Decorative sheets and decorative materials

Abstract

To provide a decorative sheet that can reproduce the touch and matte feel of woody material and has excellent stain resistance, and a decorative material having the decorative sheet.SOLUTION: A decorative sheet has a substrate, an adhesion layer provided on at least one side of the substrate, and a surface protective layer provided on the other side of the adhesion layer, which is opposite the side on which the substrate is provided. The surface protective layer has nonwoven fabric, and a resin part including a resin filled into at least some of gaps among the fibers of the nonwoven fabric. A side of the surface protective layer that is opposite the adhesion layer side has a 85° gloss value of 3.0 or more and 6.0 or less as measured in accordance with JIS Z 8741: 1997, and also has a pure water contact angle of 80° or more.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present disclosure relates to a decorative sheet and a decorative material including the same. [Background technology]

[0002] Decorative sheets have traditionally been used to decorate and protect the surfaces of interior and exterior components of buildings, interior and exterior components of vehicles such as automobiles, or furniture, fixtures, home appliances, etc. In recent years, as natural wood has become less available due to logging, there has been an increasing demand for decorative sheets that have a wood grain pattern and can provide a texture and matte finish similar to that of wood materials.

[0003] For example, Patent Document 1 discloses such a decorative sheet, which comprises a base material, a decorative layer, a raised layer formed in a pattern, and a surface protective layer covering the base material and the raised layer. The decorative sheet of Patent Document 1 can impart an excellent tactile feel to the raised portions. Furthermore, by forming the surface protective layer from an ionizing radiation-curable resin composition, various functions such as stain resistance and scratch resistance can be imparted to the decorative sheet.

[0004] Furthermore, among decorative sheets with wood grain patterns, decorative sheets that can be painted with stain paint (stainable decorative sheets) have been proposed so that general consumers can paint the surfaces of architectural interior materials, furniture, etc. themselves (DIY: Do It Yourself) (Patent Document 2, etc.). The decorative sheet in Patent Document 2 has a configuration in which a paper substrate and a nonwoven fabric are bonded together with an adhesive, and the side of the nonwoven fabric opposite the substrate is a fibrous part that maintains voids between the fibers, ensuring ink-receptivity that allows colorants such as stain paint to penetrate. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] JP 2015-171811 A [Patent Document 2] JP 2019-64131 A DISCLOSURE OF THE INVENTION [Problem to be solved by the invention]

[0006] However, the decorative sheet of Patent Document 1 has a raised layer formed from resin, which limits its ability to achieve a texture equivalent to that of wood materials. In particular, it has been difficult to achieve the texture of plywood or natural wood fibers.

[0007] Decorative sheets with stainability such as those in Patent Document 2 are designed to be colored, and have the opposite effect of stain resistance. Furthermore, the decorative sheet in Patent Document 2 has exposed fibrous portions with voids on the surface, which means that the mechanical properties of the surface, such as scratch resistance, are poor, and the sheet is prone to damage during processing or transportation. The present disclosure has been made in consideration of the above-mentioned problems, and aims to provide a decorative sheet that can reproduce the feel and matte finish of wood materials and has excellent resistance to contamination, and a decorative material that includes such a decorative sheet. [Means for solving the problem]

[0008] In order to solve the above problems, the present disclosure provides the following [1] to

[10] . [1] A decorative sheet comprising a substrate, an adhesive layer provided on at least one side of the substrate, and a surface protective layer provided on the other side of the adhesive layer on the side on which the substrate is provided, wherein the surface protective layer comprises a nonwoven fabric and a resin portion containing a resin filled in at least some of the voids between the fibers of the nonwoven fabric, and wherein the side on which the adhesive layer is provided and the other side of the surface protective layer have an 85-degree gloss value measured in accordance with JIS Z 8741:1997 of 3.0 or more and 6.0 or less, and the contact angle of pure water on the side on which the adhesive layer is provided and the other side of the surface protective layer is 80 degrees or more. [2] The decorative sheet according to [1], wherein the 85-degree gloss value is 4.0 or more and 5.6 or less. [3] The decorative sheet according to [1] or [2], wherein the hardness of the resin portion measured by nanoindentation is 150 MPa or more. [4] The decorative sheet according to any one of [1] to [3], wherein the hardness of the resin portion measured by nanoindentation is less than 240 MPa. [5] The decorative sheet according to any one of [1] to [4], wherein the resin portion comprises a cured product of an ionizing radiation curable resin composition. [6] The decorative sheet according to any one of [1] to [5], wherein the thickness of the surface protective layer is 35 μm or more. [7] The decorative sheet according to any one of [1] to [6], wherein the thickness of the surface protective layer is 250 μm or less. [8] The decorative sheet according to any one of [1] to [7], further comprising a decorative layer between the substrate and the adhesive layer. [9] The decorative sheet according to [8], wherein the decorative layer includes a wood grain pattern.

[10] A decorative material comprising the decorative sheet according to any one of [1] to [9] and an adherend. [Effects of the Invention]

[0009] According to the present disclosure, decorative sheets and decorative materials can be obtained that can reproduce the feel and matte finish of wood materials and also have excellent stain resistance. [Brief explanation of the drawings]

[0010] [Figure 1] 1 is a schematic cross-sectional view of an example of a decorative sheet of the present disclosure. DETAILED DESCRIPTION OF THE INVENTION

[0011] [Decorative sheet] The decorative sheet of the present disclosure comprises a substrate, an adhesive layer provided on at least one side of the substrate, and a surface protective layer provided on the other side of the adhesive layer on the side on which the substrate is provided, wherein the surface protective layer comprises a nonwoven fabric and a resin portion containing a resin filled in at least some of the voids between the fibers of the nonwoven fabric, and the surface protective layer on the side on which the adhesive layer is provided and the other side have an 85-degree gloss value measured in accordance with JIS Z 8741:1997 of 3.0 or more and 6.0 or less, and the contact angle of pure water on the surface protective layer on the side on which the adhesive layer is provided and the other side has a contact angle of 80 degrees or more.

[0012] <About 85 degree gloss value> In the decorative sheet of the present disclosure, the surface of the surface protective layer on which the adhesive layer is provided and the other surface (hereinafter simply referred to as the "surface of the surface protective layer") must have an 85° gloss value (hereinafter simply referred to as the "85° gloss value") of 3.0 or more and 6.0 or less, measured in accordance with JIS Z 8741: 1997. In this specification, the 85° gloss value means the average value of measurements taken at 10 locations.

[0013] The 85° gloss value is an index showing the degree of resin filling in the nonwoven fabric. The relationship between the degree of resin filling and the 85° gloss value is presumed as follows: If the amount of resin is too small relative to the void volume of the nonwoven fabric, the degree of resin filling will be insufficient. In this case, the voids inside the surface protective layer are filled with resin, but nonwoven fabric with no resin-filled voids will be exposed on the surface of the surface protective layer. In this case, the random orientation of the nonwoven fabric fibers scatters incident light on the surface of the surface protective layer, resulting in a low 85-degree gloss value. With such decorative sheets, dirt, colorants, etc. can enter the voids in the nonwoven fabric exposed on the surface of the surface protective layer, making it impossible to achieve sufficient contamination resistance. On the other hand, if the amount of resin is too high relative to the void volume of the nonwoven fabric, the nonwoven fabric will be buried in the resin, and the unevenness caused by the fibers of the nonwoven fabric on the surface of the surface protective layer will be reduced or will disappear. In this case, the 85-degree gloss value of the surface of the surface protective layer will be high. Such a decorative sheet will not provide a satisfactory feel to the touch. In addition, the gloss will be too high, making it impossible to express the matte finish that wood materials have.

[0014] When the amount of resin is appropriate relative to the void volume of the nonwoven fabric, the resin fills the voids in the nonwoven fabric, and the nonwoven fabric is coated with the resin so that the surface of the surface protective layer retains the irregularities caused by the fibers of the nonwoven fabric. In such decorative sheets, the 85° gloss value of the surface of the surface protective layer is in the range of 3.0 to 6.0. Such decorative sheets have an excellent feel and matte finish, and exhibit a design similar to that of wood materials. Furthermore, since there are fewer voids into which dirt, colorants, etc. can penetrate, the surface protective layer has excellent contamination resistance. Furthermore, since the voids are filled with resin, the hardness of the surface protective layer is increased, resulting in excellent scratch resistance. The lower limit of the 85° gloss value is preferably 3.5 or more, more preferably 4.0 or more, and the upper limit is preferably 5.8 or less, more preferably 5.6 or less.

