JP6352707B2 - Substrate - Google Patents

Description

  The present invention relates to a substrate by imparting a functional substance to a surface layer. In particular, the present invention relates to a substrate having antibacterial or antiviral properties as a functional substance.

Conventionally, it has been required to impart antibacterial properties to a substrate for housing.
Specifically, a decorative board having functionalities such as antifouling property and wiping property is provided by adding or applying a functional substance such as a photocatalyst to a decorative board such as a melamine decorative board.
Patent Document 1 proposes a functional building material that is coated with a resin coating film containing a functional material having a function and is fixed in the vicinity of the surface.
Patent Document 2 discloses a method for producing an antibacterial polyester decorative board by applying an unsaturated polyester resin to which an antibacterial agent made of a calcium-based ceramic fired powder having an antibacterial metal supported on the surface of the paper is applied. Proposed.
As bases for housing, antibacterial properties are imparted to bases for use in decorative panels, decorative sheets, wallpaper, flooring, tiles, glass, doors, ceilings, furniture, kitchens (including cooking utensils), baths, toilets, toilets, etc. It has been.

In addition, as a substrate other than the housing substrate, a substrate for the sanitary field represented by food processing and medical products, a substrate that is assumed to come into contact with the human body (for example, clothing, helmet, mobile phone, car seat, etc.), We have been providing antibacterial properties to substrates such as home appliances, stationery, foot care related products, pet related products and health related products.
As a base other than for a house, Patent Document 3 proposes an antibacterial product including a substrate, a metal thin film formed on the substrate, and an antibacterial coating layer formed on the metal thin film.

JP 2008-80210 A Japanese Patent Application Laid-Open No. 07-304619 Japanese Unexamined Patent Publication No. 2000-177048

However, as shown in FIG. 4, when the functional substance 14 such as a photocatalyst contacts the substrate surface layer 12 for a long time, the substrate surface layer 12 may be deteriorated. Specifically, discoloration of the surface layer of the substrate and loss of functional substances may occur. As a result, there is a problem that not only the functionality is deteriorated, but also the design of the substrate is deteriorated due to the discoloration of the surface layer 12, and the appearance of the substrate is deteriorated due to the surface irregularities.
In some cases, the functional substance 14 may be added or applied to the surface layer of the substrate. In such a case, the functional substance is buried in the surface layer 12 of the surface layer and there are few exposed portions on the surface layer, so that sufficient functionality cannot be exhibited. There was a problem. Furthermore, there is a case in which high antibacterial functionality is required in which the virus inactivity is equivalent to 1/1000 or less. In such a case, there is a problem that the functionality cannot be sufficiently expressed.
In view of such problems, the present invention provides a substrate that prevents deterioration of the surface layer and is excellent in functionality. In particular, the present invention provides a substrate excellent in antibacterial and antiviral properties.

An embodiment of the present invention is a substrate having a structure in which a substrate and a substrate surface layer are provided on the surface of the substrate, the cation carrier particles are arranged exposed on the substrate surface layer, and a functional substance is supported on the cation carrier particles. .
The cation carrier particle in the embodiment refers to a particle having an isoelectric point higher than the isoelectric point of the functional substance supported on the cation carrier particle. Here, the isoelectric point means that the positive and negative charges of the solute particles as a whole when the hydrogen ion concentration of the solution is changed in a particle having both an anion functional group and a cation functional group. This is the hydrogen ion exponent when the charge average of the whole particle becomes 0 in a state where it becomes zero and does not move even when an electric field is applied, and the value is expressed as pH. This isoelectric point is a value defined by a substance, and as an example, the isoelectric point of a functional substance often has a pH of 5-6. On the other hand, as the cation carrier particles, those having an isoelectric point higher than that of the functional substance can be used. In particular, the isoelectric point of the cation carrier particles is more preferably pH 7 or higher. The isoelectric point can be measured by any one of electrophoresis, electroosmosis, and streaming potential methods.

