JP2022056410A - Water-based decorative sheet for building materials and its manufacturing method, and decorative board for building materials using water-based decorative sheet for building materials - Google Patents

Abstract

To provide an aqueous decorative sheet for a building material more improved in solvent resistance than a prior aqueous decorative sheet for a building material, and a decorative board for a building material using the same.SOLUTION: An aqueous decorative sheet for a building material is provided, comprising in a thickness direction in order: a fibrous base material having a basis weight of 60 g/m2 or less; an aqueous decorative layer laminated on the fibrous base material; and an aqueous surface protective layer laminated on the aqueous decorative layer, wherein (1) the aqueous decorative layer contains a crosslinked cured product A including at least one selected from the group consisting of a casein resin, and a polyester resin, (2) the aqueous surface protective layer contains a crosslinked cured product B including at least one selected from the group consisting of a (meth)acrylic acid (co)polymer, a (meth)acrylic acid ester (co)polymer, a polyester resin, and a urethane resin, (3) the aqueous surface protective layer further contains a water-soluble silicone, and (4) the aqueous decorative sheet has a detected amount of a non-aqueous solvent having no hydroxyl group in gas chromatography measurement of less than 1 mg/m2 (provided that such an embodiment that a polyester resin is contained in the aqueous decorative layer, and a (meth)acrylic acid (co)polymer and/or a (meth)acrylic acid ester (co)polymer is (are) contained in the aqueous surface protective layer is excluded.).SELECTED DRAWING: None

Description

The present invention relates to a water-based decorative sheet for building materials and a method for producing the same, and a decorative board for building materials using the water-based decorative sheet for building materials.

Conventionally, various decorative sheets have been used for surface makeup of fittings, floors, walls, etc. used for interior materials of buildings. For example, a decorative sheet composed of a laminate having a fibrous base material, a decorative layer (solid decorative layer and / or a pattern layer), and a surface protective layer in order in the thickness direction is widely used. .. Among them, in order to reduce the environmental load, it is known that the ink for forming the decorative layer and the surface protective layer is a water-based ink.

As a conventional example of manufacturing a decorative sheet using water-based ink, a high acid value acrylic resin, a urethane resin, etc. are neutralized to form a salt to make it water-soluble, or an emulsion or the like is used when a non-water-soluble resin is used. It is used in the form of a dispersion of water dispersed in water. However, since the resin obtained by neutralizing the high acid value resin is a salt, it is often water-soluble even in a dry coating film, and it is said that the physical characteristics of building materials such as chemical resistance are insufficient due to this. .. In order to improve this problem, Patent Document 1 discloses that a high acid value resin is combined with an oxazoline-based curing agent to react with an acidic group of the resin to improve the physical characteristics of building materials.

By the way, when manufacturing a decorative sheet using water-based ink, there is a case where a printing machine that manufactures a decorative sheet using conventional oil-based ink is diverted to manufacture, but once the decorative sheet is manufactured using oil-based ink. It is inevitable that not a little oil-based ink will remain in the printing machine even if it is thoroughly washed. Further, there is a problem that the slightly remaining oil-based ink causes cross-linking inhibition of the cross-linking curable resin on the decorative layer and the surface protective layer formed by using the water-based ink, and deteriorates the physical properties of the building material such as solvent resistance. ..

Therefore, it is desired to develop a water-based decorative sheet for building materials, which has improved solvent resistance as compared with the conventional water-based decorative sheet for building materials.

Japanese Unexamined Patent Publication No. 2004-292747

An object of the present invention is to provide a water-based decorative sheet for building materials having improved solvent resistance as compared with a conventional water-based decorative sheet for building materials, and a decorative board for building materials using the same. It is also an object of the present invention to provide a method for producing the water-based decorative sheet for building materials.

As a result of diligent research, the present inventor has made a fibrous base material, a water-based decorative layer laminated on the fibrous base material, and a water-based surface protective layer laminated on the water-based decorative layer in order in the thickness direction. In the water-based decorative sheet for building materials provided with the above, it has been found that the above object can be achieved when each layer is composed of a specific material, and the present invention has been completed.

That is, the present invention relates to the following water-based decorative sheet for building materials and a method for producing the same, and a decorative board for building materials using the water-based decorative sheet for building materials.
1. 1. A fibrous base material having a basis weight of 60 g / m ² or less, a water-based decorative layer laminated on the fibrous base material, and a water-based surface protective layer laminated on the water-based decorative layer are provided in this order in the thickness direction. A water-based decorative sheet for building materials
(1) The aqueous decorative layer contains a crosslinked cured product A containing at least one selected from the group consisting of casein resin and polyester resin.
(2) The aqueous surface protective layer is crosslinked containing at least one selected from the group consisting of (meth) acrylic acid (co) polymer, (meth) acrylic acid ester (co) polymer, polyester resin and urethane resin. Contains cured product B,
(3) The water-based surface protective layer further contains water-soluble silicone, and the water-based surface protective layer further contains water-soluble silicone.
(4) The aqueous decorative sheet has a detection amount of a water-insoluble solvent having no hydroxy group of less than 1 mg / m ² in gas chromatography measurement.
A water-based decorative sheet for building materials (provided that the water-based decorative layer contains a polyester resin and the water-based surface protective layer contains a (meth) acrylic acid (co) polymer and / or a (meth) acrylic acid ester ( Co) Except for embodiments containing a polymer.)
2. 2. Item 2. The water-based decorative sheet for building materials according to Item 1, wherein the cross-linked cured product A is a reaction-cured product of at least one cross-linked curable resin selected from the group consisting of the casein resin and the polyester resin and isocyanate. ..
3. 3. The crosslinked cured product B is at least one crosslinked product selected from the group consisting of the (meth) acrylic acid (co) polymer, the (meth) acrylic acid ester (co) polymer, the polyester resin and the urethane resin. Item 2. The water-based decorative sheet for a building material according to Item 1 or 2, which is a reaction-cured product of a curable resin and an isocyanate.
4. The casein resin, the polyester resin, the (meth) acrylic acid (co) polymer, the (meth) acrylic acid ester (co) polymer, the polyester resin, and the urethane resin all have the lowest film-forming temperature (MFT). The water-based decorative sheet for building materials according to any one of Items 1 to 3 above, wherein the relationship between) and the glass transition temperature (Tg) satisfies MFT> Tg.
5. The cross-linked cured product A is a cross-linked cured product containing the casein resin, and the cross-linked cured product B is the (meth) acrylic acid (co) polymer, the (meth) acrylic acid ester (co) polymer, and the urethane. Item 2. The water-based decorative sheet for building materials according to any one of Items 1 to 4, which is a crosslinked cured product containing at least one selected from the group consisting of resins.
6. Item 2. The water-based decorative sheet for building materials according to any one of Items 1 to 4, wherein the cross-linked cured product A is a cross-linked cured product containing the polyester resin, and the cross-linked cured product B is a cross-linked cured product containing the polyester resin. ..
7. Items 1 to 4 and 6 above, wherein the polyester resin is at least one selected from the group consisting of a copolymer containing a monomer containing a sulfonic acid metal salt as a constituent unit and an alkydcarboxylic acid group neutralizer. A water-based decorative sheet for building materials described in Crab.
8. Item 2. The water-based decorative sheet for building materials according to any one of Items 1 to 7, wherein the water-based decorative layer is a solid decorative layer and / or a pattern layer.
9. Item 2. The water-based decorative sheet for building materials according to any one of Items 1 to 8, wherein a gloss adjusting layer is further provided between the water-based decorative layer and the water-based surface protective layer and / or on the water-based surface protection layer.
10. A ridge layer is further provided between the water-based decorative layer and the water-based surface protective layer and / or on the water-based surface protection layer, and the ridge layer forms a convex portion on the outermost surface of the water-based decorative sheet for building materials. The water-based decorative sheet for building materials according to any one of the above items 1 to 9.
11. Item 2. The water-based decorative sheet for building materials according to any one of Items 1 to 10, wherein the water-based surface protective layer further contains at least one selected from the group consisting of an antibacterial agent, an antiviral agent and an anti-allergen agent.
12. A fibrous base material having a basis weight of 60 g / m ² or less, a water-based decorative layer laminated on the fibrous base material, and a water-based surface protective layer laminated on the water-based decorative layer are provided in this order in the thickness direction. A method for manufacturing water-based decorative sheets for building materials.
(1) The aqueous decorative layer contains a crosslinked cured product A containing at least one selected from the group consisting of casein resin and polyester resin.
(2) The aqueous surface protective layer is crosslinked containing at least one selected from the group consisting of (meth) acrylic acid (co) polymer, (meth) acrylic acid ester (co) polymer, polyester resin and urethane resin. Contains cured product B,
(3) The water-based surface protective layer further contains water-soluble silicone, and the water-based surface protective layer further contains water-soluble silicone.
(4) The aqueous decorative sheet has a detection amount of a water-insoluble solvent having no hydroxy group of less than 1 mg / m ² in gas chromatography measurement.
(5) A water-based decorative layer coating film is formed on the fibrous base material using a water-based ink A containing at least one cross-linking curable resin selected from the group consisting of casein resin and polyester resin, and then continuously. Aqueous ink B containing at least one crosslinkable curable resin selected from the group consisting of (meth) acrylic acid (co) polymer, (meth) acrylic acid ester (co) polymer, polyester resin and urethane resin. A water-based decorative sheet for building materials, which comprises a heat-curing step after obtaining a laminate by forming a coating film for an aqueous surface protective layer using the above, and then winding the laminate on a roll I. Production method (However, an embodiment in which the aqueous decorative layer contains a polyester resin and the aqueous surface protective layer contains a (meth) acrylic acid (co) polymer and / or a (meth) acrylic acid ester (co) polymer. except for.).
13. Item 12. The method for producing a water-based decorative sheet for building materials, which comprises the heat curing step after winding the laminate on the roll I and then winding it back on another roll II.
14. Item 2. The method for producing a water-based decorative sheet for building materials according to Item 12 or 13, wherein the heat curing step is at 40 ° C. or higher for 24 hours or longer.
15. A decorative board for building materials comprising a laminate including a decorative board base material and the water-based decorative sheet for building materials according to any one of Items 1 to 11 above, in order in the thickness direction.

