JP2022073943A - Decorative sheet with adhesive and structure - Google Patents

Abstract

To provide a decorative sheet with an adhesive developing functions such as deodorant, anti-viral, and anti-allergenic and to provide a structure.SOLUTION: A decorative sheet (11, 12, 13) with an adhesive comprises a decorative sheet layer (1) and an adhesive layer (9) provided on an opposite side of the decorative sheet layer. The decorative sheet layer (1) comprises a surface layer (2), a decorative layer (3), a mixed sheet layer (5) and a core layer (4). The surface layer comprises a cured material of a functional composition comprising a main component that includes the following (A) to (C) and one or more function-expressing substances selected from the group consisting of the following (m) to (o). (A) hydrolyzed condensate of silicon alkoxide. (B) An organosilica sol by substituting aqueous silica sol with a hydrophilic solvent. (C) An acrylic copolymer having a hydrophilic group and a hydrophobic group. (m) A deodorant substance. (n) An antiviral substance. (o) An antiallergenic substance.SELECTED DRAWING: Figure 1

Description

The present disclosure relates to a decorative sheet with an adhesive and a structure.

Conventionally, melamine decorative sheets have been mainly used as housing interior materials. Residential interior materials are used, for example, on vertical surfaces. Examples of housing interior materials used for vertical surfaces include surface materials for fittings and finishing materials for wall surfaces. Residential interior materials are also used on horizontal surfaces such as tables and desks.

In recent years, melamine decorative sheets are also used, for example, in the refurbishment and refurbishment of commercial facilities such as supermarkets and exhibition halls, and public facilities such as schools and nursing care facilities.
It is preferable that the construction period for new refurbishment and refurbishment is short. Patent Documents 1 and 2 disclose decorative sheets for the purpose of shortening the construction period in new refurbishment and refurbishment. The surface of this decorative sheet is made of melamine resin. In addition, this decorative sheet has an adhesive layer.

Japanese Unexamined Patent Publication No. 2018-20563 Japanese Unexamined Patent Publication No. 2017-19272

For example, in various facilities where an unspecified number of people come and go, it is preferable that the cosmetic sheet exhibits functions such as deodorant, antiviral, and antiallergen. In one aspect of the present disclosure, it is preferable to provide, for example, a decorative sheet and a structure with a pressure-sensitive adhesive that exhibit functions such as deodorant, antiviral, and antiallergen.

One aspect of the present disclosure is that the surface layer (2), the decorative layer (3), the mixed paper layer (5), and the core layer (4) are the surface layer, the decorative layer, the mixed paper layer, and the core layer. A decorative sheet layer (1) laminated in this order, or in the order of the surface layer, the decorative layer, the core layer, and the mixed papermaking layer, and an adhesive provided on the opposite side of the decorative sheet layer from the surface layer. A layer (9) is provided, and the surface layer comprises one or more function-expressing substances selected from the group consisting of the following main components (A) to (C) and the following (m) to (o). A decorative sheet (11, 12, 13) with an adhesive, which comprises a cured product of a functional composition comprising.
(A) Hydrolyzed condensate of silicon alkoxide (B) Organo silica sol in which an aqueous silica sol is replaced with a hydrophilic solvent (C) Acrylic copolymer having a hydrophilic group and a hydrophobic group (m) Deodorant substance (n) Antiviral property Substance (o) Anti-allergenic substance A decorative sheet with a pressure-sensitive adhesive, which is one aspect of the present disclosure, exhibits functions such as deodorization, anti-virus, and anti-allergen.

It is sectional drawing which shows the structure of the decorative sheet with an adhesive of Example 1. FIG. It is sectional drawing which shows the structure of the decorative sheet with an adhesive of Example 83. It is sectional drawing which shows the structure of the decorative sheet with an adhesive of Example 86. It is sectional drawing which shows the main part of the structure of Example 87. It is sectional drawing which shows the main part of the structure of Example 88.

An exemplary embodiment of the present disclosure will be described with reference to the drawings.
1. 1. Decorative sheet with adhesive (1) (A) Hydrolyzed condensate of silicon alkoxide The decorative sheet with adhesive of the present disclosure includes a decorative sheet layer. The decorative sheet layer includes a surface layer. The surface layer contains a cured product of the functional composition. The functional composition contains (A) a hydrolyzed condensate of silicon alkoxide (hereinafter, also referred to as (A) component).

The component (A) has a grid-like skeleton. The component (A) uniformly disperses the function-expressing substance described later. Therefore, even if the amount of the function-expressing substance added is at least, the function-expressing substance is effective.
Examples of the silicon alkoxide include silicon alkoxide having a structure represented by the following chemical formula 1. n is an integer.

Examples of the silicon alkoxide having the structure represented by the chemical formula 1 include tetramethyl orthosilicate (Si (OCH ₃ ) ₄ ), tetraethyl orthosilicate (Si (OC _{2H 5) 4) and tetrapropyl orthosilicate (Si (OC 3 ) ) .} H ₇ ) ₄ ) and the like can be mentioned. Silicon alkoxide is synthesized, for example, by a reaction between silicon tetrachloride and an alkyl alcohol, or a reaction between metallic silicon and an alkyl alcohol.

When silicon alkoxide and water are mixed and reacted, hydrolysis proceeds according to the reaction formula shown in Chemical Formula 2. m is an integer.

Methanol, ethanol, isopropanol, ethyl cellosolve, mixed alcohol and the like are used as solvents to stabilize the hydrolyzed solution.
As commercial products of hydrolysis condensate of silicon alkoxide, "HAS-1" (SiO ₂ content 20.7 to 21.5% by mass, ethanol / isopropanol / methanol mixed solvent), "HAS-6" (SiO ₂ containing) Examples thereof include an amount of 17.6 to 18.4% by mass, ethanol / methanol mixed solvent), "HAS-10" (SiO ₂ content 10.0 to 10.4% by mass, ethanol / isopropanol / methanol mixed solvent), and the like. .. "HAS-1", "HAS-6", and "HAS-10" are trade names manufactured by Corcourt Co., Ltd.

(2) (B) Organo silica sol obtained by substituting an aqueous silica sol with a hydrophilic solvent The adhesive-attached decorative sheet of the present disclosure comprises a decorative sheet layer. The decorative sheet layer includes a surface layer. The surface layer contains a cured product of the functional composition. The functional composition contains (B) an organosilica sol in which an aqueous silica sol is replaced with a hydrophilic solvent (hereinafter, also referred to as a component (B)).

Examples of the organosilica sol as the component (B) include a colloidal solution in which colloidal silica having an average particle diameter of 1 to 40 nm is stably dispersed in an organic solvent. It is more preferable that the average particle size of colloidal silica is 7 to 30 nm.

The silica concentration in the component (B) is preferably in the range of 1 to 50% by mass. The silica concentration in the component (B) is more preferably 40% by mass or less. When the silica concentration in the component (B) is 40% by mass or less, gelation can be suppressed. The average particle size of colloidal silica is the particle size at an integrated value of 50% in the particle size distribution obtained by the laser diffraction / scattering method.

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

When the organosilica sol is dispersed in a hydrophilic solvent among organic solvents, the amount of hydroxyl groups on the surface of the silica particles becomes sufficiently large, the hydroxyl groups on the surface of the silica particles adhere to the melamine resin, and the surface durability of the decorative sheet with an adhesive is improved. Excellent. When the organosilica sol is dispersed in a hydrophobic solvent, the amount of hydroxyl groups on the silica surface is insufficient, and for example, the adhesion of the melamine resin layer tends to be inferior.

Here, the hydrophilic solvent is a solvent having an affinity with water. The hydrophilic solvent is a polar solvent. The hydrophilic solvent has, for example, a hydrophilic group such as a hydroxyl group, a carboxyl group, or a carbonyl group in the molecule. Examples of the hydrophilic solvent include a protic polar solvent and an aprotic polar solvent. Examples of the protonic polar solvent include alcohol solvents such as methyl alcohol, ethyl alcohol, isopropanol, ethylene dialcohol and propanol, and cellosolve solvents such as methyl cellosolve, ethyl cellosolve, butyl cellosolve and n-propyl cellosolve. Examples of the aprotic polar solvent include acetone, dimethyl sulfoxide (DMSO), N, N-dimethylformamide (DME), pyridine and the like.

(3) (C) Acrylic copolymer having a hydrophilic group and a hydrophobic group The adhesive decorative sheet of the present disclosure comprises a decorative sheet layer. The decorative sheet layer includes a surface layer. The surface layer contains a cured product of the functional composition. The functional composition contains (C) an acrylic copolymer having a hydrophilic group and a hydrophobic group (hereinafter, also referred to as a component (C)).

As the acrylic polymer of the component (C), a copolymer of a monomer having a hydrophilic group exhibiting an affinity with a pigment and a monomer having a hydrophobic group that controls compatibility and forms a steric hindrance is preferable. .. In such an acrylic polymer, the hydrophilic group adsorbs the function-expressing substance and the hydrophobic group suppresses aggregation, so that the function-expressing substance can be uniformly dispersed.

The organosilica sol having a particle size of about 20 to 30 nm aggregates to form a large aggregate having a particle size of 600 to 1000 nm. The component (C) uniformly disperses the aggregate of the organosilica sol. Therefore, the light scattering property of the cured product of the functional composition is enhanced, and the appearance defect due to the interference of light can be reduced.

Examples of the hydrophilic group include 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. Examples of the monomer having a hydrophilic group include acrylic acid, acrylamide, methacrylic acid, poly (ethylene glycol) acrylate and methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, t-butylaminoethyl methacrylate, dimethylaminoethyl acrylate, and diethylamino. Ethyl acrylate, methacrylic amide, dimethacrylic amide, dimethylaminopropyl methacrylic amide, ethylene glycol methacrylate phosphate, 2- (methacrylicloyloxy) methylphthalate, 2- (methacrylicloyloxy) ethyl succinate, 3-sulfopropylmethacrylate, 3-sulfo Examples thereof include propyl acrylate.

Examples of the hydrophobic group include an alkyl group and a phenyl group. Examples of the monomer having a hydrophobic group include methyl methacrylate, butyl methacrylate, hexyl acrylate, hexyl ethyl acrylate, benzyl acrylate, benzyl methacrylate, phenoxyethyl acrylate, phenoxyethyl methacrylate, and a mixture thereof.

(4) Main component The adhesive-attached decorative sheet of the present disclosure includes a decorative sheet layer. The decorative sheet layer includes a surface layer. The surface layer contains a cured product of the functional composition. The functional composition contains a main component containing the components (A) to (C).

In the main component, the component (B) is preferably blended in an amount of 0.5 to 12 parts by mass, more preferably 1 to 9 parts by mass with respect to 1 part by mass (in terms of solid content) of the component (A). When the blending ratio of the component (A) is equal to or higher than the above lower limit value, the effect of expressing the functionality of the surface layer is further improved. When the blending ratio of the component (A) is not more than the above upper limit value, the solvent resistance of the surface layer is improved. The functional expression effect is, for example, an effect of expressing functions such as deodorant, antiviral, and antiallergen.

The component (C) is 0.005 to 0.3 parts by mass (in terms of solid content), more preferably 0.01 to 0.07 parts by mass (in terms of solid content) with respect to 1 part by mass (in terms of solid content) of the component (B). (Solid content conversion) is preferable. When the blending ratio of the component (C) is not more than the above upper limit value, the cohesiveness of colloidal silica is suppressed, and the appearance deterioration due to the interference of light on the surface layer can be suppressed. Further, when the blending ratio of the component (C) is not more than the above lower limit value, the viscosity of the functional composition becomes appropriate and a uniform surface layer can be formed. As a result, fingerprints are less noticeable on the surface layer, and for example, a decorative sheet with an adhesive has a clearer pattern on printing paper.

The main component including the component (A), the component (B), and the component (C) improves the dispersibility of the function-expressing substance to be added. Specifically, since the function-expressing substance enters into the lattice-shaped coating film structure of the component (A), the function-expressing substance can be uniformly applied, and even when the amount of the function-expressing substance added is small, the function-expressing substance can be uniformly applied. Efficient expression of function becomes possible. In particular, when the function-expressing substance contains solid particles, for example, solid particles having an average particle diameter of 200 to 5000 nm, the above effects can be easily obtained. The average particle size referred to here is the particle size at an integrated value of 50% in the particle size distribution obtained by the laser diffraction / scattering method.

(5) Function-expressing substance The adhesive-attached decorative sheet of the present disclosure includes a decorative sheet layer. The decorative sheet layer includes a surface layer. The surface layer contains a cured product of the functional composition. The functional composition comprises a functional expression substance. The function-expressing substance is at least one selected from the group consisting of (m) deodorant substance, (n) antiviral substance, and (o) antiallergenic substance.

For example, it is preferable to mix the main component and the function-expressing substance and stir with a homogenizer at 6000 to 10000 rpm for 5 to 10 minutes. The homogenizer pressurizes a mixture of the main component and the function-expressing substance at high pressure. When the mixture passes through the slit (gap), a strong shearing force is applied to the mixture. Therefore, in the functional composition, the functional expression substance can be uniformly dispersed.

As a function-expressing substance, there is (m) a deodorant substance. (M) The deodorant substance is, for example, a porous material. (M) As the deodorant substance, for example, there is a physical adsorption type deodorant substance. Examples of the physical adsorption type deodorant substance include activated carbon and the like. The physical adsorption type deodorant substance exhibits a deodorizing effect by adsorbing an odor or gas in the pores of the porous material. When a physically adsorbed deodorant substance is exposed to heat such as high temperature heat or frictional heat after adsorbing a gas at room temperature, the adsorption performance is deteriorated and the adsorbed gas may be re-emitted.