The cationic carrier particles refer to inorganic, metal, and combinations thereof. Specifically, if a functional substance having an isoelectric point of pH 5 to 6 is used, particles having an isoelectric point higher than the isoelectric point of the functional substance can be used as the cation carrier particles. . Specific examples of the cation carrier particles include cerium, zirconium, aluminum, alumina-containing particles, silicon oxide (for example, silica), diatomaceous earth, iron, cobalt, copper, chromium, nickel, tin, cadmium, magnesium, manganese. Further, a metal oxide or metal hydrate containing a selected metal such as tungsten, vanadium, or yttrium can be used. The isoelectric point of alumina (Al ₂ O ₃ ) is pH: 7.4 to 9.2, the isoelectric point of boehmite (AlOOH) is pH 7.7 to 9.4, cadmium hydroxide (Cd ( The isoelectric point of OH) ₂ ) is pH 10.5 or higher, the isoelectric point of cadmium oxide (CdO) is pH 7.7, the isoelectric point of iron hydrate (Fe (OH) ₂ ) is pH 12, and the oxidation The isoelectric point of iron (Fe ₃ O ₄ ) is pH 12, the isoelectric point of copper oxide (CuO) is pH 9.5, and the isoelectric point of copper hydrate (Cu (OH) ₂ ) is pH 7.7. It is. In particular, it is desirable to use alumina-containing particles.

  The cation carrier particles have an effect of easily attracting bacteria and viruses. In the first place, since bacteria and viruses contain proteins and fats, they are anionic substances, and the anionic substances have the property of being attracted to a cationic substance that is the opposite electrode. That is, the bacteria and viruses present on the surface layer of the substrate are attracted to the cation carrier particles, and the bacteria and viruses are reduced by the functional substance carried on the cation carrier particles. As a decorative board, since bacteria and viruses do not multiply, it becomes easy to obtain antibacterial and antiviral effects. In particles that are not cationic carrier particles, the bacteria and viruses present on the surface of the substrate are less frequently brought into contact with the functional substance, so that the bacteria and viruses remain and multiply, and it is difficult to obtain antibacterial and antiviral effects.

  In addition, the cation carrier particles have a property that the functional substance is easily supported at regular intervals. When a functional substance is supported on particles that are not cationic carrier particles, the functional substance aggregates. When the functional substance aggregates, the contact frequency between the fungus or virus and the functional substance decreases, and the expected action of reducing the fungus or virus is not exhibited. As a result, it takes time to reduce the bacteria and viruses, so that the antibacterial and antiviral effects are hardly exhibited. On the other hand, since the cation carrier particles are supported at regular intervals without aggregating the functional substance, the contact frequency between the fungus or virus and the functional substance does not decrease. Reduces virus and facilitates antibacterial and antiviral effects. Therefore, the cation carrier particles have an effect of holding the functional substance at regular intervals and attracting bacteria and viruses, and can improve antibacterial and antiviral effects.

When a fungus or virus comes into contact with a functional substance, the fungus or virus can be reduced by completely decomposing or damaging a part thereof. In order to obtain this effect, it is supported on the cation carrier particles.
Furthermore, it is desirable to use alumina-containing particles for the cation carrier particles. The alumina-containing particles are those having an alumina content of 5 wt% to 100 wt%. Specifically, it is desirable to use alumina particles and strontium aluminate. By containing alumina, a functional substance can be supported. Furthermore, when the content of alumina is less than 5 wt%, it may be difficult to carry depending on the type of functional substance. When the content of alumina is 15 wt% or more, it can be supported regardless of the type and particle diameter of the functional substance, and the functionality can be expressed.

Another embodiment is a decorative board according to the above embodiment, wherein the average particle diameter of the cation carrier particles is 0.1 μm to 55 μm.
In another embodiment, in the above-described embodiment, the cation carrier particle is a substrate that is exposed at an area ratio of 0.1% or more with respect to the surface of the substrate surface layer.
Another embodiment is a substrate according to the above embodiment, wherein the functional substance is a visible light responsive photocatalyst.
In another embodiment, the visible light responsive photocatalyst is the platinum-supported titania catalyst, the copper-supported titania catalyst, the iron-supported titania catalyst, the nitrogen-doped titania catalyst, the sulfur-doped titania catalyst, the carbon-doped titania catalyst, the oxidation A decorative board that is one of tungsten.
In particular, the isoelectric point in the visible light responsive photocatalyst is preferably pH 5-6.
In another embodiment, a resin layer is used as the substrate surface layer in the above embodiment, and the resin layer contains at least one of a silicone resin and a silane coupling agent.
Further, it is a substrate on which an inorganic sol is attached to the surface layer of the cation-carrying particles.

