JP2023007526A - Composition, transfer sheet, melamine resin overlayed board and method for producing melamine resin overlayed board - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a composition that enables substances having deodorizing, anti-viral, or anti-allergen functions to be uniformly dispersed, offering excellent functionality.

SOLUTION: A composition includes (A) a hydrolytic condensate of silicon alkoxide, (B) organosilica sol dispersed in a hydrophilic solvent, (C) and an acrylic polymer having a hydrophilic group and a hydrophobic group. A melamine resin overlayed board includes a core layer, a decorative layer, and a cured layer of the composition, in the stated order. The decorative layer includes a cured product of a melamine resin layer.

SELECTED DRAWING: Figure 1

COPYRIGHT: (C)2023,JPO&INPIT

Description

[Cross reference to related applications]
This international application claims priority based on Japanese Patent Application No. 2020-76030 filed with the Japan Patent Office on April 22, 2020. The entire contents are incorporated by reference into this international application.

TECHNICAL FIELD The present disclosure relates to a composition, a transfer sheet, a decorative melamine laminate, and a method for making a decorative melamine laminate.

A decorative melamine board is obtained by using a melamine resin-containing patterned paper as a design layer, and heating and pressurizing the melamine resin-containing patterned paper and a core material such as a ferr resin-impregnated paper with a press. The melamine decorative board can be finished in various ways by changing the pattern, color tone, etc. of the pattern paper.

Such a melamine decorative board is widely used for furniture such as counters and desks, interior materials such as walls and floors, and the like, because of its excellent physical properties such as surface hardness, heat resistance and abrasion resistance.

In recent years, melamine decorative panels are prone to attracting fingerprints and oil stains, and as airtightness increases in houses, there are concerns about living odors. There is a growing demand for cleaner environments.

JP 2012-176515 A JP 2017-205928 A JP 2018-27694 A

The applicant has disclosed a decorative panel (Patent Document 1) having anti-fingerprint properties and oil-wiping properties. In some cases, sufficient odor was not obtained. In addition, the applicant discloses a decorative board (Patent Document 2) that imparts deodorant performance and reduces household odors and chemical odors, but the method of Patent Document 2 imparts antiviral or antiallergenic properties In some cases, it was difficult to evenly apply the substance to the surface, and sufficient antiviral or antiallergenic properties could not be obtained.

One aspect of the present disclosure is a composition comprising (A) a hydrolytic condensate of silicon alkoxide, (B) an organosilica sol dispersed in a hydrophilic solvent, and (C) a hydrophilic group and a hydrophobic group. It comprises an acrylic polymer and at least one substance selected from the group consisting of (m) a deodorant substance, (n) an antiviral substance, and (o) an antiallergenic substance.

One aspect of the present disclosure is a transfer sheet comprising a sheet-like substrate and a cured layer of the composition described above formed on one side of the sheet-like substrate.

One aspect of the present disclosure is a decorative melamine board that includes, in this order, a core layer, a decorative layer, and a cured layer of the composition described above. The decorative layer contains a cured melamine resin layer.

One aspect of the present disclosure is a method for manufacturing a decorative melamine board, and the decorative melamine board includes, in this order, a core layer, a decorative layer containing a cured product of a melamine resin, and a surface layer. A method for manufacturing a decorative melamine board includes curing the composition described above to form a surface layer.

According to one aspect of the present disclosure, a substance exhibiting functionality such as deodorant, antiviral, and antiallergenic properties (hereinafter referred to as a substance exhibiting functionality) can be uniformly dispersed, A composition is provided.

Further, according to one aspect of the present disclosure, there are provided a transfer sheet and a decorative melamine board containing a cured product of such a composition and having excellent functionality, and a method for producing the decorative melamine board.

FIG. 2 is a cross-sectional view of the configuration of the melamine decorative board of Example 1. FIG. FIG. 11 is a cross-sectional view of the configuration of the melamine decorative board of Example 32; FIG. 10 is a cross-sectional view of the configuration of the melamine decorative board of Example 94;

The present disclosure will be described in detail below.

(A) The hydrolyzed condensate of silicon alkoxide forms a lattice-like skeleton, and when the function-expressing substance described later is added, it is uniformly dispersed, and the addition of a small amount of the function-expressing substance exerts its effect. Specific silicon alkoxides include those having a structure (n is an integer) represented by the following chemical formula 1. More specifically, tetramethyl orthosilicate (Si(OCH ₃ ) ₄ ), tetraethyl orthosilicate ( Si(OC ₂ H ₅ ) ₄ ) and tetrapropyl orthosilicate (Si(OC ₃ H ₇ ) ₄ ). Silicon alkoxides are mainly synthesized by reaction of silicon tetrachloride and alkyl alcohol, or reaction of metallic silicon and alkyl alcohol.
<Chemical Formula 1>

ケイ素アルコキシドと水とを混合させ反応させると、化学式２に示す反応式（ｍは整数）に従って加水分解が進行する。加水分解液を安定させるために、メタノール、エタノール、イソプロパノール、エチルセロソルブ、混合アルコール等が溶媒として用いられる。
＜化学式２＞

When silicon alkoxide and water are mixed and reacted, hydrolysis proceeds according to the reaction formula (m is an integer) shown in Chemical Formula 2. Methanol, ethanol, isopropanol, ethyl cellosolve, mixed alcohols, etc. are used as solvents to stabilize the hydrolyzate.
<Chemical Formula 2>

ケイ素アルコキシドの加水分解縮合物の市販品としては、「ＨＡＳ－１」（ＳｉＯ_２含有量２０．７～２１．５質量％、エタノール／イソプロパノール／メタノール混合溶媒）、「ＨＡＳ－６」（ＳｉＯ_２含有量１７．６～１８．４質量％、エタノール／メタノール混合溶媒）、「ＨＡＳ－１０」（ＳｉＯ_２含有量１０．０～１０．４質量％、エタノール／イソプロパノール／メタノール混合溶媒）（以上は商品名であり、コルコート株式会社製である。）が挙げられる。

Commercially available hydrolytic condensates of silicon alkoxides include "HAS-1" (SiO ₂ content: 20.7 to 21.5% by mass, ethanol/isopropanol/methanol mixed solvent), "HAS-6" (SiO ₂ content 17.6-18.4% by mass, ethanol/methanol mixed solvent), "HAS-10" (SiO ₂ content 10.0-10.4% by mass, ethanol/isopropanol/methanol mixed solvent) (above It is a trade name and is manufactured by Colcoat Co., Ltd.).

The (B) component organosilica sol is, for example, a colloidal solution in which colloidal silica having an average particle size of 1 to 40 nm (more preferably an average particle size of 7 to 30 nm) is stably dispersed in an organic solvent. The silica concentration is preferably in the range of 1 to 50% by mass, more preferably 40% by mass or less to prevent gelation. The average particle size of colloidal silica is the particle size at an integrated value of 50% in the particle size distribution determined by the laser diffraction/scattering method.

Commercial products of organosilica sol include "IPA-ST", "IPA-ST-ZL", "methanol silica sol", "NPC-ST-30", "MEK-AC-2140Z" manufactured by Nissan Chemical Industries, Ltd., "EG-ST", "DMAC-ST", etc., "OSCAL" manufactured by Catalysts and Chemicals Co., Ltd., "Quatron (registered trademark)" manufactured by Fuso Chemical Industry Co., Ltd., "Highlink (registered trademark)" manufactured by Clariant Japan Co., Ltd. ) OG silica organosol” and the like.

Among organic solvents, the organosilica sol dispersed in a hydrophilic solvent has a sufficient amount of hydroxyl groups on the surface of the silica particles, and the hydroxyl groups on the surface of the silica particles adhere to the melamine resin, resulting in excellent surface durability of the decorative board. . In an organosilica sol dispersed in a hydrophobic solvent, the amount of hydroxyl groups on the silica surface is insufficient, and the adhesion of the melamine resin layer tends to be poor.

Here, a hydrophilic (polar) solvent is a solvent having an affinity for water, for example, a hydrophilic organic solvent having a hydrophilic group such as a hydroxyl group, a carboxyl group, or a carbonyl group in its molecule. Hydrophilic (polar) solvents include protic polar solvents and aprotic polar solvents. Specific examples of protic polar solvents include alcohol solvents such as methyl alcohol, ethyl alcohol, isopropanol, ethylenedialcohol and propanol, and cellosolve solvents such as methyl cellosolve, ethyl cellosolve, butyl cellosolve and n-propyl cellosolve. Aprotic polar solvents include acetone, dimethylsulfoxide (DMSO), N,N-dimethylformamide (DME), pyridine and the like.

