protective layer can be formed uniformly by spraying using the spray gun, and the interaction between the photocatalyst and the organic matter in the printed layer can be well blocked.

  When only the printed layer is used outdoors, discoloration, dirt adhesion, deterioration, deformation, etc. occur due to the influence of ultraviolet rays, temperature, moisture, etc., but when the protective layer and the photocatalyst layer are laminated, the photocatalytic function of the photocatalyst layer provides weather resistance. improves. In this case, if the photocatalyst layer is laminated directly on the printed material layer without laminating the protective layer, the above effect is alleviated, but the printed material layer is deteriorated due to the photocatalytic function, so that the weather resistance is lowered. . The protective layer is used to suppress deterioration due to the photocatalytic function of the printed material layer made of an organic material.

  The spray gun used for forming the protective layer is not particularly limited and can be used from a low pressure system to a high pressure system, but a low pressure system is preferred for the following reasons. Moreover, although the gas to be used is not particularly limited, air is preferable because it is simple. As the spray gun, an air atomization low-pressure spray gun is particularly preferable.

  The air atomization low pressure type spray gun is applied by a jet stream of compressed air. The “air atomization low-pressure system” is a system in which the coating liquid is atomized and applied by air pressure, and the air pressure of the spray gun is 100 kPa or less, preferably 20 kPa to 70 kPa, particularly preferably 30 kPa to 50 kPa. The amount of air is not particularly limited, but is preferably 500 to 10,000 L / min, and particularly preferably 1500 to 3200 L / min.

When using the above-mentioned air atomization low pressure spray gun, compared to other application methods,
(1) A large area can be neatly applied without uneven coating.
(2) Even when the printed material layer has irregularities, it can be uniformly applied.
(3) The internal pressure of the air cap is low, the speed of the particles in the coating liquid is slowed down, and the amount of the coating liquid that does not rebound even on the printed layer increases, resulting in good coating efficiency.
(4) A coating solution having a low dilution rate (high solid content) can be applied, and the coating solution cost can be reduced and the environment can be improved.

  The thickness of the protective layer is 1 μm to 10 μm, more preferably 1.3 μm to 6 μm, and particularly preferably 2 μm to 4 μm. Here, the “film thickness” means the film thickness after the solvent in the coating liquid is distilled off (dried) and polymerized or crosslinked. If the protective layer is too thin, deterioration of the organic matter in the printed layer due to the photocatalytic function of the photocatalyst particles may not be suppressed. If the protective layer is too thick, the effect of suppressing deterioration of the organic matter will increase even if it is thicker than that. In some cases, it may be disadvantageous in terms of cost, or the coating performance may be poor and a good protective layer may not be formed.

  The construction method of the advertisement / notification media having the air purification function according to the present invention is such that after the protective layer is formed, the photo-catalyst layer is formed after the reactive silane compound is polymerized or crosslinked after 24 hours at the construction site. It is preferable.

Among the reactive silane compounds, preferred alkoxysilane compounds have an alkoxysilyl group (for example, —Si (OR) ₃ ), which causes hydrolysis with moisture in the air to form silanol (for example, —Si (OH) ₃ ). change. Silanol further causes a dehydration reaction with the adjacent silanol, and the crosslinking reaction proceeds to become a polymer. Since the formed silicon-oxygen crosslinking (silane crosslinking) is chemically stable, a protective layer excellent in photocatalytic function blocking property, heat resistance, acid resistance, UV resistance and the like can be formed.

  The protective layer preferably contains a resin as a binder polymer in addition to the reactive silane compound. Such a resin is used to improve the coatability and coating properties of the protective layer, but the entire layer has a functional group capable of binding to the reactive silane compound at the end of the resin or at the pendant. This is particularly preferable from the viewpoint of improving the cross-linking property. The functional group is not particularly limited, and examples thereof include a hydroxyl group; a carboxyl group; an amino group; an epoxy group; and a crosslinkable silyl group such as an alkoxysilyl group. The resin (main chain) in the protective layer is not particularly limited, and examples thereof include vinyl resins, ester resins, and silicone resins. Particularly preferred is a silicone resin in terms of compatibility with the reactive silane compound, blocking of the photocatalytic function of the photocatalyst particles, and the like. As the resin used together with the reactive silane compound in the protective layer, a modified silicone resin having a functional group having a crosslinking performance is particularly preferable.