(M) As the deodorant substance, for example, there is a chemisorbent type deodorant substance. Chemically adsorbed deodorant substances are removed by changing the odor to other substances by chemical reactions such as neutralization action by acid / alkali and oxidation / reduction action. Chemisorbent deodorant substances, once adsorbing an odor or gas and changing to another substance, do not easily re-emit the odor or gas. Therefore, as the (m) deodorant substance, a chemisorbent type deodorant substance is suitable. Examples of chemically adsorbed deodorant substances include silica (silicon dioxide), copper oxide, alumina, titanium oxide, zinc oxide, iron oxide, metal oxides such as zirconium hydride, zirconium hydride, magnesium hydroxide, and hydroxide. Examples thereof include metal hydroxides such as aluminum, ferrous hydroxide, and copper hydroxide.

(M) The deodorant substance can suppress the living odor generated in the house. Examples of daily odors include acidic odors, neutral odors, basic odors, and complex odors thereof. Houses in recent years are more airtight and highly insulated than conventional houses. Therefore, the interior of a house in recent years has become a closed space with no gaps. As a result, it is easier to feel the odor of life in recent houses. (M) The deodorant substance can suppress the daily odor.

As the chemically adsorbed deodorant substance, for example, one or more selected from the group consisting of zinc oxide, silica, zeolite, copper oxide, and zirconium oxide is preferable. For example, as a chemisorbent-type deodorant substance, it is preferable that zinc oxide and silica are contained and the mixing ratio of both is the former: the latter = 45 to 85:55 to 15 in terms of mass ratio.

(M) As the deodorant substance, a fine particle deodorant substance is preferable. The average particle size of the fine particle deodorant substance is preferably 0.2 to 10 μm. When the (m) deodorant substance is a fine particle deodorant substance, the (m) deodorant substance has good dispersibility in the functional composition. The average particle size referred to here is the particle size at an integrated value of 50% in the particle size distribution obtained by the laser diffraction / scattering method.

For neutral odors such as acetaldehyde and formaldehyde, and basic odors such as ammonia trimethylamine, (m) when modified silica, for example, amino-modified silica is used as the deodorizing substance, the deodorizing effect is high. For sulfur-based gases such as hydrogen sulfide and mercaptans, and acidic odors such as isovaleric acid acetate and butyric acid, zinc oxide is used as the (m) deodorant substance to have a high deodorizing effect. Zeolites may be zeolite silver-containing substances (ie, silver-containing zeolites).

The blending amount of the (m) deodorant substance with respect to the main component is preferably 30 to 60 parts by mass (in terms of solid content) with respect to 100 parts by mass of the solid content of the main component. (M) When the blending amount of the deodorant substance is less than the above lower limit value, the deodorizing effect tends to be small. (M) When the blending amount of the deodorant substance exceeds the above upper limit value, whitening unevenness is likely to occur on the surface layer. The whitening unevenness here means a partially whitish and blurred part occurring on the surface layer.

As the function-expressing substance, there is (n) an antiviral substance. (N) The antiviral substance exhibits antiviral properties. Examples of the antiviral substance include a photocatalyst. Examples of the photocatalyst include titanium oxide and the like. The photocatalyst generates active oxygen by excitation light and inactivates the virus. The effect of the photocatalyst lasts semi-permanently in principle. Photocatalysts cannot exhibit their performance without irradiation with light.

(N) Examples of the antiviral substance include organic antiviral substances. Organic antiviral substances destroy the outer wall membrane of viral proteins. Viruses whose outer wall membrane is destroyed inhibit protein synthesis. Alternatively, organic antiviral substances denature proteins and inactivate viruses. Organic antiviral substances are characterized in that their effects appear faster than photocatalytic substances.

As the organic antiviral substance, for example, one or more selected from the group consisting of a triazine-imidazole-thiazole substance, an amino-modified polyvinyl alcohol, and an amino-modified acrylic polymer is preferable. These organic antiviral substances are suitable for decorative sheets with adhesives that require solvent resistance and stain resistance.

The organic antiviral substance is preferably in the form of fine particles. The fine particle-like organic antiviral substance is preferably selected from the group consisting of, for example, particles carrying a triazine-imidazole-thiazole substance, amino-modified polyvinyl alcohol particles, and amino-modified acrylic polymer particles. The average particle size of the fine particle organic antiviral substance is preferably 0.5 to 3 μm. When the average particle size of the fine particle organic antiviral substance is 0.5 to 3 μm, the dispersibility of the fine particle organic antiviral substance in the functional composition is good. The average particle size referred to here is the particle size at an integrated value of 50% in the particle size distribution obtained by the laser diffraction / scattering method.

The blending amount of the (n) antiviral substance in the functional composition is preferably 35 to 75 parts by mass (in terms of solid content) with respect to 100 parts by mass of the solid content of the main component. (N) If the blending amount of the antiviral substance does not reach the above lower limit value, the antiviral effect tends to be small. (N) When the blending amount of the antiviral substance exceeds the above upper limit value, uneven whitening tends to occur on the surface layer.

As the function-expressing substance, there is (o) an anti-allergenic substance. (O) Anti-allergenic substances exhibit anti-allergenic properties. Invisible dust is floating in the air, and the dust contains allergen substances such as cedar pollen, dead mites, and dung. Allergenic substances cause allergies.

(O) As the anti-allergenic substance, a composite of an anion-modified organic compound and a carrier is preferable. The complex exerts the effect of reducing the allergen substance by chemically adsorbing it to the protein of the allergen substance. The complex can be physically attached to the surface layer. Therefore, the complex can maintain its anti-allergenicity for a long time.

(O) The same reduction effect is exhibited even when the anti-allergenic substance is only an anion-modified organic compound. However, when (o) the anti-allergenic substance is only an anion-modified organic compound, it becomes difficult to (o) fix the anti-allergenic substance to the surface layer. As a result, it is difficult to maintain anti-allergenicity for a long period of time.

Examples of the anion-modified organic compound include anion-modified linear alkanes and anion-modified polyvinyl alcohol. Examples of the anion-modified linear alkane include a linear alkane modified with an acidic anion group such as a carboxyl group, a phosphoric acid group, and a sulfonic acid group. Examples of the counter ion of the acidic anion group include sodium ion and potassium ion. Examples of the anion-modified polyvinyl alcohol include polyvinyl alcohol modified with a basic anion group such as a carboxyl group and a sulfonic acid group.

In addition, examples of the carrier include inorganic particles and organic particles. Examples of the inorganic particles include silver oxide particles and the like. Examples of the organic particles include acrylic particles such as base-modified acrylic particles and styrene particles such as base-modified styrene particles. As the carrier, one or more selected from the group consisting of styrene particles and silver oxide is preferable.

(O) As the anti-allergenic substance, a fine particle anti-allergenic substance is preferable. The average particle size of the fine particle antiallergenic substance is preferably 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 obtained by the laser diffraction / scattering method.

In the functional composition, the blending amount of (o) the anti-allergenic substance is preferably 3 to 50 parts by mass (in terms of solid content) with respect to 100 parts by mass of the solid content of the main component. (O) If the blending amount of the anti-allergen substance does not reach the above lower limit value, the anti-allergen effect tends to be small. (O) When the blending amount of the anti-allergenic substance exceeds the above upper limit value, uneven whitening is likely to occur on the surface layer.

When (m) a deodorant substance and (n) an antiviral substance are used in combination, (m) the ratio of the mass of the (n) antiviral substance to the mass of the deodorant substance (m: n in the following). The mixing ratio) is preferably 0.5 to 2.50, and more preferably 0.60 to 2.0. The m: n compounding ratio is a value obtained by dividing the mass of (n) the antiviral substance by the mass of (m) the deodorant substance.

When the m: n compounding ratio is out of the above range, the balance between deodorant property and antiviral property is likely to be lost.
In the functional composition, the total amount of the (m) deodorant substance and (n) antiviral substance is preferably 60 to 150 parts by mass with respect to 100 parts by mass of the solid content of the main component. It is more preferably 75 to 115 parts by mass. When the total amount of the (m) deodorant substance and (n) antiviral substance is within the above range, the cosmetic sheet with an adhesive is particularly excellent in appearance, deodorant property, and antiviral property. When the total amount of the (m) deodorant substance and (n) antiviral substance is less than the above lower limit, the deodorant and antiviral properties are slightly inferior. When the total amount of the (m) deodorant substance and (n) antiviral substance exceeds the above upper limit, whitening unevenness is likely to occur on the surface layer.

When (m) a deodorant substance and (o) an anti-allergenic substance are used in combination, (m) the ratio of the mass of the (o) anti-allergenic substance to the mass of the deodorant substance (m: o in the following). The mixing ratio) is preferably 0.03 to 2.0, and more preferably 0.08 to 1.8. The m: o compounding ratio is a value obtained by dividing the mass of (o) the anti-allergenic substance by the mass of (m) the deodorant substance.

When the m: o compounding ratio is out of the above range, the balance between deodorant property and anti-allergenic property is likely to be lost.
In the functional composition, the total amount of the (m) deodorant substance and (o) anti-allergenic substance is preferably 30 to 16 parts by mass with respect to 100 parts by mass of the solid content of the main component, which is 35. It is more preferably up to 110 parts by mass. If the total amount of the (m) deodorant substance and (o) anti-allergenic substance is within the above range, the cosmetic sheet with an adhesive having particularly excellent appearance, deodorant property, and anti-allergen property is obtained. When the total amount of the (m) deodorant substance and (o) anti-allergenic substance is less than the above lower limit, the deodorant and anti-allergenic properties are slightly inferior. When the total amount of the (m) deodorant substance and (o) anti-allergenic substance exceeds the above upper limit, whitening unevenness is likely to occur on the surface layer.

When (n) an antiviral substance and (o) an antiallergenic substance are used in combination, (n) the ratio of the mass of the (o) antiallergenic substance to the mass of the antiviral substance (n: o in the following). The mixing ratio) is preferably 1: 0.01 to 2.0, and more preferably 0.06 to 1.50. The n: o compounding ratio is a value obtained by dividing (o) the mass of the anti-allergenic substance by (n) the mass of the anti-viral substance.

When the n: o compounding ratio is out of the above range, the balance between the antiviral property and the anti-allergenic property is likely to be lost.
In the functional composition, the total amount of the (n) antiviral substance and (o) antiallergenic substance is preferably 15 to 200 parts by mass with respect to 100 parts by mass of the solid content of the main component, 35. It is more preferably up to 125 parts by mass. When the total amount of the (n) antiviral substance and the (o) antiallergenic substance is within the above range, the cosmetic sheet with an adhesive having particularly excellent appearance, antiviral property, and antiallergen property is obtained. When the total amount of the (n) antiviral substance and (o) antiallergenic substance is less than the above lower limit, the antiviral and antiallergenic properties are slightly inferior. When the total amount of the (n) antiviral substance and the (o) antiallergenic substance exceeds the above upper limit, whitening unevenness is likely to occur on the surface layer.

When (m) a deodorant substance, (n) an antiviral substance and (o) an antiallergenic substance are used in combination, the m: n blending ratio is preferably 0.20 to 7.0. It is more preferably 0.6 to 4.5. The m: o blending ratio is preferably 0.05 to 5.5, more preferably 0.15 to 3.0.

In the functional composition, the total amount of (m) deodorant substance, (n) antiviral substance, and (o) antiallergenic substance is 30 to 170 with respect to 100 parts by mass of the solid content of the main component. It is preferably parts by mass, more preferably 50 to 120 parts by mass.

If the total amount of m: n compounding ratio, m: o compounding ratio, and (m) deodorant substance, (n) antiviral substance, and (o) antiallergenic substance is within the above range. , Appearance, deodorant property, anti-virus property, anti-allergenic property are well-balanced and excellent, and even when the amount of the functional composition applied is small, the synergistic effect has the same or higher function than the function exhibited by the function-expressing substance alone. It becomes a decorative sheet with an adhesive that demonstrates. Of course, in order to make any function stand out in a desired range, the blending amount of any of (m) deodorant substance, (n) antiviral substance, and (o) antiallergenic substance should be appropriately adjusted. Can be done.

(6) Decorative layer The decorative sheet with an adhesive of the present disclosure includes a decorative sheet layer. The decorative sheet layer includes a decorative layer. The decorative layer contains, for example, a cured product of melamine resin. The decorative layer includes, for example, a melamine resin impregnated pattern paper. The melamine resin impregnated pattern paper is, for example, a decorative paper having a basis weight of about 80 to 140 g / m ² impregnated with a resin solution containing a melamine resin as a main component (hereinafter referred to as a melamine resin solution) and dried. be. The impregnation rate defined by the formula 1 in the melamine resin impregnated pattern paper is preferably in the range of 70 to 160%.

For example, an overlay layer is provided on the melamine resin impregnated pattern paper. For example, a melamine resin-impregnated overlay paper is arranged on the overlay layer. The melamine resin-impregnated overlay paper is, for example, an overlay paper having a basis weight of about 16 to 60 g / m ² impregnated with a melamine resin solution and dried. The overlay layer has a function of protecting the pattern of the decorative paper, for example. The overlay layer contains, for example, a cured product of melamine resin.

(7) Surface layer The adhesive-attached decorative sheet of the present disclosure includes a decorative sheet layer. The decorative sheet layer includes a surface layer. The surface layer is located, for example, on the surface of the decorative sheet layer. The surface layer is laminated on the overlay layer, for example. The surface layer contains a cured product of the functional composition. The functional composition contains a main component containing the components (A) to (C) and one or more functional expression substances selected from the group consisting of (m) to (o).

Examples of the method for forming the surface layer include a coating method and a transfer method. The coating method is a method of applying a coating liquid containing a functional composition on a decorative layer. In the transfer method, a transfer sheet is prepared. The transfer sheet includes a sheet-like substrate and a cured layer formed on one side of the sheet-like substrate. The cured layer is a layer composed of a cured product of the functional composition.