The acrylic polymer of component (C) is preferably a copolymer of a monomer having a hydrophilic group that exhibits affinity with the pigment and a monomer having a hydrophobic group that controls compatibility and forms steric hindrance. . In such an acrylic polymer, the hydrophilic group adsorbs the functional substance, and the hydrophobic group suppresses aggregation, thereby uniformly dispersing the functional substance. In fact, the organosilica sol having a particle size of about 20 to 30 nm aggregates to form an aggregate having a large particle size of 600 to 1000 nm, but by being uniformly dispersed, the cured layer of the functional composition The scattering property is enhanced, and appearance defects due to light interference can be reduced.

The hydrophilic group includes an anionic group such as a carboxyl group, a sulfonic acid group and a phosphoric acid group, and a cationic group such as an amino group and an ammonium group. Acrylamide, methacrylic acid, poly(ethylene glycol) acrylates and methacrylates, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, t-butylaminoethyl methacrylate, dimethylaminoethyl acrylate, diethylaminoethyl acrylate, methacrylamide, dimethacrylamide, dimethylaminopropyl methacryl amide, ethylene glycol methacrylate phosphate, 2-(methacryloyloxy)methyl phthalate, 2-(methacryloyloxy)ethyl succinate, 3-sulfopropyl methacrylate, 3-sulfopropyl acrylate and the like.

Hydrophobic groups include alkyl groups and phenyl groups. Specifically, monomers having a hydrophobic group include methyl methacrylate, butyl methacrylate, hexyl acrylate, hexylethyl acrylate, benzyl acrylate, benzyl methacrylate, phenoxyethyl acrylate, phenoxyethyl methacrylate, mixtures thereof, and the like. is mentioned.

In the composition described above, the component (B) organosilica sol is 0.5 to 12 parts by mass, more preferably 1 to 12 parts by mass, based on 1 part by mass (in terms of solid content) of the silicon alkoxide hydrolysis condensate of the component (A). It is preferable to mix 9 parts by mass. When the blending ratio of component (A) is equal to or higher than the lower limit, the functional expression effect is improved, and when it is equal to or lower than the upper limit, solvent resistance is improved.

The acrylic polymer having a hydrophilic group and a hydrophobic group of component (C) is 0.005 to 0.3 parts by mass, more preferably 0.01 to 0 It is preferable to blend 0.07 parts by mass (in terms of solid content). If the blending ratio of component (C) exceeds the upper limit, the cohesiveness of colloidal silica increases. can be suppressed. In addition, when the blending ratio of the component (C) is at least the lower limit, the blended solution has a suitable viscosity, and a uniform low refractive index layer can be molded. melamine decorative board.

A composition containing (A) a hydrolytic condensate of silicon alkoxide, (B) an organosilica sol dispersed in a hydrophilic solvent, and (C) an acrylic polymer having a hydrophilic group and a hydrophobic group has the function of adding Improves the dispersibility of the expressed substance. Specifically, since the function-expressing substance penetrates into the grid-like coating structure of component (A), the function-expressing substance can be uniformly coated, and even a small amount of addition can efficiently exert its function. become. In particular, such an effect is likely to be obtained when the function-exhibiting substance contains solid particles, specifically solid particles having an average particle diameter of 200 to 5000 nm. The average particle size referred to here is the particle size at an integrated value of 50% in the particle size distribution determined by the laser diffraction/scattering method.

The functional substance is preferably at least one selected from the group consisting of (m) deodorant substance, (n) antiviral substance, and (o) antiallergenic substance. It is preferable to mix the above-described composition with the function-expressing substance and stir the mixture with a homogenizer at 6000 to 10000 rpm for 5 to 10 minutes. The homogenizer presses the composition to a high pressure, and a strong shearing force is applied to the composition when it passes through the slit (gap).

Next, the (m) deodorizing substance that exhibits deodorizing properties will be described as an example of the function-exhibiting substance. Porous materials, for example, physical adsorption type deodorizing substances such as activated carbon, exhibit a deodorizing effect by adsorbing odors (gases) in the pores of the porous materials. Physically adsorbing deodorant substances may re-release the adsorbed gas due to a decrease in adsorption performance when exposed to heat such as high-temperature heat or frictional heat after adsorbing gas at room temperature. .

On the other hand, chemisorption-type deodorant substances remove odors by converting them into other substances through chemical reactions such as neutralization, oxidation, and reduction by acids and alkalis. Once adsorbed and decomposed into other substances, it is less likely to be re-released, so it can be used favorably. Chemically adsorbed deodorants include silica (silicon dioxide), copper oxide, alumina, titanium oxide, zinc oxide, iron oxide, metal oxides such as zirconium oxide, zirconium hydroxide, magnesium hydroxide, and aluminum hydroxide. , ferrous hydroxide, and copper hydroxide.

The (m) deodorizing substances that exhibit these deodorizing properties include melamine decorative sheets with excellent heat resistance and abrasion resistance, and living odors generated in the house, namely, acidic odors, neutral odors, and It is preferable to use the chemically adsorbed deodorizing substance described above because it can deal with complex odors of basic odors. Houses in recent years are designed to be highly airtight and highly insulated compared to the past, and are closed spaces with no gaps. Therefore, it is easier to feel the smell of daily life. In order to suppress such living odors, commercially available deodorant products are generally used. However, the melamine decorative board itself has a deodorant property, so that the daily life odor can be further reduced.

Specifically, at least one selected from the group consisting of zinc oxide, silica, zeolite, copper oxide, and zirconium oxide is preferable as the chemisorption type deodorizing substance. For example, it is preferable to use both zinc oxide and silica as metal oxides, and the mixing ratio of the former to the latter is 45 to 85:55 to 15 by mass. The deodorizing substance is particularly preferably in the form of fine particles, specifically those having an average particle size of 0.2 to 10 μm, because of their good dispersibility in the composition. The average particle size referred to here is the particle size at an integrated value of 50% in the particle size distribution determined by the laser diffraction/scattering method. In particular, modified silica, such as amino-modified silica, is effective against neutral odors such as acetaldehyde and formaldehyde and basic odors such as ammonia trimethylamine. is preferably zinc oxide because of its high deodorant effect. The zeolite may also be a zeolite silver-containing material (ie, a zeolite containing silver).

The amount of (m) the deodorizing substance in the composition is preferably 30 to 60 parts by mass (in terms of solid content) per 100 parts by mass of the solid content of the composition. (m) If the content of the deodorizing substance is less than the lower limit, the deodorizing effect tends to be reduced, and if it exceeds the upper limit, uneven whitening tends to occur on the surface of the decorative melamine laminate. The term "uneven whitening" as used herein refers to a state in which the surface of the melamine decorative board is partially blurred with a whitish appearance.

Next, the (n) antiviral substance that exhibits antiviral properties will be described in detail as an example of the substance exhibiting function. As an antiviral substance, there is a photocatalyst in which titanium oxide and the like are mainly used. Photocatalysts can inactivate viruses by generating active oxygen from the excitation light of light, and in principle can exert their effect semipermanently, but they have the disadvantage that they cannot exert their performance without light irradiation.

On the other hand, organic antiviral substances destroy the outer membrane of viral proteins, and the proteins whose outer membrane is destroyed are inhibited in protein synthesis. Alternatively, organic antiviral substances denature proteins and inactivate viruses. Organic antiviral substances are characterized in that they exhibit their effects more quickly than photocatalytic substances.

The organic antiviral substance is preferably at least one selected from the group consisting of triazine-imidazole-thiazole substances, amino-modified polyvinyl alcohol, and amino-modified acrylic polymers. These organic antiviral substances are suitable for decorative melamine laminates that require solvent resistance and stain resistance. The organic antiviral substance is particularly particulate, specifically selected from the group consisting of triazine-imidazole-thiazole-supported particles, amino-modified polyvinyl alcohol particles, and amino-modified acrylic polymer particles. At least one is preferred. The average particle size of the particulate organic antiviral substance is preferably 0.5 to 3 μm because of its good dispersibility in the composition. The average particle size referred to here is the particle size at an integrated value of 50% in the particle size distribution determined by the laser diffraction/scattering method.

The amount of the (n) antiviral substance in the composition is preferably 35 to 75 parts by mass (in terms of solid content) per 100 parts by mass of the solid content of the composition. (n) If the amount of the antiviral substance is less than the lower limit, the antiviral effect tends to be reduced, and if the amount exceeds the upper limit, uneven whitening occurs on the surface of the decorative melamine board.

Next, the (o) antiallergenic substance exhibiting antiallergenicity will be described in detail as an example of the substance exhibiting function. Invisible dust floats in the air, and the dust contains allergen substances such as cedar pollen, mite carcasses and feces, and causes allergies. The (o) anti-allergenic substance is preferably a composite of an anion-modified organic compound and a carrier. The conjugate exhibits an allergen-reducing effect through a chemical adsorption reaction with the protein of the allergen.