  The solvent of the coating liquid for forming the protective layer is not particularly limited, but methanol, ethanol, n-propanol, 2-propanol, n-butanol, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monoethyl And alcohols such as ether and propylene glycol monobutyl ether; ketones such as methyl ethyl ketone and methyl isobutyl ketone;

  The polymerization or crosslinking time is preferably 24 hours or longer. Further, as shown below, the formation of the protective layer or the photocatalyst layer is preferably performed when the relative humidity is 75% or less, and is preferably performed on a sunny or cloudy day.

<Photocatalyst layer>
In the present invention, the photocatalyst layer is formed for environmental protection and environmental purification by performing photocatalytic function of the photocatalyst particles to purify the air around the outdoor structure. As a forming method, a coating liquid containing titanium oxide particles as photocatalyst particles is sprayed on the surface of the protective layer formed by polymerization or crosslinking of a reactive silane compound using a spray gun. And

  The coating solution for the photocatalyst layer contains titanium oxide particles that are photocatalyst particles. The titanium oxide particles that are photocatalyst particles are not particularly limited as long as they have a photocatalytic function, and can be appropriately selected according to the purpose. The titanium oxide may be any one of anatase type titanium oxide, rutile (Rutile) type titanium oxide, and brookite type titanium oxide, but anatase type titanium oxide is preferable because of its excellent photocatalytic function. .

  It is also preferable from the viewpoint of coating properties and the like to contain other inorganic particles in the photocatalyst layer. Although there is no limitation in particular as another particle, Silicon dioxide etc. are mentioned.

  The solvent of the coating liquid for forming the photocatalyst layer is not particularly limited, but methanol, ethanol, n-propanol, 2-propanol, n-butanol, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monoethyl And alcohols such as ether and propylene glycol monobutyl ether; ketones such as methyl ethyl ketone and methyl isobutyl ketone;

  The spray gun used for forming the photocatalyst layer is not particularly limited and can be used from a low pressure type to a high pressure type, but a low pressure type is preferred for the following reasons. The gas to be used is not particularly limited, but air is preferable because it is simple. As the spray gun, an air atomization low-pressure spray gun is particularly preferable.

  In the present invention, the photocatalyst particles having a low dilution rate (high solid content) can be applied using a spray gun. The coating solution for the photocatalyst layer is not particularly limited as long as it contains titanium oxide particles that are photocatalyst particles, and for example, it may not contain a binder. When the binder is not contained, the dilution ratio of the photocatalyst particles becomes low (high solid content concentration), so that the effect of using an air atomization low pressure type spray gun is particularly exhibited.

  Moreover, in the photocatalyst layer obtained using the air atomization low pressure type spray gun, since it coats uniformly, it is thought that the substantial surface area of a photocatalyst particle increases and high catalyst capability is acquired.

As in the case of the protective layer, the air atomization low-pressure type spray gun is applied by a jet air flow of compressed air. When the air atomization low-pressure type spray gun is used, another application method is used. Compared to
(1) A large area can be applied neatly and without uneven coating.
(2) Even when the printed material layer and the protective layer are uneven, it can be applied uniformly.
(3) The internal pressure of the air cap is low, the speed of the particles in the coating liquid is reduced, and the coating liquid does not rebound even in the protective layer, so that the coating amount increases and the coating efficiency is good.
(4) The photocatalyst particles having a low dilution rate (high solid content) can be applied, and the coating solution cost can be reduced and the environment can be improved.

  The film thickness of the photocatalyst layer is 0.03 μm to 1 μm, more preferably 0.05 μm to 0.3 μm, and particularly preferably 0.1 μm to 0.3 μm. Here, “film thickness” refers to the film thickness after the solvent in the coating liquid has been distilled off. If the photocatalyst layer is too thick, interference fringes appearing on the surface appear rainbow-colored, or the coating liquid flows downward before drying, resulting in a non-uniform coating or a disadvantage in cost. There is. On the other hand, if the film thickness is too thin, it may not have a sufficient photocatalytic function. When the film thickness is the wavelength of visible light, that is, 0.4 μm to 0.7 μm, the surface may appear iridescent due to interference, which may adversely affect the expression of the printed matter.

  Also, the method for constructing the advertisement / notification media having the air purification function of the present invention performs the formation of the protective layer and the photocatalyst layer using a spray gun when the relative humidity at the construction site is 75% or less. It is preferable.