  According to the structure of the above embodiment, the functional substance is supported on the cation carrier particles and does not directly contact the substrate surface layer. For this reason, deterioration of the substrate surface layer can be prevented by the functional material, and discoloration of the substrate surface layer and dropping of the functional material can be prevented. Further, since the functional substance is not buried in the surface layer of the substrate and exposed on the surface of the substrate, the original functionality can be exhibited.

FIG. 1 is a schematic cross-sectional view of a substrate according to an embodiment of the present invention. FIG. 2 is a diagram showing an area portion that is a basis for calculating the area ratio of the exposed portion of the cation carrier particles. FIG. 3 compares (a) a schematic cross-sectional view of a substrate according to an embodiment of the present invention and (b) a schematic cross-sectional view of a decorative board according to another embodiment. FIG. 4 is a schematic sectional view of a conventional substrate.

Hereinafter, specific embodiments of the present invention will be described in detail with reference to the drawings. The substrate 1 according to the embodiment of the present invention has a substrate and a substrate surface layer on the surface of the substrate, the cation carrier particles 13 are disposed so as to be exposed on the substrate surface layer 12, and the functional substance 14 is supported on the cation carrier particles 13. It has a structure.
The substrate used in the embodiment can be used as a substrate for housing, a substrate for the sanitary field, and a substrate for other applications. As a base for a house, antibacterial properties have been imparted to a base for uses such as a decorative board, a decorative sheet, wallpaper, flooring, window glass, a door, a ceiling, furniture, a toilet, and a toilet. Further, it can be used as a substrate for food processing, medical products and the like as a substrate for the hygiene field. It can be used as a substrate for contact with the human body (for example, clothing, helmet, mobile phone, car seat, etc.), home appliances, stationery, foot care related products, pet related products, health related products, etc. .

The substrate of the embodiment may have a configuration in which a substrate and a substrate surface layer are stacked on the substrate, or may be configured by only the substrate. Since the functional substance can be imparted within the thickness range from the substrate surface layer to 1 cm from the substrate surface, the region can be distinguished and used as the “substrate surface layer”.
The substrate preferably contains at least one selected from long paper, resin film, metal film, inorganic fiber sheet, resin plate, inorganic plate, metal plate, and resin-impregnated sheet.

Long paper is plain paper or long paper (so-called wallpaper) with a design printed on its surface. It is a cloth, paper, or vinyl (synthetic resin) used as an interior finishing material for walls and ceilings in buildings. This sheet may be a sheet that is attached to the surface of the inner wall base material using an adhesive for the purpose of protecting the ground or decorating.
The resin film is composed of either a thermosetting resin, a thermoplastic resin, or a resin composite containing both, and the color may be transparent or colored, and the thickness About, it can be set to the optimal thickness in time.

The metal film is composed of either one kind of metal or a metal body containing a plurality of metals, and what is frequently used is a metal foil. Although copper etc. can be used as a metal film, it is not specifically limited. Moreover, about the thickness of a metal film, it can be set as the optimal thickness timely according to a use.
An inorganic fiber sheet is a fiber made of an inorganic substance, and is made of amorphous fibers such as glass fibers and rock wool, polycrystalline fibers such as carbon fibers and alumina fibers, and single crystals such as wollastonite and potassium titanate fibers. This includes materials selected from fibers and the like, and refers to those formed into a sheet shape.

The resin plate is composed of either a thermosetting resin, a thermoplastic resin, or a resin composite containing both, and may be a single layer of resin, or a plurality of layers of resin and resin, or A plurality of layers may be formed of a resin and a substance other than the resin, or a plurality of layers may be laminated.
An inorganic plate is a fiber made of an inorganic material, such as amorphous fibers such as glass fibers and rock wool, polycrystalline fibers such as carbon fibers and alumina fibers, and single crystal fibers such as wollastonite and potassium titanate fibers. , Including those selected from ceramic, gypsum, concrete, calcium silicate plate, etc., and may be a single layer of an inorganic material, or a plurality of layers of an inorganic material and an inorganic material, or multiple layers of a material other than an inorganic material and an inorganic material. However, a laminate of a plurality of layers may be used.