(o) The anion-modified organic compound that constitutes the anti-allergenic substance exerts a similar reduction effect, but the anion-modified organic compound alone is difficult to adhere to the surface of the decorative melamine board and has anti-allergenic properties. durability tends to be poor. Therefore, it is preferable to include the anion-modified organic compound in the form of a complex with a carrier, which is a solid component. A composite with a carrier can be physically fixed to the surface of the decorative melamine board, so it is particularly preferable for the decorative melamine board, which requires durability.

Examples of anion-modified organic compounds include anion-modified linear alkanes and anion-modified polyvinyl alcohols. Examples of anion-modified linear alkanes include linear alkanes modified with acidic anionic groups such as carboxyl groups, phosphoric acid groups, and sulfonic acid groups. Examples of counter ions for acidic anion groups include sodium ions and potassium ions. Anion-modified polyvinyl alcohols include polyvinyl alcohols modified with acidic anion groups such as carboxyl groups and sulfonic acid groups. Examples of the carrier include inorganic particles or organic particles, such as acrylic particles such as base-modified acrylic particles, styrene particles such as base-modified styrene particles, and silver oxide particles. At least one selected from the group consisting of styrene particles and silver oxide is preferable as the carrier. (o) The anti-allergenic substance is preferably in the form of fine particles, specifically those having an average particle size of 1 to 8 μm. The average particle size referred to here is the particle size at an integrated value of 50% in the particle size distribution determined by the laser diffraction/scattering method.

The amount of the (o) anti-allergenic substance in the composition is preferably 3 to 50 parts by mass (in terms of solid content) per 100 parts by mass of the solid content of the composition. (o) If the amount of the anti-allergenic substance is less than the lower limit, the anti-allergen effect tends to be reduced, and if it exceeds the upper limit, uneven whitening tends to occur on the surface of the decorative melamine board.

Next, the blending amounts of these functional substances, ie, (m) deodorant substance, (n) antiviral substance, and (o) antiallergenic substance in combination, will be described.

When (m) deodorant substance and (n) antiviral substance are combined, the blending ratio by mass is (m) deodorant substance:(n) antiviral substance = 1:0.5 to 2. 0.50, more preferably 1:0.60 to 2.0. When the blending ratio is less than the lower limit or exceeds the upper limit, the product having both deodorant and antiviral properties is slightly poorly balanced.

In addition, the total amount of (m) the deodorant substance and (n) the antiviral substance in the composition is preferably 60 to 150 parts by mass with respect to 100 parts by mass of the solid content of the composition. More preferably, it is 75 to 115 parts by mass. If the total blending amount is within this range, the decorative laminate will be particularly excellent in appearance, deodorizing properties, and antiviral properties. That is, when the total amount is less than the lower limit, the deodorant and antiviral properties are slightly inferior, and when the total amount exceeds the upper limit, uneven whitening tends to occur in appearance.

When (m) deodorant substance and (o) anti-allergenic substance are combined, the mixing ratio by mass is (m) deodorant substance:(o) anti-allergenic substance = 1:0.03 to 2. .0, more preferably 1:0.08 to 1.8. When the blending ratio is less than the lower limit or exceeds the upper limit, the product having both deodorant and anti-allergenic properties is slightly poorly balanced.

In addition, the total amount of (m) the deodorant substance and (o) the anti-allergenic substance in the composition is preferably 30 to 16 parts by mass relative to 100 parts by mass of the solid content of the composition, and more It is preferably 35 to 110 parts by mass. If the total blending amount is within this range, the decorative laminate will be particularly excellent in appearance, deodorizing properties, and anti-allergenic properties. That is, if the total amount is less than the lower limit, the deodorant and anti-allergen properties are slightly inferior, and if it exceeds the upper limit, uneven whitening tends to occur in appearance.

When (n) antiviral substance and (o) antiallergenic substance are combined, the blending ratio by mass is (n) antiviral substance:(o) antiallergenic substance = 1:0.01 to 2. 0.0, more preferably 1:0.06 to 1.50. When the blending ratio is less than the lower limit or exceeds the upper limit, the product having both antiviral and antiallergenic properties is slightly poorly balanced.

In addition, the total amount of (n) antiviral substance and (o) antiallergenic substance in the composition is preferably 15 to 200 parts by mass relative to 100 parts by mass of the solid content of the composition, and more It is preferably 35 to 125 parts by mass. If the total amount is within this range, the decorative laminate will be particularly excellent in appearance, antiviral properties, and antiallergenic properties. That is, when the total amount is less than the lower limit, the antiviral and anti-allergenic properties are slightly inferior, and when the total amount exceeds the upper limit, uneven whitening tends to occur in appearance.

When (m) deodorant substance, (n) antiviral substance and (o) antiallergenic substance are combined, the blending ratio is the mass ratio, and (m) deodorant substance: (n) antiviral Substance: (o) Anti-allergenic substance = 1: 0.20-7.0: 0.05-5.5 is preferred, more preferably 1: 0.6-4.5: 0.15-3.0 is. In addition, the total amount of (m) deodorant substance, (n) antiviral substance, and (o) antiallergenic substance in the composition is 30 to 170 parts per 100 parts by mass of the solid content of the composition. It is preferably parts by mass, more preferably 50 to 120 parts by mass. If the blending ratio and total blending amount are within this range, the appearance, deodorant, antiviral, and antiallergenic properties are well-balanced, and due to synergistic effects, even with a small amount of application, functions equivalent to or greater than those exhibited alone can be achieved. It becomes a decorative board that demonstrates. Of course, the amounts of (m) deodorant substance, (n) antiviral substance, and (o) antiallergenic substance can be appropriately adjusted in order to highlight each function within a desired range.

The decorative layer contains a cured melamine resin. The decorative layer includes melamine resin-impregnated pattern paper obtained by impregnating a decorative paper having a basis weight of about 80 to 140 g/m ² with a resin solution containing melamine resin as a main component (hereinafter referred to as melamine resin solution) and drying the impregnated paper. On top of the melamine resin-impregnated pattern paper, an overlay paper with a basis weight of about 16 to 60 g/m ² is impregnated with a melamine resin liquid and dried to protect the pattern of the decorative paper. may be provided. The overlay layer also contains a cured melamine resin. On the surface of the decorative layer or the surface of the overlay layer, a cured layer of a composition containing the composition described above or a functional material (hereinafter referred to as a functional composition) is formed as a surface layer. As a means for forming a cured layer, when the decorative paper or overlay paper is impregnated with the melamine resin liquid, a coating liquid containing a composition or a functional composition is applied to the surface after impregnation with the melamine resin liquid. A transfer method using a transfer sheet in which a functional composition is applied to a sheet-like base material, or the like is adopted. For example, in the transfer method, first, a laminate having, in this order, a transfer sheet in which a cured layer of a functional composition is formed on one side of a sheet-like substrate, melamine resin-impregnated pattern paper, and a core material is heated. Compress. Alternatively, when a melamine resin-impregnated overlay paper is used, the melamine resin-impregnated overlay paper is further placed on the melamine resin-impregnated pattern paper and hot-pressed. In the laminate, the cured layer side of the transfer sheet faces the melamine resin impregnated pattern paper or the melamine resin impregnated overlay paper. After that, the sheet-like substrate is removed.

The impregnation rate of the melamine resin liquid defined by Equation 1 is preferably in the range of 70 to 160%.
<Formula 1>

転写法で用いるシート状基材としては、プラスチックフィルム、金属箔等が挙げられる。プラスチックフィルムとしては、ポリエステルフィルム、ポリエチレンフィルム、ポリプロピレンフィルム、セロファン、ジアセチルセルロースフィルム、トリアセチルセルロースフィルム、アセチルセルロースブチレートフィルム、ポリ塩化ビニルフィルム、ポリ塩化ビニリデンフィルム、ポリビニルアルコールフィルム、エチレンビニルアルコールフィルム、ポリスチレンフィルム、ポリカーボネートフィルム、ポリメチルペンテンフィルム、ポリスルフォンフィルム、ポリエーテルケトンフィルム、ポリエーテルスルフォンフィルム、ポリエーテルイミドフィルム、ポリイミドフィルム、フッ素樹脂フィルム、ナイロンフィルム、アクリルフィルム等を使用することができる。

Sheet-like substrates used in the transfer method include plastic films and metal foils. Plastic films include polyester film, polyethylene film, polypropylene film, cellophane, diacetylcellulose film, triacetylcellulose film, acetylcellulose butyrate film, polyvinyl chloride film, polyvinylidene chloride film, polyvinyl alcohol film, ethylene vinyl alcohol film, Polystyrene film, polycarbonate film, polymethylpentene film, polysulfone film, polyetherketone film, polyethersulfone film, polyetherimide film, polyimide film, fluororesin film, nylon film, acrylic film and the like can be used.

Examples of metal foil include gold foil, silver foil, copper foil, zinc foil, indium foil, aluminum foil, tin foil, iron foil (including stainless steel (SUS) foil), and titanium foil.

