JP2017100438A - Anti-virus decorative sheet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a decorative sheet having satisfactory functionality without causing the deterioration of designability.SOLUTION: A decorative sheet has a substrate, a surface resin layer put on one side or both sides of the substrate, and functional substance present on the surface resin layer. An amount of the functional substance present on the surface resin layer is 0.02-0.21 g/m.SELECTED DRAWING: Figure 1

Description

The present invention relates to a decorative board.

Conventionally, a decorative board provided with functionalities such as antifouling properties and antibacterial properties by adding or applying a functional substance such as a photocatalyst to a decorative board such as a melamine decorative board has been provided.

Patent Document 1 proposes a functional building material covered with a resin coating film containing a functional material having functions such as antibacterial and antiviral properties.

Patent Document 2 discloses an antifouling decorative board in which a photocatalyst is supported on a silicone resin layer.

JP 2008-80210 A JP 2003-276117 A Japanese Patent No. 3486588

Since the building material described in Patent Document 1 includes silica fine particles in which an antiviral substance such as tannic acid is supported in a resin coating film, most of the antiviral substance is embedded in the resin layer on the surface of the decorative board. End up. For this reason, there were few exposed parts of the antiviral substance in the building material surface layer, and there existed a problem that sufficient functionality could not be expressed. In addition, building materials and decorative boards are required to have high antibacterial and antiviral properties equivalent to a virus inactivity of 99.9% or more (the concentration of uninactivated virus is 1/1000 or less). In such a case, there was a problem that the functionality could not be fully expressed.
In addition, the decorative board described in Patent Document 2 is intended for antifouling properties, and does not describe at all how much photocatalyst should be supported in order to maintain antiviral properties.
Furthermore, in the decorative board described in these well-known documents, when the functional substance is white or colored like a photocatalyst, there was a problem that the designability of the decorative board deteriorates.
In the decorative board of Patent Document 3, the combined use of a photoantibacterial agent and a photocatalyst is disclosed, but there is a problem that the design of the decorative board is deteriorated due to an excessive amount of the catalyst.

In addition, a functional substance may be added or applied to the surface layer of the decorative board. In such a case, the functional substance is buried in the surface resin layer of the surface layer, and there are few exposed parts on the surface layer. There was a problem that could not be expressed.

This invention is made | formed in view of such a problem, and it aims at providing the decorative board excellent in functionality, without reducing the designability. In particular, an object is to provide a decorative board having excellent antibacterial and antiviral properties.

The decorative board of the present invention comprises a substrate, a surface layer resin layer laminated on one or both sides of the substrate, and a functional substance present on the surface layer resin layer, and the functionality in the surface layer resin layer. The amount of the substance present is 0.02 to 0.21 g / m ² , preferably 0.03 to 0.21 g / m ² .

In the decorative board of the present invention, since the amount of the functional substance in the surface resin layer is 0.02 to 0.21 g / m ² , the function of the functional substance can be sufficiently exhibited, and the functionality is improved. It can prevent that the designability of a decorative board falls by a substance.
When the amount of the functional substance present in the surface resin layer is less than 0.02 g / m ² , the amount of the functional substance is too small, so that virus inactivity is practically required -3.00 or higher. A numerical value indicating that the virus function is excellent cannot be obtained, and sufficient antibacterial and antiviral properties cannot be exhibited. On the other hand, when the abundance of the functional substance in the surface resin layer exceeds 0.21 g / m ² , the design of the decorative board is lowered by the functional substance. Moreover, when the abundance of the functional substance in the surface resin layer exceeds 0.21 g / m ² , the antiviral function is deteriorated. The reason for this is not clear, but it is presumed that functional substances such as photocatalysts are densely packed and specific surface properties are lowered. In the decorative board of the present invention, when the abundance of the functional substance in the surface resin layer is 0.5 g / m ² or more, the antiviral function further decreases. The virus inactivity is a numerical value represented by the common logarithm log (1-X) (negative), where the amount of the original virus is 1 and the amount of virus inactivated after the virus inactivation treatment is X. The greater the absolute value, the higher the ability to inactivate the virus. For example, when 99.9% of the original virus is inactivated, the virus inactivity is expressed as log (1−0.999) = − 3.00. The ratio of the amount of virus inactivated after virus inactivation treatment to the total amount of virus before virus inactivation treatment in% (in this case, 99.9%) is referred to as virus inactivity.
The abundance of the functional substance in the surface resin layer in the decorative board of the present invention is preferably 0.03 g / m ² or more. This is because the virus inactivity is equivalent to -4.76 (virus inactivity 99.998%) or superior in antiviral properties, and thus exhibits sufficient antibacterial and antiviral properties. This is because it can be applied to medical applications such as operating rooms that require immediate effects and reproducibility for antiviral functions. In the decorative board of the present invention, when a melamine resin is employed as the surface resin layer and a photocatalyst is employed as the functional substance, the abundance of the photocatalyst is preferably 0.033 to 0.111 g / m ² . This is because it is possible to prevent the photocatalyst from dropping and the melamine resin from deteriorating.