Next, the transfer sheet, the decorative layer, the mixed papermaking layer, and the core layer are laminated in this order to form a laminated body. Alternatively, the transfer sheet, the decorative layer, the core layer, and the mixed papermaking layer are laminated in this order to form a laminated body. The orientation of the transfer sheet is such that the cured layer faces the decorative layer. When the decorative layer comprises an overlay layer, the cured layer of the transfer sheet is in contact with the overlay layer. When the decorative layer does not include an overlay layer, the cured layer of the transfer sheet is in contact with, for example, the melamine resin impregnated pattern paper constituting the decorative layer. Next, the laminate is hot-press molded. Next, the sheet-like substrate of the transfer sheet is removed. The cured layer of the transfer sheet is transferred and becomes a surface layer.

Examples of the sheet-like substrate used in the transfer method include a plastic film and a metal foil. Examples of plastic films include polyester film, polyethylene film, polypropylene film, cellophane, diacetyl cellulose film, triacetyl cellulose film, acetyl cellulose butyrate film, polyvinyl chloride film, polyvinylidene chloride film, polyvinyl alcohol film, and ethylene vinyl alcohol film. , Polystyrene film, polycarbonate film, polymethylpentene film, polysulfone film, polyether ketone film, polyether sulfone film, polyetherimide film, polyimide film, fluororesin film, nylon film, acrylic film and the like.

Examples of the metal foil include gold foil, silver foil, copper foil, zinc foil, indium foil, aluminum foil, tin foil, iron foil (including stainless steel (SUS) foil), titanium foil and the like.
The method for producing a transfer sheet is, for example, a method of applying a coating liquid containing a functional composition to a sheet-like substrate. As a method of applying the coating liquid to the sheet-like substrate, for example, a spray coating method, a gravure coating method, a bar coating method, a knife coating method, a roll coating method, a blade coating method, a die coating method, a curtain coating method, and a reverse coating method. , Commacoat method, etc.

When the functional composition contains (m) a deodorant substance, the thickness of the surface layer is preferably 2.0 to 6.5 μm in a dry state regardless of whether the coating method or the transfer method is used. When the thickness of the surface layer is 2.0 μm or more, the deodorizing performance is higher. When the thickness of the surface layer is 6.5 μm or less, uneven whitening is unlikely to occur on the surface layer.

When the functional composition contains (n) an antiviral substance, the thickness of the surface layer is preferably 1.5 to 3.5 μm in a dry state regardless of whether the coating method or the transfer method is used. When the thickness of the surface layer is 1.5 μm or more, the antiviral performance is higher. When the thickness of the surface layer is 3.5 μm or less, uneven whitening is unlikely to occur on the surface layer.

When the functional composition contains (o) an anti-allergenic substance, the thickness of the surface layer is preferably 2.0 to 8.0 μm in a dry state regardless of whether the coating method or the transfer method is used. When the thickness of the surface layer is 2.0 μm or more, the anti-allergen performance is higher. When the thickness of the surface layer is 8.0 μm or less, uneven whitening is unlikely to occur on the surface layer.

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 likely to be destroyed, and uneven whitening is likely to occur on the surface layer.

The pH of the coating liquid means the pH measured in the coating liquid adjusted so that the solid content concentration is 20% by mass. The solid content concentration is the concentration of the solid content of the main component and the function-expressing substance contained in the functional composition. Further, the pH value is obtained based on the operation of the glass electrode method by a method according to JIS Z8802: 2011 "pH measuring method".

(8) Mixed Paper Layer The decorative sheet with an adhesive of the present disclosure includes a decorative sheet layer. The decorative sheet layer includes a mixed papermaking layer. The mixed paper layer is a layer composed of mixed paper.

The mixed paper is based on, for example, magnesium silicate mixed paper having water of crystallization. The magnesium silicate mixed paper having bound water is a mixed paper containing a magnesium silicate compound having bound water. Magnesium silicate mixed paper is produced by making a slurry containing pulp and a magnesium silicate compound having bound water, dehydrating and drying the paper. At this time, a coagulating binder, a chemical, an organic fiber, an inorganic fiber, a fixing agent and the like may be added to the slurry.

In order to make the slurry into paper, it is preferable to use a round net paper machine, a long net multi-cylinder paper machine, a long net-circle net combination paper machine, an inclined paper machine, or the like. The basis weight of the magnesium silicate mixed paper is preferably 60 to 400 g / m ² . Magnesium silicate mixed paper has self-extinguishing property and can suppress the spread of flame. Examples of the pulp include natural pulp such as wood pulp, cotton pulp, and plant fiber pulp. As the pulp, it is particularly preferable to use a chemical pulp obtained by chemically treating wood pulp having a short fiber length, such as broad-leaved bleached kraft pulp and softwood kraft pulp, because it has high paper strength and excellent impregnation property. Hardwood bleached kraft pulp and softwood kraft pulp may be used in combination. The hardwood bleached kraft pulp and the softwood kraft pulp may be either bleached or unbleached.

Examples of the magnesium silicate compound having bound water include hydrous magnesium silicate [Mg ₈ Si ₁₂ O ₃₀ (OH ₂ ) ₄ (OH) ₄ 6 to 8H ₂ O] (sepiolite) and hydrous magnesium silicate [Mg ₃ Si ₄ O ₁₀ ]. (OH) ₂ ] (Tark), Hydrous Magnesium Aluminum Silate [Mg ₅ Si ₈ O ₂₀ (OH) ₂ (H ₂ O) 4.4H ₂ O] (Attapulsite), Hydrous Magnesium Aluminum Silate [(Mg, Fe, Al) ) ₃ (Al, Si) ₄ O ₁₀ (OH) _{2.4H 2 O} ] (vermiculite) and the like. In particular, sepiolite is preferable because it is excellent in nonflammability and water resistance.

When the mass of the magnesium silicate mixed paper is 100% by mass, the content of the magnesium silicate compound is preferably 40 to 95% by mass, more preferably 55 to 85% by mass. If the content of the magnesium silicate compound is less than 40% by mass, the nonflammable performance of the magnesium silicate mixed paper tends to decrease, and if it exceeds 95% by mass, the paper strength such as the tensile strength of the magnesium silicate mixed paper tends to decrease.
The mixed paper is, for example, a thermosetting resin-impregnated paper formed by impregnating a magnesium silicate mixed paper with a resin solution having a thermosetting resin and drying the mixed paper. The mixed paper is, for example, a flame retardant-impregnated paper formed by impregnating a magnesium silicate mixed paper with a flame retardant and drying it. By using the thermosetting resin-impregnated paper or the flame retardant-impregnated paper, the balance is improved and the warp of the finished decorative sheet with an adhesive can be suppressed. The fibrous substrate used for the thermosetting resin-impregnated paper or the flame retardant-impregnated paper may have heat resistance.
Examples of the thermosetting resin used for the thermosetting resin-impregnated paper include amino-formaldehyde resin, phenol-aldehyde resin, vinyl ester resin and the like. The amino-formaldehyde resin can be obtained by condensing formaldehyde with an amino compound such as melamine, urea, acetoguanamine or benzoguanamine.
The phenol-aldehyde resin is obtained by reacting phenols and aldehydes at a ratio of 1 to 1.3 mol of aldehydes to 1 mol of phenolic hydroxyl groups under a basic catalyst. Examples of the phenols include phenol, cresol, xylenol, octylphenol, phenylphenol, bisphenol A, bisphenol S, bisphenol F and the like.

Examples of aldehydes include formaldehyde, paraformaldehyde, glyoxal and the like.
If necessary, the phenol-aldehyde resin may be a modified phenol-aldehyde resin modified with a modifier that promotes plasticization, such as parasulphonamide, tung oil, phosphate esters, and glycols.
Examples of the basic catalyst include alkali metals such as sodium and potassium, and oxides and hydroxides of alkaline earth metals such as magnesium and calcium. In addition, examples of other basic catalysts include, for example, amines such as triethylamine and triethanolamine, ammonia and the like.
The vinyl ester resin is obtained by reacting an epoxy resin with an unsaturated monobasic acid using an esterification catalyst. Examples of the epoxy resin include bisphenol A-based epoxy resin, halogenated bisphenol A-based epoxy resin, diglycidyl ether as an adduct of bisphenol A and an alkylene oxide such as ethylene oxide or propylene oxide, bisphenol F-based epoxy resin, and novolak-based epoxy. Examples thereof include resins and cresol novolac epoxy resins.

Examples of the unsaturated monobasic acid include acrylic acid, methacrylic acid, crotonic acid, monomethylmalate, monopropylmalate, sorbic acid, mono (2-ethylhexyl) malate and the like, and even if polybasic acid is used in combination. good. Polybasic acids used in combination with unsaturated monobasic acids include, for example, succinic acid, maleic acid, fumaric acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, adipic acid, azelaic acid, 1,12-dodecanedioic acid. Other examples include dimer acid and the like.
As the esterification catalyst, for example, tertiary amines such as dimethylbenzylamine and tributylamine; quaternary ammonium salts such as trimethylbenzylammonium chloride; inorganic salts such as lithium chloride and chromium chloride; 2-ethyl-4-methyl. Imidazole compounds such as imidazole; tetramethylphosphonium chloride, diethylphenylpropylphosphonium chloride, triethylphenylphosphonium chloride, benzyltriethylphenylphosphonium chloride, dibenzylethylmethylphosphonium chloride, benzylmethyldiphenylphospho Phosphonium salts such as nium chloride and tetraphenylphosphonium bromide; secondary amines; tetrabutylurea; triphenylphosphine; tritrilphosphine; triphenylstibin and the like can be mentioned.

(9) Core layer The adhesive-attached decorative sheet of the present disclosure includes a decorative sheet layer. The decorative sheet layer includes a core layer.