When applying a coating liquid containing a functional composition to a sheet-like substrate by a transfer method, a known method such as a spray coating method, a gravure coating method, a bar coating method, a knife coating method, a roll coating method, a blade A coating method, a die coating method, a curtain coating method, a reverse coating method, a comma coating method, or the like can be used. The transfer sheet obtained by such a method is laminated on the melamine resin-impregnated paper so that the coating surface, that is, the surface on the side of the cured layer of the functional composition, is in contact with the melamine resin-impregnated paper as the uppermost layer, and the core It is hot pressed with the core material forming the layers.

The coating thickness of the coating liquid containing the functional composition will be described in detail. (m) In the case of containing a deodorizing substance, the coating thickness of the coating liquid containing the functional composition (hereinafter referred to as the deodorant function-exhibiting composition) is 2.0 to 6.5 μm is preferred. When the coating thickness is at least the lower limit, the deodorizing performance is further exhibited. If the coating thickness exceeds the upper limit, the appearance tends to be whitened unevenly. (n) In the case of containing an antiviral substance, the coating thickness of the coating solution containing the functional composition (hereinafter referred to as the antiviral function expressing composition) is 1.5 to 3.5 μm is preferred. If the coating thickness is less than the lower limit, it is difficult to exhibit antiviral performance. If the coating thickness exceeds the upper limit, the appearance tends to be whitened unevenly. The coating thickness of the coating solution containing the above-mentioned (o) functional composition containing an anti-allergenic substance (hereinafter referred to as anti-allergenic function-exhibiting composition) is 2.0 to 8.0 μm in the state is preferable. If the coating thickness is less than the lower limit, the anti-allergen performance is difficult to exhibit. If the coating thickness exceeds the upper limit, the appearance tends to be whitened unevenly.

Moreover, the pH of the coating liquid containing the functional composition is preferably 3 or more in both the coating method and the transfer method. If the pH is less than 3, the lattice structure of the component (A) is destroyed, and uneven whitening tends to occur on the surface of the decorative board. The pH of the coating liquid is the pH measured in the coating liquid adjusted so that the solid content concentration (concentration in the coating liquid of the above-described solid content contained in the functional composition) is 20% by mass. Say. Also, the pH value is determined based on the operation of the glass electrode method in accordance with JIS Z8802:2011 "pH measurement method".

In addition, the coating thickness of the coating liquid containing the composition not containing the function exhibiting substance is preferably 2.0 to 8.0 μm in a dry state in both the coating method and the transfer method, and the coating thickness is less than the lower limit. , the adhesion of fingerprints is conspicuous, and if the coating thickness exceeds the upper limit, the appearance tends to be unevenly whitened. Moreover, the pH of the coating liquid is preferably 3 or higher, as in the case of containing the function exhibiting substance. The method of measuring pH is the same as in the case of containing a substance exhibiting function.

The core material consists of an organic fibrous base material such as kraft paper or bleached kraft paper, and a binder resin such as phenol-formaldehyde resin, melamine-formaldehyde resin, or other thermosetting resin as the main component. A thermosetting resin-impregnated core paper obtained by impregnating and drying can be used.

In addition to the thermosetting resin-impregnated core paper described above, nonwoven fabrics, woven fabrics, etc. made of inorganic fibers such as glass fibers, rock wool, carbon fibers, and ceramic fibers are used as base materials, and inorganic fillers and binder components are included. A prepreg that is impregnated with a slurry and dried may also be used. This is because nonflammability can be imparted. In particular, glass fiber nonwoven fabrics are preferred because they are excellent in heat resistance, flame resistance, and slurry impregnation.

Examples of inorganic fillers include endothermic metal hydroxides such as aluminum hydroxide and magnesium hydroxide, and examples of inorganic substances other than endothermic metal hydroxides include calcium carbonate, talc, fly ash, and the like. The above can be used. As the endothermic metal hydroxide, it is preferable to use aluminum hydroxide or magnesium hydroxide because it contains water of crystallization, is decomposed at high temperature, absorbs heat, and releases bound water, and is superior in nonflammability.

When an endothermic metal hydroxide and an inorganic substance other than the endothermic metal hydroxide are used in combination, the amount of the endothermic metal hydroxide blended with respect to 1 part by mass of the inorganic substance other than the endothermic metal hydroxide is An amount of 2 to 15 parts by mass is preferable because a smooth and good surface appearance can be obtained. In addition, when the amount of the endothermic metal hydroxide compounded is 2 parts by mass or more with respect to 1 part by mass of the inorganic substance other than the endothermic metal hydroxide, the non-flammable performance is excellent. In addition, when the blending amount of the endothermic metal hydroxide is 15 parts by mass or less with respect to 1 part by mass of the inorganic substance other than the endothermic metal hydroxide, the metal hydroxide in the slurry is less likely to settle. As a result, it becomes easy to control the impregnation amount of the slurry. In addition, since the blending amount of the endothermic metal hydroxide is 15 parts by mass or less with respect to 1 part by mass of the inorganic substance other than the endothermic metal hydroxide, it is possible to reduce the wear of the blade used for cutting the decorative board. .

Binders include thermosetting resins such as amino-formaldehyde resins, phenol-formaldehyde resins, and mixed resins thereof. The blending ratio of the solid content of the binder component and the inorganic filler is desirably 5-20:95-80 in mass ratio. If the binder component is too much, the noncombustible performance tends to be lowered, and if it is too small, the adhesion between the prepregs tends to be poor.

The impregnation rate (%) of the slurry into the inorganic fiber base material is preferably in the range of 500 to 3000% by the calculation method shown in Equation 1 above. If the impregnation rate exceeds the upper limit, a large amount of solid content falls off, making it difficult to handle.

Other core materials that can be used include calcium silicate, plywood, medium-density fiberboard, particle board, and the like, and there are no particular restrictions on the core material.

The backer material is laminated on the back surface of the core material and thermocompressed to suppress warping due to shrinkage of the decorative melamine board. Examples of the backer material include melamine-impregnated paper, phenol-impregnated paper, etc., using a fibrous base material as the base material. α-cellulose paper, titanium paper, kraft paper, bleached kraft paper and the like can be used as the fibrous base material.

The present disclosure will be described below with reference to Examples, Experimental Examples, and Comparative Examples, but the present disclosure is not limited to the examples shown below.

[Example 1]
1. Production of composition containing component (A), component (B), and component (C) (A) Tetraethyl orthosilicate (ethyl silicate) hydrolyzate (trade name: HAS-1) as a hydrolytic condensate of silicon alkoxide ”, Colcoat Co., Ltd.) 100 parts by mass (solid content conversion), and (B) “NPC-ST-30” (trade name, manufactured by Nissan Chemical Industries, Ltd., average Particle diameter 10 to 15 nm, ethylene glycol mono-n-propyl ether dispersed silica sol, SiO ₂ 30% by mass) is 600 parts by mass (in terms of solid content), and (C) as an acrylic polymer having a hydrophilic group and a hydrophobic group, "DISPERBYK -2009" (solution of acrylic copolymer, 44% by mass of acrylic copolymer, 1-methoxy-2-propyl acetate, ethylene glycol monobutyl ether) (trade name, manufactured by BYK Chemie Japan Co., Ltd.) 13.2 parts by mass (solid content conversion ) was obtained.

2. Manufacture of deodorant function-exhibiting composition 1 above. containing 74% by mass of zinc oxide and 26% by mass of amino-modified silica with respect to 100 parts by mass of the solid content of the composition containing components (A), (B), and (C), and average particles 40 parts by mass of (m) deodorant substance having a diameter of 350 nm was blended and stirred with a homogenizer at 8100 rpm for 10 minutes to obtain deodorant functional composition (M).

3. Manufacture of Transfer Sheet A transfer sheet (M) was obtained by coating a plastic film with a coating liquid containing the deodorizing functional composition (M) so that the film thickness after drying was 4.5 μm. The coating liquid was prepared so that the solid content concentration, ie, the concentration of the above-mentioned solid content in the coating liquid contained in the functional composition, was 20% by mass. Moreover, the pH of the coating liquid was 5.8. The pH of the coating solution was measured using a glass electrode pH meter (product name: LAQUA model number F-71, manufactured by Horiba, Ltd.). The same applies to other examples, comparative examples, and experimental examples below.

4. Production of melamine resin-impregnated pattern paper (M) A brown decorative paper for decorative board having a basis weight of 100 g/m ² is impregnated with a resin liquid (AA) containing melamine-formaldehyde resin as a main component to obtain a melamine resin-impregnated pattern paper. (M) was obtained. The impregnation rate of the melamine resin-impregnated pattern paper (M) defined by Equation 1 was 140%. The surface of the decorative paper was printed with a wood grain pattern having a conduit portion.