The metal plate is composed of one kind of metal or a metal body containing a plurality of metals, and may be a single metal layer, a metal-metal multiple layer, or a metal and a metal other than a metal. A plurality of layers of these materials may be used, or a plurality of layers may be further laminated.
The resin-impregnated sheet is composed of a so-called prepreg in which a sheet made of inorganic fibers is impregnated with resin or a resin-impregnated paper in which paper is impregnated with resin, and is mainly used for a housing such as a decorative board. Is.
The material of the substrate surface layer used in the above embodiment is not particularly limited, and organic materials, inorganic materials, metal materials, and composites of these materials can be used.

Organic materials used for the substrate surface layer include thermosetting resins, thermoplastic resins, and composites thereof. Specific thermosetting resins include phenolic resins, polyester resins, epoxy resins, polyimide resins, fluorine Resins and the like can be used, and as specific thermoplastic resins, nylon, polyethylene, polystyrene, polyvinyl chloride, and the like can be used.
As the inorganic material used for the substrate surface layer, inorganic materials such as ceramics, metal materials, glass, and composites thereof can be used.

  The cationic carrier particle is not particularly limited as long as it is higher than the charge zero point of the functional substance and can carry the functional substance, but is preferably alumina-containing particles. Furthermore, the alumina-containing particles are those having an alumina content of 5 wt% to 100 wt%. Specifically, it is desirable to use alumina particles and strontium aluminate. By containing alumina, a functional substance can be supported. Furthermore, when the content of alumina is less than 5 wt%, it may be difficult to carry depending on the type of functional substance. When the alumina content is 15 wt% or more, it can be supported regardless of the type and particle size of the functional substance, and sufficient functionality can be exhibited.

In one embodiment, the average particle size of the cation carrier particles can be 0.1 to 55 μm. When the average particle size is less than 0.1 μm, the amount of the functional substance supported is small and the functionality tends not to be sufficiently developed. When the average particle size exceeds 55 μm, the appearance of the substrate surface layer tends to be defective. It is in.
When the average particle diameter of the cation carrier particles is less than 0.1 μm, the cation carrier particles are easily embedded in the surface layer of the substrate, and the cation carrier particles which are functional substances are hardly supported. If the average particle diameter of the cation carrier particles exceeds 55 μm, irregularities may be formed on the surface layer of the substrate, which may cause problems in appearance and design. Furthermore, when the average particle diameter of the cation carrier particles is 0.5 to 5 μm, the function as a functional substance is exhibited, and there is no problem in appearance and design.

  In the above embodiment, the cation carrier particles are exposed with an area ratio of 0.1% or more with respect to the surface of the substrate surface layer. In another embodiment, the cation carrier particles are exposed with an area ratio of 0.2% or more with respect to the surface of the substrate surface layer. Furthermore, as another embodiment, the cation carrier particles are present with an area ratio of 0.3% or more with respect to the surface of the substrate surface layer. Here, the area ratio means the total ratio of the surface area B of the melamine resin to which the cation carrier particles are exposed on the entire melamine resin surface A in FIG. If the cationic carrier particles are exposed to an area ratio of less than 0.1% with respect to the surface resin layer surface, the functionality of the functional substance tends to be insufficient.

  The functional substance can be a functional material having functions such as antibacterial, antiviral, antiallergenic and deodorizing properties. As one embodiment, as the antibacterial functional substance, a visible light type photocatalyst can be used as a functional material of a substrate that is assumed to be used indoors. For example, titanium oxide carrying platinum group such as platinum, palladium, rhodium, ruthenium, iron, copper or the like can be used. In one embodiment, the functional substance is selected from platinum-supported titanium oxide, iron-supported titanium oxide, copper-supported titanium oxide, nitrogen-doped titania catalyst, sulfur-doped titania catalyst, carbon-doped titania catalyst, and tungsten oxide.

In the substrate of the embodiment of the present invention, the spray liquid containing the cation carrier particles is sprayed onto the surface having the substrate surface layer, and after drying, the cation carrier particles are exposed and fixed on the surface of the substrate surface layer by thermocompression bonding. Then, the functional substance can be supported on the surface of the cation carrier particles by immersing the substrate on which the cation carrier particles are arranged in a solution containing the functional substance.
In the substrate manufacturing method of the above embodiment, when the cation carrier particles are thermocompression bonded to the surface of the substrate surface, a release cushion material made of polyethylene terephthalate (PET) is interposed between the cation carrier particles and the thermocompression press surface. Can be done. As a result, the cation carrier particles can be prevented from being buried in the surface layer of the substrate, and can be exposed and fixed on the surface of the substrate surface layer.