The water-based decorative sheet for building materials of the present invention has improved solvent resistance as compared with the conventional water-based decorative sheet for building materials. Therefore, even if a water-insoluble solvent (oil-based ink or the like) comes into contact with the outermost surface of the water-based decorative sheet for building materials, the coloring (picture) of the decorative layer is suppressed. The water-based decorative sheet for building materials of the present invention can be used as a decorative board for building materials by laminating it with a decorative board substrate.

It is sectional drawing which shows an example of the water-based decorative sheet for building materials of this invention. It is sectional drawing which shows an example of the water-based decorative sheet for building materials of this invention. It is sectional drawing which shows an example of the water-based decorative sheet for building materials of this invention. It is sectional drawing which shows an example of the water-based decorative sheet for building materials of this invention. It is sectional drawing which shows an example of the decorative board for a building material of this invention.

1. 1. Water-based decorative sheet for building materials The water-based decorative sheet for building materials of the present invention comprises, in order in the thickness direction, a fibrous base material having a basis weight of 60 g / m ² or less, a water-based decorative layer laminated on the fibrous base material, and a water-based decorative layer. A water-based decorative sheet for building materials provided with a water-based surface protective layer laminated on the water-based decorative layer.
(1) The aqueous decorative layer contains a crosslinked cured product A containing at least one selected from the group consisting of casein resin and polyester resin.
(2) The aqueous surface protective layer is crosslinked containing at least one selected from the group consisting of (meth) acrylic acid (co) polymer, (meth) acrylic acid ester (co) polymer, polyester resin and urethane resin. Contains cured product B,
(3) The water-based surface protective layer further contains water-soluble silicone, and the water-based surface protective layer further contains water-soluble silicone.
(4) The aqueous decorative sheet has a detection amount of a water-insoluble solvent having no hydroxy group of less than 1 mg / m ² in gas chromatography measurement.
(However, the aqueous decorative layer contains a polyester resin and the aqueous surface protective layer contains a (meth) acrylic acid (co) polymer and / or a (meth) acrylic acid ester (co) polymer. Except for the mode of inclusion.).

The water-based decorative sheet for building materials of the present invention having the above-mentioned characteristics has improved solvent resistance as compared with the conventional water-based decorative sheet for building materials. Therefore, even if a water-insoluble solvent (oil-based ink or the like) comes into contact with the outermost surface of the water-based decorative sheet for building materials, the coloring (picture) of the decorative layer is suppressed. The water-based decorative sheet for building materials of the present invention can be used as a decorative board for building materials by laminating it with a decorative board substrate.

Hereinafter, the water-based decorative sheet for building materials of the present invention will be described with reference to the drawings.

In the present specification, the direction in which the water-based surface protective layer 3 is laminated when viewed from the fibrous sheet 1 is referred to as "upper" or "front surface", and the water-based surface protective layer 3 is referred to as the fibrous sheet 1 as viewed from the fibrous sheet 1. The direction opposite to the stacking direction is referred to as "bottom" or "back surface". The "front (side) surface" or "outermost layer (side) surface" of the water-based decorative sheet for building materials or the decorative board for building materials is visually recognized after the construction of the water-based decorative sheet for building materials or the decorative board for building materials. Means a face. In the following, the term "outermost layer side" is also abbreviated as "outermost layer side".

1 to 4 are schematic cross-sectional views showing an example of the water-based decorative sheet A for building materials of the present invention. In the water-based decorative sheet for building materials exemplified in FIG. 1, a water-based decorative layer 2 (solid decorative layer or a pattern layer) and a water-based surface protective layer 3 are laminated on a fibrous base material 1, and the water-based decorative layer 2 is laminated. And the water-based surface protective layer 3 are both formed of water-based ink. In the water-based decorative sheet for building materials exemplified in FIG. 2, the water-based decorative layer 2 is composed of a combination of a solid decorative layer 2-1 and a pattern layer 2-2 in the water-based decorative sheet for building materials exemplified in FIG. It is an aspect to be done. The water-based decorative sheet for building materials exemplified in FIG. 3 is the water-based decorative sheet for building materials exemplified in FIG. 1 between the water-based decorative layer 2 and the water-based surface protective layer 3 and / or the water-based surface protective layer 3. This is an embodiment further provided with a gloss adjusting layer 4 on the top. Although the details will be described later, the gloss adjusting layer 4 contributes to imparting design to the water-based decorative sheet for building materials by combining high gloss (gloss) and low gloss (mat). The water-based decorative sheet for building materials exemplified in FIG. 4 is the water-based decorative sheet for building materials exemplified in FIG. 1 between the water-based decorative layer 2 and the water-based surface protective layer 3 and / or the water-based surface protective layer 3. This is an embodiment in which a convex portion is formed on the outermost surface of the water-based decorative sheet for building materials by further providing a raised layer 5 on the top. Although the details will be described later, the raised layer 5 contributes to imparting a feel based on the convex portion to the water-based decorative sheet for building materials. In FIG. 4, in the embodiment in which the raised layer 5 is formed between the water-based decorative layer 2 and the water-based surface protective layer 3, the water-based surface protective layer 4 is coated along the shape of the convex portion of the raised layer 5. Note that FIGS. 3 and 4 are examples, and the gloss adjusting layer 4 and / or the rising layer 5 may be formed in the water-based decorative sheet for building materials shown in FIG. FIG. 5 is a schematic cross-sectional view showing an example of the decorative board for building materials of the present invention, in which the water-based decorative sheet A for building materials of the present invention is laminated on the decorative board base material 6 via an adhesive layer 7. be.

Hereinafter, each layer constituting the water-based decorative sheet for building materials of the present invention will be described. In the following description, the lower and upper limits of the numerical range represented by "-" mean "greater than or equal to or less than" (for example, if α to β, it is greater than or equal to α and less than or equal to β).

Fibrous base material As the fibrous base material (fiber sheet), a material having a basis weight of 60 g / m ² or less is used.

Specifically, general paper for wallpaper (pulp-based sheet size-treated with a known sizing agent); flame-retardant paper (pulp-based sheet treated with flame-retardant agents such as guanidine sulfamate and guadinin phosphate). ); Inorganic paper containing inorganic additives such as aluminum hydroxide and magnesium hydroxide; High-quality paper; Tissue paper (thin paper); Fiber-blended paper (pulp and synthetic fiber mixed and paper-made), etc. You can choose the one that meets the requirements of.

The fibrous substrate used in the present invention includes those that are classified as non-woven fabrics. In the present invention, from the viewpoint of improving the adhesion to the decorative layer, it is preferable to use general paper for wallpaper, flame-retardant paper, etc. among the fibrous base materials exemplified above.

The basis weight of the fibrous base material may be 60 g / m ² or less (generally referred to as coated paper), but among them, 50 g / m ² or less is preferable, and 40 g / m ² or less is more preferable. The lower limit of the basis weight is not limited, but is preferably 20 g / m ² or more, and more preferably 30 g / m ² or more. In the present invention, although it depends on the combination of the resin components contained in the decorative layer and the water-based surface protective layer, the basis weight of the fibrous base material is particularly 30 g / m ² from the viewpoint of enhancing the solvent resistance of the water-based decorative sheet for building materials. More than 40 g / m ² or less is preferable.

If necessary, the surface (front surface) of the fibrous base material may be subjected to a corona discharge treatment in order to enhance the adhesion of the water-based ink forming the decorative layer. The method and conditions of the corona discharge treatment may be carried out according to a known method. Further, the back surface of the fibrous base material may be subjected to a corona discharge treatment in order to improve the adhesion to the decorative board base material when manufacturing the decorative board.

Water-based decorative layer The water-based decorative layer is a layer that imparts a desired pattern (design) to a water-based decorative sheet for building materials, and the type of decoration is not limited. For example, when the water-based decorative layer is a pattern layer, wood grain pattern, leather pattern, stone grain pattern, sand grain pattern, tiled pattern, brickwork pattern, cloth pattern, geometric figure, character, symbol, abstract pattern, Flower patterns, landscapes, characters, etc. can be mentioned. Further, the water-based decorative layer may be a solid decorative layer instead of the pattern pattern layer. Further, the water-based decorative layer may be a combination (lamination) of the pattern pattern layer and the solid decorative layer. In the present invention, the aqueous decorative layer is characterized by containing a crosslinked cured product A containing at least one crosslinkable curable resin (binder resin) selected from the group consisting of casein resin and polyester resin. Here, "cross-linked cured product A containing a cross-linked curable resin" means a cross-linked cured product of a cross-linked curable resin, and more specifically, a cross-linked cured product A obtained by reacting a cross-linked curable resin with a curing agent. Means that

In the present invention, the water-based decorative layer (solid decorative layer and / or pattern layer) is formed by a known printing method using water-based ink. As the water-based ink for forming the water-based decorative layer, for example, a known colorant (dye or pigment), binder resin and isocyanate (curing agent) are dissolved (or dispersed) in an water-based solvent (or water-based dispersion medium). ), And examples thereof include water-based inks obtained.