[0015] <Contact angle> In the present disclosure, the contact angle of pure water between the surface of the surface protection layer on which the adhesive layer is provided and the other surface (hereinafter simply referred to as "contact angle") is 80 degrees or more. If the contact angle on the surface of the surface protection layer is less than 80 degrees, dirt easily adheres to the surface protection layer and the adhered dirt is difficult to wipe off, making it impossible to obtain sufficient contamination resistance. In other words, a contact angle of 80 degrees or more makes it difficult for dirt to adhere to the surface protection layer and makes it easy to wipe off any dirt that does adhere. The contact angle is more preferably 82 degrees or more, and even more preferably 83 degrees or more. The upper limit is preferably 88 degrees or less. In this specification, the contact angle is a value measured in accordance with the sessile drop method defined in JIS R 3257:1999, and is the average value of the measurement results at any 10 points.

[0016] <Hardness measured by nanoindentation method> In the decorative sheet of the present disclosure, the hardness of the resin portion measured by nanoindentation (hereinafter sometimes simply referred to as "hardness") is preferably 150 MPa or more. When the resin portion of the surface protective layer has a hardness of 150 MPa or more, the surface protective layer itself has sufficient hardness, and a decorative sheet with excellent scratch resistance can be obtained. The hardness of the resin portion is preferably 160 MPa or more, and more preferably 170 MPa or more. On the other hand, considering the handleability of the decorative sheet, it is preferable that the decorative sheet has excellent flexibility. If the resin portion has too high a hardness and insufficient flexibility, cracks may occur in the surface protective layer when the decorative sheet is deformed during the manufacturing process or when attached to an adherend. When the surface of such a surface protective layer is rubbed or another object is pressed against it, scratches due to cracks may easily occur. In other words, there is a risk that sufficient scratch resistance may not be obtained. Furthermore, cracks may cause the decorative sheet to appear white. Therefore, the hardness of the resin portion is preferably less than 240 MPa, and more preferably 220 MPa or less. In the present disclosure, the hardness of the resin portion refers to the hardness of the resin itself, excluding nonwoven fabric and the like.

[0017] The hardness of the resin portion is measured by the following procedure. First, a sample is prepared by cutting the decorative sheet so that the cross section of each layer is exposed. The obtained sample is placed in a microarea mechanical property evaluation device (HYSITRON TI950 TriboIndenter, manufactured by BRUKER). The indenter described below is scanned over an area of ​​approximately 5 μm square to obtain an image. In the obtained image, the measurement point is a location that is 1 μm or more away from the area recognized as the fibers and filler of the nonwoven fabric. At the measurement point, hardness is measured using a Berkovich indenter (material: diamond triangular pyramid) under the following measurement conditions. In this specification, the hardness of the resin portion refers to the average hardness value at any five measurement points on the surface of the surface protection layer. (Measurement conditions) Indenter used: Berkovich indenter (model number: TI-0039, manufactured by BRUKER) Indentation condition: Displacement control method Maximum indentation depth: 100nm Load application time: 10 seconds (speed: 10 nm / sec) Hold time: 5 seconds Loading / unloading time: 10 seconds (speed: 10 nm / sec)

[0018] <Layer structure of decorative sheet> The decorative sheet of the present disclosure will be described with reference to the drawings. Fig. 1 is a schematic cross-sectional view of an example of a decorative sheet of the present disclosure. The decorative sheet 10 of Fig. 1 comprises a substrate 20, a decorative layer 30, an adhesive layer 40, and a surface protective layer 50. The decorative layer 30, the adhesive layer 40, and the surface protective layer 50 are laminated in this order on one surface 20a of the substrate 20. The surface protection layer 50 includes a nonwoven fabric 51 and a resin portion 52 containing a resin filled in voids between fibers that make up the nonwoven fabric 51. The resin fills at least a portion of the voids. In FIG. 1, the decorative layer 30 has a colored layer 31 and a patterned layer 32 .

[0019] <Base material> The substrate serves as a support for the other layers to be deposited. The substrate can be selected from paper substrates, resin substrates, etc. without any limitation. Paper substrates are preferably used for the purpose of reducing costs and being environmentally friendly.

[0020] Examples of paper substrates that can be used include fine paper, tissue paper, linter paper, kraft paper, reinforced inter-paper paper, resin-impregnated paper, wallpaper backing paper, and flame-retardant paper obtained by mixing or impregnating a flame retardant into any of these papers. The paper substrate may contain additives such as flame retardants, inorganic agents, dry strength agents, wet strength agents, colorants, sizing agents, and fixing agents, as needed.

[0021] In the case of a paper substrate, there is no particular restriction on the thickness (i.e., basis weight), but considering the durability and handling of the decorative sheet, a basis weight of 20 g / m2 More than 150g / m 2 The following range is preferable, and 25 g / m 2 More than 120g / m 2 More preferably, the range is 35 g / m 2 More than 100g / m 2 More preferably, the range is 40 g / m 2 More than 60g / m 2 The following ranges are even more preferred:

[0022] Examples of resin substrates include those made of various synthetic resins. Examples of synthetic resins include olefin resins such as polyethylene resin, polypropylene resin, and polymethylpentene resin; vinyl resins such as polyvinyl chloride resin, polyvinylidene chloride resin, polyvinyl alcohol resin, vinyl chloride-vinyl acetate copolymer resin, ethylene-vinyl acetate copolymer resin, and ethylene-vinyl alcohol copolymer resin; polyester resins such as polyethylene terephthalate resin, polybutylene terephthalate resin, and ethylene naphthalate-isophthalate copolymer resin; acrylic resins such as polymethyl methacrylate resin, polyethyl methacrylate resin, and polybutyl acrylate resin; polyamide resins such as nylon 6 and nylon 66; cellulose resins such as cellulose triacetate resin and cellophane; polystyrene resin; polycarbonate resin; polyarylate resin; and polyimide resin. The resin substrate may contain additives such as flame retardants, antioxidants, plasticizers, colorants, antioxidants, UV absorbers, and light stabilizers, as needed.

[0023] There are no particular restrictions on the thickness of the resin substrate, but taking into consideration the durability and ease of handling of the decorative sheet, it is preferably 50 μm or more and 250 μm or less, more preferably 80 μm or more and 230 μm or less, and even more preferably 100 μm or more and 200 μm or less.

[0024] The above-mentioned substrates may be used alone or in any combination to form a laminate. For example, a laminate of different types of paper substrates, a laminate of different types of resin substrates, or a laminate of a paper substrate and a resin substrate may be used. When the substrate is a laminate, an adhesive layer may be further provided between each layer of the laminate.

[0025] <Decorative layer> The decorative sheet of the present disclosure preferably has a decorative layer to improve its design. The decorative layer may be provided between the substrate and the surface protective layer, and is preferably provided between the substrate and the adhesive layer. The decorative layer may be a layer consisting of only a colored layer provided to cover the base material, a layer consisting of only a patterned layer provided to cover a portion of the base material to form a pattern, or a layer combining a colored layer and a patterned layer. These layer configurations may be determined depending on the desired pattern.

[0026] The pattern imparted by the decorative layer is not particularly limited and may be selected as desired, but in the present disclosure, a wood grain pattern is preferred. Wood grain patterns include straight grain patterns, cross grain patterns, figured grain patterns, end grain patterns, etc., and any of these may be used.

[0027] The decorative layer is preferably formed from a resin composition containing at least a binder resin and a colorant such as a pigment or dye, and can be formed by appropriately mixing other components used as desired, such as a matting agent, an extender pigment, a stabilizer, a solvent, and weathering agents such as an ultraviolet absorber or a light stabilizer. In other words, the decorative layer is a layer that preferably contains at least a binder resin and a colorant such as a pigment or dye, and can also contain the other components used as desired.