The core layer contains, for example, one or more prepregs containing a fibrous substrate. The prepreg is produced, for example, by impregnating a fibrous substrate with a slurry containing a binder component and drying it. The prepreg is produced by impregnating a fibrous substrate with a slurry containing, for example, a binder component and an endothermic metal hydroxide, and drying the prepreg.
Examples of the fibrous base material used for the prepreg include an organic fiber base material and an inorganic fiber base material. Examples of the organic fiber base material include non-woven fabrics and woven fabrics made of organic fibers containing organic components. Examples of the organic component contained in the organic fiber include polyethylene, polypropylene, vinylon, polyvinylidene chloride, polyvinylidene chloride, polyacrylonitrile, polyamide, polyester, polyurethane and the like, or variants thereof, ethylene-vinyl acetate copolymer and the like. Examples thereof include various copolymers typified by the above, or mixtures thereof.
Examples of the inorganic fiber base material include non-woven fabrics and woven fabrics made of inorganic fibers containing an inorganic component. Examples of the inorganic component contained in the inorganic fiber include glass fiber, rock wool, carbon fiber and the like.
When the inorganic fiber base material is used, the nonflammability of the decorative sheet with an adhesive is further improved as compared with the case where the organic fiber base material is used. Among the inorganic fiber base materials, the non-woven fabric containing glass fiber has no fiber direction. Therefore, when a non-woven fabric containing glass fiber is used, the warp of the decorative sheet with an adhesive is suppressed. Further, when a non-woven fabric containing glass fiber is used, the heat resistance, flame resistance, and slurry impregnation property of the decorative sheet with an adhesive are further improved.
In the prepreg used for the core layer, the basis weight of the inorganic fiber base material is preferably in the range of 10 to 200 g / m ² . The prepreg constituting the core layer preferably further contains a binder component in addition to the fibrous base material. The binder component is made of, for example, a thermoplastic resin.
The binder component plays a role as a binder. The binder component binds the materials constituting the prepreg, between the prepregs, and the core layer composed of the prepreg and the layer adjacent to the core layer.
As the binder component, a thermoplastic resin is preferable. The prepreg of the core layer preferably contains an acrylic resin emulsion. Acrylic resin emulsion is preferable as the thermoplastic resin as a binder component. In particular, it is more preferable to use an acrylic resin emulsion having a glass transition temperature (Tg) of −20 ° C. or higher because the adhesion and moldability of the core layer are improved. Among them, it is more preferable to use an acrylic resin emulsion having an average particle size of 150 to 300 nm because the binding force of the core layer and the bendability and smoothness of the decorative sheet with an adhesive can be further improved. It is presumed that the reason why the smoothness is improved is that the acrylic resin emulsion is fine particles. The acrylic resin emulsion is obtained by emulsion polymerization or suspension polymerization in water using (meth) acrylic acid ester as a main monomer. Examples of the monomer used for producing the acrylic resin emulsion include esters of (meth) acrylic acid such as methyl, ethyl, propyl, butyl and hydroxyethyl. In addition to these monomers, other copolymerizable monomers or polyfunctional monomers may be copolymerized.
The average particle size is a value calculated based on the scattered light detected during laser irradiation using a laser light diffraction / scattering type particle size measuring device (ELS-8000 manufactured by Otsuka Electronics Co., Ltd.).
The mixing ratio of the thermoplastic resin in the slurry impregnated in the fibrous base material in the prepreg is preferably 3 to 17% by mass in terms of solid content. When the compounding ratio of the thermoplastic resin is 17% by mass or less, the nonflammability of the decorative sheet with an adhesive is further improved, and the synthetic resin exudes from the prepreg during thermal pressure molding of the decorative sheet layer. Can be suppressed. Further, when the compounding ratio of the thermoplastic resin is 3% by mass or more, the adhesion between the prepregs is further improved, and the amount of the slurry impregnated into the fibrous substrate is further easily controlled.
The amount of the thermoplastic resin in the core layer is preferably 10 to 100 g / m ² . The amount of the thermoplastic resin in the core layer is the weight of the thermoplastic resin in the core layer of a unit area. When the amount of the thermoplastic resin is 100 g / m ² or less, the nonflammability of the decorative sheet with an adhesive is further improved. Further, when the amount of the thermoplastic resin is 100 g / m ² or less, it is possible to prevent the thermoplastic resin from seeping out when the decorative sheet layer is manufactured by thermal pressure molding.
When the amount of the thermoplastic resin in the core layer is 10 g / m ² or more, the adhesion between the prepregs constituting the core layer is further improved. Further, when the amount of the thermoplastic resin is 10 g / m ² or more, the amount of the slurry impregnated can be more easily controlled when the fibrous base material is impregnated with the slurry to produce the core layer.
The prepreg constituting the core layer preferably contains a heat-absorbing metal hydroxide in addition to the above-mentioned binder component in the fibrous base material.
The endothermic metal hydroxide is a metal hydroxide that can cause an endothermic reaction. Many endothermic metal hydroxides contain water of crystallization. Endothermic metal hydroxides decompose at high temperatures and release water. Since the reaction of the endothermic metal hydroxide is an endothermic reaction, the endothermic metal hydroxide has the effect of suppressing the temperature rise during combustion. When the core layer contains an endothermic metal hydroxide, the nonflammability of the adhesive decorative sheet is improved.
Examples of the heat-absorbing metal hydroxide include aluminum hydroxide, magnesium hydroxide, calcium hydroxide and the like, and aluminum hydroxide and magnesium hydroxide are particularly preferable. The solid content of the slurry impregnated in the fibrous substrate is 100 parts by mass. When the content of the endothermic metal hydroxide in the slurry is 20 to 95 parts by mass, the adhesiveness and non-combustible performance of the decorative sheet with an adhesive are improved.
The average particle size of the endothermic metal hydroxide can be, for example, in the range of 1 to 50 μm. This average particle diameter is an arithmetic average diameter calculated from the particle size distribution (volume distribution) detected by the laser diffraction / scattering method (microtrack method). When the average particle size of the endothermic metal hydroxide is within the above range, the dispersibility of the endothermic metal hydroxide in the slurry is improved, and the impregnation property of the slurry into the fibrous substrate is improved. In addition, the surface of the decorative sheet with an adhesive becomes smooth.
The amount of the endothermic metal hydroxide in the core layer is preferably in the range of 50 to 600 g / m ² . The amount of endothermic metal hydroxide in the core layer is the weight of the endothermic hydroxide in the core layer of a unit area. When the amount of the endothermic metal hydroxide in the core layer is within this range, the adhesion between the prepregs constituting the core layer becomes high, and the nonflammability of the decorative sheet with an adhesive is improved.
The slurry for the core layer may also contain an inorganic filler other than the endothermic metal hydroxide, a silane coupling agent, a flame retardant, and the like. Examples of the inorganic filler other than the heat-absorbing metal hydroxide include carbonates such as calcium carbonate, magnesium carbonate and zinc carbonate, silica, talc and fly ash. The average particle size of the inorganic filler is, for example, in the range of 0.05 to 20 μm. When the average particle size of the inorganic filler is within this range, the slurry impregnation property into the fibrous substrate is further improved. The average particle size of the inorganic filler is a value calculated by the arithmetic mean diameter calculated from the particle size distribution (volume distribution) detected by the laser diffraction / scattering method (microtrack method).
Among the inorganic fillers, it is particularly preferable to select carbonate, and among the carbonates, calcium carbonate is particularly preferable. When carbonate is selected, workability and machinability in the manufacturing process of the decorative sheet with an adhesive are further improved. As calcium carbonate, heavy calcium carbonate, light calcium carbonate (precipitated calcium carbonate) and the like can be used. The average particle size of calcium carbonate is, for example, 0.05 to 10 μm, more preferably 0.1 to 5 μm. When the average particle size of calcium carbonate is 0.05 μm or more, aggregation of calcium carbonate is less likely to occur in the slurry, and the impregnation property of the slurry into the fibrous substrate is improved. Further, when the average particle size of calcium carbonate is 10 μm or less, the surface of the decorative sheet with an adhesive is further smoothed, and the appearance of the decorative sheet with an adhesive is improved.
Light calcium carbonate means calcium carbonate that is chemically produced by burning limestone. The heavy calcium carbonate means fine powdered calcium carbonate produced by dry or wet pulverizing white crystalline limestone.
The blending ratio of the endothermic metal hydroxide in the total inorganic filler contained in the prepreg constituting the core layer can be 30 to 100% by mass. When the blending ratio is within this range, the nonflammability and machinability of the decorative sheet layer and the decorative sheet with an adhesive are further improved.
The slurry impregnated in the fibrous substrate for producing the prepreg constituting the core layer contains, for example, a silane coupling agent. When the slurry contains a silane coupling agent, the prepreg has a boiling resistance in the Japanese Industrial Standards JIS K-6902: 2007 "Thermosetting Resin High Pressure Decorative Board Test Method" as compared with the case where the silane coupling agent is not contained. The weight increase rate is further reduced, and the adhesion between the prepreg and the mixed paper layer is further improved. The blending ratio of the silane coupling agent in the prepreg constituting the core layer is preferably in the range of 0.1 to 10% by mass in the total components of the slurry in terms of solid content.
Examples of the silane coupling agent include (meth) acryloyloxy group-containing silanes such as 3- (meth) acryloyloxypropyltrimethoxysilane and 3- (meth) acryloyloxypropyltriethoxysilane, vinyltrimethoxysilane, and vinyltriethoxy. Vinyl group-containing silane such as silane, epoxy group-containing silane such as 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane Styryl group-containing silanes such as 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3- (2-aminoethyl) aminopropyltrimethoxysilane, 3phenylaminopropyltrimethoxysilane and other amino group-containing silanes. , 3-Mercaptopropyltrimethoxysilane, 3-Mercaptopropyltriethoxysilane, 3-Mercaptopropylmethyldimethoxysilane and other mercapto group-containing silanes. In particular, when an epoxy group-containing silane or an amino group-containing silane is used, the crosslink density in the prepreg is further improved.
The amount of the silane coupling agent is preferably in the range of 1 to 20 g / m ² . When the amount of the silane coupling agent is within this range, the effect of the above-mentioned silane coupling agent becomes more remarkable. The amount of the silane coupling agent is the weight of the silane coupling agent contained in the core layer of a unit area.
The core layer preferably contains a flame retardant. The flame retardant is included, for example, in the slurry for forming the prepreg.
As the flame retardant, for example, a phosphorus-based flame retardant, a nitrogen-based flame retardant, and a phosphorus / nitrogen-based flame retardant are preferable. Examples of the phosphorus-based flame retardant include a phosphoric acid ester, a phosphorus-containing polyol, and a phosphorus-containing amine. Examples of the nitrogen-based flame retardant include melamine cyanurate, triazine compound, guanidine compound and the like. Examples of the phosphorus / nitrogen flame retardant include guanidine phosphate, guanylurea phosphate and the like.

The phosphorus / nitrogen flame retardant is a compound having both functions of a phosphorus flame retardant and a nitrogen flame retardant. Phosphorus-nitrogen flame retardants have both phosphorus and nitrogen atoms in one molecule. When a phosphorus / nitrogen flame retardant is exposed to a high temperature, phosphorus blocks oxygen by a strong dehydrating action, and nitrogen generates ammonia gas or the like to block oxygen. Therefore, the phosphorus / nitrogen flame retardant improves the heat insulating / flame retardant effect and makes the prepreg hard to burn. The total nitrogen content of the flame retardant is preferably in the range of 1 to 50% by mass. The blending ratio of the flame retardant is preferably in the range of 0.1 to 15% by mass with respect to all the components of the slurry in terms of solid content. When the thermosetting resin in the decorative sheet layer is an amino-formaldehyde resin, particularly a melamine-formaldehyde resin, the flame retardant contained in the core layer is preferably a nitrogen-based flame retardant. In this case, the adhesive strength between the core layer and other layers is improved.
The amount of the flame retardant is preferably in the range of 1 to 100 g / m ² . Within this range, the effect of the above-mentioned flame retardant becomes more remarkable. The amount of flame retardant is the weight of the flame retardant in the core layer of a unit area.
When the fibrous substrate is impregnated with the slurry for producing the core layer, it is preferable that the impregnation rate defined in the above formula 1 is in the range of 500 to 1200%. When the impregnation rate is 1200% or less, the loss of the slurry solid content from the prepreg can be suppressed, and the prepreg can be easily handled. When the impregnation rate is 500% or more, delamination of the prepreg is less likely to occur.
(10) Adhesive layer The decorative sheet with an adhesive of the present disclosure includes an adhesive layer. The pressure-sensitive adhesive layer is provided on the side of the decorative sheet layer opposite to the surface layer.

The pressure-sensitive adhesive layer has a pressure-sensitive adhesive. The pressure-sensitive adhesive layer may have not only the pressure-sensitive adhesive but also a release paper. The surface of the pressure-sensitive adhesive layer may be covered with a release paper. Examples of the pressure-sensitive adhesive include an acrylic pressure-sensitive adhesive containing an acrylic polymer and a pressure-sensitive adhesive, a solvent rubber-based pressure-sensitive adhesive containing styrene-butadiene, and the like.

Examples of the monomer constituting the acrylic polymer of the acrylic pressure-sensitive adhesive include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, and butyl (meth) acrylate. Meta) Acrylic acid alkyl ester and the like can be mentioned. (Meta) acrylic acid means methacrylic acid or acrylic acid. In addition, examples of the tackifier include rosin-based, terpene-based, phenol-based, and kumaron-based tackifiers. The release paper is, for example, a known release paper coated with a silicone release agent. The thickness of the pressure-sensitive adhesive layer is, for example, 50 to 180 μm. When the thickness of the pressure-sensitive adhesive layer is within this range, the adhesive strength of the pressure-sensitive adhesive layer is higher.
(11) Structure of Decorative Sheet Layer The decorative sheet with an adhesive of the present disclosure includes a decorative sheet layer. In the decorative sheet layer, a surface layer, a decorative layer, a mixed papermaking layer, and a core layer are laminated in this order.

The mixed papermaking layer is, for example, a balance layer. The balance layer enhances the smoothness of the decorative sheet layer and suppresses the warp of the decorative sheet with an adhesive. For example, the decorative layer is made of a relatively hard material and the core layer is made of a relatively soft material. The balance layer preferably has, for example, a hardness intermediate between the hardness of the decorative layer and the hardness of the core layer. In this case, the warp of the decorative sheet with the adhesive can be suppressed.

The mixed papermaking layer is a layer containing paper as a base material. When the fibrous base material of the core layer is glass fiber, the surface smoothness of the decorative sheet layer can be improved by the mixed papermaking layer.
The thickness of the decorative layer is preferably 0.05 mm or more and 0.15 mm or less. When the thickness of the decorative layer is 0.05 mm or more and 0.15 mm or less, the total thickness of the layers other than the decorative layer in the decorative sheet layer is preferably larger than 0.15 mm and 1.8 mm or less, and 0.2 mm or more and 1. It is more preferably 3 mm or less.

When the thickness of the decorative sheet with an adhesive is 0.44 mm to 066 mm, it is easy to apply the decorative sheet with an adhesive on a curved surface of 100R (R is a radius, the unit is mm). The decorative layer contains a relatively hard thermosetting resin. When a deforming force such as shrinkage stress acts on the decorative layer due to heat, moisture, etc., the mixed papermaking layer and the core layer suppress the deformation of the decorative layer due to the thickness of the mixed papermaking layer and the core layer, and make up with an adhesive. Suppresses deformation such as warpage of the sheet.
The portion of the decorative sheet layer excluding the surface layer can be obtained, for example, by laminating a decorative layer, a mixed papermaking layer, and a core layer, and hot-press molding with a press machine such as a flat plate press or a continuous press.
As a method of providing the pressure-sensitive adhesive layer on the back surface of the decorative sheet layer, for example, a method of pressure-bonding and laminating the pressure-sensitive adhesive layer on the back surface of the decorative sheet layer after manufacturing the decorative sheet layer can be mentioned.
As shown in FIG. 1, the decorative sheet 11 with an adhesive of the present disclosure includes a decorative sheet layer 1 and an adhesive layer 9 provided on the back surface of the decorative sheet layer 1. The decorative sheet layer 1 preferably has a laminated structure in which a core layer 4, a mixed papermaking layer 5, a decorative layer 3, and a surface layer 2 are laminated in this order from the bottom. "Bottom" means the side of the pressure-sensitive adhesive layer 9. When the decorative sheet layer 1 has such a laminated structure, the color of the material of the core layer 4 is unlikely to appear on the surface of the decorative sheet layer 1, and the decorative sheet 11 with an adhesive is excellent in smoothness.
As shown in FIG. 2, the overlay layer 8 may be laminated and formed on the decorative layer 3. In this case, the decorative sheet 12 with an adhesive has excellent wear resistance, although the sharpness of the pattern of the decorative layer 3 is slightly inferior.
As shown in FIG. 3, the decorative sheet layer 1 may have a laminated structure in which a balance layer 5, a core layer 4, a decorative layer 3, and an overlay layer 8 are laminated in this order from the bottom.

The thickness of the decorative sheet layer is preferably 0.2 to 2.0 mm. When the thickness of the decorative sheet layer is within this range, the warp of the decorative sheet with an adhesive can be further suppressed. When the thickness of the decorative sheet layer is 0.2 to 0.8 mm, the decorative sheet with an adhesive is also excellent in bending workability at room temperature.

The adhesive decorative sheet is attached, for example, on a substrate. Examples of the base material include a wood-based base material, an inorganic-based base material, a plastic-based base material, a metal base material, and a composite base material of a decorative material and a base material.

Examples of the decorative material include a melamine-based resin decorative board, a polyester-based resin coating, an acrylic resin coating, and the like. The adhesive decorative sheet can be used as a surface material for, for example, a table, a counter, a desk, a wall, or the like. Decorative sheets with adhesive are used as surface materials for commercial furniture such as office furniture and restaurant furniture, and as surface materials for school furniture based on JIS S 1021: 2011 "School furniture-classroom desks and chairs". Can be used.