Examples of the colorant include inorganic pigments such as carbon black, titanium white, zinc flower, petal pattern, dark blue, and cadmium red; azo pigments, lake pigments, anthraquinone pigments, quinacridone pigments, phthalocyanine pigments, isoindolinone pigments, and dioxazine pigments. Organic pigments such as; metal powder pigments such as aluminum powder and bronze powder; pearl luster pigments such as titanium oxide-coated mica and bismuth oxide chloride; fluorescent pigments; luminous pigments and the like. These colorants can be used alone or in admixture of two or more. These colorants may be used together with fillers such as silica, extender pigments such as organic beads, neutralizers, surfactants and the like.

As the binder resin, as described above, at least one crosslinkable resin selected from the group consisting of casein resin and polyester resin is used. The polyester resin is at least selected from the group consisting of a copolymer containing a monomer containing a sulfonic acid metal salt as a constituent unit and an alkydcarboxylic acid group neutralizer (neutralized with a base such as amine). One type is preferable. Among these crosslinkable curable resins, casein resin is preferably used from the viewpoint of enhancing the solvent resistance of the aqueous decorative layer. From the viewpoint of forming a uniform coating film, the crosslinkable curable resin is preferably one in which the relationship between the minimum film forming temperature (MFT: Minimum film forming temperature) and the glass transition temperature (Tg) satisfies MFT> Tg.

Here, the minimum film-forming temperature (MFT) in the present specification is a value measured by using a temperature gradient hot plate type minimum film-forming temperature measuring device according to JIS K 6804: 2003. Further, the glass transition temperature (Tg) in the present specification is a value measured by differential thermal analysis (DTA) or differential scanning calorimetry (DSC) according to JIS K 7121: 2012.

The copolymer containing the monomer containing the sulfonic acid metal salt as a constituent unit is preferably one having a number average molecular weight of 10,000 to 20,000, a low acid value (5 or less), and high hydrophilicity. The alkydcarboxylic acid group neutralizer preferably has a number average molecular weight of 2000 to 8000 and a high acid value (50 to 100). Specific examples of these include sodium 4-styrenesulfonate-methacrylic acid copolymer, potassium allylsulfonate-N-isopropylacrylamide, magnesium 2-acrylamide-2-methylpropanesulfonate-styrene copolymer and the like. Be done. Here, the number average molecular weight in the present specification is an average molecular weight measured by a gel permeation chromatography (GPC) method. As the solvent used in the GPC method, a solvent usually used can be appropriately selected, and examples thereof include tetrahydrofuran (THF) and N-methyl-2-pyrrolidinone (NMP).

The crosslinked cured product A is a reaction cured product of at least one crosslinkable resin selected from the group consisting of the casein resin and the polyester resin, which are the binder resins, and isocyanate (curing agent).

The isocyanate (curing agent) is not limited, but polyisocyanate can be preferably used. for example,
(1) Aliphatic polyisocyanate compound (for example, tetramethylene diisocyanate, hexamethylene diisocyanate),
(2) Alicyclic polyisocyanate compounds (for example, 1,4 cyclohexadiisocyanate, isophorone diisocyanate, 1-methyl-2,4-cyclohexadiisocyanate, 1-methyl-2,6-cyclohexadiisocyanate),.
(3) Aromatic polyisocyanate compounds (for example, xylylene diisocyanate, 4,4'-diphenyl diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, m-phenylenedi isocyanate, p-phenylenedi isocyanate, 4 , 4'-diphenylmethane diisocyanate, 1,5-naphthylene diisocyanate),
And so on.

As the isocyanate (curing agent), a hydrophilically treated isocyanate is particularly preferable. For example, a terminal isocyanate group-containing compound obtained by a reaction between a diisocyanate compound and an active hydrogen group-containing compound; a terminal isocyanate group-containing compound obtained by a reaction of a diisocyanate compound; and the like can be mentioned.

Examples of the terminal isocyanate group-containing compound obtained by the reaction of the diisocyanate compound and the active hydrogen group-containing compound, the terminal isocyanate group-containing compound obtained by the reaction of the diisocyanate compound, and the like include a terminal isocyanate group-containing compound having a urethane structure and a urea structure. Terminal isocyanate group-containing compounds, terminal isocyanate group-containing compounds having a uretdione structure, terminal isocyanate group-containing compounds having an isocyanurate structure, terminal isocyanate group-containing compounds having a carbodiimide structure, terminal isocyanate group-containing compounds having a uretonimine structure, and biuret structures. Examples thereof include a terminal isocyanate group-containing compound having an allophanate structure, a terminal isocyanate group-containing compound having an allophanate structure, and a mixture thereof.

The ratio of the crosslinkable curable resin to the isocyanate in the water-based ink is not limited, but it is preferable that the isocyanate curing agent is contained in an amount of 20 parts by mass or more and 50 parts by mass or less with respect to 100 parts by mass of the crosslinkable resin. It is more preferable that the amount is 30 parts by mass or more. When the content ratio of isocyanate is within such a range, the solvent resistance of the aqueous decorative layer can be enhanced.

As the aqueous solvent (or aqueous dispersion medium), for example, water or a mixed solvent consisting of water and an organic solvent can be used. The organic solvent may be any water-soluble solvent having a hydroxy group, and examples thereof include lower alcohols such as ethanol, isopropyl alcohol and n-propyl alcohol, as well as glycols and glycol esters. These aqueous solvents (or aqueous dispersion media) can be used alone or in admixture of two or more. Further, in the case of a mixed solvent, the ratio of water to the organic solvent can be appropriately adjusted within the range of water: organic solvent 20:80 to 100: 0 (mass ratio).

Known printing methods for forming the water-based decorative layer include, for example, a gravure printing method, an offset printing method, a screen printing method, a flexographic printing method, an electrostatic printing method, an inkjet printing method, and the like. When forming a solid water-based decorative layer, for example, a roll coat method, a knife coat method, an air knife coat method, a die coat method, a lip coat method, a comma coat method, a kiss coat method, a flow coat method, and a dip coat method. Various coating methods such as the method can be mentioned.

The thickness of the water-based decorative layer is not particularly limited and can be appropriately set according to the product characteristics of the water-based decorative sheet for building materials, but the layer thickness is preferably about 0.1 to 15 μm, more preferably 4 to 8 μm. When the water-based decorative layer is a combination (lamination) of the pattern pattern layer and the solid decorative layer, the total thickness can be adjusted within the range of the thickness.

Aqueous surface protective layer The aqueous surface protective layer is the outermost layer of the aqueous decorative sheet for building materials. Although the present invention includes an embodiment in which a gloss adjusting layer and / or a raised layer is formed on the water-based surface protective layer, the ratio of the exposed area is the largest when the water-based decorative sheet for building materials is visually recognized, and it is solid. The water-based surface protective layer is positioned as the outermost layer of the water-based decorative sheet for building materials in that it is formed in a shape.

In the present invention, the aqueous surface protective layer is at least one crosslink cured selected from the group consisting of (meth) acrylic acid (co) polymer, (meth) acrylic acid ester (co) polymer, polyester resin and urethane resin. It is characterized by containing a crosslinked cured product B containing a sex resin and further containing a water-soluble silicone. Here, "cross-linked cured product B containing a cross-linked curable resin" means a cross-linked cured product of a cross-linked curable resin, and more specifically, a cross-linked cured product B obtained by reacting a cross-linked curable resin with a curing agent. Means that The water-based surface protective layer is not particularly limited as long as it is transparent so that the water-based decorative layer can be visually recognized, and may be colorless transparent, colored transparent, translucent or the like.

In the present invention, the water-based surface protective layer is formed by a known printing method using a water-based ink. As the water-based ink for forming the water-based surface protective layer, for example, it is obtained by dissolving (or dispersing) a binder resin, isocyanate (curing agent) and water-soluble silicone in an water-based solvent (or water-based dispersion medium). Examples include water-based inks.

As the binder resin, as described above, at least one kind of cross-linking selected from the group consisting of (meth) acrylic acid (co) polymer, (meth) acrylic acid ester (co) polymer, polyester resin and urethane resin. Use a curable resin. Here, (meth) acrylic means acrylic or methacrylic. Further, the (co) polymer means a homopolymer or a copolymer.

Specific examples of the (meth) acrylic acid (co) polymer and the (meth) acrylic acid ester (co) polymer include poly (meth) acrylic acid, poly (meth) acrylic acid methyl, and poly (meth) acrylic acid. Ethyl, poly (meth) propyl acrylate, poly (meth) butyl acrylate, methyl (meth) acrylate-(meth) butyl acrylate copolymer, ethyl (meth) acrylate- (meth) butyl acrylate copolymer. Combined, ethylene- (meth) methyl acrylate copolymer, ethylene- (meth) ethyl acrylate copolymer, styrene- (meth) methyl acrylate copolymer, styrene- (meth) ethyl acrylate copolymer, etc. Examples thereof include homopolymers and / or copolymers of (meth) acrylic acid or (meth) acrylic acid ester.