[0028] The binder resin is not particularly limited, and preferred examples include urethane resin, acrylic polyol resin, acrylic resin, polyester resin, alkyd resin, amide resin, butyral resin, styrene resin, urethane-acrylic copolymer, vinyl chloride-vinyl acetate copolymer resin, vinyl chloride-vinyl acetate-acrylic copolymer resin, nitrocellulose resin (nitrocellulose), cellulose acetate resin, and the like. Furthermore, curable resins such as two-component curable resins containing various polyols such as acrylic polyol as the base resin and various isocyanates as the curing agent may also be used. These may be used alone or in combination.

[0029] The colorant can be appropriately selected from known pigments, such as inorganic pigments such as titanium white, lead white, carbon black, iron black, yellow lead, titanium yellow, red iron oxide, cadmium red, ultramarine blue, and cobalt blue; organic pigments or dyes such as quinacridone red, isoindolinone yellow, nickel azo complexes, and phthalocyanine blue; metal pigments consisting of scaly foil flakes of aluminum, brass, etc.; and pearlescent pigments consisting of scaly foil flakes of titanium dioxide-coated mica, basic lead carbonate, etc.

[0030] The thickness of the decorative layer is not particularly limited, but in order to improve the design, it is preferably 0.1 μm or more, more preferably 0.5 μm or more, and even more preferably 1 μm or more, with the upper limit being preferably 10 μm or less, more preferably 9 μm or less, and even more preferably 7.5 μm or less. When the decorative layer is formed from two or more layers, it is preferable that the total thickness of the layers be within the above range.

[0031] <Adhesive layer> The adhesive layer is a layer provided on at least one surface of the substrate, and is provided to bond the substrate and the nonwoven fabric together.

[0032] The adhesive used to form the adhesive layer is not particularly limited, and any known adhesive can be used. Among them, a resin containing a thermoplastic urethane resin is preferred. By using such an adhesive, excellent adhesion between the substrate and the nonwoven fabric can be obtained.

[0033] Thermoplastic urethane resins are urethane resins that do not have a crosslinked structure and have a linear or branched skeletal structure, such as copolymers in which monomers are copolymerized with urethane bonds formed by condensation of an isocyanate group and a compound having a hydroxyl group, such as an alcohol group. Examples of such thermoplastic urethane resins include urethane resins made of linear polymers obtained by reacting a polyol having a hydroxyl group at its terminal with a polyisocyanate.

[0034] Examples of polyols include compounds having two or more hydroxyl groups in the molecule, such as polyethylene glycol, polypropylene glycol, acrylic polyol, polyester polyol, polyether polyol, polycarbonate polyol, polycaprolactone polyol, and polyurethane polyol. Examples of polyisocyanates include compounds having two or more isocyanate groups in the molecule, such as aromatic isocyanates such as 2,4-tolylene diisocyanate, xylene diisocyanate, naphthalene diisocyanate, and 4,4'-diphenylmethane diisocyanate, and aliphatic (or alicyclic) isocyanates such as 1,6-hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, isophorone diisocyanate, hydrogenated tolylene diisocyanate, and hydrogenated diphenylmethane diisocyanate. Examples of polyisocyanates also include adducts or polymers of the above-mentioned various polyisocyanates, such as adducts of tolylene diisocyanate and tolylene diisocyanate trimer.

[0035] The adhesive may contain a resin other than a thermoplastic urethane resin as long as good adhesion between the substrate and the nonwoven fabric can be ensured. Resins that can be used in combination with the thermoplastic urethane resin include, for example, one-component curing and two-component curing curable urethane resins, as well as polyolefin resins, acrylic resins, and epoxy resins. These resins can be used alone or in combination. To particularly improve adhesion, the content of the thermoplastic urethane resin in the adhesive is preferably 50% by mass or more, more preferably 80% by mass or more, even more preferably 90% by mass or more, even more preferably 98% by mass or more, and particularly preferably 100% by mass. In other words, it is particularly preferred to use only a thermoplastic urethane resin.

[0036] In the present disclosure, the adhesive may be a mixture of additives such as weathering agents such as ultraviolet absorbers and light stabilizers, extender pigments, solvents, stabilizers, plasticizers, etc. In other words, the adhesive layer may be formed from a resin composition containing additives in addition to the above-mentioned resin.

[0037] In the present disclosure, a portion of the adhesive may penetrate into the voids of the nonwoven fabric constituting the surface protective layer. This improves the adhesion between the substrate and the nonwoven fabric. Note that the area where the adhesive penetrates into the voids between the fibers of the nonwoven fabric is understood to be excluded from the surface protective layer and incorporated into the adhesive layer.

[0038] The thickness of the adhesive layer can be determined taking into consideration the materials of the substrate and nonwoven fabric, the thickness of the nonwoven fabric, penetration into the voids of the nonwoven fabric, etc. In consideration of the adhesion between the substrate and the nonwoven fabric layer, the thickness of the adhesive layer is preferably 2 μm or more, more preferably 3 μm or more, even more preferably 5 μm or more, and even more preferably 8 μm or more. In consideration of the strength of the decorative sheet itself, the upper limit of the thickness of the adhesive layer is preferably 30 μm or less, more preferably 27 μm or less, even more preferably 23 μm or less, and even more preferably 20 μm or less. As mentioned above, in consideration of the penetration of the adhesive into the nonwoven fabric, the thickness of the adhesive layer is preferably less than the thickness of the nonwoven fabric. The thickness of the adhesive layer is determined by measuring the thickness at any 30 points on a cross-sectional image taken using various electron microscopes such as a transmission electron microscope (TEM), a scanning electron microscope (SEM), or a scanning transmission electron microscope (STEM), and averaging the thicknesses of the 30 points.

[0039] <Surface protective layer> The surface protective layer is a layer provided on at least one side of the substrate, and is preferably the outermost layer. The surface protective layer is a layer that imparts to the decorative sheet a texture and matte finish similar to that of wood materials, as well as surface properties such as scratch resistance and stain resistance. The surface protection layer includes a nonwoven fabric and a resin portion containing a resin that fills at least some of the voids between the fibers that make up the nonwoven fabric. The "resin" here is different from the resin that makes up the adhesive.

[0040] When the amount of resin is low relative to the void volume of the nonwoven fabric, the degree of resin filling is insufficient, and the 85° gloss value is less than 3.0, the surface of the surface protection layer tends to have large undulations due to the fibers of the nonwoven fabric, and the arithmetic mean roughness (Ra) and maximum height (Rz) tend to be large. On the other hand, when the amount of resin is too high relative to the void volume of the nonwoven fabric, and the 85° gloss value exceeds 6.0, the nonwoven fabric tends to be buried in the resin on the surface, and the arithmetic mean roughness (Ra) and maximum height (Rz) tend to be small. In the present disclosure, the surface of the surface protection layer preferably has an arithmetic mean roughness (Ra) of 2.7 μm or more, more preferably 3.0 μm or more, and preferably 8.0 μm or less, and more preferably 7.0 μm or less. Furthermore, the maximum height (Rz) is preferably 21.0 μm or more, preferably 22.0 μm or more, and preferably 50.0 μm or less, and more preferably 45.0 μm or less. When the arithmetic mean roughness (Ra) and maximum height (Rz) are within the above ranges, the 85-degree gloss value of the surface of the surface protection layer tends to be within the range of 3.0 to 6.0. Furthermore, when the arithmetic mean height (Ra) and maximum height (Rz) are within the above ranges, a surface protection layer with excellent tactile feel can be obtained. In this specification, the arithmetic mean roughness (Ra) and maximum height (Rz) are measured in accordance with JIS B0601:2001, and are the arithmetic mean roughness and maximum height when the cutoff value is 2.5 mm, and are the average values ​​of the measurement results at 10 arbitrary points. In this specification, the cutoff value refers to the cutoff value (λc) for the roughness curve.