In the decorative board of the present invention, it is desirable that the ceramic particles are exposed and disposed on the surface resin layer, and the functional substance is supported on the exposed surface of the ceramic particles.
When the functional substance is supported on the exposed surface of the ceramic particles, the functional substance does not directly contact the surface resin layer. For this reason, it is possible to prevent deterioration of the surface resin layer due to the functional substance, and it is possible to prevent the functional substance from falling off due to discoloration of the surface resin layer, deterioration of the surface resin layer, or the like. In addition, when the functional substance is supported on the exposed surface of the ceramic particles, the functional substance is not embedded in the surface resin layer and is exposed on the decorative board surface, so that it has antibacterial and antiviral properties. Thus, the original function as a functional substance can be exhibited, and the effect can be maintained for a long time.
Further, an oxidation resistant resin layer made of an oxidation resistant resin may be provided on the surface resin layer, and a functional substance may be supported on the resin layer made of the oxidation resistant resin.
Like the ceramic particles, the functional substance does not directly contact the surface resin layer. For this reason, it is possible to prevent deterioration of the surface resin layer due to the functional substance, and it is possible to prevent the functional substance from falling off due to discoloration of the surface resin layer, deterioration of the surface resin layer, or the like.
As the oxidation resistant resin, a silicone resin or a fluororesin can be used.

In the decorative board of the present invention, it is desirable that the isoelectric point of the ceramic particles is higher than the isoelectric point of the functional substance. The isoelectric point here means that when the concentration of hydrogen ions in the solution is changed, the positive and negative charges of the particles that become the solute become zero as a whole, and the whole particle does not move even when an electric field is applied. Is the hydrogen ion exponent when the average charge is 0, and the value is expressed as pH. This isoelectric point is a value defined by the substance, and as an example, the isoelectric point of the functional substance is often pH 5-6, whereas the ceramic particle has an isoelectric point of the functional substance. What has a higher isoelectric point can be used. In particular, the isoelectric point of the ceramic particles is more preferably pH 7 or higher. The isoelectric point can be measured by electrophoresis (JIS R1638).

Specifically, the ceramic particles are at least one selected from cerium, zirconium, strontium, aluminum, silicon, iron, cobalt, copper, chromium, nickel, tin, cadmium, magnesium, manganese, tungsten, vanadium, yttrium, and the like. Metal oxide or metal hydrate particles containing these metals, aluminum oxide-containing particles, silica-containing particles, and ceramic particles made of diatomaceous earth can be used. Regarding the isoelectric point, 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 water. The isoelectric point of the oxide (Cd (OH) ₂ ) is pH 10.5 or more, the isoelectric point of cadmium oxide (CdO) is pH 7.7, and the isoelectric point of iron hydrate (Fe (OH) ₂ ). Is pH 12, the isoelectric point of iron oxide (Fe ₃ O ₄ ) is pH 12, the isoelectric point of copper oxide (CuO) is pH 9.5, the isoelectric point of copper hydrate (Cu (OH) ₂ ) Has a pH of 7.7. It is desirable that these components are combined so that the isoelectric point of the ceramic particles is higher than the isoelectric point of the functional substance. Among the compounds constituting the above ceramic particles, it is particularly desirable to use aluminum oxide-containing particles.

Ceramic particles have the 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 the opposite cation substance. In other words, the bacteria and viruses present on the surface of the decorative board are attracted to the ceramic particles, and the functional substances carried on the ceramic particles can reduce the bacteria and viruses, and the bacteria and viruses do not grow. It becomes easier to obtain antibacterial and antiviral effects. In the case of particles that are not ceramic particles, the frequency of bacteria and viruses present on the surface layer of the decorative board coming into contact with the functional substance is low, so that the bacteria and viruses remain or multiply, making it difficult to obtain antibacterial and antiviral effects.

Further, the ceramic particles have a property that it is easy to carry functional substances at regular intervals. When a functional substance is supported on particles that are not ceramic particles, the interval between the functional substances tends to be narrow. For this reason, 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, and the antibacterial and antiviral effects are hardly exhibited. On the other hand, since the ceramic particles used in the present invention are carried at regular intervals, there is no decrease in the frequency of contact of the fungus and virus with the functional substance, the fungus and virus are reduced at a desired time, and the antibacterial, Antiviral effect is likely to be manifested. As described above, the ceramic 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 functional substance can completely decompose the fungus or virus or damage a part thereof, so that the fungus or virus can be reduced.
The above-described effect can be obtained by supporting a functional substance on ceramic particles.

In the decorative board of the present invention, it is desirable to use aluminum oxide-containing particles as ceramic particles. Further, specifically, it is desirable to use particles made of either alumina or strontium aluminate as the ceramic particles. Alumina is most easily used among the ceramic particles, and can efficiently use the action of reducing bacteria and viruses described above. In addition, since strontium aluminate has a phosphorescent action, it can sustain the action of reducing bacteria and viruses for a long time even in an environment without light.