As the polyester resin, a copolymer containing a monomer containing a sulfonic acid metal salt as a constituent unit and an alkydcarboxylic acid group neutralizer (neutralized with a base such as amine) are described in detail as in the description of the aqueous decorative layer. At least one selected from the group consisting of is preferred.

Among these crosslinkable curable resins, (meth) acrylic acid (co) polymer, (meth) acrylic acid ester (co) polymer, polyester resin and urethane resin are selected from the viewpoint of enhancing the solvent resistance of the aqueous surface protective layer. At least one selected from the above group is preferable, and polyester resin is particularly preferable. The crosslinkable curable resin is preferably one in which the relationship between the minimum film forming temperature (MFT) and the glass transition temperature (Tg) satisfies MFT> Tg from the viewpoint of forming a uniform coating film.

The crosslinked cured product B is at least selected from the group consisting of the (meth) acrylic acid (co) polymer, the (meth) acrylic acid ester (co) polymer, the polyester resin and the urethane resin, which are the binder resins. It is a reaction-cured product of a kind of cross-linking curable resin and isocyanate (curing agent). The description of the isocyanate (curing agent) and the aqueous solvent (or aqueous dispersion medium) is the same as the description of the aqueous decorative layer.

The ratio of the crosslinkable curable resin to the isocyanate in the water-based ink is not limited, but it is preferable that the isocyanate curing agent is contained in an amount of 20 parts by mass or more and 50 parts by mass or less with respect to 100 parts by mass of the crosslinkable resin. It is more preferable that the amount is 30 parts by mass or more. When the isocyanate content is within such a range, the solvent resistance of the aqueous surface protective layer can be enhanced.

The water-soluble silicone has a structure in the molecule formed by alternately bonding silicon having an organic group and oxygen, and the side chains or ends of silicone oil containing a polysiloxane skeleton as a main component are modified to make it water-soluble. It is a sexualized one. Examples of the water-soluble silicone include amino-modified silicone, epoxy-modified silicone, polyether (polyoxyethylene, polyoxyethylene / polyoxypropylene, etc.) -modified silicone, amide polyether-modified silicone, and carboxypolyether-modified silicone. ..

By adding the water-soluble silicone, the leveling property when the water-based ink for forming the water-based surface protective layer is applied is improved, and a uniform coating film can be formed. In addition, the water-soluble silicone can be used. The smoothness of the aqueous surface protective layer can be enhanced by the action of floating on the surface of the coating film. It is considered that the solvent resistance can be improved by improving the leveling property and the smoothness.

The ratio of the cross-linking curable resin to the water-soluble silicone in the water-based ink is not limited, but it is preferable to contain 5 parts by mass or more and 25 parts by mass or less of the water-soluble silicone with respect to 100 parts by mass of the cross-linking curable resin. It is more preferably 10 parts by mass or more and 20 parts by mass or less. When the content ratio of the water-soluble silicone is within such a range, the solvent resistance of the water-based surface protective layer can be enhanced.

Known printing methods for forming the water-based surface protective layer include, for example, a gravure printing method, a roll coating method, a knife coating method, an air knife coating method, a die coating method, a lip coating method, a comma coating method, a kiss coating method, and a flow. Various coating methods such as a coating method and a dip coating method can be mentioned.

The thickness of the water-based surface protective layer is not particularly limited and can be appropriately set according to the product characteristics of the water-based decorative sheet for building materials, but the layer thickness is preferably about 1 to 50 μm, more preferably 3 to 10 μm.

In addition, the water-based surface protective layer includes dyes, colorants such as pigments, fillers such as inorganic fillers, weather resistant agents, defoaming agents, leveling agents, and thixotropic property-imparting agents within a range that does not affect the predetermined solvent resistance. , Various additives such as flame retardant, antibacterial agent, antiviral agent, antiallergen agent and the like may be added. In the present invention, in particular, an embodiment in which the aqueous surface protective layer contains at least one selected from the group consisting of antibacterial agents, antiviral agents and antiallergen agents can be adopted. Further, although the inorganic filler is often used mainly as a matting agent, the effect of suppressing the curing shrinkage of the aqueous surface protective layer can be expected by including the inorganic filler in the aqueous surface protective layer.

In the present invention, the crosslinked cured product A contained in the aqueous decorative layer is a crosslinked cured product containing a casein resin, and the crosslinked cured product B contained in the aqueous surface protective layer is (meth) acrylic acid (co). The combination of such resin components is included in the scope of the present invention because the desired solvent resistance cannot be obtained in the embodiment of the crosslinked cured product containing the polymer and / or the (meth) acrylic acid ester (co) polymer. It stipulates that it is not. On the other hand, when the crosslinked cured product A contained in the aqueous decorative layer is a crosslinked cured product containing a casein resin, the crosslinked cured product B contained in the aqueous surface protective layer is (meth) acrylic acid (co-). ) A crosslinked cured product containing at least one selected from the group consisting of a polymer and a (meth) acrylic acid ester (co) polymer. When the cross-linked cured product A contained in the water-based decorative layer is a cross-linked cured product containing a polyester resin, the cross-linked cured product B contained in the water-based surface protective layer is a cross-linked cured product containing a polyester resin. Is preferable. By combining these resin components between the crosslinked cured product A and the crosslinked cured product B, the solvent resistance of the water-based decorative sheet for building materials can be further improved.

Examples of the antibacterial agent include an inorganic antibacterial agent and an organic antibacterial agent. Inorganic antibacterial agents are particularly desirable because they are generally safer, more durable, and more heat resistant than organic antibacterial agents. The inorganic antibacterial agent is one in which an antibacterial metal such as silver, copper, zinc and the like is supported on various inorganic carriers. The amount of the antibacterial agent added is preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the resin component of the aqueous surface protective layer, but the details can be appropriately adjusted according to the type of the antibacterial agent.

The above-mentioned antiviral agent can be roughly classified into an organic type and an inorganic type. Examples of the organic antiviral agent include a quaternary ammonium salt type, a quaternary phosphonium salt type, a pyridine type, a pyrithione type, a benzimidazole type, an organic iodine type, an isothiazolin type, an anion type, and an ether type. Examples of the inorganic antiviral agent include those in which metal ions such as silver, copper and zinc are supported on a carrier such as zeolite, apatite, zirconia, glass and molybdenum oxide. The amount of the antiviral agent added is preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the resin component of the aqueous surface protective layer, but the details can be appropriately adjusted according to the type of the antiviral agent.

Among the above organic antiviral agents, benzimidazole-based antiviral agents, anionic antiviral agents, or ether-based antiviral agents that maintain the particle shape are preferably used. Here, maintaining the particle shape means that the particles exist in the state of particles without being dissolved in the composition (ink before curing) that becomes the curable resin of the water-based surface protective layer. Therefore, in the process of forming the aqueous surface protective layer, the particles of the imidazole compound, the particles of the anionic compound, or the ether compound are likely to emerge, and the particles or the anion of the imidazole compound are on the outermost surface side of the aqueous surface protective layer. It is possible to facilitate uneven distribution of particles of the system compound or the ether system compound. Then, by unevenly distributing the particles of the imidazole compound, the particles of the anionic compound, or the particles of the ether compound on the outermost surface side of the aqueous surface protective layer, an antiviral agent necessary for obtaining a predetermined antiviral property. Since the amount of the virus added can be suppressed, it is possible to easily suppress the deterioration of the scratch resistance of the aqueous surface protective layer.

As the anionic antiviral agent, for example, those containing a styrene resin, a styrene polymer derivative compound and an unsaturated carboxylic acid derivative compound are preferable. Further, the styrene polymer derivative compound and the unsaturated carboxylic acid derivative compound preferably contain at least one structure among the structures of styrene, Na sulfonic acid, acrylic acid, maleic acid, and fumaric acid, and include all the structures. Is more preferable. This is because there are roughly two types of viruses in terms of the presence or absence of an envelope, and it is considered that the structures of antiviral agents that can effectively inhibit the activity of each type are different. Therefore, for example, if the effect is expected only against influenza virus, which is a non-enveloped virus, it is sufficient that only the styrene polymer derivative compound is contained, and among them, if only the styrene resin alone is contained, the effect is sufficient. It may be obtained.

As the inorganic antiviral agent, a silver-based antiviral agent is preferable from the viewpoint of non-biotoxicity and excellent safety, and among them, a phosphoric acid-based glass silver-supporting compound or a silver zeolite compound, and a molybdenum oxide silver compound salt compound are used. It is more preferable because the amount of addition can be suppressed because the antiviral performance is exhibited even in a small amount.

When the silver-based antiviral agent is contained in the water-based surface protective layer, the color changes depending on the water-based surface protection layer (when the color changes due to heat / light in the state of the added paint, or when the water-based surface protection layer is formed, heat / light In this case, it can be improved by adding an ultraviolet inhibitor, a light stabilizer, or the like in a timely manner. For example, for the molybdenum oxide silver double salt compound, a discoloration improving effect can be expected by using a benzotriazole-based compound.