[0041] The resin fills at least some of the voids between the fibers of the nonwoven fabric. "Filling at least some of the voids between the fibers" can mean (1) a state in which the resin has sufficiently penetrated into the substrate side of the nonwoven fabric, leaving almost no voids inside the surface protective layer, while voids remain on the surface of the surface protective layer even though the fibers are covered with the resin, or (2) a state in which voids that are not completely filled with resin exist randomly within the nonwoven fabric. While the present disclosure allows for voids to remain within the surface protective layer, a high void filling rate is preferred in consideration of factors such as stain resistance, scratch resistance, and the 85° gloss value of the surface of the surface protective layer. The filling rate is preferably 80% or more, more preferably 85% or more, and even more preferably 90% or more. The degree of resin filling into voids can also be expressed by the ratio of the arithmetic mean roughness before and after filling. If the arithmetic mean roughness of the surface of the nonwoven fabric before filling with resin is Ra0 and the arithmetic mean roughness of the surface of the surface protective layer of the decorative sheet is Ra, the ratio of the arithmetic mean roughness before and after filling is expressed as Ra / Ra0. As mentioned above, when the amount of resin is small and the degree of resin filling into voids is insufficient, the arithmetic mean roughness Ra tends to be large due to the unevenness of the nonwoven fabric, and the change in the arithmetic mean roughness before and after filling is small. Therefore, Ra / Ra0 is close to 1. On the other hand, when the amount of resin is too large, the nonwoven fabric tends to be embedded in the resin, which tends to reduce the arithmetic mean roughness Ra, and therefore Ra / Ra0 tends to be small. Furthermore, when the resin is difficult to impregnate, the nonwoven fabric tends to be embedded in the resin, which tends to reduce the arithmetic mean roughness Ra, and therefore Ra / Ra0 tends to be small. Ra / Ra0 is preferably within the range of 0.15 to 0.45. By having Ra / Ra0 within the above range, the resin can be sufficiently filled into the gaps between the fibers of the nonwoven fabric, while leaving the roughness due to the fibers of the nonwoven fabric on the surface of the surface protective layer. That is, by having Ra / Ra0 within the above range, the 85° gloss value on the surface of the surface protective layer can be easily satisfied within the range of 3.0 to 6.0, making it possible to obtain a decorative sheet with excellent tactile feel and excellent stain resistance. Ra / Ra0 is more preferably 0.15 to 0.35, and even more preferably 0.15 to 0.30. The arithmetic mean roughness Ra0 is measured in accordance with JIS B0601:2001, with a cutoff value of 2.5 mm, and is the average of measurement results at 10 random locations.

[0042] The thickness of the surface protective layer is preferably set taking into consideration the physical properties of the decorative sheet, such as strength, mass, and flexibility, as well as the thickness of the decorative sheet. The thickness of the surface protective layer is preferably 35 μm or more, more preferably 40 μm or more, and even more preferably 45 μm or more. The upper limit of the thickness of the surface protective layer is preferably 120 μm or less, more preferably 110 μm or less, and even more preferably 100 μm or less.

[0043] <<Nonwoven fabric>> The nonwoven fabric gives the decorative sheet a texture similar to that of wood fibers, and also plays a role in supporting the resin between the fibers. The fibers constituting the nonwoven fabric are not particularly limited, and examples thereof include thermoplastic resin fibers, natural fibers, regenerated fibers, semi-synthetic fibers, etc. In the present embodiment, the fibers can be used alone or in combination of two or more types.

[0044] Preferred examples of thermoplastic resin fibers include thermoplastic resin fibers made of (meth)acrylic resins such as poly(meth)acrylate esters; polyvinyl acetal (butyral resins) such as polyvinyl butyral; polyester resins such as polyethylene terephthalate and polybutylene terephthalate; polyolefin resins such as polyethylene and polypropylene; styrene resins such as polystyrene and α-methylstyrene; acetal resins such as polyoxymethylene; thermoplastic elastomers such as polyolefin thermoplastic elastomers, polystyrene thermoplastic elastomers, polydiene thermoplastic elastomers, urethane thermoplastic elastomers, polyester thermoplastic elastomers, and fluororesin thermoplastic elastomers; fluororesins such as vinyl chloride resins, urethane resins, and ethylene-tetrafluoroethylene copolymers, polyamide resins, polyimide resins, polylactic acid resins, polycarbonate resins, polyvinyl acetal resins, and liquid crystalline polyester resins. Among these thermoplastic resin fibers, in consideration of dimensional stability, thermoplastic resin fibers made of resins such as polyester resin, polyolefin resin, and urethane resin are preferred, and thermoplastic resin fibers made of polyester resin and polyolefin resin are more preferred.

[0045] In this embodiment, the thermoplastic resin constituting the thermoplastic resin fiber may be a single type or a combination of multiple types, and may be, for example, a composite fiber such as a double-structure fiber in which the core is a polyester resin and the sheath is a polyolefin resin.

[0046] Natural fibers include fibers made from natural materials such as cotton, wool, and silk; regenerated fibers include rayon, cupra, and lyocell; and semi-synthetic fibers include triacetate and promix.

[0047] The fiber diameter of the fibers constituting the nonwoven fabric is not particularly limited. Considering the ease of obtaining a texture very similar to that of wood and the resin impregnation property described below, the average fiber diameter of the nonwoven fabric is preferably 0.5 μm or more, more preferably 1 μm or more, with the upper limit being preferably 50 μm or less, more preferably 30 μm or less, and even more preferably 20 μm or less. Nonwoven fabrics made of fibers having an average fiber diameter in this range tend to easily obtain a texture very similar to that of wood. The average fiber diameter of the fibers constituting the nonwoven fabric can be measured by using an electron microscope (300x magnification) to measure the fiber width (diameter) of 30 fibers present at any location on the nonwoven fabric and averaging the values ​​obtained for each measurement.

[0048] The fibers constituting the nonwoven fabric can be formed, for example, by forming fleece by the spunbonding method and then bonding the formed fleece by the thermal bonding method, the spunlace method (hydroentanglement method), etc. Furthermore, nonwoven fabrics formed by these methods tend to have a texture very similar to that of wood.

[0049] The basis weight of the fibers constituting the nonwoven fabric (before impregnation with the resin) is preferably 10 g / m 2 More preferably, 15 g / m 2 The upper limit is preferably 40 g / m 2 Less than 30 g / m, more preferably 2 More preferably 20 g / m or less 2The following is a summary. By using a nonwoven fabric with a basis weight within the above range, the resin can easily penetrate deep into the nonwoven fabric, improving the strength of the surface protective layer itself. In addition, it is easy to adjust the 85° gloss value within a specified range, and an excellent tactile feel can be imparted to the decorative sheet.

[0050] The thickness of the nonwoven fabric used to form the surface protective layer is not particularly limited, but is preferably selected taking into consideration the strength, mass, flexibility, and other physical properties of the decorative sheet, as well as the thickness of the decorative sheet. Furthermore, the thickness of the nonwoven fabric used is preferably selected taking into consideration that the thickness of the nonwoven fabric will decrease as a result of the bonding process with the adhesive layer and the resin filling process. The thickness of the nonwoven fabric (before resin impregnation) is preferably 80 μm or more, more preferably 90 μm or more, and even more preferably 100 μm or more. The upper limit of the thickness of the nonwoven fabric is preferably 300 μm or less, more preferably 250 μm or less, and even more preferably 200 μm or less.

[0051] The 85° gloss value of the nonwoven fabric itself, i.e., the 85° gloss value of the nonwoven fabric before being impregnated with resin, is preferably 1.5 to 4.0, more preferably 2.0 to 3.0. By using a nonwoven fabric having the above 85° gloss value, when the nonwoven fabric is impregnated with resin to form a surface protective layer, the 85° gloss value can be easily adjusted to within the range of 3.0 to 6.0.

[0052] The arithmetic mean roughness (Ra0) of the surface of the nonwoven fabric itself is preferably 10 μm or more and 30 μm or less, and more preferably 15 μm or more and 30 μm or less. Furthermore, the maximum height (Rz0) of the surface of the nonwoven fabric itself is preferably 80 μm or more and 160 μm or less, and more preferably 100 μm or more and 140 μm or less. By using a nonwoven fabric having the above arithmetic mean roughness and maximum height, an excellent tactile feel can be imparted to the decorative sheet. The arithmetic mean roughness (Ra0) and maximum height (Rz0) are measured in accordance with JIS B0601:2001, and are the arithmetic mean roughness and maximum height when the cutoff value is 2.5 mm, and are the average values ​​of the measurement results at 10 random locations.