  When the relative humidity is higher than 75%, a whitening phenomenon (brushing) may occur. Whitening phenomenon (brushing) is a phenomenon in which the surface of the paint film becomes white and blurring as if it is hazy. Immediately after coating, moisture in the air condenses on the coating surface due to rapid evaporation of the coating solvent. A phenomenon that occurs. The relative humidity is more preferably 60% or less, and particularly preferably 50% or less.

  In addition, the present invention is an advertisement / notification medium having an air purification function, which is constructed by using the above-described method for constructing an advertisement / notification medium having an air purification function. If the above construction method for advertisement / notification media having air purification function is used, it is possible to construct advertisement / notification media having air purification function in a simple process. It is extremely excellent in both the effects of removing nitrogen oxides and the like.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples. However, the present invention is not limited to these examples unless it exceeds the gist.

Example 1
As the printing medium, “NSG1200GMRT-54” available from NIP Corporation was used, and various images with different image area areas were printed by an inkjet printing apparatus to provide a printing layer.

  What was used as a printing medium is a printing material layer in which 40.5% by mass of a printing material layer, 12.6% by mass of an adhesive layer, and 46.9% by mass of a release sheet are sequentially laminated. Was a film (29.7 mass%) containing polyethylene terephthalate (PET) and an aromatic polymer as a binder (10.8 mass%) coated with an acrylate copolymer. That is, the outermost surface of the printing material layer to which the protective layer is applied was an acrylate copolymer.

  The printed medium to be printed had a size of 1370 mm × 1000 mm × 0.170 mm (thickness), and was wound to a diameter of 200 mm and transferred to the construction site with the printed layer inside. Next, the release sheet was peeled off from the printing medium at the installation site of the announcement medium, which is a construction site, and attached to a substrate provided around the construction site.

After that, as a protective layer, Ishihara Sangyo Co., Ltd. 2-pack type “ST-K152” (solid content concentration of 10% by mass) was manufactured by Seiwa Sangyo Co., Ltd. using an air atomization low pressure spray gun. Using “Clean Boy 300E”, it was applied in two portions. The total coating amount of the two times was 60 g / m ² , and the total dry film thickness of the obtained protective layer was 3 μm. The air atomization low pressure spray gun used had an air pressure of 39 kPa and an air volume of 2000 L / min. The outdoor relative humidity, which is the construction site at the time of application, was 50%.

  The above-mentioned two-component type “ST-K152” manufactured by Ishihara Sangyo Co., Ltd. dissolves a main agent “ST-K152a” in which a modified silicone resin is dissolved in a solvent and an alkoxysilane compound, which is a reactive silane compound, in the solvent. It is a mixture of the auxiliary agent “ST-K152c”. The main agent and auxiliary agent were mixed immediately before coating to prepare a coating solution.

  After coating as described above, it is installed outdoors for about one day (24 hours) at an air temperature of about 20 ° C., and the protective layer is formed by proceeding with drying of the solvent in the coating solution and polymerization of the silane compound and crosslinking with the modified silicone resin. After being provided, a photocatalyst layer was provided on the protective layer as follows at the installation site.

As the photocatalyst layer, “ST-K252” (solid content concentration: 0.4% by mass) manufactured by Ishihara Sangyo Co., Ltd. containing titanium dioxide as a photocatalyst is the same as that used for applying the protective layer. Using an apparatus using an atomizing low pressure spray gun, coating was performed in two portions. The total coating amount of the two times was 50 g / m ² , and the total dry film thickness of the obtained protective layer was 0.2 μm. The air atomization low pressure spray gun used had an air pressure of 39 kPa and an air volume of 2000 L / min. The relative humidity at the time of application was 50%. After the photocatalyst layer was applied, it was left outdoors for about 1 hour at a temperature of about 20 ° C., and the solvent in the coating solution was distilled off to complete an advertisement / notification medium having an air purification function.

  Since both the protective layer and the photocatalyst layer were colorless and transparent, the printed notice media, the photograph, and the like were visible in exactly the same manner as before the protective layer and the photocatalyst layer were provided. In addition, since the protective layer and the photocatalyst layer are provided at the installation site, that is, at the stage of transfer to the installation site, the “printed medium after printing” is not provided with the protective layer and the photocatalyst layer. In addition, the protective layer and the photocatalyst layer could not be scratched or worn. In particular, the photocatalyst layer is easily damaged by mechanical impact, but such a possibility has not occurred during the transfer.

  The above notification media is cut into 50 mm × 100 mm, and a mixed gas set at a concentration of 1 ppm is supplied for 3 hours per minute for 5 hours in a sealed container in which gas flows while irradiating ultraviolet rays with the following illuminance for 5 hours from the front. The amount of NOx decomposition was measured and calculated.