The anti-allergen agent contains either an inorganic compound or an organic compound, and each of them may be used alone or may be a mixture of two or more different substances. The inorganic compound is preferably a material that supports a metal. The amount of the anti-allergen agent added is preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the resin component of the aqueous surface protective layer, but the details can be appropriately adjusted according to the type of the anti-allergen agent.

As the inorganic material of the inorganic compound, for example, at least one selected from the group consisting of titanium oxide, calcium phosphate, calcium silicate, zirconium phosphate, zeolite, silica alumina, magnesium silicate and magnesium phosphate is preferable, and among them, titanium oxide and phosphorus are preferable. Zirconium phosphate or the like is preferable.

As the metal supported on the inorganic material, for example, at least one selected from the group consisting of gold, silver, platinum, zinc and copper is preferable, and among these, silver, zinc and the like are preferable. As commercially available products, for example, "Parafine ANV-100: silver-supported inorganic compound" manufactured by Ohara Palladium, "Atomy Ball TZ-R: zinc-supported on titanium oxide" manufactured by JGC Catalysts and Chemicals can be preferably used. Anti-allergen agents are those that act effectively against various allergens such as mites and pollen.

As the organic compound, at least one monomer component selected from the group consisting of a water-insoluble polymer containing a phenolic hydroxyl group or a polyphenol compound supported on an inorganic solid acid, styrene sulfonic acid and a salt thereof. It is preferably a polymer containing.

As the water-insoluble polymer containing a phenolic hydroxyl group, for example, "Allerbuster (trade name)" manufactured by Sekisui Chemical Co., Ltd., "Marcalinker M (trade name)" manufactured by Maruzen Petroleum Co., Ltd., etc. are used as commercial products. can do. In addition, examples of the combination of the polyphenol compound and the zirconium compound include "Allelimove (trade name)" manufactured by Toagosei Co., Ltd. These anti-allergen agents act effectively against various allergens such as mites and pollen.

As at least one monomer component selected from the group consisting of styrene sulfonic acid and a salt thereof, a material as shown in Japanese Patent No. 6136433 can be used. Suitable examples include homopolymers of styrene sulfonate, styrene sulfonate-styrene sulfonic acid copolymers, styrene sulfonate-styrene copolymers, styrene sulfonic acid-styrene copolymers, styrene sulfonates. -Styrene sulfonic acid-Styrene ternary copolymer and the like can be mentioned.

In addition, when the organic compound and the inorganic compound are mixed, for example, an anionic phenol-based material and a zinc-based material having anti-allergenic properties can be mentioned.

Examples of anionic phenolic materials include tannin, tannic acid-sulfuric acid, phenol sulfonic acid formaldehyde resin, noboratec type resin sulfone compound, noboratsk type resin methanesulfonic acid, resole type resin methanesulfonic acid, and benzylated phenolsulfone. It is appropriately selected from an acid, a thiophenol compound, a dihydroxy-diphenyl sulfone compound, a ligant compound, a metal chelate compound thereof and the like, and used.

The zinc-based material is appropriately selected from a water-soluble zinc compound, a water-insoluble zinc compound, a zinc-metal oxide composite material, and the like, and the water-insoluble zinc compound and / or the water-insoluble zinc-metal oxide composite particles are used. It is preferable that the metal oxide is dispersed in water, has an average particle size of 50 μm or less, and contains at least one of titania, silica, and alumina. Here, the average particle size in the present specification is a value that can be obtained as the mass average value D50 in the particle size distribution measurement by the laser optical diffraction method.

Gloss Adjusting Layer The decorative sheet for water-based building materials of the present invention may further include a gloss adjusting layer between the water-based decorative layer and the water-based surface protective layer and / or on the water-based surface protection layer. Such a gloss adjusting layer contributes to imparting design to the water-based decorative sheet for building materials by combining high gloss (gloss) and low gloss (mat).

Since the gloss adjusting layer becomes a part of the constituent elements of the decorative sheet for water-based building materials of the present invention and the gloss adjusting layer is formed on the water-based surface protective layer, it can be used as a water-based ink for forming the gloss adjusting layer. It is preferably the same as the water-based ink for forming the water-based surface protective layer described above. That is, as the water-based ink for forming the gloss adjusting layer, for example, a binder resin, an isocyanate (curing agent) and a water-soluble silicone are dissolved (or dispersed) in an aqueous solvent (or an aqueous dispersion medium). Examples include water-based inks. Further, the binder resin is at least one kind of crosslink curable selected from the group consisting of (meth) acrylic acid (co) polymer, (meth) acrylic acid ester (co) polymer, polyester resin and urethane resin. Resin is mentioned.

When the gloss adjusting layer is a low gloss (matte) layer, it can be adjusted by the type, content, etc. of the inorganic filler used as a matting agent. Examples of the inorganic filler serving as a matting agent include silica, talc, clay, barium sulfate, barium carbonate, calcium carbonate, magnesium carbonate, etc., and the material can be freely designed such as oil absorption, average particle size, and pore volume. Among the above, silica is preferable, and fine powdered silica is particularly preferable, because it has a high degree of design and is excellent in designability and coating stability as a water-based ink. Further, in order to adjust the degree of gloss, unsaturated polyester resin, acrylic resin, vinyl chloride / vinyl acetate copolymer and the like can be mixed.

When the water-based decorative layer has a pattern pattern layer, the gloss adjustment layer is provided so as to synchronize with the portion of the pattern to be expressed by the pattern pattern layer in which the gloss is reduced and the concave portion is to be visually expressed. A pattern having a visual recess can be obtained. For example, when the water-based decorative layer is a wood grain pattern pattern layer, the conduit portion is visually recessed due to the gloss difference by synchronizing the wood grain conduit pattern formed by the low gloss adjustment layer with the conduit portion of the wood grain pattern. You can get the pattern that became. It should be noted that the gloss adjusting layer can be set as a higher gloss layer than the water-based decorative layer so as to impart a design by combining the gloss mats, and the gloss adjusting layer is provided in synchronization with the pattern layer. In addition, it may be provided without synchronization. When forming the gloss adjusting layer, it can be formed by a known printing method as in the case of the water-based surface protective layer.

The thickness of the gloss adjusting layer is not limited, but is preferably 0.1 to 10 μm, and more preferably 0.6 to 7 μm.

The decorative sheet for water-based building materials of the present invention is provided with a layering layer between the water-based decorative layer and the water-based surface protective layer and / or on the water-based surface protective layer, and the layering layer is a water-based decorative sheet for building materials. A convex portion may be formed on the outermost surface. The raised layer contributes to imparting a feel based on the convex portion to the water-based decorative sheet for building materials.

Since the raised layer becomes a part of the constituent elements of the decorative sheet for water-based building materials of the present invention and the raised layer is formed on the water-based surface protective layer, the above-mentioned water-based ink for forming the raised layer is described above. It is preferably the same as the water-based ink for forming the surface protective layer. That is, as the water-based ink for forming the overlay layer, for example, it is obtained by dissolving (or dispersing) a binder resin, an isocyanate (curing agent), and a water-soluble silicone in an aqueous solvent (or an aqueous dispersion medium). Examples include water-based inks. Further, the binder resin is at least one kind of crosslink curable selected from the group consisting of (meth) acrylic acid (co) polymer, (meth) acrylic acid ester (co) polymer, polyester resin and urethane resin. Resin is mentioned.

The thickness of the raised layer (height of the convex portion based on the flat portion of the water-based surface protection layer) is such that the ten-point average roughness (Rz) of the surface of the water-based decorative sheet for building materials is in the range of 10 to 35 μm. It is preferable that it is. When the ten-point average roughness (Rz) of the surface of the water-based decorative sheet for building materials is 10 μm or more, a sufficient tactile sensation can be imparted to the decorative sheet surface, and the ten-point average roughness (Rz) is 35 μm or less. If there is, it is easy to obtain the bendability of the decorative sheet.

Further, the occupied area of the raised layer is preferably in the range of 2 to 25% with respect to the area of the flat surface of the water-based decorative sheet for building materials. When the occupied area is 2% or more, a sufficient tactile sensation can be imparted to the surface of the decorative sheet, and when the occupied area is 25% or less, the bending processability of the decorative sheet can be easily obtained. In addition, it is suitable from the viewpoint of the tactile sensation of the surface of the decorative sheet, and it is easy to secure stain resistance. The occupied area of the raised layer means the ratio of the area of the horizontal cross section of the raised layer to the area of the flat surface of the decorative sheet with respect to the flat portion of the water-based surface protection layer.

The shape of the convex portion formed by the raised layer is not particularly limited, and may be a fixed shape such as a circle, a quadrangle, or a hexagon that are regularly arranged, or an irregular pattern. .. When forming the raised portion, it can be formed by a known printing method as in the case of the water-based surface protective layer.

Vesicles of various additives contained in each layer of the water-based decorative sheet for building materials The various additives (inorganic fillers, etc.) added to each layer of the water-based decorative sheet for building materials of the present invention are vesicled. Is preferable. The method for vesicle-forming various additives is not particularly limited, and vesicles can be formed by a known method, and the supercritical reverse-phase evaporation method is particularly preferable.