[0053] <<Resin part>> The resin portion maintains the shape of the nonwoven fabric and prevents the adhesion of dirt and colorants, making the decorative sheet stain-resistant. It also provides the surface protection layer with appropriate hardness to ensure scratch resistance. Furthermore, by combining with the nonwoven fabric, it gives the decorative sheet a matte finish similar to that of wood.

[0054] The contact angle of the surface protective layer can be adjusted by selecting the resin used in the surface protective layer. For example, the degree of hydrophilicity of the surface of the surface protective layer can be changed by the functional groups in the resin used in the surface protective layer, thereby changing the contact angle. For example, the lower the proportion of highly polar functional groups contained in the resin constituting the surface protective layer, the more lipophilic the surface of the surface protective layer tends to be, resulting in a higher contact angle. Examples of highly polar functional groups include hydroxyl groups, amino groups, and carboxyl groups. On the other hand, for example, the higher the proportion of low-polarity or non-polar functional groups contained in the resin constituting the surface protective layer, the more lipophilic the surface of the surface protective layer tends to be, resulting in a higher contact angle. Examples of low-polarity and non-polar functional groups include phenyl groups and methyl groups. Furthermore, when the low-polarity polymer chain is long, the polarity of the polymer chain also tends to be low, resulting in a higher contact angle. Methods for changing the polarity of the resin constituting the surface protective layer include using a resin with a low content of highly polar functional groups or using a resin with low-polarity functional groups. Furthermore, in the case of a curable resin, increasing the crosslink density reduces the polarity of the resin forming the surface protective layer, thereby increasing the contact angle. When the resin forming the surface protective layer is formed by a condensation reaction of multiple resins, the contact angle can also be controlled by setting the mixing ratio so that functional groups with high polarity are consumed.

[0055] As the type of resin used for the resin portion, a curable resin is preferably used in consideration of imparting sufficient hardness to the surface protective layer to ensure scratch resistance. Examples of the curable resin include ionizing radiation curable resins and thermosetting resins. Among them, in consideration of scratch resistance and productivity, it is particularly preferable to use an ionizing radiation curable resin. The resin portion may contain various additives and solvents as necessary in addition to the above-mentioned resins. That is, a resin composition containing the above-mentioned resins can be used to form the resin portion. Therefore, the resin portion preferably contains a cured product of a curable resin composition, and particularly preferably contains a cured product of an ionizing radiation-curable resin composition.

[0056] The content of the cured product of the curable resin composition is preferably 50% by mass or more, more preferably 70% by mass or more, even more preferably 90% by mass or more, and most preferably 100% by mass, based on the total amount of the resin portion.

[0057] The thermosetting resin composition is a composition that contains at least a thermosetting resin and is a resin composition that is cured by heating. Examples of thermosetting resins include acrylic resins, urethane resins, phenolic resins, urea melamine resins, epoxy resins, unsaturated polyester resins, silicone resins, etc. In addition to these thermosetting resins, a curing agent, a curing catalyst, etc. are added to the thermosetting resin composition as needed.

[0058] Representative examples of ionizing radiation curable resin compositions include electron beam curable resin compositions and ultraviolet light curable resin compositions. Among these, electron beam curable resin compositions are preferred because they do not require a polymerization initiator and therefore have little odor, and they can easily achieve good scratch resistance by increasing the crosslink density.

[0059] The ionizing radiation curable resin composition is a composition containing a compound having an ionizing radiation curable functional group (hereinafter also referred to as "ionizing radiation curable compound"). The ionizing radiation-curable functional group is a group that crosslinks and cures upon irradiation with ionizing radiation, and preferred examples thereof include functional groups having an ethylenic double bond such as a (meth)acryloyl group, a vinyl group, and an allyl group. Further examples of the ionizing radiation-curable functional group include an epoxy group and an oxetanyl group. In this specification, the term "(meth)acryloyl group" refers to an acryloyl group or a methcroyl group, and the term "(meth)acrylate" refers to an acrylate or a methacrylate. Furthermore, ionizing radiation refers to electromagnetic waves or charged particle beams that have an energy quantum capable of polymerizing or crosslinking molecules. Typically, ultraviolet (UV) rays or electron beams (EB) are used, but it also includes other electromagnetic waves such as X-rays and gamma rays, and charged particle beams such as alpha rays and ion beams. Specifically, the ionizing radiation curable compound can be appropriately selected from polymerizable monomers and polymerizable oligomers (sometimes referred to as "polymerizable prepolymers") that are commonly used as ionizing radiation curable resins.

[0060] The ionizing radiation curable compound is preferably a compound having two or more ethylenically unsaturated bond groups, and more preferably a polyfunctional (meth)acrylate compound having two or more ethylenically unsaturated bond groups. Either a monomer or an oligomer can be used as the polyfunctional (meth)acrylate compound. The number of ethylenically unsaturated bond groups affects the hardness of the resin portion. The greater the number of ethylenically unsaturated bond groups, the higher the hardness tends to be.

[0061] Among the polyfunctional (meth)acrylate compounds, examples of bifunctional (meth)acrylate monomers include ethylene glycol di(meth)acrylate, bisphenol A tetraethoxydiacrylate, bisphenol A tetrapropoxydiacrylate, and 1,6-hexanediol diacrylate. Examples of trifunctional or higher (meth)acrylate monomers include trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol tetra(meth)acrylate, and isocyanuric acid-modified tri(meth)acrylate. Examples of the polyfunctional (meth)acrylate oligomer include acrylate polymers such as urethane (meth)acrylate, epoxy (meth)acrylate, polyester (meth)acrylate, and polyether (meth)acrylate.

[0062] Urethane (meth)acrylates can be obtained, for example, by reacting a polyhydric alcohol and an organic diisocyanate with a hydroxy (meth)acrylate.

[0063] Preferred epoxy (meth)acrylates are (meth)acrylates obtained by reacting a tri- or higher functional aromatic epoxy resin, alicyclic epoxy resin, aliphatic epoxy resin, or the like with (meth)acrylic acid; (meth)acrylates obtained by reacting a di- or higher functional aromatic epoxy resin, alicyclic epoxy resin, aliphatic epoxy resin, or the like with a polybasic acid and (meth)acrylic acid; and (meth)acrylates obtained by reacting a di- or higher functional aromatic epoxy resin, alicyclic epoxy resin, aliphatic epoxy resin, or the like with a phenol and (meth)acrylic acid.

[0064] The weight-average molecular weight of a resin affects the resin's ability to impregnate a nonwoven fabric. Specifically, resins with a high weight-average molecular weight have high viscosity, making it difficult to penetrate into the voids of the nonwoven fabric, making it difficult to achieve a high filling rate, and they tend to be difficult to handle. Resins with a low weight-average molecular weight easily penetrate into the voids of the nonwoven fabric, but tend to experience greater shrinkage upon curing. However, factors that affect the resin's ability to impregnate include the size of the voids between the fibers of the nonwoven fabric, the basis weight of the fibers constituting the nonwoven fabric, and viscosity adjustment based on the presence or absence of a solvent in the resin composition. The weight-average molecular weight of a resin also affects the hardness of the resin portion. Specifically, the higher the weight-average molecular weight, the lower the hardness of the resin portion. Considering the hardness of the resin portion and the impregnation ability of the nonwoven fabric, it is recommended to select a resin with a weight-average molecular weight of preferably 1,000 or more, more preferably 2,000 or more, and preferably 20,000 or less, more preferably 15,000 or less. The weight average molecular weight in this specification is an average molecular weight measured by GPC (gel permeation chromatography) and converted into standard polystyrene.

[0065] The above ionizing radiation curable resins can be used alone or in combination of two or more. As mentioned above, the number of ethylenically unsaturated bond groups and the weight average molecular weight affect the hardness of the resin portion. By mixing multiple compounds with different numbers of ethylenically unsaturated bond groups and different weight average molecular weights, the hardness of the resin portion can be adjusted to a predetermined range.