The construction using the decorative sheet with an adhesive can be performed, for example, based on the following steps (a) to (2).
(B) Prepare a decorative sheet with an adhesive and a base material.

(B) Wipe off the dirt on the surface of the base material. If the base material has recesses, putty treatment is performed. If the base material has protrusions, polish it to make it smooth.
(C) A composite is formed by adhering and adhering a decorative sheet with an adhesive to the base material obtained in the step (a) above. The complex consists of a decorative sheet with an adhesive and a base material.

(2) Finish the end portion of the complex obtained in the step (c) above.
For example, an electric circular saw, a cutter knife, scissors, or the like can be used when cutting the decorative sheet with an adhesive to a predetermined size or when finishing and cutting the corners of the decorative sheet with an adhesive. In order to further strengthen the adhesion between the adhesive-attached decorative sheet and the base material, the base material may be treated with an aqueous primer or a solvent-based primer before the step (c).

A decorative sheet with an adhesive may be attached to the base material and adhered, and then the end portion of the decorative sheet with the adhesive may be cut with an electric trimmer to finish.
2. 2. Structure The structure of the present disclosure comprises a base material and a decorative sheet with an adhesive. The adhesive decorative sheet is adhered to the substrate.

3. 3. Example (1) Example 1
(1-1) Production of main component The main component was produced by mixing the following components.

Tetraethyl orthosilicate (ethyl silicate) hydrolyzate (trade name "HAS-1", manufactured by Corcote Co., Ltd.): 100 parts by mass "NPC-ST-30" (trade name, manufactured by Nissan Chemical Industry Co., Ltd., average particle diameter 10) ~ 15 nm, ethylene glycol mono n-propyl ether dispersed silica sol, SiO ₂ 30% by mass): 600 parts by mass (solid content equivalent)
"DISPERBYK-2009" (Acrylic copolymer solution, 44% by mass of acrylic copolymer, 1-methoxy-2-propylacetate, ethylene glycol monobutyl ether) (trade name, manufactured by Big Chemie Japan Co., Ltd.): 13.2 parts by mass (solid) Minute conversion)
"HAS-1" is the component (A). "NPC-ST-30" is an organosilica sol dispersed in a hydrophilic solvent. "NPC-ST-30" is the component (B). "DISPERBYK-2009" is a component (C).

(1-2) Production of functional composition A fine particle (m) deodorant substance was produced. (M) The composition of the deodorant substance was 74% by mass of zinc oxide and 26% by mass of amino-modified silica. (M) The average particle size of the deodorant substance was 350 nm.

The functional composition (M) is obtained by mixing 100 parts by mass of the main component produced in (1-1) above and 40 parts by mass of the (m) deodorant substance and stirring at 8100 rpm for 10 minutes using a homogenizer. Got The function of the functional composition (M) is deodorant.

(1-3) Production of Transfer Sheet A transfer sheet (M) was obtained by applying a coating liquid containing the functional composition (M) to a plastic film. The film thickness of the coating film obtained by applying the coating liquid was 4.5 μm after the coating film was dried. The coating film obtained by applying the coating liquid is a layer of the cured product of the functional composition (M). The layer of the cured product of the functional composition (M) becomes a surface layer.

The solid content concentration of the coating liquid was 20% by mass. The solid content concentration is the mass ratio of the solid content of the functional composition (M) to the total mass of the coating liquid. The pH of the coating liquid was 5.8. The pH of the coating liquid was measured using a glass electrode type pH meter (product name: LAQUA model number F-71, manufactured by HORIBA, Ltd.).

(1-4) Production of Melamine Resin Impregnated Pattern Paper (M) A resin liquid (AA) containing a melamine-formaldehyde resin as a main component was impregnated into a decorative paper to obtain a melamine resin impregnated pattern paper (M). The basis weight of the decorative paper was 100 g / m ² . On the surface of the decorative paper, a wood grain pattern having a conduit was printed. In the melamine resin impregnated pattern paper (M), the impregnation rate defined by the formula 1 was 140%. The melamine resin impregnated pattern paper (M) constitutes a decorative layer.

(1-5) Manufacture of mixed papermaking Paper Magnesium silicate mixed papermaking (trade name: GP-18, manufactured by Tigalex Co., Ltd.) was prepared. The basis weight of the magnesium silicate mixed paper was 180 g / m ² . The magnesium silicate mixed paper contains 80% by mass of hydrous magnesium silicate (sepiolite), 10% by mass of pulp, 5% by mass of glass fiber, and 5% by mass of an organic binder.

Guanidine phosphate (Apinone 307, manufactured by Sanwa Chemical Co., Ltd., total nitrogen content 31%) is impregnated into magnesium silicate mixed paper so that the impregnation rate defined in Equation 1 is 20%, and dried. , Manufactured mixed paper impregnated with guanidine phosphate. Guanidine phosphate is a flame retardant. The content of guanidine phosphate per unit area in the mixed paper impregnated with guanidine phosphate was 36 g / m ² . The guanidine phosphate impregnated mixed paper constitutes a mixed paper layer.

(1-6) Production of prepreg The following components were mixed to produce a mixture.
Acrylic resin emulsion (Part No. RAX-208, manufactured by Aika Kogyo Co., Ltd.): 32 parts by mass Aluminum hydroxide: 300 parts by mass 3-glycidoxypropyltrimethoxysilane: 2.7 parts by mass Guanidin phosphate (Apinone 303, Sanwa) Made by Chemical Co., Ltd., total nitrogen content 39%): 29 parts by mass Acrylic resin emulsion is a binder. The glass transition temperature (Tg) of the acrylic resin emulsion was 60 ° C. The main monomers in the acrylic resin emulsion were 2-ethylhexyl acrylate and methyl methacrylate. The average particle size of the acrylic resin emulsion was 200 nm.

Aluminum hydroxide is an endothermic metal hydroxide. The average particle size of aluminum hydroxide was 8 μm. 3-glycidoxypropyltrimethoxysilane is a silane coupling agent. Guanidine phosphate is a flame retardant.

Water was added to the above mixture to obtain a slurry. The slurry was impregnated into a glass fiber nonwoven fabric and dried to produce a prepreg. The impregnation rate defined in Equation 1 in the prepreg was 850%. The prepreg was a glass fiber cloth base material prepreg. The mass part in the description of the prepreg is a solid content conversion value. The prepreg constitutes the core layer.

(1-7) Production of Decorative Sheet Layer In order from the bottom, one prepreg, one guanidine phosphate-impregnated mixed paper, one melamine resin-impregnated pattern paper (M), and a transfer sheet (M) are laminated. , A laminate was formed. The orientation of the transfer sheet (M) was such that the layer of the cured product of the functional composition (M) faces the melamine resin impregnated pattern paper (M). The guanidine phosphate impregnated mixed paper formed a balance layer. The cured product layer of the functional composition (M) became a surface layer.

The laminate was hot-press molded using a flat plate press at a temperature of 132 ° C., a pressure of 70 kgf / cm ² , and a treatment time of 64 minutes to obtain a decorative sheet layer (M) having a thickness of 0.48 mm.
(1-8) Manufacture of Decorative Sheet with Adhesive An adhesive sheet (manufactured by Niei Kako Co., Ltd.) was attached to the back surface of the decorative sheet layer (M) to obtain a decorative sheet with an adhesive having a thickness of 0.55 mm. .. The back surface is the surface of the decorative sheet layer (M) opposite to the surface layer. The pressure-sensitive adhesive sheet includes a silicone release paper and a pressure-sensitive adhesive layer formed by applying an acrylic pressure-sensitive adhesive containing an acrylic resin as a main component on the silicone release paper. The thickness of the pressure-sensitive adhesive sheet was 136 μm.

(2) Examples 2 to 14
Basically, a decorative sheet with an adhesive was produced in the same manner as in Example 1. However, it differs in the following points.

In Example 2, when the functional composition (M) was produced, 60 parts by mass of the (m) deodorant substance was blended with 100 parts by mass of the main component.
In Example 3, when the functional composition (M) was produced, 30 parts by mass of the (m) deodorant substance was blended with 100 parts by mass of the main component.

In Example 4, when the main component was produced, the blending amount of the component (C) "DISPERBYK-2009" was set to 9.3 parts by mass.
In Example 5, when the main component was produced, the blending amount of the component (C) "DISPERBYK-2009" was 16.8 parts by mass.

In Example 6, when the main component was produced, the blending amount of the component (B) "NPC-ST-30" was 400 parts by mass.
In Example 7, when the main component was produced, the blending amount of the component (B) "NPC-ST-30" was set to 900 parts by mass.

In Example 8, the average particle size of the (m) deodorant substance was set to 200 nm.
In Example 9, the average particle size of the (m) deodorant substance was set to 1000 nm.
In Example 10, when the transfer sheet was produced, the film thickness of the coating film obtained by applying the coating liquid was set to 2.0 μm after the coating film was dried.

In Example 11, when the transfer sheet was produced, the film thickness of the coating film obtained by applying the coating liquid was 6.5 μm after the coating film was dried.
In Example 12, the composition of the (m) deodorant substance was such that it contained 45% by mass of zinc oxide and 55% by mass of amino-modified silica.

In Example 13, the composition of the (m) deodorant substance was such that it contained 85% by mass of zinc oxide and 15% by mass of amino-modified silica.
In Example 14, (n) an antiviral substance was produced instead of (m) a deodorant substance. (N) The antiviral substance was a triazine-imidazole-thiazole-based organic synthetic antiviral substance. (N) The average particle size of the antiviral substance was 1000 nm.

In Example 14, 100 parts by mass of the main component and 50 parts by mass of (n) the antiviral substance were mixed and stirred at 8100 rpm for 10 minutes using a homogenizer to obtain a functional composition (N). The function of the functional composition (N) is antiviral.

In Example 14, a transfer sheet (N) was produced instead of the transfer sheet (M). The transfer sheet (N) was obtained by applying a coating liquid containing the functional composition (N) to a plastic film. The film thickness of the coating film obtained by applying the coating liquid was 2.2 μm after the coating film was dried. The pH of the coating liquid was 8.3.

In Example 14, a decorative sheet layer was produced using a transfer sheet (N) instead of the transfer sheet (M).
(3) Examples 15-19
Basically, a decorative sheet with an adhesive was produced in the same manner as in Example 14. However, it differs in the following points.

In Example 15, when the main component was produced, the blending amount of the component (C) "DISPERBYK-2009" was 26.4 parts by mass. Further, when the functional composition (N) was produced, the blending amount of the (n) antiviral substance was 35 parts by mass.

In Example 16, when the main component was produced, the blending amount of the component (C) "DISPERBYK-2009" was 26.4 parts by mass. Further, when the functional composition (N) was produced, the blending amount of the (n) antiviral substance was set to 75 parts by mass.

In Example 17, when the main component was produced, the blending amount of the component (C) "DISPERBYK-2009" was set to 9.3 parts by mass.
In Example 18, when the main component was produced, the blending amount of the component (C) "DISPERBYK-2009" was 16.8 parts by mass.

In Example 19, when the main component was produced, the blending amount of the component (C) "DISPERBYK-2009" was 26.4 parts by mass. Further, when the transfer sheet was produced, the film thickness of the coating film obtained by applying the coating liquid containing the functional composition (N) was set to 3.5 μm after the coating film was dried.

(4) Examples 20-21
Basically, a decorative sheet with an adhesive was produced in the same manner as in Example 19. However, it differs in the following points.

In Example 20, when the transfer sheet was produced, the film thickness of the coating film obtained by applying the coating liquid containing the functional composition (N) was set to 1.5 μm after the coating film was dried.
In Example 21, (n) the average particle size of the antiviral substance was set to 3000 nm. Further, when the transfer sheet was produced, the film thickness of the coating film obtained by applying the coating liquid containing the functional composition (N) was set to 2.2 μm after the coating film was dried.

(5) Example 22
Basically, a decorative sheet with an adhesive was produced in the same manner as in Example 21. However, in Example 22, the average particle size of (n) the antiviral substance was set to 500 nm.

(6) Example 23
Basically, a decorative sheet with an adhesive was produced in the same manner as in Example 1. However, it differs in the following points.

In Example 23, (o) an anti-allergenic substance was produced instead of (m) a deodorant substance. (O) The average particle size of the anti-allergenic substance was 2000 nm. (O) The anti-allergenic substance is an organic synthetic anti-allergenic substance (“Allerbuster BV”, manufactured by Sekisui Material Solutions Co., Ltd.), which is a complex of a sodium salt of an acidic anion-modified linear alkane and styrene particles. there were.

In Example 23, 100 parts by mass of the main component and 10 parts by mass of the (o) anti-allergenic substance were mixed and stirred at 8100 rpm for 10 minutes using a homogenizer to obtain a functional composition (O). The function of the functional composition (O) is anti-allergenic.

In Example 23, a transfer sheet (O) was produced instead of the transfer sheet (M). The transfer sheet (O) was obtained by applying a coating liquid containing the functional composition (O) to a plastic film. The film thickness of the coating film obtained by applying the coating liquid was 4.0 μm after the coating film was dried. The pH of the coating liquid was 6.8.

In Example 23, the decorative sheet layer was manufactured by using the transfer sheet (O) instead of the transfer sheet (M). The thickness of the decorative sheet with the adhesive was 0.55 mm.
(7) Examples 24 to 31
Basically, a decorative sheet with an adhesive was produced in the same manner as in Example 23. However, it differs in the following points.

In Example 24, when the functional composition (O) was produced, (o) an anti-allergenic substance was blended in an amount of 3 parts by mass with respect to 100 parts by mass of the main component.
In Example 25, when the functional composition (O) was produced, 50 parts by mass of (o) an anti-allergenic substance was blended with 100 parts by mass of the main component.