First, put the notification media in a sealed container, adjust the humidity in the container to 65% using a precision humidity generator, and adjust the illuminance to 10 W / m ² with an illuminance meter. Irradiated. Then, while continuing to irradiate ultraviolet rays for 5 hours, a mixed gas set to a concentration of 1 ppm using a gas blender was supplied at 3 L / min for 5 hours, and the amount of NOx discharged from the sealed container was measured with a nitrogen oxide measuring device and an ion Using a chromatograph, the measurement was performed by a conventional method, and the NOx adsorption amount, the NO removal amount, the NO ₂ generation amount, and the NOx desorption amount were calculated therefrom.

The test equipment type and specifications were as follows.
(1) Precision humidity generator: SRG-112-3 (Daiichi Kagaku) (Humidity 0 to 100% adjustable, maximum ventilation 3.0 L / min)
(2) Nitrogen oxide measuring device: APNA-370 (manufactured by Horiba) (nitrogen oxide concentration detection lower limit 0.1 ppb)
(3) Gas blender: BG-2C (manufactured by Coflock) (Line 1 ≦ 3.0 L / min, Line 2 ≦ 50 mL / min)
(4) Ultraviolet irradiation device: Black light EL10BCR (manufactured by Toshiba) 2 (5) Illuminance meter: Optical power meter C9536-01, H9958-01 (manufactured by Hamamatsu Photonics)
(6) Ion chromatograph: IC-2001 (manufactured by Tosoh) (NOx ion concentration detection limit 1 ppb)

The test conditions were as follows.
(1) Type of mixed gas: Nitric oxide (NO) 66.3 ppm / nitrogen balance (2) Gas supply concentration: Supply diluted by gas blender to 1 ppm (3) Water vapor concentration: 50%
(4) Flow rate: 3.0 L / min (humidity 50% pure air, 1 ppm NO added)
(5) Illuminance of ultraviolet rays: 10 W / m ^{2 on the} surface of the test piece

As a result, the NOx adsorption amount = 0.572 μmol, the NO removal amount = 6.814 μmol, the NO ₂ generation amount = 0.460 μmol, and the NOx desorption amount = 0.219 μmol.

And the NOx removal amount was calculated by the following formula.
NOx removal amount = NOx adsorption amount + NO removal amount−NO ₂ production amount−NOx desorption amount

As a result, the removal amount of NOx is 10.14 μmol, and converted to 1000 m ² , 2.028 mol, that is, 75.03 g [the mass of NOx 1 mol is (the mass of 1 mol of NO 30 g + the mass of 1 mol of NO ₂ 44 g) / Calculated using 2 = 37 g. Assuming that the ultraviolet irradiation time per day outdoors is 8 hours, the amount of decomposition at 1000 m ² is calculated to be 75 g × 8 (daily irradiation time) / 5 (test time) = 120 g.

It is equivalent to 120 / 0.57 = 210.5 if calculated using the amount of NOx that Poplar reduces per day in the "Air Cleaner Tree Planting Manual" edited by the Environmental Rehabilitation and Conservation Organization. becomes the EdaCho poplar When 5m × 5m = 25m ² corresponds to 5260m ^2), it was found that the effect is greater. In addition, similar results were obtained with various images having different areas of the used image area.

Example 2
In order to study by changing the material of the printing material layer, a test sheet was obtained by applying the polymer shown in Table 1 on a polyethylene terephthalate (PET) film to a dry film thickness of 100 μm. The molecular weight of the polymer that is the material of the printing material layer was the most general one.

  This test sheet does not have an adhesive layer and a release sheet, but was used as a model of a printing medium in which the printing material layer was changed. In addition, a polyethylene terephthalate (PET) film itself, a cloth (material cellulose) made of 100% cotton, and kent paper (material cellulose) were also evaluated as test sheets in addition to the material of the printing material layer.

  In Example 1, it replaces with "NSG1200GMRT-54" and the test sheet No. shown in Table 1 obtained above is shown. A model “advertisement / notification media” was prepared in the same manner as in Example 1 except that 1 to 7 were used.

  The obtained model “advertisement / notification media” was evaluated in the same manner as in Example 1 and judged according to the following criteria. The ratio of NOx removed (removal rate) to the number of moles of supplied NO is defined as “NOx removal rate”. The results are shown in Table 1.