5. Preparation of prepreg A slurry containing melamine-formaldehyde resin and phenol-formaldehyde resin as binder components and inorganic fillers such as aluminum hydroxide and calcium carbonate as inorganic fillers was added to a glass fiber base material of 50 g/m ² according to the formula The prepreg was obtained by soaking and drying so that the impregnation rate based on 1 was 1200%. The mass ratio of the solid content of the binder component and the inorganic filler in the slurry was 8:92.

6. Manufacture of Backer 80 g/m ² of decorative paper for decorative board was impregnated with a resin liquid containing melamine-formaldehyde resin as a main component so that the impregnation rate shown by Equation 1 was 150%, and dried to obtain a backer. rice field.

7. Manufacture of decorative board In order from the bottom, 1 barker, 5 prepregs, 1 melamine resin impregnated pattern paper (M), 1 transfer sheet (M) are laminated, and the laminate is laminated using a flat finishing plate. It was hot-pressed under the conditions of 140° C., 100 kg/cm ² and 90 minutes, and the plastic film was peeled off to obtain a decorative melamine board.

[Example 2]
The procedure was carried out in the same manner as in Example 1, except that (m) 60 parts by mass of the deodorizing substance was blended.

[Example 3]
The procedure was carried out in the same manner as in Example 1 except that (m) 30 parts by mass of the deodorizing substance was blended.

[Example 4]
The procedure was carried out in the same manner as in Example 1, except that 9.3 parts by mass of "DISPERBYK-2009" as the component (C) was blended.

[Example 5]
The procedure was carried out in the same manner as in Example 1, except that 16.8 parts by mass of "DISPERBYK-2009" as component (C) was blended.

[Example 6]
The procedure was carried out in the same manner as in Example 1, except that 400 parts by mass of "NPC-ST-30" as the component (B) was blended.

[Example 7]
The procedure was the same as in Example 1, except that 900 parts by mass of "NPC-ST-30" as the component (B) was blended.

[Example 8]
Example 1 was carried out in the same manner as in Example 1, except that the average particle size of the (m) deodorant substance was changed to 200 nm.

[Example 9]
The procedure was carried out in the same manner as in Example 1, except that the average particle size of the (m) deodorant substance was changed to 1000 nm.

[Example 10]
The procedure was carried out in the same manner as in Example 1, except that the coating solution containing the deodorizing functional composition (M) was applied so that the film thickness after drying was 2.0 μm.

[Example 11]
The procedure was carried out in the same manner as in Example 1, except that the coating solution containing the deodorizing functional composition (M) was applied so that the film thickness after drying was 6.5 μm.

[Example 12]
Example 1 was carried out in the same manner as in Example 1, except that the (m) deodorant substance containing 45% zinc oxide and 55% amino-modified silica was used.

[Example 13]
Example 1 was carried out in the same manner as in Example 1, except that the (m) deodorant substance containing 85% zinc oxide and 15% amino-modified silica was used.

[Example 14]
1. Production of antiviral function-exhibiting composition Triazine-imidazole-thiazole-based organic A synthetic antiviral substance having an average particle size of 1000 nm (n) is blended with 50 parts by mass of the antiviral substance and stirred with a homogenizer at 8100 rpm for 10 minutes to give an antiviral function expressing composition (N ).

2. Manufacture of Transfer Sheet A transfer sheet (N) was obtained by coating a plastic film with a coating solution containing the antiviral function-expressing composition (N) so that the film thickness after drying was 2.2 μm. The pH of the coating liquid was 8.3.

3. Production of Decorative Laminate The procedure was carried out in the same manner as in Example 1, except that the transfer sheet (N) was used instead of the transfer sheet (M).

[Example 15]
In Example 14, 26.4 parts by mass of component (C) "DISPERBYK-2009" was blended, and 35 parts by mass of (n) antiviral substance was blended.

[Example 16]
In Example 14, 26.4 parts by mass of component (C) "DISPERBYK-2009" was blended, and 75 parts by mass of (n) antiviral substance was blended.

[Example 17]
The procedure was carried out in the same manner as in Example 14, except that 9.3 parts by mass of "DISPERBYK-2009" as component (C) was blended.

[Example 18]
The procedure of Example 14 was repeated except that 16.8 parts by mass of "DISPERBYK-2009" as the component (C) was blended.

[Example 19]
In Example 14, 26.4 parts by mass of the component (C) "DISPERBYK-2009" was blended, and the coating liquid containing the antiviral function expression composition was dried so that the film thickness was 3.5 μm. It implemented similarly except having coated.

[Example 20]
The procedure was carried out in the same manner as in Example 19, except that the coating solution containing the composition exhibiting antiviral function was applied so that the film thickness after drying was 1.5 μm.

[Example 21]
In Example 19, (n) the average particle size of the antiviral substance was set to 3000 nm, and the coating liquid containing the composition exhibiting antiviral function was applied so that the film thickness after drying was 2.2 μm. was similarly performed.

[Example 22]
The procedure was carried out in the same manner as in Example 21, except that the average particle size of (n) the antiviral substance was changed to 500 nm.

[Example 23]
1. Production of Antiallergenic Function Exhibiting Composition With respect to 100 parts by mass of the solid content of the composition containing the components (A), (B), and (C) of Example 1, (o) as an antiallergenic substance , an organic synthetic anti-allergenic substance ("Allerbuster BV", manufactured by Sekisui Material Solutions Co., Ltd.), which is a composite of a sodium salt of an acidic anion group-modified linear alkane and styrene particles, having an average particle size of 2000 nm, is 10 masses. The parts were combined and stirred with a homogenizer at 8100 rpm for 10 minutes to obtain an anti-allergenic composition (O).

2. Manufacture of Transfer Sheet A transfer sheet (O) was obtained by coating a plastic film with a coating solution containing the anti-allergenic function exhibiting composition (O) so that the film thickness after drying was 4.0 μm. Incidentally, the pH of the coating liquid was 6.8.

3. Production of Decorative Laminate The procedure was carried out in the same manner as in Example 1, except that the transfer sheet (O) was used instead of the transfer sheet (M).

[Example 24]
Example 23 was carried out in the same manner as in Example 23 except that (o) 3 parts by mass of the antiallergenic substance was added.

[Example 25]
The same procedure as in Example 23 was carried out, except that (o) 50 parts by mass of the anti-allergenic substance was blended.

[Example 26]
In Example 23, (o) an organic synthetic anti-allergenic substance ("Allerbuster BV ”, manufactured by Sekisui Material Solutions Co., Ltd.) was performed in the same manner.

[Example 27]
In Example 23, (o) as the anti-allergenic substance, an organic synthetic anti-allergenic substance ("Allerbuster BV", manufactured by Sekisui Material Solutions Co., Ltd.) was used in the same manner.

[Example 28]
The procedure was carried out in the same manner as in Example 23, except that the coating solution containing the anti-allergenic composition was applied so that the film thickness after drying was 2.0 μm.

[Example 29]
The procedure was carried out in the same manner as in Example 23, except that the coating solution containing the anti-allergenic composition was applied so that the film thickness after drying was 8.0 μm.

[Example 30]
The procedure of Example 23 was repeated except that 900 parts by mass of "NPC-ST-30" as the component (B) was blended.

[Example 31]
The procedure of Example 23 was repeated except that 300 parts by mass of "NPC-ST-30" as the component (B) was blended.

[Example 32]
1. Manufacture of thermosetting resin-impregnated core paper Kraft paper with a basis weight of 200 g/m ² was impregnated with a resin liquid containing phenol-formaldehyde resin as the main component so that the impregnation rate defined by Equation 1 was 50%. and dried to obtain a phenol resin-impregnated core paper as a thermosetting resin-impregnated core paper.

2. Manufacture of decorative board From the bottom, 5 sheets of phenolic resin-impregnated core paper, 1 sheet of melamine resin-impregnated pattern paper (M) similar to Example 1, and 1 sheet of transfer sheet (M) are laminated in order, and the laminate is flattened. Using a finishing plate, the laminate was thermocompressed under the conditions of 140° C., 100 kg/cm ² and 90 minutes, and the plastic film was peeled off to obtain a decorative melamine board.

[Example 33]
Example 2 was repeated except that phenolic resin impregnated core paper was used instead of prepreg and no backer was used.

[Example 34]
Example 3 was repeated except that phenolic resin impregnated core paper was used instead of prepreg and no backer was used.

[Example 35]
The procedure was carried out in the same manner as in Example 32, except that the average particle size of the (m) deodorant substance was changed to 200 nm.

[Example 36]
The procedure was carried out in the same manner as in Example 32, except that the average particle size of the (m) deodorant substance was changed to 1000 nm.

[Example 37]
The procedure was carried out in the same manner as in Example 32, except that the coating liquid containing the deodorizing function-exhibiting composition was applied so that the film thickness after drying was 2.5 μm.

[Example 38]
The procedure of Example 32 was repeated except that the coating liquid containing the composition exhibiting deodorant function was applied so that the film thickness after drying was 6.5 μm.