In another embodiment, the transfer film is sprayed with a spray liquid containing cationic carrier particles, and then the inorganic carrier particle-adhering surface of the transfer film is opposed to the resin surface of the substrate having the substrate surface layer. There is a method of thermal transfer.
In the substrate of the above embodiment, when a resin layer is used as the substrate surface layer, the resin layer contains at least one of a silicone resin and a silane coupling agent.
As the silicone resin, silicone resin, modified silicone oil, or the like can be used. As the modified silicone oil, a silicone oil having one or more functional groups in the molecule can be used. The position at which the functional group is introduced is not particularly limited, and the functional group may be introduced at any position of one end, both ends or side chains of the polysiloxane main chain. Moreover, as a functional group, a hydroxyl group, an amino group, a methoxy group, a hydrazino group, an epoxy group, a methacryl group, a carboxyl group, a carbinol group etc. can be introduce | transduced, for example.

  As the silane coupling agent, those having a functional group such as vinyl group, propenyl group, butadienyl group, styryl group, acryloyl group, methacryloxy group, amino group, mercapto group, and isocyanate group are preferred. For example, vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriisopropoxysilane, allyltrimethoxysilane, 3-glycidoxypropyl, triairoxysilane, 2- (3,4-epoxycyclohexyl), p-stiltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, diallyldimethylsilane, 3-mercaptopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane.

In order to contain the silicone resin or coupling agent in the substrate surface layer, at least one of the silicone resin or coupling agent is added to the substrate surface layer by including at least one of the silicone resin or coupling agent in the resin solution. An impregnation method can be used.
When a silicone resin is contained in the substrate surface layer, water repellency can be imparted to the surface of the substrate surface layer. When the functional substance is supported on the cation carrier particles, as schematically shown in FIG. 3A, the functional substance 14 attached not only to the surface of the cation carrier particles 13 but also to the surface of the substrate surface is shown in FIG. As shown in 3 (b), water repellency on the surface of the substrate containing a silicone resin or a coupling agent avoids the surface of the substrate and adheres to the surface of the cationic carrier as much as possible, and directly contacts the surface of the substrate. The amount of the functional substance to be reduced can be further reduced.

When a coupling agent is contained in the substrate surface layer, the substrate surface layer can be provided with curability, and can be prevented from being embedded in the substrate surface layer when the cation carrier particles are thermocompression bonded.
By containing a silicone resin and a coupling agent in the substrate surface layer, the cationic carrier particles can be immobilized without being buried, and there is an effect of making it difficult for the functional substance to adhere to the substrate surface layer. Specifically, even if the functional substance that has become excessive during the process adheres to the surface of the substrate surface, it can be easily removed after the cleaning process.
Furthermore, contaminated water containing bacteria, viruses, and the like is easily attracted to hydrophilic cation carrier particles and functional substances, and the functionality due to oxidative degradation and the like is easily exhibited. In particular, when the surface layer of the substrate is formed of a melamine resin, the above actions and effects can be easily obtained.

Further, it is desirable to attach an inorganic sol to the surface layer of the cation-carrying particles. The immobilization of functional substances can be reinforced. As the inorganic sol, silica sol, alumina sol, silica-alumina sol, titania sol and the like can be used, and it is desirable to use silica sol.
Specifically, a decorative board as a base for a house can be composed of a non-combustible base material such as core paper or magnesia cement generally used for a decorative board. The core paper may be used alone or a laminated body in which a plurality of core papers are laminated. The number of core papers is not particularly limited, but may be 1 to 20 sheets. As the core paper, for example, aluminum hydroxide paper can be used. The core paper can be impregnated with a phenolic resin. Moreover, a core paper and a magnesia cement incombustible base material can be laminated to form a substrate.

  The magnesia incombustible base material can be used alone to constitute a substrate by being laminated or disposed at the center of the core paper. The magnesia cement incombustible plate is formed into a plate shape by mixing magnesium oxide (MgO) and magnesium chloride (MgCl2), adding aggregate and water and kneading. As the aggregate, inorganic fibers such as rock wool and glass wool, and organic fibers such as wood chips and pulp can be used. Moreover, in order to raise the intensity | strength of a magnesia cement incombustible board, the glass fiber layer formed in mesh shape etc. can be provided as an intermediate | middle layer.