[0066] When the ionizing radiation curable compound is an ultraviolet ray curable compound, the ionizing radiation curable resin composition preferably contains additives such as a photopolymerization initiator and a photopolymerization accelerator. The photopolymerization initiator may be one or more selected from acetophenone, benzophenone, α-hydroxyalkylphenone, Michler's ketone, benzoin, benzil dimethyl ketal, benzoyl benzoate, α-acyloxime ester, thioxanthones, and the like. The photopolymerization accelerator can reduce polymerization inhibition caused by air during curing and increase the curing rate, and examples thereof include one or more selected from p-dimethylaminobenzoic acid isoamyl ester, p-dimethylaminobenzoic acid ethyl ester, etc.

[0067] The resin portion may contain a filler, which provides a matte design to the surface protective layer and also improves the abrasion resistance of the surface protective layer. Examples of fillers include inorganic particles such as silica and alumina, and resin beads made of acrylic resin. In consideration of abrasion resistance, the filler is preferably inorganic particles, and more preferably silica particles. The average particle diameter of the filler is preferably 3 μm or more and 20 μm or less. In this specification, the average particle diameter refers to the mass average value d50 measured in particle size distribution measurement by laser light diffraction method.

[0068] The content of the filler is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, per 100 parts by mass of resin, in consideration of the matte effect and improvement in abrasion resistance. The upper limit of the filler content is preferably 70 parts by mass or less, more preferably 60 parts by mass or less, per 100 parts by mass of resin, in consideration of the scratch resistance, contamination resistance, tactile feel, etc. of the surface.

[0069] <Manufacturing method of decorative sheet> The decorative sheet of the present disclosure can be produced through step 1 of providing an adhesive layer on a substrate, step 2 of bonding the adhesive layer to a nonwoven fabric, and step 3 of filling the voids between the fibers that make up the nonwoven fabric with a resin to form a surface protective layer. Step 1 may include step 1-1 of providing a decorative layer on the substrate, and step 1-2 of providing an adhesive layer on the decorative layer.

[0070] In step 1-1, a decorative layer is provided on the substrate. If no decorative layer is provided, step 1-1 can be omitted. The decorative layer is preferably formed by printing the resin composition used to form the decorative layer using gravure printing, silk screen printing, gravure offset printing, flexographic printing, ink jet printing, or the like, and it is more preferable to use gravure printing for large lots and ink jet printing for small lots.

[0071] In step 1-2, an adhesive layer is provided on the decorative layer. For example, a resin composition containing a resin appropriately selected from those exemplified as resins capable of forming an adhesive layer is applied to the decorative layer to form the adhesive layer. In this case, the resin composition may be applied by any of the known methods exemplified as the resin composition application methods for the decorative layer.

[0072] In step 2, the adhesive layer and the nonwoven fabric are bonded together. A nonwoven fabric is placed on the adhesive layer formed in step 1-2. The adhesive layer and the nonwoven fabric are then bonded together by extrusion lamination (sand lamination), dry lamination, thermocompression bonding, etc. At this time, by controlling conditions such as the pressing force and heating temperature, part of the adhesive layer is filled into some of the voids in the nonwoven fabric on the substrate side.

[0073] In step 3, a resin composition that forms a resin portion is applied to the surface of the nonwoven fabric. The applied resin composition permeates into the nonwoven fabric. As a result, the resin composition fills the voids in the nonwoven fabric. The resin composition that forms the surface protective layer can be applied by any of the known methods listed above as examples of the resin composition application method for the decorative layer. The amount of resin composition to be applied is determined based on the basis weight of the fibers that make up the nonwoven fabric, the 85° gloss value of the resulting surface protective layer, and the feel. To ensure good application and resin impregnation, the viscosity of the coating solution is preferably adjusted to a value within the range of 15 to 40 seconds when measured using a Zahn Cup 417 No. 3 (manufactured by Rigo Co., Ltd.). After the resin composition is filled into the voids in the nonwoven fabric, the resin composition is cured by a method appropriate for the type of resin, thereby forming a surface protective layer.

[0074] [Decorative materials] The decorative material of the present disclosure comprises an adherend and the decorative sheet of the present disclosure described above. The decorative material of the present disclosure is, for example, laminated such that the surface of the adherend that requires decoration faces the surface of the substrate opposite the surface on which the surface protective layer or the like of the decorative sheet is provided.

[0075] <Adherent material> Examples of the adherend include flat plates, curved plates, and other plate materials, three-dimensional objects, sheets (or films), etc. Examples of the material of the adherend include wood members, metal members, ceramic members, and resin members. Examples of raw materials for wood members include various types of wood such as cedar, cypress, pine, lauan, etc. Examples of shapes of wood members include wood veneers, wood plywood, particle boards, wood fiberboards such as MDF (medium density fiberboard), and three-dimensional shaped products. Examples of raw materials for the metal member include iron, aluminum, etc. Examples of shapes of the metal member include plate material, steel plate, three-dimensional shaped article, sheet, etc. Examples of raw materials for ceramic members include glass, ceramics such as porcelain, non-cement ceramic materials such as gypsum, and non-ceramic ceramic materials such as ALC (aerated lightweight concrete) boards. Examples of shapes of ceramic members include plates and three-dimensional objects. Examples of raw materials for the resin member include polyolefin resins such as acrylic resin, polyester resin, polystyrene resin, and polypropylene resin, ABS (acrylonitrile-butadiene-styrene copolymer) resin, phenolic resin, vinyl chloride resin, cellulose resin, rubber, etc. Examples of shapes of the resin member include plates, three-dimensionally shaped articles, and sheets. The components constituting the adherend can be used alone or in combination of two or more types. The decorative material of the present disclosure is preferable when the adherend contains a polypropylene-based resin, in that it can improve the weather resistance of the adherend.

[0076] The adherend may be selected from the above according to the intended use. When the adherend is used as an interior or exterior member of a building such as a wall, ceiling, or floor, or as a fitting or fixture member such as a window frame, door, handrail, baseboard, molding, or other such member, the material of the adherend is preferably at least one member selected from wood members, metal members, and resin members. When the adherend is used as an exterior member such as an entrance door, or as fittings such as a window frame or door, the material of the adherend is preferably at least one member selected from metal members and resin members.

[0077] The thickness of the adherend may be appropriately selected depending on the application and material, and is preferably 0.1 mm to 10 mm, more preferably 0.3 mm to 5 mm, and even more preferably 0.5 mm to 3 mm.

[0078] <Adhesive layer for decorative materials> In order to obtain excellent adhesion, the adherend and the decorative sheet are preferably bonded together via an adhesive layer (adhesive layer for decorative materials).

[0079] The adhesive used in the adhesive layer for a decorative material is not particularly limited, and known adhesives can be used, and preferred examples include heat-sensitive adhesives and pressure-sensitive adhesives. Examples of resins used in adhesives constituting the adhesive layer for a decorative material include acrylic resins, polyurethane resins, vinyl chloride resins, vinyl acetate resins, vinyl chloride-vinyl acetate copolymer resins, styrene-acrylic copolymer resins, polyester resins, and polyamide resins, and these can be used alone or in combination. Two-component curing polyurethane adhesives and polyester adhesives that use an isocyanate compound or the like as a curing agent can also be used. The adhesive layer for the decorative material may also contain a pressure-sensitive adhesive, which may be appropriately selected from acrylic, urethane, silicone, rubber, and other pressure-sensitive adhesives.

[0080] There are no particular restrictions on the thickness of the adhesive layer for decorative materials, but to obtain excellent adhesiveness, it is preferably from 1 μm to 100 μm, more preferably from 5 μm to 50 μm, and even more preferably from 10 μm to 30 μm. [Example]

[0081] Next, the present disclosure will be described in more detail by way of examples, but the present disclosure is not limited to these examples in any way.

[0082] 1. Evaluation and Measurement The decorative sheets of the Examples and Comparative Examples were evaluated as follows. Furthermore, as a Reference Example, Nonwoven Fabric 1 described below was evaluated in the same manner as below (except for 1-2 and 1-6). The results are shown in Table 1.

[0083] 1-1.85 degree gloss value The 85-degree gloss value of the decorative sheets of the Examples and Comparative Examples was measured in accordance with JIS Z 8741:1997. A three-angle surface glossmeter (manufactured by BYK-Gardner) was used for the measurement. Measurements were taken at 10 random locations within the surface, and the average value obtained was used as the 85-degree gloss value of the Examples, Comparative Examples, and Reference Examples.