In Example 26, the average particle size of (o) the anti-allergenic substance was set to 5000 nm.
In Example 27, the average particle size of (o) the anti-allergenic substance was set to 1000 nm.
In Example 28, when the transfer sheet was produced, the film thickness of the coating film obtained by applying the coating liquid containing the functional composition (O) was set to 2.0 μm after the coating film was dried.

In Example 29, when the transfer sheet was produced, the film thickness of the coating film obtained by applying the coating liquid containing the functional composition (O) was set to 8.0 μm after the coating film was dried.
In Example 30, when the main component was produced, the blending amount of the component (B) "NPC-ST-30" was set to 900 parts by mass.

In Example 31, when the main component was produced, the blending amount of the component (B) "NPC-ST-30" was set to 300 parts by mass.
(8) Example 32
Basically, a decorative sheet with an adhesive was produced in the same manner as in Example 1. However, it differs in the following points.

In Example 32, when producing the mixed paper, the magnesium silicate mixed paper was impregnated with a resin solution containing a vinyl ester resin as a main component instead of guanidine phosphate. The composition of the resin solution containing vinyl ester resin as a main component was 61-65% of bisphenol vinyl ester, 13-17% of methacrylic monomer, 20% of propylene glycol monomethyl ether acetate (diluent), and 2% of acrylic acid. The mixed paper in Example 32 was a vinyl ester resin-impregnated mixed paper.

(9) Example 33
Basically, a decorative sheet with an adhesive was produced in the same manner as in Example 2. However, in Example 33, the thickness of the pressure-sensitive adhesive sheet was 80 μm.

(10) Example 34
Basically, a decorative sheet with an adhesive was produced in the same manner as in Example 3. However, in Example 34, the thickness of the pressure-sensitive adhesive sheet was 50 μm.

(11) Example 35
Basically, a decorative sheet with an adhesive was produced in the same manner as in Example 1. However, it differs in the following points.

In Example 35, a pressure-sensitive adhesive sheet (manufactured by Niei Kako Co., Ltd.) having a thickness of 140 μm coated with a solvent rubber-based pressure-sensitive adhesive (styrene-isoprene block copolymer) was used as the pressure-sensitive adhesive sheet.
(12) Example 36
Basically, a decorative sheet with an adhesive was produced in the same manner as in Example 9. However, it differs in the following points.

In Example 36, when the mixed paper is produced, the magnesium silicate mixed paper (trade name: GP-12, manufactured by Tigalex Co., Ltd.) is replaced with the magnesium silicate mixed paper (trade name: GP-18, manufactured by Tigalex Co., Ltd.). Made) was used. The basis weight of GP-12 was 120 g / m ² . GP-12 contained 80% by mass of hydrous magnesium silicate (sepiolite), 10% by mass of pulp, 5% by mass of glass fiber, and 5% by mass of an organic binder.

(13) Example 37
Basically, a decorative sheet with an adhesive was produced in the same manner as in Example 1. However, it differs in the following points.

In Example 37, when the mixed paper is produced, the magnesium silicate mixed paper (trade name: GP-35, manufactured by Tigalex Co., Ltd.) is replaced with the magnesium silicate mixed paper (trade name: GP-18, manufactured by Tigalex Co., Ltd.). Made) was used. The basis weight of GP-35 was 350 g / m ² . GP-35 contained 80% by mass of hydrous magnesium silicate (sepiolite), 10% by mass of pulp, 5% by mass of glass fiber, and 5% by mass of an organic binder.

(14) Example 38
Basically, a decorative sheet with an adhesive was produced in the same manner as in Example 1. However, it differs in the following points. In Example 38, in the decorative sheet layer, mixed paper, prepreg, melamine resin impregnated pattern paper, and surface layer are laminated in this order from the bottom.

(15) Example 39
Basically, a decorative sheet with an adhesive was produced in the same manner as in Example 15. However, it differs in the following points. In Example 39, the impregnation rate of guanidine phosphate in the mixed paper was set to 5%.

(16) Example 40
Basically, a decorative sheet with an adhesive was produced in the same manner as in Example 16. However, it differs in the following points. In Example 40, the impregnation rate of guanidine phosphate in the mixed paper was set to 50%.

(17) Example 41
Basically, a decorative sheet with an adhesive was produced in the same manner as in Example 19. However, it differs in the following points. In Example 41, when producing mixed paper, an impregnated resin containing melamine resin as a main component was used instead of guanidine phosphate.
(18) Example 42
Basically, a decorative sheet with an adhesive was produced in the same manner as in Example 20. However, it differs in the following points. In Example 42, when producing mixed paper, an impregnated resin containing a phenol resin as a main component was used instead of guanidine phosphate.

(19) Examples 43 to 45
Basically, a decorative sheet with an adhesive was produced in the same manner as in Example 1. However, it differs in the following points.

In Example 43, (m) zeolite was used as the deodorant substance.
In Example 44, (m) copper oxide was used as the deodorant substance.
In Example 45, (m) zirconium oxide was used as the deodorant substance.

(20) Examples 46 to 47
Basically, a decorative sheet with an adhesive was produced in the same manner as in Example 14. However, it differs in the following points.

In Example 46, (n) amino-modified polyvinyl alcohol particles were used as the antiviral substance.
In Example 47, (n) amino-modified acrylic particles were used as the antiviral substance.

(21) Examples 48 to 49
Basically, a decorative sheet with an adhesive was produced in the same manner as in Example 23. However, it differs in the following points.

In Example 48, (n) as the anion-modified organic compound in the anti-allergenic substance, a basic anion-modified polyvinyl alcohol was used instead of the sodium salt of the acidic anion-modified linear alkane.

In Example 49, silver oxide particles were used instead of the styrene particles as the carrier of the (n) anti-allergenic substance.
(22) Example 50
Basically, a decorative sheet with an adhesive was produced in the same manner as in Example 1. However, it differs in the following points.

In Example 50, a melamine resin impregnated pattern paper (Mt) was produced instead of the melamine resin impregnated pattern paper (M). The method for producing the melamine resin impregnated pattern paper (Mt) was as follows.

<Manufacturing of melamine resin impregnated pattern paper (Mt)>
A resin liquid (AA) containing a melamine-formaldehyde resin as a main component is applied to a decorative paper printed with a brown wood grain pattern having a basis weight of 100 g / m ² so that the impregnation rate defined by Equation 1 becomes 140%. Impregnated into. Next, a coating liquid containing the functional composition (M) produced in Example 1 was applied to the decorative paper so that the film thickness after drying was 4.5 μm, and the melamine resin impregnated pattern paper ( Mt) was obtained. A wood grain pattern having a conduit portion was printed on the surface of the decorative paper.

From the bottom, 5 prepregs and 1 melamine resin impregnated pattern paper (Mt) are laminated and hot-press molded using a flat finish plate at 140 ° C., 100 kg / cm ² , and a treatment time of 90 minutes. A decorative sheet layer (Mt) was obtained.

A decorative sheet with an adhesive was produced in the same manner as in Example 1 except that the decorative sheet layer (Mt) obtained as described above was used.
(23) Example 51
Basically, a decorative sheet with an adhesive was produced in the same manner as in Example 14. However, it differs in the following points.

In Example 51, a decorative sheet layer (Mt) was used instead of the decorative sheet layer (M). The decorative sheet layer (Mt) was manufactured using a melamine resin impregnated pattern paper (Nt). The method for producing the melamine resin-impregnated pattern paper (Nt) was as follows.

<Manufacturing of melamine resin impregnated pattern paper (Nt)>
A resin solution (AA) containing melamine-formaldehyde resin as the main component is applied to decorative paper printed with a brown wood grain pattern with a basis weight of 100 g / m ² so that the impregnation rate defined in Equation 1 is 140%. Impregnated with impregnated paper was obtained. Next, the surface of the impregnated paper is coated with a coating liquid containing the functional composition (N) produced in Example 14 so that the film thickness after drying is 2.2 μm, and impregnated with a melamine resin. A pattern paper (Nt) was obtained. A wood grain pattern having a conduit portion was printed on the surface of the decorative paper.

In order from the bottom, 5 sheets of prepreg and 1 sheet of melamine resin impregnated pattern paper (Nt) are laminated and hot-press molded using a flat finish plate at 140 ° C., 100 kg / cm ² , and a treatment time of 90 minutes. A decorative sheet layer was obtained.

(24) Example 52
Basically, a decorative sheet with an adhesive was produced in the same manner as in Example 23. However, it differs in the following points.

In Example 52, a melamine resin impregnated pattern paper (Ot) was produced instead of the melamine resin impregnated pattern paper (M). The method for producing the melamine resin impregnated pattern paper (Ot) was as follows.

<Manufacturing of melamine resin impregnated pattern paper (Ot)>
A resin solution (AA) containing melamine-formaldehyde resin as the main component is applied to decorative paper printed with a brown wood grain pattern with a basis weight of 100 g / m ² so that the impregnation rate defined in Equation 1 is 140%. Impregnated with impregnated paper was obtained. Next, the surface of the impregnated paper is coated with a coating liquid containing the functional composition (O) produced in Example 23 so that the film thickness after drying is 4.0 μm, and impregnated with a melamine resin. A pattern paper (Ot) was obtained. A wood grain pattern having a conduit portion was printed on the surface of the decorative paper.

Five prepregs and one melamine resin impregnated pattern paper (Ot) are laminated in order from the bottom, and hot-press molded using a flat finish plate at 140 ° C., 100 kg / cm ² , and a treatment time of 90 minutes. A decorative sheet layer was obtained.

(25) Comparative Examples 1 to 3
Basically, a decorative sheet with an adhesive was produced in the same manner as in Example 1. However, it differs in the following points.

In Comparative Example 1, when the main component is produced, (A) a siloxane graft-type polymer in which an acrylic resin and a siloxane are compounded instead of (A) a hydrolyzed condensate of silicon alkoxide (trade name "ZX-036"). , Made by Fuji Kasei Kogyo Co., Ltd.). The hydroxyl value of "ZX-036" was 119. The solvent species in "ZX-036" was butyl acetate / 2-propanol.

In Comparative Example 2, when the main component is produced, (b) hydrophobic silica sol (trade name “Silohobic”, manufactured by Fuji Silysia Chemical Ltd.) is used instead of (B) component “NPC-ST-30”. ) Was used.

In Comparative Example 3, when the main component is produced, instead of (C) an acrylic polymer having a hydrophilic group and a hydrophobic group, a (x) reactive (meth) acrylic polymer, a methacryloyl functional group-containing acrylic polymer (trade name). "RA-3705MB", manufactured by Negami Kogyo Co., Ltd.) 100 parts by mass was used. In addition, when producing the main component, 1,6-bis (t-butylperoxycarbonyloxy) hexane (trade name "Kayaren 6-70", manufactured by Kayaku Akzo Corporation), which is a thermal polymerization initiator, is used as 0. 4 parts by mass were blended.

(26) Comparative Examples 4 to 9
Basically, a decorative sheet with an adhesive was produced in the same manner as in Comparative Example 3. However, it differs in the following points.

In Comparative Example 4, the surface layer did not contain a function-expressing substance.
In Comparative Examples 5 to 9, the types, blending amounts, physical properties, etc. of each component were set as shown in Tables 4-1 and 4-2.

(27) Examples 53 to 67
Basically, a decorative sheet with an adhesive was produced in the same manner as in Example 1. However, the types, blending amounts, physical characteristics, etc. of each component are as shown in Table 5-1 and Table 5-2.

The (m) deodorant substance in Tables 5-1 and 5-2 is the (m) deodorant substance produced in Example 1. The (n) antiviral substance in Tables 5-1 and 5-2 is the (n) antiviral substance produced in Example 14. The (o) anti-allergenic substance in Tables 5-1 and 5-2 is the (o) anti-allergenic substance produced in Example 23.

(28) Examples 68 to 86
Basically, a decorative sheet with an adhesive was produced in the same manner as in Example 1. However, the types, blending amounts, physical characteristics, etc. of each component are as shown in Tables 6-1 and 6-2.

The (m) deodorant substance in Tables 6-1 and 6-2 is the (m) deodorant substance produced in Example 1. The (n) antiviral substance in Tables 6-1 and 6-2 is the (n) antiviral substance produced in Example 14. The (o) anti-allergenic substance in Tables 6-1 and 6-2 is the (o) anti-allergenic substance produced in Example 23.

Further, in Example 77, as the component (A), "HAS-6", which is a hydrolysis condensate of (A1) tetraethyl orthosilicate (ethyl silicate), was used instead of "HAS-1".

Further, in Example 78, as the component (A), “HAS-10”, which is a hydrolysis condensate of (A2) tetraethyl orthosilicate (ethyl silicate), was used instead of “HAS-1”.

Further, in Example 79, (B1) "IPA-ST" (trade name, manufactured by Nissan Chemical Industries, Ltd.) was used instead of "NPC-ST-30" as the component (B). "IPA-ST" is an isopropyl alcohol-dispersed silica sol. The average particle size of the silica sol is 10 to 15 nm. The mass ratio of SiO ₂ in "IPA-ST" is 30% by mass.

Further, in Example 80, (B2) "MEK-AC-2140Z" (trade name, manufactured by Nissan Chemical Industries, Ltd.) was used instead of "NPC-ST-30" as the component (B). "MEK-AC-2140Z" is a methyl ethyl ketone dispersed silica sol. The average particle size of the silica sol is 10 to 15 nm. The mass ratio of SiO ₂ in "MEK-AC-2140Z" is 40% by mass.