<Criteria for NOx removal rate>
○: NOx removal rate is 10% or more Δ: NOx removal rate is 1% or more and less than 10% ×: NOx removal rate is less than 1%

ＰＭＭＡ：ポリメチルメタクリレート
ＭＭＡ ：メチルメタクリレート
ＢＡ ：ブチルアクリレート
ＰＶＣ ：ポリ塩化ビニル
ＰＰ ：ポリプロピレン
ＰＥＴ ：ポリエチレンテレフタレート

PMMA: Polymethyl methacrylate MMA: Methyl methacrylate BA: Butyl acrylate PVC: Polyvinyl chloride PP: Polypropylene PET: Polyethylene terephthalate

  From Table 1, the NOx removal rate is 10% or more only when (meth) acrylic acid ester (co) polymer is used as the material of the printing material layer (test sheets 1 and 2), and 10% for other materials. (Test sheets 3 to 7). From this, it was found that the (meth) acrylic acid ester (co) polymer is excellent as a material for the printing material layer.

Example 3
In place of “NSG1200GMRT-54”, “advertisement / notification media” was prepared in the same manner as in Example 1 using commercially available films shown in Table 2 as printing media.

  The obtained “advertisement / notification media” was evaluated in the same manner as in Example 1. The results are shown in Table 3.

  From the results shown in Table 3, in the case where the (meth) acrylic acid ester (co) polymer was used as the material of the printing material layer (printed medium symbols A and B), the NOx removal rate was 10% or more, The other materials were less than 10%. From this, it was found that the (meth) acrylic acid ester (co) polymer is excellent as a material of the printing material layer that is the outermost layer of the printing medium.

Example 4
In order to evaluate the weather resistance of the printed material layer or the printed layer, the following evaluations were performed for the printing medium symbols A, B, C, D, and F without the protective layer and the photocatalyst layer and with the protective layer and the photocatalyst layer. It was. Printing was the same as in Example 1. In addition, the coating method, coating conditions, thickness of each layer, and the like were performed in the same manner as in Example 1. The results are shown in Table 4.

<Evaluation method of weather resistance>
JIS K 5600-7-7: 2008 General test method for paints-Part 7: Long-term durability of coating film-Section 7: Accelerated weather resistance and accelerated light resistance (xenon lamp method) The evaluation was performed by visually inspecting the printed image.

The test conditions were as follows.
Method: Method 1 Accelerated weather resistance (daylight filter)
Equipment: Super-Xenon Weather Meter SX75 Suga Test Instruments Co., Ltd. Radiation Light Source: Xenon Arc Lamp 7.5 kW Water-cooled Illuminometer: Main Unit Receiver (EC) Irradiance Meter RAX34C Suga Test Instruments Co., Ltd. Standard Temperature: 65 ± 2 ° C
Specimen wetting cycle: B [Discontinuous operation Wetting time 18 minutes Drying time 102 minutes]
Test time: 100 hours Irradiance: 100 W / m ² (Adjusted wavelength range: 300 to 400 nm)
Integrated irradiance: 36 mJ / m ²

  From the results shown in Table 4, the weather resistance was good when the protective layer and the photocatalyst layer were provided on the (meth) acrylic acid ester (co) polymer (printed medium symbols A and B). . On the other hand, when a protective layer and a photocatalyst layer were provided on polyvinyl chloride, the weather resistance was good for the printing medium with the printing medium symbol C, but the printed image with the printing medium symbol D was printed. Discoloration was observed, and the weather resistance was poor. Further, in the case where both the protective layer and the photocatalyst layer were not provided, discoloration was seen in the printed image regardless of the material of the surface of the printing material layer, and the weather resistance was poor.

Comparative Example 1
Desired printing is performed on the surface of the printing material layer of the printing medium, and the release sheet of the printing medium is peeled on the spot, and the adhesive layer is bonded to the substrate to form a printed material layer. In the same manner as in Example 1, the coating liquid was sprayed onto the surface of the printed material layer using an air atomization low-pressure spray gun to form a protective layer and a photocatalyst layer.

  When this was transferred to a construction site around the outdoor structure, the photocatalyst layer was scratched and worn, resulting in poor print images and could not be used as an advertising / notification medium.

Comparative Example 2
The layer was formed in the same manner as in Example 1 except that the protective layer was not provided. However, discoloration was observed in the printed image, and the accelerated light resistance (xenon lamp method) was poor.
In addition, the protective layer was formed only with a silicone resin (polyorganosiloxane) that does not contain a reactive silane compound in the protective layer and is not polymerized or crosslinked. However, discoloration was seen in the printed image, and accelerated light resistance (xenon lamp) Law) was bad.