The method for forming the substrate surface layer on the substrate surface, which is a substrate composed of a plurality of or a single core paper and / or a magnesia cement incombustible substrate, is not particularly limited and can be performed by a general method. For example, by laminating melamine resin impregnated paper on one or both sides of the substrate and hot pressing, the melamine resin of the melamine resin impregnated paper penetrates into the core paper, where the curing reaction proceeds, and the melamine resin for the core paper The adhesive strength of the impregnated paper can be developed.
Also, the resin that can be used for the resin layer of the substrate surface layer includes melamine resin, diallyl phthalate (DAP) resin, polyester resin, olefin resin, vinyl chloride resin, acrylic resin, epoxy resin, urethane resin, phenol resin, silicone resin Of these, it is desirable to use a melamine resin.

  The melamine resin is a resin having improved dimensional stability and toughness without impairing optical and visual characteristics of the melamine resin such as translucency. As the melamine resin, known resins can be adopted as long as they are resins having melamine and its derivatives as monomers. The melamine resin may be a resin composed of a single monomer or a copolymer composed of a plurality of monomers. Examples of the melamine derivative include derivatives having a functional group such as an alkoxymethyl group such as an imino group, a methylol group, a methoxymethyl group, or a butoxymethyl group. Further, a compound obtained by reacting a lower alcohol with a melamine derivative having a methylol group and partially or completely etherified can be used as a monomer. Monomethylol melamine, dimethylol melamine, trimethylol melamine, tetramethylol melamine, pentamethylol melamine, hexamethylol melamine and other derivatives having a methylol group (hereinafter referred to as “methylolated melamine”) are copolymerized with melamine as a crosslinking agent. Can be used.

The melamine resin impregnated paper is prepared by impregnating the pattern paper with melamine resin at a predetermined impregnation rate, and then heating and drying. The pattern paper can be impregnated with the melamine resin by immersing the pattern paper in a melamine resin-containing solution using, for example, an aqueous formaldehyde solution as a solvent. Further, in order to impart bending workability to the melamine resin-impregnated paper, it is possible to impregnate a solution containing a plasticizer together with the melamine resin. As the plasticizer, for example, ε-caprolactam, acetoguanamine, p-toluenesulfonic acid amide, urea and the like can be used. For example, titanium paper is used as the pattern paper. The basis weight of the pattern paper can be set to 80 to 150 g / m ² in consideration of the thickness and weight of the pattern paper. The temperature for heating and drying can be set to 100 to 150 ° C. in order to firmly fix the melamine resin to the pattern paper.

For the formation of the resin layer as the substrate surface layer, a lamination step of laminating a resin-impregnated paper such as melamine resin on one or both sides of a substrate made of a core paper laminate, and a substrate on which a resin-impregnated paper such as melamine resin is laminated It is manufactured through a hot-pressure forming process for hot-press forming. The heating conditions can be a decorative board temperature of 125 to 150 ° C., and the pressing conditions can be 1.96 to 9.80 MPa (20 to 100 kg / cm ² ). When the temperature is less than 125 ° C. or the pressure is less than 1.96 MPa, the adhesion of the phenol resin-impregnated paper to the substrate is insufficient, and peeling easily occurs. On the other hand, when the temperature exceeds 150 ° C. or when the pressure exceeds 9.80 MPa, cracks may occur.

As an example, the base was a decorative board that is a base for a house.
Example 1
(Primary melamine impregnation process)
A paper roll having a thickness of 0.2 to 0.3 mm is immersed in a solution containing a melamine resin, and the roll paper is passed while being immersed in the solution so that the temperature of the solution is 20 ° C. and the immersion time is 2 minutes. This impregnated the melamine resin.
(Drying process)
The roll paper that passed through the melamine solution was dried by a dryer (ESPEC, OVEN PH-201) so that the temperature was 100 ° C. and the drying time was 30 seconds.

(Secondary melamine impregnation process)
The paper roll that has undergone the drying step is immersed in a solution composed of a melamine resin, silicone, and a silane coupling agent. The melamine resin, the silicone, and the silane coupling agent were impregnated by passing the roll paper while being immersed in the solution so that the temperature of the solution was 20 ° C. and the immersion time was 30 minutes.
(Drying / cutting process)
The roll paper that passed through the melamine solution was dried by a dryer (ESPEC, OVEN PH-201) so that the temperature was 100 ° C. and the drying time was 2. After drying, it was cut into 910 mm × 1820 mm.
(Alumina particle spray process)
A spray liquid composed of alumina particles having an average particle diameter of 0.5 μm and ethanol was prepared. The spray liquid was filled in the spray at room temperature and sprayed on the cut melamine-impregnated paper.