Further, in Example 81, (C1) "DISPERBYK-2000" (trade name, manufactured by Big Chemie Japan Co., Ltd.) was used instead of "DISPERBYK-2009" as the component (C). "DISPERBYK-2000" is a solution of an acrylic copolymer. "DISPERBYK-2000" contains 40% by mass of an acrylic copolymer. The solvent of "DISPERBYK-2000" is 1-methoxy-2-propyl acetate and ethylene glycol monobutyl ether.

Further, in Example 82, (C2) “DISPERBYK-2008” (trade name, manufactured by Big Chemie Japan Co., Ltd.) was used instead of “DISPERBYK-2009” as the component (C). "DISPERBYK-2008" is a solution of an acrylic copolymer. "DISPERBYK-2008" contains 60% by mass of an acrylic copolymer and 40% of polypropylene glycol.

(29) Example 83
Example 83 is an example in which an overlay layer is formed above the decorative layer. The upper side is the side of the surface layer. An overlay paper having a basis weight of 22 g / m ² was impregnated with the resin solution (AA) produced in Example 1 to obtain a melamine resin-impregnated overlay paper. The impregnation rate defined by Formula 1 in the melamine resin impregnation overlay was 260%.

A melamine resin-impregnated pattern paper was obtained by impregnating a decorative paper on which a wood grain pattern was printed with a melamine resin. The impregnation rate defined by the formula 1 in the melamine resin impregnated pattern paper was 100%. A prepreg and a mixed paper were produced in the same manner as in Example 1. A transfer sheet was produced in the same manner as in Example 68.

From the bottom, one prepreg, one mixed paper, one melamine resin impregnated pattern paper, one melamine resin impregnated overlay paper, and one transfer sheet were laminated to form a laminate. Hot pressure molding was performed using a flat finish plate at 140 ° C., 100 kg / cm ² , and a treatment time of 90 minutes. Next, the plastic film of the transfer sheet was peeled off to obtain a decorative sheet layer.

Next, an adhesive sheet (manufactured by Niei Kako Co., Ltd.) was attached to the back surface of the decorative sheet layer to obtain a decorative sheet with an adhesive having a thickness of 0.55 mm. The pressure-sensitive adhesive sheet includes a silicone release paper and a pressure-sensitive adhesive layer formed by applying an acrylic pressure-sensitive adhesive containing an acrylic resin as a main component on the silicone release paper. The thickness of the pressure-sensitive adhesive sheet was 136 μm.

(30) Examples 84 to 86
Basically, a decorative sheet with an adhesive was produced in the same manner as in Example 83. However, it differs in the following points.

In Example 84, the transfer sheet produced in Example 69 was used.
In Example 85, the transfer sheet produced in Example 70 was used.
In Example 86, when the decorative sheet layer is manufactured, one sheet of guanidine phosphate impregnated mixed paper, one sheet of glass fiber cloth base material prepreg, one sheet of melamine resin impregnated pattern paper, and melamine resin impregnated overlay are used in this order from the bottom. The same procedure was carried out except that one sheet of paper and one transfer sheet were laminated. The guanidine phosphate impregnated mixed paper constitutes a dipping mixed paper layer. The soaked papermaking layer functions as a balance layer.

(31) Example 87
Examples 87 to 100 are construction examples using the decorative sheet with an adhesive of the present disclosure.
<Preparation of base material>
I prepared a school desk. The school desk was equipped with a surface material made of melamine veneer. The size of the surface layer material was 650 mm in width and 450 mm in length. The width of 650 mm and the length of 450 mm were the sizes in accordance with JIS S 1021: 2011. The surface layer material was used as the base material.
<Cut of cosmetic sheet with adhesive>
A decorative sheet with an adhesive produced in Example 83 was prepared. The adhesive decorative sheet was cut into a size of 650 mm in width and 450 mm in length using an electric circular saw. Next, the corners of the cut decorative sheet with adhesive were cut into a curved surface using scissors. As a result, the shape of the corner of the decorative sheet with adhesive matched the shape of the corner of the desk.
<Smoothing and surface treatment of the base material>
The dirt on the surface of the substrate was wiped off. Next, the recesses on the surface of the base material were treated with an acrylic resin-based putty. In addition, the convex portion on the surface of the base material was polished using sandpaper to smooth the surface of the base material.

Next, the surface of the base material was subjected to a base treatment. The base treatment was a treatment in which an aqueous primer was applied and sufficiently dried. The amount of the aqueous primer applied was 80 g / m ² . The water-based primer was a synthetic rubber-based dedicated water-based primer (product number: RA-910, manufactured by Aica Kogyo Co., Ltd.). RA-910 is a slow-drying type primer. The drying time is about 2 hours.
<Adhesion of decorative sheet with adhesive and base material>
One end of the decorative sheet with an adhesive was aligned with one end of the substrate and attached. Next, apply a squeegee (spatula) to the surface of the adhesive decorative sheet and slide it from one end to the other end so that wrinkles do not occur, and use the adhesive decorative sheet as a base material. I pasted it on. Next, the metal roller was rolled on the decorative sheet with the adhesive, and the decorative sheet with the adhesive was pressed against the base material and adhered.
<Finishing>
The periphery of the adhesive decorative sheet was chamfered with sandpaper to finish. FIG. 4 shows a structure composed of a base material 30 and a decorative sheet 11 with an adhesive. In FIG. 4, "20" represents a layer of primer.

(32) Example 88
<Preparation of base material>
I prepared a desk for a restaurant. The desk was equipped with a surface material made of Lauan plywood. The surface layer material is the base material of the base. The size of the surface layer material was 600 mm in width and 1200 mm in length. The surface layer material was used as the base material.
<Cut of cosmetic sheet with adhesive>
The adhesive decorative sheet produced in Example 83 was cut into a size of 600 mm in width and 1200 mm in length using a cutter knife.
<Smoothing treatment of base material>
The surface of the base material was finished to be smooth as in Example 87. No primer treatment was performed.
<Adhesion of decorative sheet with adhesive and base material>
This was done in the same manner as in Example 87.
<Finishing>
This was done in the same manner as in Example 87. FIG. 5 shows a structure composed of a base material 30 and a decorative sheet 11 with an adhesive.

(33) Example 89
<Preparation of base material>
A round table made of China plywood was prepared. The shape of the top plate of the round table was a circle with a diameter of 800 mm. The top plate of the round table was used as the base material.
<Cut of cosmetic sheet with adhesive>
The decorative sheet with an adhesive produced in Example 83 was cut into a rectangular shape having a width of 800 mm and a length of 800 mm using an electric circular saw.
<Smoothing and surface treatment of the base material>
Basically, the base material was smoothed and grounded in the same manner as in Example 87. However, a solvent-based primer was used for the base treatment. The solvent-based primer was a synthetic rubber-based dedicated solvent-based primer (product number: RQ-900P, manufactured by Aica Kogyo Co., Ltd.). The coating amount of the solvent-based primer was 120 g / m ² . RQ-900P is a quick-drying primer that dries in about 10 minutes.
<Adhesion of decorative sheet with adhesive and base material>
This was done in the same manner as in Example 87.
<Finishing>
The peripheral edge of the adhesive decorative sheet was cut using an electric trimmer. As a result, the peripheral edge of the decorative sheet with the adhesive coincided with the peripheral edge of the base material.

(34) Example 90
<Manufacturing of decorative sheets with adhesive>
Basically, a decorative sheet with an adhesive was produced in the same manner as in Example 83. However, it differs in the following points.

In Example 90, the melamine resin impregnated overlay paper was not used. A plain decorative paper was impregnated with a melamine resin to produce a melamine resin impregnated pattern paper. The impregnation rate defined by the formula 1 in the melamine resin impregnated pattern paper was 100%. Using a melamine resin-impregnated pattern paper, a decorative sheet with an adhesive having a thickness of 0.45 mm was obtained.
<Smoothing and surface treatment of the base material>
The base of the school toilet was used as the base material. The surface of the substrate was a vertical surface. The base material was a calcium silicate plate. Dirt on the surface of the substrate was wiped off with alcohol or a dry cloth. The recesses on the surface of the substrate were treated with an epoxy putty consisting of a main agent and a curing agent. The convex portion of the surface of the base material was polished with sandpaper to smooth the surface of the base material.

Next, the surface of the base material was subjected to a base treatment. The base treatment was a treatment in which an aqueous primer was applied and sufficiently dried. The amount of the aqueous primer applied was 80 g / m ² . The water-based primer was a synthetic rubber-based dedicated water-based primer (product number: RA-910, manufactured by Aica Kogyo Co., Ltd.).
<Adhesion of decorative sheet with adhesive and base material>
One end of the adhesive cosmetic sheet is aligned and attached to one end of the substrate, then a squeegee (spatula) is applied to the surface of the adhesive cosmetic sheet, from one end to the other. A decorative sheet with an adhesive was attached to the base material by sliding it toward the portion so as not to cause wrinkles. Next, the metal roller was rolled on the decorative sheet with the adhesive, and the decorative sheet with the adhesive was pressed against the base material and adhered.

(35) Example 91
<Preparation of cosmetic sheet with adhesive>
The adhesive decorative sheet produced in Example 83 was cut into a size of 900 mm in width and 900 mm in length using an electric circular saw.
<Smoothing and surface treatment of the base material>
The base material was the base of the wall surface of the convenience store. The surface of the substrate was a vertical surface. The base material was a galvanized steel sheet. Dirt on the surface of the substrate was wiped off with alcohol or a dry cloth. The recesses on the surface of the substrate were treated with an epoxy putty consisting of a main agent and a curing agent. The convex portion on the surface of the base material was polished using a grinder to smooth the surface of the base material.

Next, the surface of the base material was subjected to a base treatment. The base treatment was a treatment in which a solvent-based primer was applied and sufficiently dried. The coating amount of the solvent-based primer was 120 g / m ² . The solvent-based primer was a synthetic rubber-based dedicated solvent-based primer (product number: RQ-900P, manufactured by Aica Kogyo Co., Ltd.).
<Adhesion of decorative sheet with adhesive and base material>
One end of the decorative sheet with an adhesive was aligned with one end of the substrate and attached. Next, apply a squeegee (spatula) to the surface of the adhesive decorative sheet and slide it from one end to the other end so that wrinkles do not occur, and use the adhesive decorative sheet as a base material. I pasted it on. Next, the metal roller was rolled on the decorative sheet with the adhesive, and the decorative sheet with the adhesive was pressed against the base material and adhered.

(36) Examples 92 to 94
Basically, the construction was carried out in the same manner as in Example 91. However, it differs in the following points.
In Example 92, the base material was a baked coated steel sheet.

In Example 93, the base material was a stainless steel plate.
In Example 94, the base material was an aluminum alloy plate.
(37) Example 95
<Preparation of cosmetic sheet with adhesive>
Similar to Example 91, a decorative sheet with an adhesive was prepared.
<Smoothing and surface treatment of the base material>
The base material was the base of the waist wall of a general house. The substrate was Lauan plywood. The dirt on the surface of the substrate was wiped off. Next, the recesses on the surface of the base material were treated with an acrylic resin-based putty. In addition, the convex portion on the surface of the base material was polished with sandpaper to smooth the surface of the base material.

Next, the surface of the base material was subjected to a base treatment. The base treatment was a treatment in which an aqueous primer was applied and sufficiently dried. The amount of the aqueous primer applied was 80 g / m ² . The water-based primer was a synthetic rubber-based dedicated water-based primer (product number: RA-910, manufactured by Aica Kogyo Co., Ltd.).
<Adhesion of decorative sheet with adhesive and base material>
One end of the decorative sheet with an adhesive was aligned with one end of the substrate and attached. Next, apply a squeegee (spatula) to the surface of the adhesive decorative sheet and slide it from one end to the other end so that wrinkles do not occur, and use the adhesive decorative sheet as a base material. I pasted it on. Next, the metal roller was rolled on the decorative sheet with the adhesive, and the decorative sheet with the adhesive was pressed against the base material and adhered.

(38) Example 96
Basically, the construction was carried out in the same manner as in Example 95. However, the base material was China plywood.
(39) Example 97
<Preparation of cosmetic sheet with adhesive>
Similar to Example 90, a decorative sheet with an adhesive was prepared. The thickness of the decorative sheet with the adhesive was 0.45 mm.
<Smoothing and surface treatment of the base material>
The wall of the school toilet was used as the base material. The surface of the substrate was a vertical surface. The surface of the base material was a curved surface of 4000R. The substrate was Lauan plywood. The dirt on the surface of the substrate was wiped off. Next, the recesses on the surface of the base material were treated with an acrylic resin-based putty. In addition, the convex portion on the surface of the base material was polished with sandpaper to smooth the surface of the base material.

Next, the surface of the base material was subjected to a base treatment. The base treatment was a treatment in which an aqueous primer was applied and sufficiently dried. The amount of the aqueous primer applied was 80 g / m ² . The water-based primer was a synthetic rubber-based dedicated water-based primer (product number: RA-910, manufactured by Aica Kogyo Co., Ltd.).
<Adhesion of decorative sheet with adhesive and base material>
One end of the decorative sheet with an adhesive was aligned with one end of the substrate and attached. Next, apply a squeegee (spatula) to the surface of the adhesive decorative sheet and slide it from one end to the other end so that wrinkles do not occur, and use the adhesive decorative sheet as a base material. I pasted it on. Next, the metal roller was rolled on the decorative sheet with the adhesive, and the decorative sheet with the adhesive was pressed against the base material and adhered.

(40) Example 98
Basically, the construction was carried out in the same manner as in Example 96. However, the wall surface of the school toilet was used as the base material. The surface of the substrate was a vertical surface. The surface of the base material was a curved surface of 4000R. The substrate was China plywood.

(41) Example 99
Basically, the construction was carried out in the same manner as in Example 90. However, it differs in the following points. The decorative sheet with an adhesive was produced in Example 83. The surface of the base material was a vertical surface. The surface of the base material was a curved surface of 4000R. The base material was a calcium silicate plate.