Examples of the vesicle treatment method include a Bangham method, an extrusion method, a hydration method, a reverse phase evaporation method, and a freeze-thaw method, in addition to the supercritical reverse phase evaporation method. Briefly explaining such a vesicle formation treatment method, in the Bangham method, chloroform or chloroform / methanol mixed solvent is put in a container such as a flask, and phospholipid is further put in and dissolved. Then, the solvent is removed using an evaporator to form a thin film composed of lipids, a dispersion liquid of the additive is added, and then hydrated and dispersed with a vortex mixer to obtain a vesicle. The extrusion method is a method of preparing a thin-film phospholipid solution and passing it through a filter instead of the mixer used as an external perturbation in the Bangham method to obtain a vesicle. The hydration method is almost the same preparation method as the Bangham method, but is a method of obtaining a vesicle by gently stirring and dispersing without using a mixer. In the reverse phase evaporation method, phospholipids are dissolved in diethyl ether or chloroform, a solution containing additives is added to form a W / O emulsion, the organic solvent is removed from the emulsion under reduced pressure, and then water is added. This is a method of obtaining vesicles. The freeze-thaw method is a method that uses cooling and heating as an external perturbation, and is a method of obtaining a vesicle by repeating this cooling and heating.

Hereinafter, the supercritical reverse phase evaporation method will be described in detail. The supercritical reverse phase evaporation method is water-soluble or hydrophilic in a mixture in which the substance forming the outer film of the vesicle is uniformly dissolved in carbon dioxide under supercritical state or temperature or pressure condition above the supercritical point. This is a method of adding an aqueous phase containing various additives as an encapsulating substance to form a capsule-shaped vesicle containing various additives as an encapsulating substance in a single layer film. The carbon dioxide in the supercritical state means carbon dioxide in a supercritical state having a critical temperature (30.98 ° C.) and a critical pressure (7.3773 ± 0.0030 MPa) or higher, and the temperature is equal to or higher than the critical point. Carbon dioxide under pressure conditions means carbon dioxide under conditions where only the critical temperature or only the critical pressure exceeds the critical conditions. By this method, a single-layer lamella vesicle having a diameter of 50 to 800 nm can be obtained. In general, vesicles are a general term for those containing a liquid phase inside vesicles having a closed membrane structure like a spherical shell, and in particular, those in which the outer membrane is composed of biolipids such as phospholipids are referred to as liposomes. ..

Examples of the phospholipids include phosphatidylcholine, phosphatidylethanolamine, phosphatidylserine, phosphatidic acid, phosphatidylglycerol, phosphatidylinositol, cardiolipin, yellow egg lecithin, hydrogenated yellow egg lecithin, soy lecithin, hydrogenated soybean lecithin and other glycerophospholipids, and sphingomyelin. , Sphingophospholipids such as ceramide phosphorylethanolamine and ceramidephosphorylglycerol.

As the substance constituting the outer membrane, a nonionic surfactant or a dispersant such as a mixture thereof with cholesterol or triacylglycerol can also be used.

Examples of the nonionic surfactant include polyglycerin ether, dialkyl glycerin, polyoxyethylene hydrogenated castor oil, polyoxyethylene alkyl ether, polyoxyethylene sorbitan fatty acid ester, sorbitan fatty acid ester, polyoxyethylene polyoxypropylene copolymer, and polybutadiene-. One or two types such as polyoxyethylene copolymer, polybutadiene-poly2-vinylpyridine, polystyrene-polyacrylic acid copolymer, polyethylene oxide-polyethylethylene copolymer, polyoxyethylene-polycaprolactum copolymer, etc. The above can be used.

Examples of the cholesterol include one or more of cholesterol, α-cholestanol, β-cholestanol, cholestane, desmosterol (5,24-cholestadien-3β-ol), sodium cholic acid, choleciferol and the like. Can be used.

The outer membrane of the liposome may be formed from a mixture of a phospholipid and a dispersant. In the hard-coated film of the present invention, by forming the outer membrane into liposomes formed from phospholipids, the compatibility between the resin composition which is the main component of each layer and various additives can be improved.

Content of water-insoluble solvent in water-based decorative sheet for building materials In the water-soluble decorative sheet for building materials of the present invention, the detection amount of the water-insoluble solvent having no hydroxy group in the gas chromatography measurement is less than 1 mg / m ² . It is characterized by that. That is, the water-based decorative sheet for building materials of the present invention has a hydroxy group because both the water-based decorative layer and the water-based surface protective layer are formed of water-based ink (preferably continuous in-line coating using water-based ink). No water-insoluble solvent (specifically, ethyl acetate, butyl acetate, methyl ethyl ketone, toluene, xylene, etc.) is not substantially contained, and the detected amount in the gas chromatography measurement is less than 1 mg / m ² . ..

2. 2. Method for Producing Water-based Decorative Sheet for Building Materials The method for producing the water-based decorative sheet for building materials of the present invention is not limited, but in the present invention, the water-based decorative layer and the water-based surface protective layer are water-based inks for forming the respective layers (in order). It is preferably formed by continuous in-line coating using water-based ink A and water-based ink B). The method for producing the water-based decorative sheet for building materials of the present invention can be specified as follows.

A fibrous base material having a basis weight of 60 g / m ² or less, a water-based decorative layer laminated on the fibrous base material, and a water-based surface protective layer laminated on the water-based decorative layer are provided in this order in the thickness direction. A method for manufacturing water-based decorative sheets for building materials.
(1) The aqueous decorative layer contains a crosslinked cured product A containing at least one selected from the group consisting of casein resin and polyester resin.
(2) The aqueous surface protective layer is crosslinked containing at least one selected from the group consisting of (meth) acrylic acid (co) polymer, (meth) acrylic acid ester (co) polymer, polyester resin and urethane resin. Contains cured product B,
(3) The water-based surface protective layer further contains water-soluble silicone, and the water-based surface protective layer further contains water-soluble silicone.
(4) The aqueous decorative sheet has a detection amount of a water-insoluble solvent having no hydroxy group of less than 1 mg / m ² in gas chromatography measurement.
(5) A water-based decorative layer coating film is formed on the fibrous base material using a water-based ink A containing at least one cross-linking curable resin selected from the group consisting of casein resin and polyester resin, and then continuously. Aqueous ink B containing at least one crosslinkable curable resin selected from the group consisting of (meth) acrylic acid (co) polymer, (meth) acrylic acid ester (co) polymer, polyester resin and urethane resin. A water-based decorative sheet for building materials, which comprises a heat-curing step after obtaining a laminate by forming a coating film for an aqueous surface protective layer using the above, and then winding the laminate on a roll I. Production method (However, an embodiment in which the aqueous decorative layer contains a polyester resin and the aqueous surface protective layer contains a (meth) acrylic acid (co) polymer and / or a (meth) acrylic acid ester (co) polymer. except for.).

That is, in the method for producing a water-based decorative sheet for building materials of the present invention, a water-based ink A containing at least one crosslinkable curable resin selected from the group consisting of caseine resin and polyester resin is used as a fibrous base material. At least selected from the group consisting of (meth) acrylic acid (co) polymer, (meth) acrylic acid ester (co) polymer, polyester resin and urethane resin to form a coating film for an aqueous decorative layer. A laminate is obtained in-line by forming a coating film for an aqueous surface protective layer using an aqueous ink B containing a kind of crosslinkable curable resin, the laminate is wound on a roll I, and then a heat curing step is performed. It is characterized by having. Here, the thermosetting step may be performed under conditions that allow the crosslinkable and curable resins of the aqueous decorative layer and the aqueous surface protective layer to be sufficiently crosslinked and cured, preferably at 40 ° C. or higher for 24 hours or longer, and at 60 to 70 ° C. for 24 to 36. It is more preferable that it is time.

When a gloss adjusting layer and / or a rising layer is formed between the water-based decorative layer and the water-based surface protective layer, a coating film for a water-based decorative layer is formed, and then a coating film for a gloss adjusting layer and / or a coating film for a gloss adjusting layer is continuously formed. Alternatively, it is preferable to form a coating film for a ridge layer and then continuously form a coating film for forming an aqueous surface protective layer to obtain an in-line laminate. When a gloss adjusting layer and / or a raised layer is formed on the water-based surface protective layer, a coating film for an aqueous decorative layer is formed, and then a coating film for continuously forming an aqueous surface protective layer is formed, and then a coating film for forming an aqueous surface protective layer is formed. It is preferable to obtain a laminate in-line by continuously forming a coating film for a gloss adjusting layer and / or a coating film for a rising layer.

Further, in the method for producing a water-based decorative sheet for building materials of the present invention, it is preferable to include the heat curing step after winding the laminate on the roll I and then winding it back on another roll II. By performing such a process, it is possible to prevent the ink continuously laminated in-line from becoming a factor of blocking, and the productivity of the water-based decorative sheet for building materials is improved.

3. 3. Decorative board for building materials The decorative board for building materials of the present invention is composed of a laminate including a decorative board base material and a water-based decorative sheet for building materials of the present invention in order in the thickness direction.

The decorative board base material is not limited, but for example, medium-density wood fiber board, high-density wood fiber board, particle board, coniferous plywood, broad-leaved plywood, early-maturing plywood, cork sheet, cork-containing composite base material, thermoplastic. At least one of resin plates (polyvinyl chloride resin, polypropylene resin, polyethylene resin, acrylic resin, ABS resin and the like as main components, or foamed thereof), metal plates, ceramic plates and the like can be mentioned. .. These decorative board base materials may be used alone or by laminating two or more kinds in combination.