(Drying process)
The melamine resin-impregnated paper sprayed with alumina particles was dried by a dryer (ESPEC, OVEN PH-201) so that the temperature was 110 ° C. and the drying time was 2 minutes.
(Combination process)
Four phenolic resin-impregnated core materials having a thickness of 0.3 to 0.4 mm are laminated, and the melamine resin-impregnated paper sprayed with the alumina particles obtained by the above process is coated on the outer surface thereof. The release cushion material made of PET is interposed between the press surface of the press machine and the alumina spray surface of the melamine resin impregnated paper, and the temperature is 143 ° C., the press pressure is 80 kg, the press time (including the temperature rise time) Thermocompression bonding was performed in 50 minutes. Thereby, the alumina particles were exposed and fixed on the melamine resin impregnated layer.
(Photocatalyst loading process)
A photocatalyst carrying solution in which a photocatalyst of Cu—TiO _{2 having} an average particle diameter of 100 nm was dispersed in a dispersant composed of an ammonium salt containing 10 wt% was prepared. The photocatalyst is supported on the alumina particles by immersing the substrate having the melamine resin impregnated layer on the surface on which the alumina particles obtained in the above step are placed in a photocatalytic level supporting liquid at 20 to 25 ° C. for 2 minutes. I let you.

(Example 2)
In the same manner as in (Primary melamine impregnation step) to (Combination step) in Example 1, a substrate having a melamine resin layer on which alumina particles were exposed and fixed was obtained. Next, a photocatalyst carrying solution in which the photocatalyst of Pt—TiO _{2 having} an average particle diameter of 100 nm was dispersed in a dispersant composed of an ammonium salt containing 10 wt% was prepared. The photocatalyst is supported on the alumina particles by immersing the substrate having the melamine resin impregnated layer on the surface on which the alumina particles obtained in the above step are placed in a photocatalytic level supporting liquid at 20 to 25 ° C. for 2 minutes. I let you.

(Comparative Example 1)
Melamine resin-impregnated paper was obtained in the same manner as in (Primary melamine impregnation step) to (Drying / cutting step) in Example 1 above. Next, four phenol resin-impregnated core materials having a thickness of 0.3 to 0.4 mm were laminated, and the melamine resin-impregnated paper obtained by the above process was placed thereon, and the temperature was 143 ° C., the press pressure was 80 kg, Thermocompression bonding was performed in a press time (including a temperature rising time) of 50 minutes. Thereby, the board | substrate which has a melamine resin impregnation layer on the surface was obtained.

(Comparative Example 2)
Melamine resin-impregnated paper was obtained in the same manner as in (Primary melamine impregnation step) to (Drying / cutting step) in Example 1 above. Next, four phenol resin-impregnated core materials having a thickness of 0.3 to 0.4 mm were laminated, and the melamine resin-impregnated paper obtained by the above process was placed thereon, and the temperature was 134 ° C., the press pressure was 80 kg, Thermocompression bonding was performed in a press time (including a temperature rising time) of 50 minutes. Thereby, the board | substrate which has a melamine resin impregnation layer on the surface was obtained.
A photocatalyst carrying solution in which a photocatalyst of Cu—TiO _{2 having} an average particle diameter of 100 nm was dispersed in a dispersant composed of an ammonium salt containing 10 wt% was prepared. The substrate having the melamine resin impregnated layer obtained in the above step on the surface was immersed in a photocatalyst level supporting liquid at 20 to 25 ° C. for 2 minutes, thereby supporting the photocatalyst on the melamine resin impregnated layer.

(Appearance evaluation)
The decorative plates carrying the photocatalysts obtained in Examples 1 and 2 and Comparative Examples 1 and 2 were evaluated for appearance according to JIS K6902 weather resistance D4. After irradiating with a carbon arc lamp at a prescribed irradiation exposure amount and holding it in a thermostat at 60 ± 3 ° C. for 48 hours, the surface layer resin layer made of melamine resin was observed for deterioration, unevenness and the like. It was judged that there was no problem that the color difference ΔE was 3 or less.
In the decorative plates of Examples 1 and 2, the color difference ΔE was 2 or less, and there was no problem. However, the decorative plate of the comparative example was discolored when the color difference ΔE exceeded 3, and the surface was rough. Deterioration of was observed.