(42) Example 100
Basically, the construction was carried out in the same manner as in Example 91. However, it differs in the following points. The surface of the substrate was a vertical surface. The surface of the base material was a curved surface of 4000R. The base material was a galvanized steel sheet. Table 19 shows the construction conditions of Examples 87 to 100.

(43) Examples 101 to 122
Basically, a decorative sheet with an adhesive was produced in the same manner as in Example 1. However, it differs in the following points.

In Examples 101 to 106, the types, blending amounts, physical properties, etc. of each component were as shown in Tables 7-1 and 7-2.
In Examples 107 to 110, the types, blending amounts, physical properties, etc. of each component were as shown in Tables 8-1 and 8-2.

In Examples 111 to 122, the types, blending amounts, physical properties, etc. of each component were as shown in Tables 9-1 and 9-2.
With respect to the above Examples and Comparative Examples, the blending amount and proportion of the main component and the functional composition containing the component (A), the component (B), and the component (C), the particle size of the functional expression substance, and the coating liquid The pH, coating amount, and type of core material of the core layer are shown in Tables 1-1 to 9-2. The coating amount is a value obtained by measuring the film thickness of the coating film obtained by applying the coating liquid after the coating film has dried.

The meanings of the descriptions in each table are as follows.
A: Hydrolyzed condensate of silicon alkoxide B: Organo silica sol in which an aqueous silica sol is replaced with a hydrophilic solvent C: Acrylic copolymer having a hydrophilic group and a hydrophobic group B / A: The mass of the component (B) is the mass of the component (A). It is the value divided by the mass.

C / B: A value obtained by dividing the mass of the component (C) by the mass of the component (B).
m: Deodorant substance n: Antiviral substance o: Anti-allergenic substance In addition, the numerical value of the mass part of the components (A), (B), and (C) in each table is the mass of solid content.

The numerical values of the blending amounts of m, n, and o are the blending amount (mass part) of the solid content of the function-expressing substance with respect to 100 parts by mass of the solid content of the main component.

4. Evaluation of Examples (1) Evaluation Method The adhesive-attached decorative sheet according to each Example and each Comparative Example was evaluated by the following method.
<Evaluation of appearance>
The appearance of the decorative sheet with an adhesive was evaluated based on JIS K 6902: 2007 "Thermosetting Resin High Pressure Decorative Sheet Test Method". Further, it was evaluated whether or not the fingerprint was conspicuous by touching the surface of the decorative sheet with the adhesive with the palm for 5 seconds, then releasing the hand and visually observing the surface. The appearance of the adhesive-attached decorative sheet was evaluated according to the following criteria.

◯: No abnormality (no uneven whitening on the surface and no noticeable fingerprints).
Δ1: Whitening unevenness occurs slightly on the surface, but the conduit portion of the wood grain pattern of the decorative layer can be recognized. Fingerprints are inconspicuous.

Δ2: There is no uneven whitening on the surface, but fingerprints are slightly conspicuous.
X: Whitening unevenness occurs remarkably on the surface, the wood grain pattern of the decorative layer is unclear, and the conduit portion cannot be recognized. Fingerprints are inconspicuous.

If the whitening unevenness occurs on the surface, the fingerprint becomes less noticeable.
<Evaluation of hydrogen sulfide deodorant performance>
A test piece having a size of 100 mm × 200 mm was cut out from the decorative sheet with an adhesive. The back surface and the side surface of the test piece were covered with aluminum tape so that the effective area was 200 cm ² . The test piece was placed in a bag. The bag was a tedler bag. 3 L of hydrogen sulfide gas was injected into the bag so that the concentration in the bag was 4 ppm. After 24 hours, the residual concentration of hydrogen sulfide in the bag was measured. Based on this measured value, the total amount of deodorized hydrogen sulfide was calculated and used as the deodorization rate (%) of hydrogen sulfide gas.
<Evaluation of ammonia deodorant performance>
A test piece having a size of 100 mm × 200 mm was cut out from the decorative sheet with an adhesive. The back surface and the side surface of the test piece were covered with aluminum tape so that the effective area was 200 cm ² . The test piece was placed in a bag. The bag was a tedler bag. 3 L of ammonia gas was injected into the bag so that the concentration in the bag would be 100 ppm. After 24 hours, the residual ammonia concentration in the bag was measured. Based on this measured value, the total amount of deodorized ammonia was calculated and used as the deodorizing rate (%).
<Antiviral performance phage test>
The test virus was bacteriophage Qβ. The test standard was JIS R 1756: 2020 "Fine Ceramics-Antiviral Test Method for Visible Light Response Photocatalytic Material-Method Using Bacteriophage Qβ". The measurement time was 24 hours.

A test piece was cut out from a decorative sheet with an adhesive. The test piece was contacted with the test bacterium virus bacteriophage Qβ. After 24 hours, the test bacterium solution was collected and the virus infectivity titer was calculated. Based on the calculated viral infectivity titer, the antiviral activity value was calculated based on the following formula.

Antiviral activity value = log (viral infectious value of unprocessed product) -log (virus infectious value of processed product)
The unprocessed product is a decorative sheet with an adhesive on which a surface layer is not formed, and the processed product is a decorative sheet with an adhesive according to each Example and each comparative example.
<Anti-allergen performance ammonia>
The test bacteria were mite allergen (Der fII) and sugi allergen (Cry jI). The measurement time was 24 hours. The measuring method was an ELISA method (enzyme immunoassay).

A test piece having a size of 50 mm × 50 mm was cut out from the decorative sheet with an adhesive. A frame of 40 mm × 40 mm was prepared on the test piece with an adhesive. 0.4 ml of the allergen solution prepared to a constant concentration was dropped into the frame, and the film was brought into close contact with the frame.

After 24 hours, the solution was collected and the allergen concentration was measured by the ELISA method. The concentration difference between the measured value and the measured value in the case of an unprocessed product was calculated and used as the allergen reduction rate (%).
<Chemical resistance>
The test solution was as follows.

q: Osban 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 Cosmetic sheet with adhesive A test piece was cut out from. The specimen was washed and then dried. 0.2 ml of the test solution was added dropwise to the test piece, and the mixture was left to stand for 24 hours. Then, the test solution was washed off with water, and the change in the test piece was visually observed and evaluated according to the following criteria.

○: No change △: No erosion, but color tone and luster changed ×: Erosion <nonflammable>
A heat-generating test of a 20-minute test was performed using an ISO5660-compliant cone calorimeter. When the total heat generation amount 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 there are no cracks or cracks penetrating to the back surface in the test body after the test. It was marked as ○. Those that do not satisfy even one of these three conditions are marked with x.

(2) Evaluation results The evaluation results are shown in Tables 10-1 to 18-2.

(3) Discussion As shown in Table 16-1, in Example 101, the amount of the (m) deodorant substance blended was small and the deodorizing performance was slightly inferior. In Example 102, (m) the amount of the deodorant substance was large, and a slight uneven whitening occurred in the appearance (Δ1). In Example 103, (n) the amount of the antiviral substance compounded was small and the antiviral performance was slightly inferior.

In Example 104, (n) the amount of the antiviral substance compounded was large, and whitening unevenness occurred slightly in appearance (Δ1). In Example 105, (o) the blending amount of the anti-allergenic substance was small and the anti-allergenic property was slightly inferior. In Example 106, (o) the amount of the anti-allergenic substance compounded was large, and whitening unevenness occurred slightly in appearance (Δ1).

As shown in Tables 8-1 and 17-1, in Example 107, although the functional composition contains the components (A), (B), and (C), the solid content 1 of the component (A) is 1. The blending amount of the component (B) was less than 0.5 parts by mass with respect to the mass part, the deodorizing performance was slightly inferior, and the chemical resistance was also slightly inferior.

In Example 108, although the functional material composition contains the component (A), the component (B), and the component (C), the blending amount of the component (B) with respect to 1 part by mass of the solid content of the component (A). Is more than 12 parts by mass, and although fingerprints are not conspicuous in appearance, slight uneven whitening occurs (Δ1).

In Example 109, although the functional composition contains the component (A), the component (B), and the component (C), the blending amount of the component (C) is 1 part by mass of the solid content of the component (B). It was less than 0.005 parts by mass, and although whitening unevenness did not occur, fingerprints were slightly conspicuous (Δ2).

In Example 110, although the functional composition contains the component (A), the component (B), and the component (C), the blending amount of the component (C) is 1 part by mass of the solid content of the component (B). It 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, in Example 111, the deodorant property was slightly inferior. In Example 112, although the fingerprints were not conspicuous in appearance, whitening unevenness was slightly generated (Δ1). In Example 113, the antiviral property was slightly inferior.

In Example 114, although the fingerprints were not conspicuous in appearance, whitening unevenness was slightly generated (Δ1). In Example 115, the deodorant property was slightly inferior. In Example 116, although the fingerprints were not conspicuous in appearance, whitening unevenness was slightly generated (Δ1).

In Example 117, the anti-allergenicity was slightly inferior. In Example 118, although the fingerprints were not conspicuous in appearance, whitening unevenness was slightly generated (Δ1). In Example 119, the antiviral property was slightly inferior.

In Example 120, although the fingerprints were not conspicuous in appearance, whitening unevenness was slightly generated (Δ1).
In Example 121, the anti-allergenicity was slightly inferior. In Example 122, although the fingerprints were not conspicuous in appearance, whitening unevenness was slightly generated (Δ1).

4. Other Embodiments Although the embodiments of the present disclosure have been described above, the present disclosure is not limited to the above-described embodiments, and can be variously modified and implemented.

(1) The function of one component in each of the above embodiments may be shared by a plurality of components, or the function of the plurality of components may be exerted by one component. Further, a part of the configuration of each of the above embodiments may be omitted. Further, at least a part of the configuration of each of the above embodiments may be added or substituted with respect to the configuration of the other embodiments.

(2) In addition to the above-mentioned decorative sheet with an adhesive, the present disclosure can be realized in various forms such as a system including the decorative sheet with an adhesive as a component, a method for manufacturing a decorative sheet with an adhesive, and the like.

1 ... Decorative sheet layer, 2 ... Surface layer, 3 ... Decorative layer, 4 ... Core layer, 5 ... Mixed papermaking layer, 8 ... Overlay layer, 9 ... Adhesive layer, 11, 12, 13 ... Decorative sheet with adhesive, 30 …Base material

Claims (11)

The surface layer (2), the decorative layer (3), the mixed paper layer (5), and the core layer (4) are the surface layer, the decorative layer, the mixed paper layer, the core layer, or the surface layer, the above. The decorative sheet layer (1) laminated in the order of the decorative layer, the core layer, and the mixed papermaking layer,
A pressure-sensitive adhesive layer (9) provided on the side of the decorative sheet layer opposite to the surface layer is provided.
The surface layer is a cured functional composition containing a main component containing the following (A) to (C) and one or more function-expressing substances selected from the group consisting of the following (m) to (o). Including things,
Decorative sheet with adhesive (11, 12, 13).
(A) Hydrolyzed condensate of silicon alkoxide (B) Organo silica sol in which an aqueous silica sol is replaced with a hydrophilic solvent (C) Acrylic copolymer having a hydrophilic group and a hydrophobic group (m) Deodorant substance (n) Antiviral property Substance (o) Anti-allergenic substance The cosmetic sheet with an adhesive according to claim 1.
The functional composition contains the (m) deodorant substance and contains.
In the functional composition, the blending amount of the (m) deodorant substance is 30 to 60 parts by mass with respect to 100 parts by mass of the solid content of the main component.
Cosmetic sheet with adhesive. The adhesive-attached cosmetic sheet according to claim 1 or 2.
The functional composition comprises the (n) antiviral substance.
In the functional composition, the blending amount of the (n) antiviral substance is 35 to 75 parts by mass with respect to 100 parts by mass of the solid content of the main component.
Cosmetic sheet with adhesive. The cosmetic sheet with an adhesive according to any one of claims 1 to 3.
The functional composition comprises the (o) anti-allergenic substance.
In the functional composition, the blending amount of the (o) anti-allergenic substance is 3 to 50 parts by mass with respect to 100 parts by mass of the solid content of the main component.
Cosmetic sheet with adhesive. The cosmetic sheet with an adhesive according to any one of claims 1 to 4.
The functional composition contains the (m) deodorant substance and contains.
The (m) deodorant substance is a chemisorbent type deodorant substance.
Cosmetic sheet with adhesive. The cosmetic sheet with an adhesive according to claim 5.
The chemically adsorbed deodorant substance comprises one or more selected from the group consisting of zinc oxide, silica, zeolite, copper oxide, and zirconium oxide.
Cosmetic sheet with adhesive. The cosmetic sheet with an adhesive according to any one of claims 1 to 6.
The functional composition comprises the (n) antiviral substance.
The (n) antiviral substance comprises one or more selected from the group consisting of a triazine-thiazole-imidazole-based substance, an amino-modified polyvinyl alcohol, and an amino-modified acrylic polymer.
Cosmetic sheet with adhesive. The cosmetic sheet with an adhesive according to any one of claims 1 to 7.
The functional composition comprises the (o) anti-allergenic substance.
The (o) anti-allergenic substance is a composite of an anion-modified organic compound and a carrier.
Cosmetic sheet with adhesive. The cosmetic sheet with an adhesive according to claim 8.
The anion-modified organic compound is one or more selected from the group consisting of an anion-modified linear alkane and anion-modified polyvinyl alcohol.
Cosmetic sheet with adhesive. The adhesive-attached cosmetic sheet according to claim 8 or 9.
The carrier comprises one or more selected from the group consisting of styrene particles and silver oxide particles.
Cosmetic sheet with adhesive. With the base material
The decorative sheet with an adhesive according to any one of claims 1 to 10 bonded to the substrate, and the decorative sheet with an adhesive.
Structure with.

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