In the decorative board of the present invention, the average particle size of the ceramic particles is preferably 0.1 μm to 55 μm.

In the decorative board of the present invention, it is desirable that the ceramic particles be exposed at an area ratio of 5 to 30% with respect to the surface resin layer surface.
If the ceramic particles are exposed at an area ratio of 5% or more with respect to the surface resin layer surface, the functional substance can be sufficiently supported, so that the function of reducing bacteria and viruses can be sufficiently exerted. Can do. Further, if the ceramic particles are exposed at an area ratio of 30% or less with respect to the surface resin layer surface, the ceramic particles carrying the functional substance are firmly bonded to the surface resin layer and are difficult to fall off. And the effect of reducing viruses can be sustained sufficiently.

In the decorative board of the present invention, the functional substance is preferably a photocatalyst, and more preferably a visible light responsive photocatalyst.

In the decorative board of the present invention, the visible light responsive photocatalyst is a platinum-supported titania catalyst, a copper-supported titania catalyst, an iron-supported titania catalyst, a nitrogen-doped titania catalyst, a sulfur-doped titania catalyst, a carbon-doped titania catalyst, or tungsten oxide. It is desirable to be. In particular, the isoelectric point of the visible light responsive photocatalyst is preferably pH 5-6.

In the decorative board of the present invention, the surface resin layer preferably contains a silicone resin and / or a silane coupling agent.

In the decorative board of the present invention, it is desirable to have a dried inorganic sol on the surface of the ceramic particles. This is because the immobilization of the functional substance can be reinforced.

In the decorative board of the present invention, it is desirable that an oxidation-resistant resin layer made of an oxidation-resistant resin is formed on the surface resin layer, and a functional substance is supported on the oxidation-resistant resin layer.
When the oxidation-resistant resin layer is formed on the surface resin layer and the functional substance is supported on the oxidation-resistant resin layer, the functional substance does not directly contact the surface resin layer. For this reason, it is possible to prevent deterioration of the surface resin layer due to the functional substance, and it is possible to prevent the functional substance from falling off due to discoloration of the surface resin layer, deterioration of the surface resin layer, or the like.

In the decorative board of the present invention, the oxidation-resistant resin is preferably at least one selected from a silicone resin or a fluororesin.
Silicone resins and fluororesins are excellent in oxidation resistance and are not easily deteriorated by functional substances.

In the decorative board of the present invention, it is desirable that a silicone resin layer is formed on the surface resin layer, and a functional substance is supported on the silicone resin layer.
If the silicone resin layer is formed on the surface resin layer and the functional substance is supported on the silicone resin layer, the functional substance does not come into direct contact with the surface resin layer. Deterioration of the surface layer resin layer can be prevented, and the functional material can be prevented from falling off due to discoloration of the surface layer resin layer, deterioration of the surface layer resin layer, or the like. Furthermore, since the silicone resin layer is excellent in oxidation resistance, it is not easily deteriorated by a functional substance.

In the decorative board of the present invention, since the abundance of the functional substance in the surface resin layer is 0.02 to 0.21 g / m ² , sufficient antibacterial and antiviral properties are obtained without impairing the design of the decorative board. Can be demonstrated.

FIG. 1 is a schematic cross-sectional view schematically showing a decorative board according to an embodiment of the present invention. FIG. 2 is an explanatory view showing an area portion that is a basis for calculating the area ratio of the exposed portion of the ceramic particles constituting the decorative board of the present invention. Fig.3 (a) is a schematic sectional drawing which shows typically the decorative board which concerns on one Embodiment of this invention, FIG.3 (b) typically shows the decorative board which concerns on other embodiment of this invention. It is a schematic sectional drawing shown. FIG. 4 is a graph showing the relationship between the abundance [g / m ² ] of functional substance (photocatalyst) and virus inactivity.

Hereinafter, the decorative board of the present invention will be described in detail.
FIG. 1 is a schematic cross-sectional view schematically showing a decorative board according to an embodiment of the present invention.

The decorative board 1 of the present invention has a substrate (not shown) and a surface resin layer 12 made of melamine resin or the like laminated on the surface of the substrate, and the ceramic particles 13 are disposed on the surface resin layer 12 so as to be exposed. The functional substance 14 is supported on the ceramic particles 13.

The board | substrate used for the decorative board of this invention is not specifically limited, Incombustible base materials, such as a core paper and a magnesia cement generally used for a decorative board, etc. can be used. The core paper may be a single core or a laminate in which a plurality of core papers are stacked. The number of core papers is not particularly limited, but can 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 phenol resin. Moreover, a core paper and a magnesia cement incombustible base material can be laminated to form a substrate.