(Functional evaluation)
In order to evaluate the antibacterial properties of the decorative plates carrying the photocatalysts obtained in Examples 1 and 2 and Comparative Examples 1 and 2, the antiviral properties of the JIS R1756 visible light responsive photocatalytic material were tested. . The measurement results were expressed as the concentration of virus that was not inactivated against E. coli, and the results are shown in Table 1.
Here, as an index for evaluation of antibacterial properties, the degree of non-inactivated virus concentration (inactivity) was used with reference to the inactivation degree of phage virus. Phage virus inactivity is an antiviral test using bacteriophage, and the concentration of virus capable of infecting E. coli is measured using phage virus Qβ concentration: 8.3 million / ml. It is the result of calculating the inactivated virus concentration. That is, the phage virus inactivity is the degree of the concentration of virus that cannot infect E. coli with respect to the concentration of phage virus Qβ, (phage virus Qβ concentration-concentration of virus that can infect E. coli). / (Phage virus Qβ concentration). In this example, the value of (concentration of virus capable of infecting E. coli) / (phage virus Qβ concentration), which is the degree of the concentration of uninactivated virus, is determined with reference to the inactivation of phage virus. Calculated as inactivity. It can be said that it is excellent in antibacterial property, so that the value of non-inactivity is low.

  In the decorative plates of Examples 1 and 2, the concentration of the virus capable of infecting E. coli was 83 / ml or less, which was equivalent to 1 / 100,000 or less when converted to non-inactivation, It was confirmed to have antiviral properties. On the other hand, in the decorative plates of Comparative Example 1 and Comparative Example 2, the concentration of the virus capable of infecting Escherichia coli was 830,000 / ml or less, which is 1/10 when converted to virus inactivity. Therefore, it was confirmed that the virus remained high and did not have antibacterial properties.

  The functional material can prevent deterioration of the surface layer of the substrate, and can exhibit the original functionality of the functional material, so that the industrial applicability is high.

DESCRIPTION OF SYMBOLS 1 Base | substrate 12 Embodiment of this invention Base | substrate surface layer 13 Cationic carrier 14 Functional substance 15 Base | substrate surface layer surface 16 Silane coupling agent impregnation resin layer surface 3 Conventional base | substrate A Resin surface area (total)
B Cation carrier particle surface area (total)

Claims (11)

A substrate having a substrate surface on the surface;
Cationic carrier particles arranged exposed on the surface of the substrate;
A photocatalyst supported on the cation carrier particles,
The substrate is made of a resin plate or a resin-impregnated sheet,
The cation carrier particles are exposed and fixed on the surface of the substrate surface layer, and the photocatalyst is supported on the surface of the cation carrier particles except for a portion in contact with the substrate. Substrate.   The substrate according to claim 1, wherein the cation carrier particles are alumina-containing particles.   The substrate according to claim 2, wherein the alumina-containing particles have an alumina content of 5 wt% or more.   2. The substrate according to claim 1, wherein the cation carrier particles are particles made of either alumina or strontium aluminate.   The substrate according to claim 1 or 2, wherein the average particle size of the cation carrier particles is 0.1 µm to 55 µm.   The substrate according to any one of claims 1 to 5, wherein the cation carrier particles are exposed with an area ratio of 0.1% or more with respect to a surface of the substrate surface layer. The substrate according to any one of claims 1 to 6 , wherein the functional substance is a visible light responsive photocatalyst. The visible light responsive photocatalyst is any one of platinum-supported titania catalyst, copper-supported titania catalyst, iron-supported titania catalyst, nitrogen-doped titania catalyst, sulfur-doped titania catalyst, carbon-doped titania catalyst, and tungsten oxide. The substrate according to claim 7 . The substrate according to claim 1, wherein the substrate surface layer is a resin layer, and the resin layer contains a silicone resin and / or a silane coupling agent. The substrate according to any one of claims 1 to 9 , wherein an inorganic sol is attached to a surface layer of the cation-carrying particles. The substrate according to any one of claims 1 to 10, wherein the photocatalyst further adheres to a surface of the substrate surface layer.

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