[0084] 1-2.Contact angle The decorative sheets of the Examples and Comparative Examples were placed on a horizontal surface with the surface protective layer facing up. A water droplet was dropped onto the surface protective layer from a direction perpendicular to the horizontal surface, and the contact angle between the layer and pure water was measured using a contact angle meter (fully automatic contact angle meter DMo-702, manufactured by Kyowa Interface Science Co., Ltd.) under the conditions described below. The above measurements were performed on 10 randomly selected locations on the surface of the surface protective layer, and the average value was used as the contact angle of the surface protective layer in the Examples and Comparative Examples. ·Dropped amount: 2.0μL Waiting time after dripping before measurement: 100 seconds

[0085] 1-3.Hardness by nanoindentation method Samples (approximately 5 mm x 1.5 mm) cut from the decorative sheets of the Examples and Comparative Examples were placed in an embedding plate. Epoxy resin was then poured into the embedding plate and allowed to harden, creating a block-shaped embedded sample. The block-shaped embedded sample was cut vertically to create a measurement sample with the cross section of the decorative sheet exposed.

[0086] The hardness of the resin portion of the surface protective layer of the measurement sample was measured by nanoindentation using a micro-area mechanical property evaluation device (HYSITRON TI950 TriboIndenter, manufactured by BRUKER). Five measurement points were selected using the method described above. At each measurement point, a Berkovich indenter (material: diamond triangular pyramid) was pressed into the surface of the surface protective layer under the following measurement conditions to measure the hardness. The average hardness at the five measurement points was taken as the hardness of the resin portion of the surface protective layer in the examples and comparative examples. (Measurement conditions) Indenter used: Berkovich indenter (model number: TI-0039, manufactured by HYSITRON) Indentation condition: Displacement control method Maximum indentation depth: 100nm Load application time: 10 seconds (speed: 10 nm / sec) Hold time: 5 seconds Loading / unloading time: 10 seconds (speed: 10 nm / sec)

[0087] 1-4.Surface roughness For the decorative sheets of the Examples and Comparative Examples, the arithmetic mean roughness (Ra) and maximum height (Rz) of the surface of the surface protective layer were measured under the following measurement conditions using a shape analysis laser microscope (VK-X1000 (control unit) / VK-X1050 (measurement unit), manufactured by Keyence Corporation) according to a method conforming to JIS B0601:2001. The measurement condition was a cutoff value of 2.5 mm. Measurements were taken at 10 random locations on the surface protective layer, and the average values ​​were used as the calculated mean roughness (Ra) and maximum height (Rz) of each Example and Comparative Example. In addition, the ratio (Ra / Ra0) of the arithmetic mean roughness (Ra) of each Example and Comparative Example to the arithmetic mean roughness (Ra0) of the Reference Example was calculated.

[0088] 1-5.Tactile sensation The decorative sheets of the Examples and Comparative Examples were subjected to a tactile evaluation by 20 random adult subjects. In the test, the subjects were asked to evaluate whether the surface protective layer felt sufficiently tactile when touched with their hands. The test results were evaluated according to the following criteria. A +: 20 out of 20 people answered that they had a sufficient sense of touch. A: Between 15 and 19 out of 20 people answered that they had a sufficient sense of touch. B: Between 11 and 14 out of 20 people answered that they had a sufficient sense of touch. C: Fewer than 10 out of 20 people answered that they had a sufficient sense of touch.

[0089] 1-6.Appearance The decorative sheets of the Examples and Comparative Examples were visually evaluated for appearance by 20 random adult subjects. In the test, when observing the decorative sheet from the surface protective layer side, the subjects were asked to score the sheet as follows: if the sheet had an appearance similar to that of natural wood, 2 points; if the sheet had a low gloss and was perceived as having a slightly different appearance from the real thing, 1 point; if the sheet had too much gloss and was perceived as having a different impression from the real thing, 0 point. The total score was calculated and evaluated according to the following criteria. A: Total score is 36 or more B: Total score is 25-35 points C: Total score is 24 points or less

[0090] 1-7.Scratch resistance The substrate side of the decorative sheet produced in the Examples and Comparative Examples was attached to MDF (manufactured by Hokushin Co., Ltd., thickness 2.7 mm) via an adhesive (two-component curing water-based adhesive, product name "BA-10L", manufactured by Japan Coating Resin Co., Ltd.) to produce a test decorative material. The amount of adhesive applied was 65 g / m 2 from 88g / m 2 The concentration was adjusted to be within the range. The test decorative material was placed in a scratch tester (Balanced Beam Adhesion / Mar Tester, manufactured by BYK-GARDNER). A scratch blade (a cylindrical blade with a diameter of 7 mm) was set so that it was in contact with the decorative sheet surface (surface of the surface protection layer) of the test decorative material at a 45° angle, and the scratch blade was moved over the test decorative material. The load (weight) was gradually increased in 100 g increments, and the test was repeated until scratches, indentations, etc. appeared on the decorative sheet surface, and the results were evaluated according to the following criteria. A +: A load of 400g caused scratches and indentations on the surface of the decorative sheet. A: A load of 300g caused scratches and indentations on the surface of the decorative sheet. B: A load of 200 g caused scratches, indentations, etc. on the surface of the decorative sheet. C: A load of 100 g caused scratches, indentations, etc. on the surface of the decorative sheet.

[0091] 1-8. Stain resistance Ink was applied to the surface protective layer of the decorative sheets of the Examples and Comparative Examples using a black marker (Teranishi Chemical Industry Co., Ltd., oil-based). After 4 hours, the ink was wiped off with a tissue soaked in ethanol, and the remaining ink was visually evaluated using the following scale. 2 points: No ink remaining 1 point: A small amount of ink remains 0 points: Most of the ink remains The above-mentioned scoring was carried out for any 10 points on the surface protective layer, the total score was calculated, and the stain resistance was evaluated according to the following criteria. A: Total score is 20 points B: Total score is 17-19 points C: Total score is 16 points or less

[0092] 2. Preparation of decorative sheets [Example 1] Paper base material (HPT30 (product number), manufactured by Hokuetsu Kishu Paper Co., Ltd., thickness: 60 μm, basis weight: 45 g / m 2 A decorative layer ink (an ink containing acrylic resin as a binder and carbon black as a pigment) was applied onto the wood grain pattern by gravure printing to form a wood grain patterned decorative layer with a thickness of 2 to 6 μm. A resin composition (two-component curing urethane adhesive) for forming an adhesive layer was applied by gravure printing to form an adhesive layer with a thickness of 4 μm. On the adhesive layer, nonwoven fabric 1 (nonwoven fabric made of rayon fiber, manufactured by Kinboshi Paper Co., Ltd., thickness: 80 μm, basis weight: 17 g / m) 2 ) was placed on the nonwoven fabric. Thereafter, the nonwoven fabric and the adhesive layer were bonded together by dry lamination. On the nonwoven fabric 1, a coating liquid 1 for the resin portion (ionizing radiation curable resin composition) having the following formulation was applied by gravure printing, and the coating liquid was allowed to penetrate into the nonwoven fabric 1. The coating amount (dry basis) was 8 g / m 2 Next, the resin portion coating liquid was crosslinked and cured by irradiating it with an electron beam (acceleration voltage: 175 kV, 5 Mrad (50 kGy)) from the nonwoven fabric 1 side. This formed a surface protection layer with a thickness of 40 μm, and the decorative sheet of Example 1 was obtained. <Coating liquid for resin parts 1> 60 parts by weight of hexafunctional electron beam curable urethane acrylate Bifunctional electron beam curable urethane acrylate 40 parts by weight Spherical silica particles (average particle size 4 μm) 20 parts by weight per 100 parts by weight of resin component

[0093] [Example 2] The amount of coating liquid 1 for resin parts applied is 13 g / m 2 A decorative sheet of Example 2 was obtained in the same manner as in Example 1, except that a surface protective layer having a thickness of 45 μm was formed.

[0094] [Example 3] Nonwoven fabric 2 (nonwoven fabric made of rayon fiber, manufactured by Kinboshi Paper Co., Ltd., thickness: 60 μm, basis weight: 10 g / m 2 A decorative sheet of Example 3 was obtained in the same manner as in Example 1, except that a surface protective layer with a thickness of 30 μm was formed using the same composition as in Example 1.