The magnesia cement incombustible base material can be used as a substrate by using it alone or by laminating it at the center of the core paper. The magnesia cement incombustible plate is manufactured by mixing magnesium oxide (MgO) and magnesium chloride (MgCl ₂ ), adding aggregate and water, kneading, and forming into a plate shape. 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 surface resin layer on the substrate surface composed of a plurality of or a single core paper and / or magnesia cement incombustible base material is not particularly limited, and can be performed by a general method. For example, a method of laminating melamine resin impregnated paper on one side or both sides of the substrate and hot pressing can be used. If the said method is used, the melamine resin of a melamine resin impregnation paper will osmose | permeate core paper, a curing reaction will advance there, and the adhesive force of the melamine resin impregnation paper with respect to a core paper will express.
The resin that can be used for the surface resin layer constituting the decorative board of the present invention includes melamine resin, diallyl phthalate (DAP) resin, polyester resin, olefin resin, vinyl chloride resin, acrylic resin, epoxy resin, urethane resin. , Phenol resin, silicone resin, guanamine resin and the like. In these, it is desirable to use a melamine resin.

Melamine resin is a resin with improved dimensional stability and toughness without impairing optical and visual properties 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 produced by impregnating a melamine resin with a predetermined impregnation rate in a pattern paper, 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.

In the decorative board of the present invention, abundance of functional materials in the surface resin layer is a 0.02~0.21g / ^{m 2,} desirably 0.025~0.21g / ^{m 2,} 0.03~0 .21g / ^{m 2} and more preferably, more desirably 0.04~0.20g / ^{m 2,} it is preferable that a 0.05~0.19g / ^{m 2.}
When the amount of the functional substance present in the surface resin layer is less than 0.02 g / m ² , the amount of the functional substance is too small, so that virus inactivity is practically required -3.00 or higher. It is not possible to obtain a numerical value indicating that the virus is excellent, and sufficient antibacterial and antiviral properties cannot be exhibited.
When the abundance of the functional substance in the surface resin layer is 0.025 g / m ² or more, the virus inactivity is equal to −4.00 or more excellent in antiviral properties, so that sufficient antibacterial activity is achieved. It can be applied to applications that require immediate effect on antiviral functions (reducing the number of viruses until the infectivity is lost within 4 hours), such as medical applications. Because. When the virus inactivity is equal to −4.00 or superior in antiviral properties, the number is such that the infectivity of influenza virus is not expressed within 4 hours (about 1000 to 3000), and norovirus Can be reduced to a number (100) where no infectivity is manifested.
When the amount of the functional substance in the surface resin layer is 0.03 g / m ² or more, the virus inactivity is equal to or less than −4.76 (virus inactivity 99.998%). Because it is an excellent value, it can exhibit sufficient antibacterial and antiviral properties, and it can be applied to applications that require immediate and reproducible antiviral functions, such as operating rooms, among medical applications. is there.
On the other hand, if the amount of the functional substance present in the surface resin layer exceeds 0.21 g / m ² , the amount of the functional substance is too large and the appearance of the decorative board may be impaired. In addition, the antiviral function is also reduced.

In the decorative board of the present invention, it is desirable that the ceramic particles are exposed and disposed on the surface resin layer, and the functional substance is supported on the exposed surface of the ceramic particles.
When the functional substance is supported on the exposed surface of the ceramic particles, the functional substance does not directly contact the surface resin layer. For this reason, it is possible to prevent deterioration of the surface resin layer due to the functional substance, and it is possible to prevent the functional substance from falling off due to discoloration of the surface resin layer, deterioration of the surface resin layer, or the like. In addition, when the functional substance is supported on the exposed surface of the ceramic particles, the functional substance is not embedded in the surface resin layer and is exposed on the decorative board surface, so that it has antibacterial and antiviral properties. Thus, the original function as a functional substance can be exhibited, and the effect can be maintained for a long time.
Further, an oxidation resistant resin layer made of an oxidation resistant resin may be provided on the surface resin layer, and a functional substance may be supported on the resin layer made of the oxidation resistant resin.
Like the ceramic particles, the functional substance does not directly contact the surface resin layer. For this reason, it is possible to prevent deterioration of the surface resin layer due to the functional substance, and it is possible to prevent the functional substance from falling off due to discoloration of the surface resin layer, deterioration of the surface resin layer, or the like.
As the oxidation resistant resin, a silicone resin or a fluororesin can be used.
Specifically, silicone resins described in International Publication Nos. 2012/117929 and 2014/0773341, commercially available silicone resins, and the like can be used as the silicone resin.

The ceramic particles are not particularly limited as long as the particles have an isoelectric point higher than that of the functional substance and can support the functional substance, but are preferably aluminum oxide-containing particles. Specifically, it is desirable to use particles made of either alumina or strontium aluminate as the ceramic particles.