Here, examples of the coniferous tree include Abies sachalinensis, Larch, Ezo pine, Sugi, Hinoki, Pine, Sequoia, and Spruce. Examples of hardwoods include lauan, cinnamon, hippo, sen, beech, oak, and meranchi. Examples of early-maturing trees include poplar, falcata, acacia, chamelele, eucalyptus, and terminaria.

When wood plywood such as softwood plywood, hardwood plywood, and early-maturing plywood is used, the number of laminated wood veneers (number of plywood) is not limited, but usually 3 to 7 is preferable, and 5 to 7 is more preferable. Further, the adhesive used for producing wood plywood is not limited, and known woodworking adhesives can be widely used. As the adhesive, for example, polyvinyl acetate, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, ethylene-acrylic acid copolymer, ionomer, butadiene-acrylic nitrile rubber, neoprene rubber, natural rubber and the like are used as active ingredients. Adhesive to be used. Further, examples of the thermosetting adhesive include melamine-based, phenol-based, and urea-based (vinyl acetate-urea-based, etc.) adhesives.

As the cork sheet, not only so-called natural cork, which is a highly elastic material obtained by peeling and processing the cork tissue of the bark of cork oak, but also so-called synthetic cork made to resemble cork can be used. The cork sheet may be a single layer, or may be a laminated body of a plurality of cork sheets having different elastic moduli and densities.

Examples of the cork-containing composite base material include a composite material obtained by laminating and laminating a cork sheet and another material (for example, a medium-density wood fiber board or a high-density wood fiber board).

The thickness of the decorative board base material is not limited, but is preferably about 2 to 15 mm, more preferably about 2 to 12 mm.

The laminating method for laminating the decorative sheet for building materials and the decorative board base material is not limited, and for example, a method of adhering each of them with an adhesive or the like can be adopted. The adhesive may be appropriately selected from known adhesives according to the type of adherend and the like. For example, urethane, acrylic, urethane-acrylic, polyvinyl acetate, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, ethylene-acrylic acid copolymer, ionomer, etc., as well as butadiene-acrylic nitrile rubber, neoprene rubber, natural Examples include rubber. These adhesives may be used alone or in combination of two or more.

Hereinafter, the present invention will be specifically described with reference to Examples, Comparative Examples, and Test Examples. However, the present invention is not limited to the contents shown in the examples.

Example 1
As a fibrous base material, thin paper having a basis weight of 30 g / m ² was prepared.

A casein resin (phosphorylated protein) having a minimum film forming temperature (MFT)> glass transition temperature (Tg) is contained as a crosslinkable curable resin on a fibrous substrate, and water and isopropyl alcohol are 1: 1. Using a water-based decorative layer-forming water-based ink, which is diluted with a water-soluble solvent blended in a ratio and 20 parts by mass of an isocyanate curing agent (HMDI derivative) is added to 100 parts by mass of a crosslink-curable resin, The solid decorative layer and the pattern layer (the wood grain pattern layer having the wood grain conduit portion) were formed by gravure printing so as to have a thickness of 2 μm in order. The solid decorative layer and the pattern layer are collectively referred to as a water-based decorative layer.

A urethane resin (a double adduct of polyisocyanate and a polyol) having a minimum film forming temperature (MFT)> glass transition temperature (Tg) is contained as a crosslinkable curable resin on the aqueous decorative layer, and water and isopropyl alcohol are added. Is diluted with a water-soluble solvent blended in a ratio of 1: 1 and 20 parts by mass of an isocyanate curing agent (HMDI derivative) is added to 100 parts by mass of a crosslink-curable resin, and water-soluble silicone is further added. A water-based surface protective layer was formed by gravure printing using a water-based ink for forming a water-based surface protective layer, which was added by 10 parts by mass with respect to 100 parts by mass of the crosslink-curable resin.

The solid decorative layer, the pattern layer, and the water-based surface protective layer are continuously formed (printed) inline, wound on roll I, rewound on roll II, and then cured at a temperature of 65 ° C. for 24 hours. A water-based decorative sheet for building materials was obtained.

Example 2
Same as Example 1 except that an acrylic resin (styrene-methyl methacrylate copolymer, which is a methacrylate ester copolymer) was used as the cross-linking curable resin of the water-based ink forming the water-based surface protective layer and the water-based decorative layer. A water-based decorative sheet for building materials was obtained.

Example 3
A polyester resin (a copolymer containing a monomer containing a sulfonic acid metal salt as a constituent unit) as a cross-linking curable resin for a water-based ink forming a water-based surface protective layer and a water-based decorative layer. ) Was used, and a water-based decorative sheet for building materials was obtained in the same manner as in Example 1.

Example 4
Except for using polyester resin (sodium metharylsulfonate-styrene copolymer, which is a copolymer containing a monomer containing a sulfonic acid metal salt as a constituent unit) as the crosslinkable curable resin of the water-based ink forming the water-based decorative layer. Obtained a water-based decorative sheet for building materials in the same manner as in Example 3.

Example 5
A water-based decorative sheet for building materials was obtained in the same manner as in Example 2 except that thin paper having a basis weight of 23 g / m ² was prepared as the fibrous base material.

Example 6
A water-based decorative sheet for building materials was obtained in the same manner as in Example 2 except that thin paper having a basis weight of 50 g / m ² was prepared as the fibrous base material.

Example 7
Except that 3 parts by mass of a phosphoric acid-based glass silver-supporting compound (manufactured by Koa Glass / PG-711) was added to 100 parts by mass of the water-based ink for forming the water-based surface protective layer used in Example 1. , A water-based decorative sheet for building materials was obtained in the same manner as in Example 1.

Example 8
An anionic phenolic material having anti-allergenic properties (“EXP20530A” manufactured by DIC Corporation) and a zinc-based material having anti-allergenic properties (“EXP20530A” manufactured by DIC Corporation) with respect to the water-based ink for forming the water-based surface protective layer used in Example 1. An aqueous decorative sheet for building materials was obtained in the same manner as in Example 1 except that EXP20530B ”) was blended. The anionic phenol-based material and the zinc-based material were blended so that the solid content ratio was 23% by mass in 100% by mass of the water-based ink for forming the water-based surface protective layer after blending.

Example 9
In Example 1, after forming the water-based decorative layer, an ink for forming a gloss adjusting layer in which 17 parts by mass of silica particles having an average particle diameter of 1.5 μm was mixed with 100 parts by mass of the ink for forming the water-based surface protective layer was used. A low-gloss adjustment layer (conduit ink layer) having a pattern synchronized with the conduit portion of the wood grain pattern of the pattern layer was formed by a plate similar to the pattern plate used for forming the pattern layer. A water-based decorative sheet for building materials was obtained in the same manner as in Example 1.

Example 10
In Example 1, after forming the water-based decorative layer, an ink for forming a raised layer containing acrylic beads (average particle size 20 μm, particle size distribution 10 to 80 μm) as organic particles in the water-based surface protective layer forming ink was used. Using a plate mold with a plate depth of 90 μm that can form an irregularly shaped ridge, a plurality of ridge layers are printed by gravure so that the area ratio is 20% with respect to the area of 100% of the water-based surface protective layer. A water-based decorative sheet for building materials was obtained in the same manner as in Example 1 except that a convex portion having a height of 20 μm was formed by forming the above.

Comparative Example 1
For building materials in the same manner as in Example 4, except that an acrylic resin (styrene-methyl methacrylate copolymer, which is a methacrylate ester copolymer) was used as the cross-linking curable resin of the water-based ink forming the water-based surface protective layer. A water-based cosmetic sheet was obtained.

Comparative Example 2
A water-based decorative sheet for building materials was obtained in the same manner as in Example 1 except that water-soluble silicone was not added to the water-based ink forming the water-based surface protective layer.

Comparative Example 3
As a fibrous base material, thin paper having a basis weight of 30 g / m ² was prepared.

Acrylic resin (acrylic polyol) is contained as a cross-linking curable resin on the fibrous base material and diluted with ethyl acetate, and the isocyanate curing agent (HMDI) is 5% by mass with respect to 100 parts by mass of the cross-linking curable resin. An oil-based decorative layer was formed by gravure printing using a partially added oil-based ink.

Acrylic resin (acrylic polyol) is contained as a cross-linking curable resin on the oil-based decorative layer and diluted with ethyl acetate, and the isocyanate curing agent (HMDI) is 15 parts by mass with respect to 100 parts by mass of the cross-linking curable resin. An oil-based surface protective layer was formed by gravure printing using an oil-based ink that had been added and further added 9 parts by mass of a slip agent (oil-based silicone oil) to 100 parts by mass of a crosslink-curable resin. As a result, an oil-based decorative sheet for building materials was obtained.

Test Example 1
Solvent resistance and gas chromatography (GC) measurements were performed on the decorative sheets for building materials produced in Examples 1 to 6 and Comparative Examples 1 to 3. In the gas chromatography measurement, GC-2010 Plus (manufactured by Shimadzu Corporation) was used to cut out a decorative sheet for building materials to be measured into a size of 10 cm × 5 cm, and the measurement was performed under the following conditions.

Column used: Inart Cap1
Column temperature: 35 ° C
Column length: 30.0m
Column inner diameter: 0.53 mm
Carrier gas: He
Carrier gas flow rate: Linear velocity 53.5 cm / sec
Liquid phase film thickness: 3.00 μm.