[Example 39]
Example 14 was repeated except that the prepreg was replaced with phenolic resin impregnated core paper and no backer was used.

[Example 40]
Example 15 was repeated except that the prepreg was replaced with phenolic resin impregnated core paper and no backer was used.

[Example 41]
Example 16 was repeated except that the prepreg was replaced with phenolic resin impregnated core paper and no backer was used.

[Example 42]
Example 19 was repeated except that phenolic resin impregnated core paper was used instead of prepreg and no backer was used.

[Example 43]
Example 20 was repeated except that the prepreg was replaced with phenolic resin impregnated core paper and no backer was used.

[Example 44]
The procedure was carried out in the same manner as in Example 39, except that the average particle size of (n) the antiviral substance was changed to 3000 nm.

[Example 45]
The procedure was carried out in the same manner as in Example 39, except that the average particle size of (n) the antiviral substance was changed to 500 nm.

[Example 46]
Example 23 was repeated except that the prepreg was replaced with phenolic resin impregnated core paper and no backer was used.

[Example 47]
Example 24 was repeated except that the prepreg was replaced with phenolic resin impregnated core paper and no backer was used.

[Example 48]
Example 25 was repeated except that the prepreg was replaced with phenolic resin impregnated core paper and no backer was used.

[Example 49]
Example 26 was repeated except that the prepreg was replaced with phenolic resin impregnated core paper and no backer was used.

[Example 50]
Example 27 was repeated except that the prepreg was replaced with phenolic resin impregnated core paper and no backer was used.

[Example 51]
Example 28 was repeated except that phenolic resin impregnated core paper was used instead of prepreg and no backer was used.

[Example 52]
Example 29 was repeated except that phenolic resin impregnated core paper was used instead of prepreg and no backer was used.

[Example 53]
Example 1 was carried out in the same manner as in Example 1 except that (m) zeolite was used as the deodorizing substance.

[Example 54]
Example 1 was carried out in the same manner as in Example 1, except that copper oxide was used as (m) the deodorizing substance.

[Example 55]
Example 1 was carried out in the same manner as in Example 1, except that zirconium oxide was used as (m) the deodorizing substance.

[Example 56]
The procedure was carried out in the same manner as in Example 14, except that (n) amino-modified polyvinyl alcohol particles were used as the antiviral substance.

[Example 57]
The procedure was carried out in the same manner as in Example 14, except that (n) amino-modified acrylic particles were used as the antiviral substance.

[Example 58]
Example 23 was carried out in the same manner as in Example 23, except that as the anion-modified organic compound (n) of the antiallergenic substance, instead of the sodium salt of the acidic anion group-modified linear alkane, an acidic anion group-modified polyvinyl alcohol was used.

[Example 59]
Example 23 was carried out in the same manner as in Example 23, except that silver oxide particles were used instead of styrene particles as (n) the carrier for the anti-allergenic substance.

[Example 60]
In the same manner as in Example 1, except that the composition containing the components (A), (B), and (C) obtained in Example 1 was used instead of the deodorant functional composition (M). Carried out.

[Example 61]
Example 1 was carried out in the same manner as in Example 1, except that the following melamine resin-impregnated patterned paper (Mt) was used and the following manufacturing method was used.

<Production of melamine resin impregnated pattern paper (Mt)>
A brown decorative paper for decorative board having a basis weight of 100 g/m ² was impregnated with a resin solution (AA) containing melamine-formaldehyde resin as a main component so that the impregnation rate defined by Equation 1 was 140%. . Then, the decorative paper is coated with a coating liquid containing the deodorizing functional composition (M) of Example 1 so that the film thickness after drying is 4.5 μm, and the melamine resin-impregnated pattern paper ( Mt) was obtained. The surface of the decorative paper was printed with a wood grain pattern having a conduit portion.

<Production of decorative board>
Laminate one sheet of barker, five sheets of prepreg, and one sheet of melamine resin-impregnated pattern paper (Mt) in this order from the bottom, and heat press mold using a flat finishing plate at 140° C., 100 kg/cm ² for 90 minutes. Then, a melamine decorative board was obtained.

[Example 62]
Example 14 was carried out in the same manner except that the following melamine resin-impregnated patterned paper (Nt) was used and the following manufacturing method was used.

<Production of melamine resin impregnated pattern paper (Nt)>
A brown decorative paper for decorative board having a basis weight of 100 g/m ² was impregnated with a resin solution (AA) containing melamine-formaldehyde resin as a main component so that the impregnation rate defined by Equation 1 was 140%. An impregnated paper was obtained. Then, the surface of the impregnated paper was coated with a coating liquid containing the antiviral function expression composition (N) of Example 14 so that the film thickness after drying was 2.2 μm, and the melamine resin impregnated pattern was obtained. A paper (Nt) was obtained. The surface of the decorative paper was printed with a wood grain pattern having a conduit portion.

<Production of decorative board>
Laminate one sheet of barker, five sheets of prepreg, and one sheet of melamine resin-impregnated pattern paper (Nt) in this order from the bottom, and heat-compress using a flat finishing plate at 140° C., 100 kg/cm ² , for 90 minutes. Then, a melamine decorative board was obtained.

[Example 63]
Example 23 was carried out in the same manner, except that the following melamine resin-impregnated patterned paper (Ot) was used and the following manufacturing method was used.

<Production of melamine resin impregnated pattern paper (Ot)>
A brown decorative paper for decorative board having a basis weight of 100 g/m ² was impregnated with a resin solution (AA) containing melamine-formaldehyde resin as a main component so that the impregnation rate defined by Equation 1 was 140%. An impregnated paper was obtained. Then, the surface of the impregnated paper was coated with a coating liquid containing the anti-allergenic function-expressing composition (O) of Example 23 so that the film thickness after drying was 4.0 μm, and the melamine resin impregnated pattern was obtained. A paper (Ot) was obtained. The surface of the decorative paper was printed with a wood grain pattern having a conduit portion.

<Production of decorative board>
Laminate one sheet of barker, five sheets of prepreg, and one sheet of melamine resin-impregnated pattern paper (Ot) in order from the bottom, and heat-compress using a flat finishing plate at 140° C., 100 kg/cm ² , for 90 minutes. Then, a melamine decorative board was obtained.

[Comparative Example 1]
In Example 1, instead of (A) the hydrolytic condensate of silicon alkoxide, a siloxane-grafted polymer in which an acrylic resin and siloxane were combined (trade name “ZX-036”, hydroxyl value 119, solvent type butyl acetate /2-propanol, manufactured by Fuji Kasei Kogyo Co., Ltd.) was used in the same manner.

[Comparative Example 2]
Example 1 was carried out in the same manner as in Example 1, except that (B) a hydrophobic silica sol (trade name “Sylophobic”, manufactured by Fuji Silysia Chemical Co., Ltd.) was used instead of the organosilica sol dispersed in the hydrophilic solvent.

[Comparative Example 3]
In Example 1, instead of the (C) acrylic polymer having a hydrophilic group and a hydrophobic group, (x) a methacryloyl functional group-containing acrylic polymer (trade name "RA-3705MB", Negami Kogyo as a reactive (meth) acrylic polymer) Co., Ltd.), and 1,6-bis(t-butylperoxycarbonyloxy)hexane (trade name “Kayaren 6-70”, manufactured by Kayaku Akzo Co., Ltd.) as a thermal polymerization initiator. The procedure was carried out in the same manner except that 4 parts by mass were blended.

[Comparative Example 4]
The procedure was carried out in the same manner as in Comparative Example 3, except that the substance exhibiting function was not contained.

[Comparative Examples 5 to 9]
It was carried out in the same manner as in Comparative Example 3, except that the conditions were changed to those shown in Tables 4-1 and 4-2.

[Examples 64 to 78]
Example 1 was carried out in the same manner except that the conditions were changed to those shown in Tables 5-1 and 5-2. In Examples 64 to 78, (m) the same deodorant substance as in Example 1 was used as the deodorant substance, and (n) the same antiviral substance as in Example 14 was used as the antiviral substance. and (o) the same anti-allergenic substance as in Example 23 was used as the anti-allergenic substance.

[Examples 79 to 93]
Example 1 was carried out in the same manner except that the conditions were changed to those shown in Tables 6-1 and 6-2. In Examples 79 to 93, (m) the same deodorant substance as in Example 1 was used as the deodorant substance, and (n) the same antiviral substance as in Example 14 was used as the antiviral substance. and (o) the same anti-allergenic substance as in Example 23 was used as the anti-allergenic substance.