In the decorative board of the present invention, the average particle size of the ceramic particles is preferably 0.1 to 55 μm, and more preferably 0.5 to 5 μm. If the average particle size of the ceramic particles is less than 0.1 μm, the ceramic particles tend to be embedded in the surface resin layer, and the functional substance tends to be less likely to be supported on the ceramic particles, and the average particle size of the ceramic particles is 55 μm. If it exceeds, ceramic particles may fall off or irregularities may be formed on the surface resin layer, which tends to cause defects in the appearance and design of the decorative board. When the average particle diameter of the ceramic particles is 0.5 to 5 μm, the functionality as a functional substance is exhibited, and there is no problem in the appearance and design of the decorative board.

In the decorative board of the present invention, it is desirable that the ceramic particles be exposed at an area ratio of 5 to 30% with respect to the surface resin layer surface.
If the ceramic particles are exposed at an area ratio of 5% or more with respect to the surface resin layer surface, the functional substance can be sufficiently supported, so that the function of reducing bacteria and viruses can be sufficiently exerted. Can do. Further, if the ceramic particles are exposed at an area ratio of 30% or less with respect to the surface resin layer surface, the ceramic particles carrying the functional substance are firmly bonded to the surface resin layer and are difficult to fall off. And the effect of reducing viruses can be sustained sufficiently.
With reference to FIG. 2, the area part that is the basis for calculating the area ratio of the exposed part of the ceramic particles will be described.
The area ratio in the decorative board of the present invention means the ratio of the total surface area B of the surface resin layer on which the ceramic particles 13 are exposed to the surface area A of the entire surface resin layer in FIG. If the ceramic particles are exposed to an area ratio of less than 5% with respect to the surface resin layer surface, the functionality of the functional substance tends to be insufficient.

In the decorative board of the present invention, the functional substance is desirably a functional material having functions such as antibacterial properties, antiviral properties, antiallergenic properties, and deodorizing properties. For example, examples of the antibacterial and antiviral functional substances include visible light responsive photocatalysts. Specific examples of the visible light responsive photocatalyst include, for example, a titanium oxide carrying a platinum group such as platinum, palladium, rhodium and ruthenium, iron, copper and the like.
In the decorative board of the present invention, the visible light responsive photocatalyst is a platinum-supported titania catalyst, a copper-supported titania catalyst, an iron-supported titania catalyst, a nitrogen-doped titania catalyst, a sulfur-doped titania catalyst, a carbon-doped titania catalyst, or tungsten oxide. It is desirable that the catalyst be a copper-supported titania catalyst. Examples of the copper-supported titania catalyst include anatase-type titanium oxide containing copper in a range of CuO / TiO ₂ (weight% ratio) = 1.0 to 3.5 described in JP-A-2006-232729. Photocatalyst composition in which cuprous oxide (copper oxide (I): Cu ₂ O) and titanium oxide described in Japanese Unexamined Patent Publication No. 2012-210557 are combined, and monovalent copper described in Japanese Patent Application Laid-Open No. 2013-166705 Titanium oxide carrying a mixture containing a compound and a divalent copper compound on the surface, and copper containing titanium oxide containing crystalline rutile-type titanium oxide and divalent copper compound described in International Publication No. 2013/094573 And titanium-containing compositions.

In the decorative board of the present invention, the surface resin layer may contain a silicone resin and / or a silane coupling agent. As the silicone resin, for example, a silicone resin, a 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.
The surface layer resin layer may constitute a pattern layer by impregnating and curing the above-described melamine resin or the like on pattern paper obtained by printing a pattern or color on titanium paper. The surface resin layer is formed by laminating a transparent paper having a filler (inorganic particles such as titanium oxide, talc and calcium carbonate) impregnated with the above-described melamine resin and the like onto a pattern layer. An overlay layer may be configured. Further, a backer layer may be provided on the back surface of the substrate made of a non-combustible base material made of a plurality or a single core paper and / or magnesia cement or the like to prevent warping.

As the silane coupling agent, for example, 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 desirable. Examples of the silane coupling agent include vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriisopropoxysilane, allyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2- (3,4 -Epoxycyclohexyl) ethyltrimethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane , 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, diallyldimethylsilane, 3-mercaptopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, etc. It is.

In the decorative board of the present invention, it is desirable to have a dried inorganic sol on the surface of the ceramic particles. After attaching the inorganic sol to the surface layer of the ceramic particles, the functional substance is supported and dried to fix the functional substance with the dried body of the inorganic sol, thereby fixing the functional substance more firmly. Because it can. As the inorganic sol, silica sol, alumina sol, silica-alumina sol, and the like can be used, and it is desirable to use silica sol.

In the decorative board of the present invention, a silicone resin layer made of a silicone resin may be formed on the surface resin layer, and a functional substance may be supported on the silicone resin layer.
If the silicone resin layer is formed on the surface resin layer and the functional substance is supported on the silicone resin layer, the functional substance does not come into direct contact with the surface resin layer. Deterioration of the surface layer resin layer can be prevented, and the functional material can be prevented from falling off due to discoloration of the surface layer resin layer, deterioration of the surface layer resin layer, or the like. Furthermore, since the silicone resin layer is excellent in oxidation resistance, it is not easily deteriorated by a functional substance.