<Solvent resistance>
Gauze was attached to a weight of 200 g / cm ² with a rubber band and soaked with MEK. Using this weight, the surface of the decorative sheet for building materials produced in Examples 1 to 6 and Comparative Examples 1 to 3 was reciprocated, and the number of times until the pattern (water-based decorative layer or oil-based decorative layer) was taken was measured. The evaluation criteria are as follows.
〇: The number of round trips until the pattern is taken is 100 or more ×: The number of round trips until the pattern is taken is less than 100 times.

<GC measurement>
Gas chromatography (Shimadzu Corporation: GC-2010plusAF) measurement was performed, and the amount of residual solvent in the decorative sheets for building materials produced in Examples 1 to 6 and Comparative Examples 1 to 3 was evaluated. The evaluation criteria are as follows.
〇: The amount of residual solvent in the water-insoluble solvent is less than 1 mg / m ² ×: The amount of residual solvent in the water-insoluble solvent is 1 mg / m ² or more.

The results of Test Example 1 are shown in Tables 1 and 2.

Test Example 2
The following physical characteristics of the water-based decorative sheets for building materials prepared in Examples 1, 7 and 8 were examined.

<Antiviral performance>
The water-based cosmetic sheets for building materials prepared in Examples 1 and 7 were subjected to an antiviral performance test by a method based on the antiviral test method (ISO21702), and the antiviral activity value against influenza virus was evaluated based on the following evaluation criteria. .. The evaluation criteria are as follows.
〇: The antiviral activity value was 2.0 or more. ×: The antiviral activity value was less than 2.0.

The results are shown in Table 3.

<Anti-allergen performance>
The allergen performance of the water-based decorative sheets for building materials produced in Examples 1 and 8 was evaluated. Specifically, the water-based decorative sheets for building materials prepared in Examples 1 and 8 were cut into small pieces, and the amount of allergen after being immersed in an aqueous mite allergen solution for one day was visually observed by a horizontal development chromatography method (mighty checker). And evaluated according to the following evaluation criteria. The evaluation criteria are as follows.
〇: A decrease in the amount of allergen was confirmed (the mite allergen level judgment was + judgment or less (that is, about 100 animals / m ² or less).
X: The decrease in the amount of allergen could not be confirmed (the mite allergen level judgment was + judgment exceeded). The results are shown in Table 4.

From the difference in the color density of the checker, it was confirmed that the water-based decorative sheet for building materials of Example 8 had anti-allergen performance as compared with the water-based decorative sheet for building materials of Example 1.

Test Example 3
The following evaluations were carried out on the water-based decorative sheets for building materials prepared in Examples 1 and 9.

<Design evaluation>
With respect to the water-based decorative sheet for building materials produced in Examples 1 and 9, the entire sheet was visually confirmed under the light source of a fluorescent lamp. The evaluation criteria are as follows.
〇: Designability due to the combination of gloss mats is recognized in the conduit part ×: Designability due to the combination of gloss mats is not recognized in the conduit portion.

The results are shown in Table 5.

Test Example 4
The following evaluations were carried out on the water-based decorative sheets for building materials prepared in Examples 1 and 10.

<Tactile evaluation>
The surface tactile sensation of the water-based decorative sheets for building materials produced in Examples 1 and 10 was evaluated. The evaluation criteria are as follows.
〇: Feeling of excitement ×: Almost no feeling of excitement.

The results are shown in Table 6.

1. 1. Fibrous base material 2. Aqueous decorative layer 2-1. Solid decorative layer 2-2. Pattern pattern layer 3. Aqueous surface protective layer 4. Gloss adjustment layer 5. Heaping layer 6. Decorative board base material 7. Adhesive layer A. Water-based decorative sheet for building materials B. Decorative board for building materials

Claims (15)

A fibrous base material having a basis weight of 60 g / m ² or less, a water-based decorative layer laminated on the fibrous base material, and a water-based surface protective layer laminated on the water-based decorative layer are provided in this order in the thickness direction. A water-based decorative sheet for building materials
(1) The aqueous decorative layer contains a crosslinked cured product A containing at least one selected from the group consisting of casein resin and polyester resin.
(2) The aqueous surface protective layer is crosslinked containing at least one selected from the group consisting of (meth) acrylic acid (co) polymer, (meth) acrylic acid ester (co) polymer, polyester resin and urethane resin. Contains cured product B,
(3) The water-based surface protective layer further contains water-soluble silicone, and the water-based surface protective layer further contains water-soluble silicone.
(4) The aqueous decorative sheet has a detection amount of a water-insoluble solvent having no hydroxy group of less than 1 mg / m ² in gas chromatography measurement.
A water-based decorative sheet for building materials (provided that the water-based decorative layer contains a polyester resin and the water-based surface protective layer contains a (meth) acrylic acid (co) polymer and / or a (meth) acrylic acid ester ( Co) Except for embodiments containing a polymer.) The water-based decorative sheet for building materials according to claim 1, wherein the cross-linked cured product A is a reaction-cured product of at least one cross-linked curable resin selected from the group consisting of the casein resin and the polyester resin and isocyanate. .. The crosslinked cured product B is at least one crosslinked product selected from the group consisting of the (meth) acrylic acid (co) polymer, the (meth) acrylic acid ester (co) polymer, the polyester resin and the urethane resin. The water-based decorative sheet for building materials according to claim 1 or 2, which is a reaction-cured product of a curable resin and isocyanate. The casein resin, the polyester resin, the (meth) acrylic acid (co) polymer, the (meth) acrylic acid ester (co) polymer, the polyester resin, and the urethane resin all have the lowest film-forming temperature (MFT). The water-based decorative sheet for building materials according to any one of claims 1 to 3, wherein the relationship between) and the glass transition temperature (Tg) satisfies MFT> Tg. The cross-linked cured product A is a cross-linked cured product containing the casein resin, and the cross-linked cured product B is the (meth) acrylic acid (co) polymer, the (meth) acrylic acid ester (co) polymer, and the urethane. The water-based decorative sheet for building materials according to any one of claims 1 to 4, which is a crosslinked cured product containing at least one selected from the group consisting of resins. The water-based decorative sheet for building materials according to any one of claims 1 to 4, wherein the cross-linked cured product A is a cross-linked cured product containing the polyester resin, and the cross-linked cured product B is a cross-linked cured product containing the polyester resin. .. Any of claims 1 to 4 and 6, wherein the polyester resin is at least one selected from the group consisting of a copolymer containing a monomer containing a sulfonic acid metal salt as a constituent unit and an alkydcarboxylic acid group neutralizer. A water-based decorative sheet for building materials described in Crab. The water-based decorative sheet for building materials according to any one of claims 1 to 7, wherein the water-based decorative layer is a solid decorative layer and / or a pattern layer. The water-based decorative sheet for building materials according to any one of claims 1 to 8, further comprising a gloss adjusting layer between the water-based decorative layer and the water-based surface protective layer and / or on the water-based surface protection layer. A ridge layer is further provided between the water-based decorative layer and the water-based surface protective layer and / or on the water-based surface protection layer, and the ridge layer forms a convex portion on the outermost surface of the water-based decorative sheet for building materials. The water-based decorative sheet for building materials according to any one of claims 1 to 9. The water-based decorative sheet for building materials according to any one of claims 1 to 10, wherein the water-based surface protective layer further contains at least one selected from the group consisting of an antibacterial agent, an antiviral agent and an anti-allergen agent. A fibrous base material having a basis weight of 60 g / m ² or less, a water-based decorative layer laminated on the fibrous base material, and a water-based surface protective layer laminated on the water-based decorative layer are provided in this order in the thickness direction. A method for manufacturing water-based decorative sheets for building materials.
(1) The aqueous decorative layer contains a crosslinked cured product A containing at least one selected from the group consisting of casein resin and polyester resin.
(2) The aqueous surface protective layer is crosslinked containing at least one selected from the group consisting of (meth) acrylic acid (co) polymer, (meth) acrylic acid ester (co) polymer, polyester resin and urethane resin. Contains cured product B,
(3) The water-based surface protective layer further contains water-soluble silicone, and the water-based surface protective layer further contains water-soluble silicone.
(4) The aqueous decorative sheet has a detection amount of a water-insoluble solvent having no hydroxy group of less than 1 mg / m ² in gas chromatography measurement.
(5) A water-based decorative layer coating film is formed on the fibrous base material using a water-based ink A containing at least one cross-linking curable resin selected from the group consisting of casein resin and polyester resin, and then continuously. Aqueous ink B containing at least one crosslinkable curable resin selected from the group consisting of (meth) acrylic acid (co) polymer, (meth) acrylic acid ester (co) polymer, polyester resin and urethane resin. A water-based decorative sheet for building materials, which comprises a heat-curing step after obtaining a laminate by forming a coating film for an aqueous surface protective layer using the above, and then winding the laminate on a roll I. Production method (However, an embodiment in which the aqueous decorative layer contains a polyester resin and the aqueous surface protective layer contains a (meth) acrylic acid (co) polymer and / or a (meth) acrylic acid ester (co) polymer. except for.). The method for producing a water-based decorative sheet for building materials according to claim 12, further comprising the heat curing step after winding the laminate on the roll I and then winding it back on another roll II. The method for producing a water-based decorative sheet for building materials according to claim 12, wherein the heat curing step is at 40 ° C. or higher for 24 hours or longer. A decorative board for building materials comprising a laminate including a decorative board base material and the water-based decorative sheet for building materials according to any one of claims 1 to 11, in order in the thickness direction.

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