Comparative Example 3
The same procedure as in Example 1 was performed except that the protective layer was provided at 0.8 μm. However, discoloration was observed in the printed image, and the accelerated light resistance (xenon lamp method) was poor.

Reference example 1
In the environment where the relative humidity was 80%, except that the protective layer and the photocatalyst layer were provided, the same as in Example 1, it was possible to use it satisfactorily satisfactorily. As a result, the surface of the coating was white and blurred, and the appearance of the printed image was slightly poor.

  The construction method of the advertisement / notification media having the air purification function of the present invention is excellent in constructing the advertisement / notification media having the air purification function in a simple process, and the advertisement / notification having the air purification function of the present invention. The advertisement / notification media with air purification function constructed using the media construction method is excellent in both the advertisement / notification effect and the effect of removing nitrogen oxides. Buildings constructed by civil engineering, architecture, etc .; billboards installed outdoors, advertising towers, etc .; structures that carry and store articles; etc., for example, structures such as buildings themselves; Structures (for example, fences, fences, panels, outer walls, etc.); outdoor signboards; incidental facilities and temporary enclosures such as public facilities; private signboards; construction signboards; ventilation towers; peers; signs; kiloposts; Bridge girder; station, bus Transportation structures such as stops and exterior structures built around them; window signs; buses, vehicles, railway vehicles, etc .; ships; airplanes; containers (used as shipping boxes and simple warehouses for cargo transportation) It is widely used as an advertising / notification medium installed on sunshade signs, vending machines, parking signboards, etc.

DESCRIPTION OF SYMBOLS 10 Printed material layer 11 Printed layer 12 Printed material layer 13 Adhesive layer 14 Release sheet 15 Printed medium 20 Protective layer 30 Photocatalyst layer 40 Side surface of outdoor structure or substrate installed on the side surface

Claims (9)

On the surface of the printing material layer of the printing medium prepared by laminating the release sheet, the adhesive layer, and the printing material layer having at least the (meth) acrylic acid ester (co) polymer on the surface Print,
At the construction site of the advertisement / notification media having the air purification function, the release sheet of the printing medium is peeled off, and the adhesive layer is applied directly to at least one side surface of the outdoor structure or on the substrate installed on the side surface. Glue to form a printed layer,
Next, at the construction site, a coating liquid containing a reactive silane compound is sprayed on the surface of the printed material layer using a spray gun to form a protective layer having a thickness of 1 μm to 10 μm.
Further, a coating liquid containing titanium oxide particles as photocatalyst particles is sprayed onto the surface of the protective layer formed by polymerization or crosslinking of the reactive silane compound using a spray gun, and the film thickness is 0.03 μm to 1 μm. A method for constructing advertisement / notification media having an air purification function, characterized in that a photocatalytic layer is formed.   The method for constructing an advertisement / notification medium having an air purification function according to claim 1, wherein the (meth) acrylic acid ester (co) polymer on the surface of the material layer to be printed is a methyl methacrylate copolymer.   The method for constructing an advertisement / notification medium having an air purification function according to claim 1 or 2, wherein the spray gun is an air atomization low-pressure type spray gun.   The air purification function according to any one of claims 1 to 3, wherein the formation of the protective layer and the formation of the photocatalyst layer using a spray gun are performed when the relative humidity at the construction site is 75% or less. Construction method of advertisement / notification media with   The atmosphere according to any one of claims 1 to 4, wherein after forming the protective layer, the photocatalyst layer is formed after the reactive silane compound is polymerized or cross-linked after 24 hours or more at the construction site. Construction method of advertisement / notification media with purification function.   The air purification function according to any one of claims 1 to 5, wherein the outdoor structure is a building, an external structure made around the building, a container, an outdoor signboard, or a vehicle body. Construction method of advertisement / notification media.   The method for constructing advertisement / notification media having an air purification function according to any one of claims 1 to 6, wherein the printing applied to the printing material layer is screen printing or inkjet printing.   A method for producing an advertisement / notification media having an air purification function, characterized in that the method for constructing an advertisement / notification media having an air purification function according to any one of claims 1 to 7 is used.   An advertisement with an air purification function, characterized in that it is constructed using the construction method of the advertisement / notification media having the air purification function according to any one of claims 1 to 7. Announcement media.

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