Next, the manufacturing method of the decorative board of this invention is demonstrated.
First, a surface resin layer is formed on a substrate surface made of a plurality of or a single core paper and / or a magnesia cement incombustible base material. Since the said board | substrate, its manufacturing method, and the said surface layer resin layer were demonstrated in description of the decorative board of this invention, it abbreviate | omits here.

As described in the decorative board of the present invention, the method of forming the surface resin layer on the substrate surface is not particularly limited and can be performed by a general method. As a specific method for forming the surface resin layer, for example, a lamination step of laminating a resin-impregnated paper such as a melamine resin on one or both sides of a substrate made of a core paper laminate, and a resin-impregnated paper such as a melamine resin are laminated. And a method including a hot-pressure forming step of hot-pressing the formed substrate. If the said method is used, the melamine resin of a melamine resin impregnation paper will osmose | permeate core paper, a curing reaction will advance there, and the adhesive force of the melamine resin impregnation paper with respect to a core paper will express.

As a heating condition at the time of hot pressing, the temperature of the decorative board can be 125 to 150 ° C., and as a pressing condition, 1.96 to 9.80 MPa (20 to 100 kg / cm ² ). Can do. When the temperature is less than 125 ° C. or when the pressure is less than 1.96 MPa, the adhesion of the resin-impregnated paper to the substrate is insufficient, and peeling tends to occur. On the other hand, when the temperature exceeds 150 ° C. or when the pressure exceeds 9.80 MPa, cracks may occur.

As a method of fixing the ceramic particles to the surface resin layer surface having the surface resin layer on the substrate, for example, a method of spraying a spray liquid containing the ceramic particles on the surface resin layer surface, drying and then thermocompression bonding can be taken. it can. By the above method, the ceramic particles can be exposed and fixed on the resin surface.

In the decorative board manufacturing method of the present invention, when ceramic particles are thermocompression bonded to the surface resin layer surface, a release cushion material made of polyethylene terephthalate (PET) is interposed between the ceramic particle spray surface and the thermocompression press surface. Can be done. This can prevent the ceramic particles from being buried in the surface resin layer, and can be exposed and fixed on the surface of the surface resin layer.

As another production method of the decorative board of the present invention, spray liquid containing ceramic particles is sprayed on the transfer film, and then the ceramic particle adhesion surface of the transfer film is opposed to the resin surface of the substrate having the surface resin layer, A method of thermally transferring ceramic particles can be mentioned.

When the surface resin layer contains a silicone resin and / or silane coupling agent, the silicone resin and / or the surface resin layer is added to the surface resin layer by including the silicone resin and / or silane coupling agent in the melamine resin solution. A method of impregnating with a silane coupling agent can be used.

As a method of supporting the functional substance on the surface of the ceramic particles exposed and fixed on the surface of the surface resin layer, for example, a solution containing the functional substance is applied to the surface resin layer on which the ceramic particles are fixed by spraying or the like. And a method of removing the solvent.
The amount of the functional substance applied to the surface resin layer can be calculated from the amount of the solution containing the used functional substance.

Moreover, the abundance of the functional substance applied to the decorative board can be measured as follows. First, the functional substance carried on the surface of the decorative board is separated. Any method can be used as long as the functional substance can be dissolved, but the functional substance is eluted from the surface of the decorative board using hydrofluoric acid, hot concentrated sulfuric acid, dissolved alkali salt, or the like. .
Subsequently, the content is analyzed by ICP (inductively coupled plasma) emission spectroscopy using the obtained eluate.
Since titanium oxide and copper are functional substances in the copper-supported titania catalyst, the sum of the value obtained by multiplying the titanium oxide content by the oxide coefficient and the value obtained by multiplying the copper content by the oxide coefficient is functional. The content of the substance. Further, the abundance can be obtained by dividing the content of the functional substance by the analyzed area of the decorative board. The oxide coefficient is the ratio of the measured element to the oxide composition formula.

Fig.3 (a) is a schematic sectional drawing which shows typically the decorative board which concerns on one Embodiment of this invention, FIG.3 (b) typically shows the decorative board which concerns on other embodiment of this invention. It is a schematic sectional drawing shown.
When the surface resin layer contains a silicone resin and / or a silane coupling agent, water repellency can be imparted to the surface of the melamine resin or the like. When the functional substance is supported on the exposed surface of the ceramic particles, as schematically shown in FIG. 3A, when the surface resin layer 12 does not contain a silicone resin and a silane coupling agent, ceramic The functional substance 14 may adhere to the surface resin layer surface 15 as well as the particle 13 surface. On the other hand, as schematically shown in FIG. 3B, when the surface resin layer 12 contains a silicone resin and / or a silane coupling agent, the surface layer contains a silicone resin and / or a silane coupling agent. Due to the water repellency of the resin layer surface 16, the functional substance 14 avoids the surface of the surface resin layer 12 and adheres as much as possible to the surface of the ceramic particles 13, so that the functional substance 14 directly contacts the surface of the surface resin layer 12. The amount of substance 14 can be further reduced. Moreover, when a surface layer resin layer contains a silane coupling agent, sclerosis | hardenability can be provided to a melamine resin etc., and when ceramic particles are thermocompression-bonded, it can prevent being embedded in a surface layer resin layer.