However, in Example 88, "HAS-6", which is a hydrolytic condensate of tetraethyl orthosilicate (ethyl silicate), was used as the component (A) instead of "HAS-1". In Example 89, "HAS-10", which is a hydrolytic condensate of tetraethyl orthosilicate (ethyl silicate), was used as the component (A) instead of "HAS-1". In Example 90, as the component (B), instead of "NPC-ST-30", "IPA-ST" (trade name, manufactured by Nissan Chemical Industries, Ltd., average particle size 10 to 15 nm, isopropyl alcohol-dispersed silica sol , SiO ₂ 30 mass %) was used. In Example 91, instead of "NPC-ST-30", "MEK-AC-2140Z" (trade name, manufactured by Nissan Chemical Industries, Ltd., average particle size 10 to 15 nm, methyl ethyl ketone dispersion silica sol, SiO ₂ 40 mass %) was used. In Example 92, instead of "DISPERBYK-2009", "DISPERBYK-2000" (acrylic copolymer solution, acrylic copolymer 40% by mass, 1-methoxy-2-propyl acetate, ethylene glycol monobutyl ether) (trade name, manufactured by BYK-Chemie Japan Co., Ltd.) was used. In Example 93, instead of "DISPERBYK-2009", "DISPERBYK-2008" (acrylic copolymer solution, acrylic copolymer 60% by mass, polypropylene glycol 40%, trade name, BYK Chemie Japan Co., Ltd.) was used as the component (C) instead of "DISPERBYK-2009". company) was used.

[Example 94]
<Production of melamine resin impregnated overlay paper>
An overlay paper having a basis weight of 22 g/m ² was impregnated with the same resin solution (AA) as in Example 1 to obtain a melamine resin-impregnated overlay paper. The impregnation rate defined by Equation 1 for the melamine resin impregnated overlay was 260%.

<Production of decorative board>
A transfer sheet similar to that of Example 79 was prepared.

Further, melamine resin-impregnated patterned paper was obtained in the same manner as in Example 1, except that the impregnation rate defined by Equation 1 was set to 100%.

Also, the same phenol resin-impregnated core paper as in Example 32 was prepared.

From the bottom, 5 sheets of phenolic resin impregnated core paper, 1 sheet of melamine resin impregnated pattern paper, 1 sheet of melamine resin impregnated overlay paper, and 1 sheet of transfer sheet were laminated, and the laminate was heated to 140°C using a flat finishing plate. , 100 kg/cm ² for 90 minutes, and the plastic film was peeled off to obtain a decorative melamine board.

[Example 95]
Example 94 was carried out in the same manner except that the transfer sheet of Example 80 was used.

[Example 96]
Example 94 was carried out in the same manner except that the transfer sheet of Example 81 was used.

[Experimental Examples 1 to 6]
Example 1 was carried out in the same manner except that the conditions were changed to those shown in Tables 7-1 and 7-2.

[Experimental Examples 7 to 10]
Example 1 was carried out in the same manner except that the conditions were changed to those shown in Tables 8-1 and 8-2.

[Experimental Examples 11 to 22]
Example 1 was carried out in the same manner except that the conditions were changed to those shown in Tables 9-1 and 9-2.

Regarding the above Examples, Experimental Examples, and Comparative Examples, the blending ratio of the functional composition and the composition containing the components (A), (B), and (C), the particle size and pH of the function-expressing substance, and the application The amount and the type of core material of the core layer are shown in Tables 1-1 to 9-2.

In addition, A, B, C, m, n, and o in the table are as follows.

A: hydrolytic condensate of silicon alkoxide B: organosilica sol dispersed in hydrophilic solvent C: acrylic polymer having hydrophilic group and hydrophobic group m: deodorant substance n: antiviral substance o: antiallergenic substance In addition, the numerical values of parts by mass of A, B, and C in the table are values based on the solid content.

In addition, the numerical values of the compounding amounts of m, n, and o are the compounding ratio of the solid content to 100 parts by mass of the solid content of the composition.

［評価方法］
上記実施例、実験例、及び比較例に係るメラミン化粧板を、以下の方法により、外観、機能性（消臭性、抗ウイルス性、又は抗アレルゲン性）、耐薬品性、及び不燃性の観点から評価した。

[Evaluation method]
The melamine decorative boards according to the above Examples, Experimental Examples, and Comparative Examples were evaluated in terms of appearance, functionality (deodorant, antiviral, or antiallergenic), chemical resistance, and nonflammability by the following methods. evaluated from

(1) Appearance The appearance of the decorative melamine board was inspected based on JIS K 6902:2007 "Test method for thermosetting resin high pressure decorative board". At the same time, the surface of the decorative melamine board was touched with the palm for 5 seconds, then the hand was removed, and the surface was visually observed to evaluate whether or not the fingerprint was conspicuous. The appearance of the melamine decorative board was evaluated according to the following criteria.

◯: No abnormality (no uneven whitening occurs on the surface, and no fingerprints are conspicuous).

Δ1: Slight whitening unevenness occurs on the surface, but the vessel part of the wood grain pattern of the decorative layer can be recognized. Fingerprints are invisible.

Δ2: No uneven whitening occurs on the surface, but fingerprints are slightly conspicuous.

x: Remarkable uneven whitening occurs on the surface, the wood grain pattern of the decorative layer is unclear, and the vessel portion cannot be recognized. Fingerprints are invisible.

In addition, if uneven whitening occurs on the surface, fingerprints become less noticeable.

(2) Deodorant rate (%)
(2-1) Hydrogen sulfide deodorant performance: A test piece cut into a size of 100 mm x 200 mm was coated with aluminum tape on the back and side surfaces so that the effective area was 200 cm ² . After placing the test piece in a Tedlar bag, 3 L of hydrogen sulfide gas was injected into the bag so that the concentration was 4 ppm, and the residual concentration of hydrogen sulfide was measured after 24 hours. Based on this measured value, the total amount of deodorized hydrogen sulfide was calculated and used as the deodorizing rate (%) of hydrogen sulfide gas.

(2-2) Ammonia deodorant performance: A test piece cut into a size of 100 mm x 200 mm was coated with aluminum tape on the back and side surfaces so that the effective area was 200 cm ² . After putting the test piece into a Tedlar bag, 3 L of ammonia gas was injected into the bag so that the concentration became 100 ppm, and the ammonia residual concentration was measured after 24 hours. Based on this measured value, the total amount of deodorized ammonia was calculated and defined as the deodorizing rate (%).

(3) Antiviral performance phage test Test virus: bacteriophage Qβ
Test standard: JIS R 1756: 2020 "Fine ceramics-Antiviral test method for visible light responsive photocatalytic materials-Method using bacteriophage Qβ"
Measurement time: 24 hours Test bacteria virus bacteriophage Qβ was brought into contact with a test piece cut out to 50 mm×50 mm. Based on the calculated virus infectivity titer, the antiviral activity value was calculated based on the following formula.

Antiviral activity value = log (viral infectivity of unprocessed product) - log (viral infectivity of processed product)
The unprocessed product is a decorative melamine board on which the cured layer of the composition is not formed, and the processed product is the decorative melamine board according to each example, each experimental example and each comparative example.

(4) Anti-allergen performance ammonia Test bacteria: mite allergen (Der fII), cedar allergen (Cry jI)
Measurement time: 24 hours Measurement method: ELISA method A 40 mm x 40 mm frame was made with an adhesive on a test piece cut out to 50 mm x 50 mm. 0.4 ml of an allergen solution prepared at a constant concentration was dropped into the frame, and the film was adhered.

After 24 hours, the solution was collected and the allergen concentration was measured by ELISA (enzyme-linked immunosorbent assay).

The concentration difference between the measured value and the unprocessed product was calculated and used as the allergen reduction rate (%).

(5) Chemical resistance <Chemicals used>
q: Osvan solution 0.025% solution r: Cresol soapy water 5.0% solution s: Sodium hypochlorite 6.0% solution t: 1% hydrochloric acid aqueous solution u: 1% sodium hydroxide aqueous solution <Test method>
After the test piece was washed and dried, 0.2 ml of the test liquid was dropped onto the test piece, left for 24 hours, and then the test liquid was washed off with water. .

<Evaluation method>
◯: No change Δ: No erosion but change in color tone and luster ×: Erosion (6) Noncombustibility A 20-minute exothermic test was performed using a cone calorimeter conforming to ISO5660. In the evaluation method, the total calorific value is 8 MJ/m ² or less, the maximum heat generation rate does not exceed 200 kW/m ² continuously for 10 seconds or more, and cracks, cracks, etc. that penetrate to the back surface of the test specimen after the test The case where there is no Those that did not satisfy even one of these three conditions were evaluated as x.

Evaluation results are shown in Tables 10-1 to 18-2.