[0095] [Example 4] The decorative sheet of Example 4 was obtained in the same manner as in Example 1, except that the resin part coating liquid 2 (ionizing radiation curable resin composition) having the following formulation was applied to a nonwoven fabric to form a surface protective layer with a thickness of 40 μm. <Coating liquid for resin parts 2> 40 parts by weight of hexafunctional electron beam curable urethane acrylate resin Bifunctional electron beam curable urethane acrylate resin 60 parts by weight Spherical silica particles (average particle size 4 μm) 20 parts by weight per 100 parts by weight of resin component

[0096] [Comparative Example 1] In the same manner as in Example 1, a decorative layer, an adhesive layer, and a nonwoven fabric were laminated on the substrate. The following resin coating liquid 3 (two-component curing resin composition) was applied to the nonwoven fabric by gravure printing, and the coating liquid was allowed to penetrate into the nonwoven fabric. The coating amount was 12 g / m 2 Thereafter, the sheet was cured at 70° C. for 48 hours. As a result, a surface protective layer with a thickness of 45 μm was formed, and a decorative sheet of Comparative Example 1 was obtained. <Coating liquid for resin parts 3> Acrylic polyol resin 100 parts by mass Hexamethylene diisocyanate 5 parts by mass Spherical silica particles (average particle diameter 5 μm) 15 parts by weight per 100 parts by weight of resin component

[0097] Comparative Example 2 The amount of coating liquid 1 for resin parts is 5 g / m 2 A decorative sheet of Comparative Example 2 was obtained in the same manner as in Example, except that a surface protective layer having a thickness of 40 μm was formed.

[0098] Comparative Example 3 The amount of coating liquid 1 for resin parts is 17 g / m 2 A decorative sheet of Comparative Example 3 was obtained in the same manner as in Example, except that a surface protective layer having a thickness of 50 μm was formed.

[0099] 3. Evaluation Results The evaluation results are shown in Table 1.

[0100] [Table 1]

[0101] The decorative sheets of Examples 1 to 4 had 85° gloss values ​​of the surface of the surface protective layer in the range of 3.0 to 6.0. All of the decorative sheets of Examples 1 to 4 had an excellent feel, an appearance similar to natural wood, and excellent stain resistance. From these results, it can be said that the resin composition sufficiently filled the gaps between the fibers of the nonwoven fabric so that ink did not get into them, and that the resin composition coated the nonwoven fabric so that the unevenness caused by the fibers of the nonwoven fabric remained on the surface. Furthermore, the decorative sheets of Examples 1 to 4 had a contact angle of 80 degrees or more, and were excellent in stain resistance.

[0102] The results of Examples 1 to 3 show that the 85-degree gloss value can be adjusted within the range of 3.0 to 6.0 by appropriately selecting the combination of the basis weight of the nonwoven fabric and the coating amount of the resin composition.

[0103] Comparative Example 1 is a decorative sheet with conventional stainability. Comparative Example 1 can be said to be an example in which the contact angle was changed by changing the type of resin, while using the same nonwoven fabric as in the Examples. Comparative Example 1 can be particularly compared with Example 2, in which the amount of resin coating liquid applied was similar. Since Comparative Example 1 has a small contact angle, it can be seen that it has poor stain resistance. This is thought to be because ink was not easily repelled in Comparative Example 1, and the ink easily soaked into the voids remaining in the nonwoven fabric. Furthermore, the scratch resistance was poor in Comparative Example 1. Whitening of the surface protective layer was observed in Comparative Example 1. From this, it is considered that the resin in the surface protective layer in Comparative Example 1 was too hard, causing cracks in the surface protective layer, and therefore, sufficient scratch resistance could not be obtained.

[0104] Examples 1 and 2, Comparative Examples 2 and 3, and Reference Example are examples in which the amount of resin composition applied to the same nonwoven fabric was changed. 2 From these results, it can be seen that the 85-degree gloss value tends to increase as the coating amount increases. Comparative Example 2 had a low 85° gloss value. The decorative sheet of Comparative Example 2, like the Reference Example, had an excellent feel to the touch but poor stain resistance. From these results, it can be said that when the amount of resin applied was small, the resin did not fill the voids in the nonwoven fabric sufficiently, and the nonwoven fabric, particularly on the surface, where the voids were not filled with resin, was exposed, resulting in a low 85° gloss value. Comparative Example 2 can be said to be "stainable" in that many voids remained in the nonwoven fabric, making it easy for ink to penetrate. The contact angle was large in Comparative Example 2. As shown in the Reference Example, the contact angle of the nonwoven fabric itself was high. In other words, the results of Comparative Example 2 indicate that the nonwoven fabric had a significant effect on the contact angle because the resin filling was insufficient and the nonwoven fabric was exposed.

[0105] Comparative Example 3 had a high 85-degree gloss value. The decorative sheet of Comparative Example 3 had almost no unevenness to the touch, and the arithmetic mean roughness and maximum height were also lower than those of Example 1, etc. Furthermore, the decorative sheet of Comparative Example 3 was often rated as having a high gloss. On the other hand, it had excellent stain resistance. From these results, it can be understood that when the amount of resin applied is too large, the nonwoven fabric is buried in the resin, reducing the unevenness on the surface of the surface protection layer, resulting in an increase in the 85-degree gloss value.

[0106] Furthermore, Comparative Example 3 has improved scratch resistance compared to Examples 1 and 2. This is thought to be because, in Comparative Example 3, the nonwoven fabric is buried as described above and the surface is covered with the cured product of the ionizing radiation-induced resin composition. The reason that Comparative Example 2 and the Reference Example have good scratch resistance is thought to be because the nonwoven fabric used was flexible and, in the above evaluation, was less susceptible to scratches. [Explanation of symbols]

[0107] 10 Decorative Sheet 20 Base material 30 decorative layer 31 Colored layer 32 Picture layer 40 Adhesive layer 50 Surface protective layer 51 Nonwoven fabric 52 Resin part

Claims

1. A substrate; an adhesive layer provided on at least one surface of the substrate; a surface protective layer provided on the adhesive layer on the side opposite to the side on which the substrate is provided; Equipped with the surface protective layer includes a nonwoven fabric and a resin portion including a resin filled in at least a portion of voids between fibers of the nonwoven fabric, the resin portion includes a cured product of a curable resin composition, the surface of the surface protective layer on which the adhesive layer is provided and the other surface thereof have an 85° gloss value of 3.0 or more and 6.0 or less, as measured in accordance with JIS Z 8741:1997; A decorative sheet, wherein the contact angle of pure water between the surface of said surface protective layer on which said adhesive layer is provided and the other surface thereof is 80 degrees or more.

2. 2. The decorative sheet according to claim 1, wherein the 85 degree gloss value is 4.0 or more and 5.6 or less.

3. 3. The decorative sheet according to claim 1, wherein the hardness of said resin portion measured by nanoindentation is 150 MPa or more.

4. 4. The decorative sheet according to claim 1, wherein the hardness of said resin portion measured by nanoindentation is less than 240 MPa.

5. 5. The decorative sheet according to claim 1, wherein the curable resin composition is an ionizing radiation curable resin composition.

6. A decorative sheet described in any one of claims 1 to 4, wherein the curable resin composition is either a composition containing a thermosetting resin or a composition containing an ionizing radiation curable resin, the thermosetting resin is one or more selected from acrylic resin, urethane resin, phenolic resin, urea melamine resin, epoxy resin, unsaturated polyester resin, and silicone resin, and the ionizing radiation curable resin is a compound having a functional group with an ethylenic double bond.

7. 7. The decorative sheet according to claim 1, wherein the surface protective layer has a thickness of 35 [mu]m or more.

8. 8. The decorative sheet according to claim 1, wherein the thickness of the surface protective layer is 250 [mu]m or less.

9. The decorative sheet according to any one of claims 1 to 8, further comprising a decorative layer between the substrate and the adhesive layer.

10. The decorative sheet according to claim 9 , wherein the decorative layer comprises a wood grain pattern.

11. A decorative material comprising the decorative sheet according to any one of claims 1 to 10 and an adherend.

Images