By including a silicone resin and / or a silane coupling agent in the surface resin layer, the ceramic particles can be immobilized without being buried, and there is an effect of making it difficult for the functional substance to adhere to the surface resin layer. Specifically, even if the functional substance that has become excessive during the process adheres to the surface resin layer, it can be easily removed after the cleaning process. Furthermore, contaminated water containing bacteria, viruses, and the like is easily attracted to hydrophilic ceramic particles and functional substances, and functionality is easily developed. In particular, when a melamine resin is used for the surface resin layer, it is easy to obtain the above actions and effects.

Furthermore, in the method for producing a decorative board of the present invention, it is desirable to attach an inorganic sol to the surface layer of the ceramic particles. This is because the immobilization of the functional substance can be reinforced. As the inorganic sol, silica sol, alumina sol, silica-alumina sol and the like can be used, and it is desirable to use silica sol.

Example 1
(Primary melamine impregnation process)
A paper roll having a thickness of 0.2 to 0.3 mm was immersed in a solution containing a melamine resin. The roll paper was impregnated with melamine resin 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 2 minutes. The moving speed of the roll paper was 10 to 20 cm / second.
(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 which passed through the drying process was immersed in a solution made of melamine resin. The paper roll was impregnated with the melamine resin 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. The moving speed of the roll paper was 10 to 20 cm / second.
(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 hours. After drying, it was cut into 910 mm × 1820 mm.

(Alumina particle spray process)
A spray solution comprising γ-alumina particles having an average particle size of 0.5 μm and ethanol was prepared. The spray liquid was filled into the spray at room temperature and sprayed on the cut melamine resin-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 sheets of 0.3 to 0.4 mm thick phenol resin-impregnated core paper are laminated, and the melamine resin-impregnated paper sprayed with the alumina particles obtained by the above process is laminated on the outer surface of the melamine resin-impregnated paper. The release cushion material made of PET is interposed between the press surface of the press machine and the alumina particle sprayed surface of the melamine resin-impregnated paper, and the temperature is 143 ° C., the press pressure is 80 kg / cm ² , the press time (temperature rise) Thermocompression bonding was performed in 50 minutes (including time). Thereby, the alumina particles were exposed and fixed on the melamine resin impregnated layer.

(Photocatalyst loading process)
A slurry in which a photocatalyst of CuO—TiO _{2 having} an average particle diameter of 100 nm is dispersed in water (solid content concentration: 25% by weight) and silica sol (SiO ₂ concentration: 3% by weight) are in a weight ratio of 4.5: 5.5. A methanol mixed solution (photocatalyst concentration of 0.05% by weight) was prepared. Using a spray on a substrate having a melamine resin impregnated layer on the surface of which alumina particles obtained in the above step are arranged, the methanol mixed solution has a photocatalyst abundance (solid content weight) of 0.111 g / m ² . This was coated and dried at 25 ° C. for 12 hours to complete the production of the decorative board having the photocatalyst supported on the exposed surface of the alumina particles.

(Example 2)
The application amount of the methanol mixed solution in the (photocatalyst carrying step) was changed to Example 2 in the same procedure as Example 1 except that the amount of photocatalyst present (solid weight) was changed to 0.056 g / m ^2. The production of such decorative panels was completed.

(Comparative Example 1)
The application amount of the methanol mixed solution in the (photocatalyst supporting step) was changed to Comparative Example 1 in the same procedure as in Example 1 except that the amount of photocatalyst present (solid content weight) was 0.220 g / m ^2. The production of such decorative panels was completed.

(Examples 3 to 10)
Is similar to Example 1, the coating amount of methanol mixed solution in (a photocatalyst supporting step), the abundance of a photocatalyst (solid weight) of ^{0.021g / m 2, 0.025g / m} 2, 0.029g ^{/ m 2, 0.033g / m 2} , 0.071g / m 2, 0.210g / m 2, 0.100g / m 2, were respectively changed so that 0.050 g / ^{m 2.}

(Comparative Example 2)
Although it is the same as that of Example 1, the coating amount of the methanol mixed solution in the (photocatalyst supporting step) was changed so that the amount of the photocatalyst present (solid content weight) was 0.500 g / m ² .

(Comparative Example 3)
Although it is the same as that of Example 1, the coating amount of the methanol mixed solution in the (photocatalyst supporting step) was changed so that the amount of the photocatalyst present (solid content weight) was 0.010 g / m ² .