［考察］
表１６－１に示すように、実験例１では、（ｍ）消臭性物質の配合量が少なく消臭性能がやや劣っていた。実験例２では、（ｍ）消臭性物質の配合量が多く、外観において僅かに白化ムラが生じた（△１）。実験例３では、（ｎ）抗ウイルス性物質の配合量が少なく抗ウイルス性能がやや劣っていた。実験例４では、（ｎ）抗ウイルス性物質の配合量が多く、外観において僅かに白化ムラが生じた（△１）。実験例５では、（ｏ）抗アレルゲン性物質の配合量が少なく抗アレルゲン性がやや劣っていた。実験例６では、（ｏ）抗アレルゲン性物質の配合量が多く、外観において僅かに白化ムラが生じた（△１）。

[Discussion]
As shown in Table 16-1, in Experimental Example 1, the amount of the (m) deodorizing substance was small, and the deodorizing performance was slightly inferior. In Experimental Example 2, the blending amount of (m) deodorant substance was large, and slight uneven whitening occurred in the appearance (Δ1). In Experimental Example 3, the amount of the (n) antiviral substance was small, and the antiviral performance was slightly inferior. In Experimental Example 4, the blending amount of (n) antiviral substance was large, and slight uneven whitening occurred in the appearance (Δ1). In Experimental Example 5, the amount of the (o) antiallergenic substance was small, and the antiallergenicity was slightly inferior. In Experimental Example 6, the amount of the (o) anti-allergenic substance was large, and slight uneven whitening occurred in the appearance (Δ1).

As shown in Table 17-1, in Experimental Example 7, although the functional composition contained components (A), (B), and (C), relative to 1 part by mass of the solid content of component (A) The blending amount of component (B) was less than 0.5 parts by mass, and the deodorizing performance was slightly inferior, and the chemical resistance was also slightly inferior. In Experimental Example 8, although the functional substance composition contained components (A), (B), and (C), the amount of component (B) per 1 part by mass of the solid content of component (A) was was over 12 parts by mass, and fingerprints were not conspicuous in appearance, but slight uneven whitening occurred (Δ1). In Experimental Example 9, although the functional composition contained components (A), (B), and (C), the amount of component (C) per 1 part by mass of the solid content of component (B) was The content was less than 0.005 parts by mass, and although uneven whitening did not occur, fingerprints were slightly conspicuous (Δ2). In Experimental Example 10, although the functional composition contained components (A), (B), and (C), the amount of component (C) per 1 part by mass of the solid content of component (B) was The amount exceeded 0.3 parts by mass, and although fingerprints were not conspicuous in appearance, slight uneven whitening occurred (Δ1).

As shown in Table 18-1, Experimental Example 11 was slightly inferior in deodorant properties. In Experimental Example 12, fingerprints were not conspicuous in appearance, but slight uneven whitening occurred (Δ1). In Experimental Example 13, the antiviral properties were slightly inferior. In Experimental Example 14, fingerprints were not conspicuous in appearance, but slight uneven whitening occurred (Δ1). In Experimental Example 15, the deodorizing property was slightly inferior. In Experimental Example 16, fingerprints were not conspicuous in appearance, but slight uneven whitening occurred (Δ1). In Experimental Example 17, the anti-allergenicity was slightly inferior. In Experimental Example 18, fingerprints were not conspicuous in appearance, but slight uneven whitening occurred (Δ1). In Experimental Example 19, the antiviral properties were slightly inferior. In Experimental Example 20, fingerprints were not conspicuous in appearance, but slight uneven whitening occurred (Δ1). In Experimental Example 21, the anti-allergenicity was slightly inferior. In Experimental Example 22, fingerprints were not conspicuous in appearance, but slight uneven whitening occurred (Δ1).

2 Cured layer of functional composition 3 Melamine resin-impregnated pattern paper 4 Prepreg 5 Phenol resin-impregnated core paper 6 Core layer 7 Backer 8 Melamine resin-impregnated overlay paper 11 Melamine decorative board 12 Melamine decorative board 13 Melamine decorative board

Here, a hydrophilic (polar) solvent is a solvent having an affinity for water, for example, a hydrophilic organic solvent having a hydrophilic group such as a hydroxyl group, a carboxyl group, or a carbonyl group in its molecule. Hydrophilic (polar) solvents include protic polar solvents and aprotic polar solvents. Specific examples of protic polar solvents include alcohol solvents such as methyl alcohol, ethyl alcohol, isopropanol, ethylenedialcohol and propanol, and cellosolve solvents such as methyl cellosolve, ethyl cellosolve, butyl cellosolve and n-propyl cellosolve. Aprotic polar solvents include acetone, dimethylsulfoxide (DMSO), N,N-dimethylformamide (DM F ), pyridine and the like.

The total amount of (m) the deodorant substance and (o) the anti-allergenic substance in the composition is preferably 30 to 160 parts by weight per 100 parts by weight of the solid content of the composition. More preferably, it is 35 to 110 parts by mass. If the total blending amount is within this range, the decorative laminate will be particularly excellent in appearance, deodorizing properties, and anti-allergenic properties. That is, if the total amount is less than the lower limit, the deodorant and anti-allergen properties are slightly inferior, and if it exceeds the upper limit, uneven whitening tends to occur in appearance.

[Example 58]
Example 23 was carried out in the same manner except that ( o ) acidic anion group-modified polyvinyl alcohol was used as the anion-modified organic compound of the anti-allergenic substance instead of the sodium salt of the acidic anion group-modified linear alkane.

[Example 59]
Example 23 was carried out in the same manner as in Example 23, except that ( o ) silver oxide particles were used instead of styrene particles as the carrier for the anti-allergenic substance.

In the composition described above, the component (B) organosilica sol is 0.5 to 12 parts by mass, more preferably 1 to 12 parts by mass, based on 1 part by mass (in terms of solid content) of the silicon alkoxide hydrolysis condensate of the component (A). It is preferable to mix 9 parts by mass. When the blending ratio of the component ( B ) is equal to or higher than the lower limit, the functional effect is improved, and when it is equal to or lower than the upper limit, the solvent resistance is improved.

(4) Anti-allergen performance
Test bacteria: mite allergen (Der fII), cedar allergen (Cry jI)
Measurement time: 24 hours Measurement method: ELISA method A 40 mm x 40 mm frame was made with an adhesive on a test piece cut out to 50 mm x 50 mm. 0.4 ml of an allergen solution prepared at a constant concentration was dropped into the frame, and the film was adhered.

Claims (14)

(A) a hydrolytic condensate of silicon alkoxide;
(B) an organosilica sol dispersed in a hydrophilic solvent;
(C) an acrylic polymer having a hydrophilic group and a hydrophobic group;
at least one substance selected from the group consisting of (m) a deodorant substance, (n) an antiviral substance, and (o) an antiallergenic substance;
A composition comprising (m) containing a deodorant substance,
2. The composition according to claim 1, wherein the amount of said (m) deodorant substance in said composition is 30 to 60 parts by mass per 100 parts by mass of solid content of said composition. (n) containing an antiviral substance,
The composition according to claim 1 or claim 2, wherein the amount of the (n) antiviral substance in the composition is 35 to 75 parts by mass with respect to 100 parts by mass of the solid content of the composition. . (o) containing an anti-allergenic substance;
Any one of claims 1 to 3, wherein the amount of the (o) anti-allergenic substance in the composition is 3 to 50 parts by mass with respect to 100 parts by mass of the solid content of the composition. A composition according to claim. (m) containing a deodorant substance,
The composition according to any one of claims 1 to 4, wherein the (m) deodorant substance comprises a chemisorbed deodorant substance. 6. The composition according to claim 5, wherein said chemically adsorbed deodorant substance contains at least one selected from the group consisting of zinc oxide, silica, zeolite, copper oxide, and zirconium oxide. (n) containing an antiviral substance,
Any one of claims 1 to 6, wherein the (n) antiviral substance comprises at least one selected from the group consisting of triazine-thiazole-imidazole-based substances, amino-modified polyvinyl alcohol, and amino-modified acrylic polymers. A composition according to claim. (o) containing an anti-allergenic substance;
The composition according to any one of claims 1 to 7, wherein the (o) anti-allergenic substance comprises a composite of an anion-modified organic compound and a carrier. 9. The composition according to claim 8, wherein said anion-modified organic compound comprises at least one selected from the group consisting of anion-modified linear alkanes and anion-modified polyvinyl alcohols. 10. The composition according to claim 8 or 9, wherein said carrier contains at least one selected from the group consisting of styrene particles and silver oxide particles. The composition according to any one of claims 1 to 10, which is used for melamine decorative boards. a sheet-like base material;
A cured layer of the composition according to any one of claims 1 to 11, formed on one side of the sheet-like substrate;
A transfer sheet. a core layer;
a decorative layer containing a cured melamine resin;
and a cured layer of the composition according to any one of claims 1 to 11, in this order. A method for producing a decorative melamine board,
The decorative melamine board includes a core layer, a decorative layer containing a cured melamine resin, and a surface layer in this order,
A method for producing a decorative melamine board, comprising curing the composition according to any one of claims 1 to 11 to form the surface layer.

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