(Evaluation of design properties)
The appearance of the decorative board according to each example and comparative example was visually observed to confirm that there was no problem.

(Antiviral evaluation)
In order to evaluate the antiviral properties of the decorative plates carrying the photocatalysts obtained in each of the examples and comparative examples, the antiviral properties were measured according to the antiviral properties test method of the visible light responsive photocatalytic material. went. The measurement result is expressed as the concentration of virus inactivated against E. coli. Here, the concentration of virus inactivated against E. coli (virus inactivity) was used as an indicator of virus concentration. Virus inactivity is an antiviral test using bacteriophage, and the concentration of virus capable of infecting E. coli is measured by using phage virus Qβ concentration: 8.3 million / ml. It is the result of having calculated the density | concentration of the virus inactivated with respect to it. That is, the virus inactivity is a degree of concentration at which E. coli cannot be infected with respect to the phage virus Qβ concentration, and (phage virus Qβ concentration−virus concentration capable of infecting E. coli) / (phage virus Qβ concentration) × 100. It can be said that the higher the virus inactivity value (the higher the absolute value of virus inactivity), the better the antiviral properties. The virus inactivity is determined from the virus inactivity, and the results are shown in Table 1 and FIG. 4 together with the abundance [g / m ² ] of the functional substance (photocatalyst).
For Examples 1 and 2, the result was that the virus inactivity was 99.99% or more (the virus inactivity is equal to or greater than −4.00, and the antiviral property is better than that). It was.
Moreover, about the comparative example 1, it was confirmed that a virus inactivity is 99.968% (a virus inactivity is -3.50).

From the result of Table 1, it has confirmed that the decorative board of this invention was excellent in antiviral property, and did not impair the designability.
FIG. 4 shows a graph showing the relationship between the abundance [g / m ² ] of the functional substance (photocatalyst) and the virus inactivity. Examples 3 to 10 are indicated by ◯, and Comparative Examples 1 to 3 are indicated by ×. From FIG. 4, in order to exhibit a function exceeding the virus inactivity of −3.00 and prevent appearance problems such as whitening, the supported amount of the photocatalyst is 0.02 g / m ^{2 to} 0.00. It can be seen that it is necessary to adjust to 21 g / m ² .

DESCRIPTION OF SYMBOLS 1 Decorative board 12 Surface resin layer 13 Ceramic particle 14 Functional substance 15 Surface resin layer surface 16 Surface resin layer surface A containing a silicone resin and / or a silane coupling agent Surface area B of the entire surface resin layer The ceramic particles are exposed Total surface area of the existing surface resin layer

The present invention relates to an antiviral decorative board.

Claims (15)

A substrate,
A surface resin layer laminated on one or both surfaces of the substrate;
A functional substance present on the surface resin layer,
The decorative board, wherein the amount of the functional substance present in the surface resin layer is 0.02 to 0.21 g / m ² . Decorative plate according to claim 1 abundance of said functional material is 0.03~0.21g / ^{m 2.} Furthermore, on the surface resin layer, ceramic particles are exposed and arranged,
The decorative board according to claim 1 or 2, wherein the functional substance is carried on an exposed surface of the ceramic particles. The decorative board according to claim 3, wherein the ceramic particles are aluminum oxide-containing particles. The decorative board according to claim 3 or 4, wherein the ceramic particles are particles made of either alumina or strontium aluminate. 6. The decorative board according to claim 3, wherein the ceramic particles have an average particle diameter of 0.1 μm to 55 μm. The said ceramic particle is a decorative board as described in any one of Claims 3-6 which are exposed with the area rate of 5-30% with respect to the said surface resin layer surface. The decorative board according to any one of claims 3 to 7, which has a dried inorganic sol on the surface layer of the ceramic particles. The decorative board according to any one of claims 1 to 8, wherein the functional substance is a photocatalyst. The decorative board according to claim 1, wherein the functional substance is a visible light responsive photocatalyst. The said visible light responsive photocatalyst is a platinum carrying | support titania catalyst, a copper carrying | support titania catalyst, an iron carrying | support titania catalyst, a nitrogen dope titania catalyst, a sulfur dope titania catalyst, a carbon dope titania catalyst, or a tungsten oxide of Claim 10. Decorative board. The said surface layer resin layer is a decorative board as described in any one of Claims 1-11 containing a silicone resin and / or a silane coupling agent. An oxidation resistant resin layer made of an oxidation resistant resin is formed on the surface resin layer, and a functional substance is supported on the oxidation resistant resin layer. The decorative board as described. The decorative board according to claim 13, wherein the oxidation-resistant resin is at least one selected from a silicone resin or a fluororesin. The decorative board according to any one of claims 1 to 12, wherein a silicone resin layer is formed on the surface resin layer, and a functional substance is supported on the silicone resin layer.

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