Stainable decorative sheet and method for coloring decorative sheet

Abstract

To provide a stainable decorative sheet which is extremely excellent in stainability, is inexpensive and is reduced in environmental loads, and a decorative sheet coloring method using the stainable decorative sheet.SOLUTION: There are provided a stainable decorative sheet that has a base material, an adhesive layer provided on at least one surface side of the base material, and a non-woven fabric layer provided on the other surface side of the surface provided with the base material of the adhesive layer, in which the non-woven fabric layer has a filling part A obtained by filling a part of a gap of a fiber constituting the non-woven fabric layer with a resin forming the adhesive layer, on a surface side provided with the adhesive layer in a thickness direction in the layer, the resin forming the adhesive layer is a thermoplastic urethane resin, and a contact angle of the thermoplastic urethane resin is 90.0° or less; and a coloring sheet coloring method using the stainable decorative sheet.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to a stainable decorative sheet and a method for coloring a decorative sheet. [Background technology]

[0002] It is common practice, mainly in Europe and the United States, for ordinary consumers to use stain paint to paint the surfaces of wooden building interior materials, furniture surfaces, etc., and to paint the surfaces of wooden furniture, etc. (DIY: Do It Yourself).Such stain paint penetrates into the wood to color it, and has the advantage of not concealing the wood grain itself or forming a film on the surface, allowing the wood's unique design and appearance, such as the grain and luster (pearl-like luster), to be utilized.

[0003] In recent years, decorative sheets made by printing wood grain patterns on the surface of a sheet-like substrate, instead of natural wood, have come to be used as interior materials for buildings, surface materials for furniture, etc., and decorative sheets that can be stained using the above-mentioned stain paint (hereinafter also referred to as "stainable decorative sheets") have been manufactured. Specifically, these stainable decorative sheets have been subjected to a surface treatment that ensures the adhesion of stain paint, assuming that the purchaser will achieve the desired texture by coating the stain paint themselves.

[0004] As such a decorative sheet, a recoatable decorative sheet has been proposed in which a pattern layer is printed on a polyvinyl chloride (PVC) resin substrate and then heat-sealed to a nonwoven fabric (see, for example, Patent Document 1). This recoatable decorative sheet can be repainted (recoated), i.e., stained, and is popular with consumers because the nonwoven fabric imparts fine irregularities to the surface, giving it a texture that closely resembles wood.

[0005] However, using a PVC substrate as the substrate has the problem of increasing the cost of the decorative sheet, and when a PVC substrate is used as the substrate, incineration can cause environmental problems by generating gases containing chlorine atoms, such as hydrogen chloride (HCl), when disposed of.

[0006] In response to the above problems, a stainable decorative sheet has been proposed that has a paper substrate and a nonwoven fabric layer, with an adhesive layer made of a polyolefin resin to improve adhesion between the paper substrate and the nonwoven fabric layer (see, for example, Patent Document 2). Changing the substrate to a paper substrate makes it necessary to provide an adhesive layer to ensure adhesion between the paper substrate and the nonwoven fabric, but this leads to problems such as the loss of the unevenness of the nonwoven fabric and the loss of the wood-like feel. Furthermore, with a decorative sheet changed to a paper substrate, it is difficult to achieve both water resistance and solvent resistance, and the solvent of the stain paint (solvent, alcohol, etc.) can penetrate into the paper substrate, resulting in a decrease in the physical properties of the decorative sheet. In this situation, the stainable decorative sheet described in Patent Document 2 makes it possible to achieve both the strength, weight, flexibility, and other physical properties of the decorative sheet while also achieving application suitability (called "stainability" in English, but the term "stainability" is also used in this specification when used as a noun) that ensures the penetration and ink-receiving ability of colorants such as water-based stain paints and oil-based stain paints. [Prior art documents] [Patent documents]

[0007] [Patent Document 1] Japanese Patent Application Publication No. 9-262934 [Patent Document 2] Japanese Patent Application Publication No. 2019-61313 Summary of the Invention [Problem to be solved by the invention]

[0008] Meanwhile, with the recent increase in telecommuting, DIY projects have become more common, and the performance requirements for stainable decorative sheets have suddenly increased, with particularly stricter requirements for applicability (stainability) that ensures the penetration and adhesion of colorants such as water-based stain paints and oil-based stain paints. As a result, the stainable decorative sheet disclosed in Patent Document 2, as well as stainable decorative sheets that use not only paper substrates but also PVC substrates and other resin substrates, are sometimes unable to meet consumer demands for stainability.

[0009] In view of the above problems, the present invention aims to provide a stainable decorative sheet that has extremely excellent stainability, is inexpensive, and has a small environmental impact, and a method for coloring a decorative sheet using said stainable decorative sheet. [Means for solving the problem]

[0010] In order to solve the above problems, the present inventors have conducted extensive research and have found that the above problems can be solved by a stainable decorative sheet having the following configuration.

[0011] 1. A substrate; an adhesive layer provided on at least one surface of the substrate; a nonwoven fabric layer provided on the other side of the adhesive layer opposite to the side on which the substrate is provided; Equipped with the nonwoven fabric layer has a filled portion A on the surface on which the adhesive layer is provided in the thickness direction of the layer, in which a resin forming the adhesive layer is filled into a part of the voids between the fibers constituting the nonwoven fabric layer, the resin forming the adhesive layer is a thermoplastic urethane resin, The contact angle of the thermoplastic urethane resin is 90.0° or less. Stainable decorative sheet. 2. A surface layer is provided on the side of the nonwoven fabric layer opposite to the side on which the adhesive layer is provided, The nonwoven fabric layer has a filling portion A on the side of the layer where the adhesive layer is provided in the thickness direction of the layer, and a filling portion B on the side of the layer where the surface layer is provided in the thickness direction of the layer, in which some of the voids in the fibers constituting the nonwoven fabric layer are filled with the resin that forms the surface layer. 3. The stainable decorative sheet according to the above item 1 or 2, wherein the substrate is a paper substrate. 4. The stainable decorative sheet according to any one of the above items 1 to 3, wherein the nonwoven fabric layer is made of at least one type of fiber selected from recycled fibers. 5. The stainable decorative sheet according to any one of 2 to 4 above, wherein the resin forming the surface layer is at least one resin selected from acrylic resins, acrylic polyol resins, and urethane resins. 6. The stainable decorative sheet according to any one of the above items 1 to 5, further comprising a decorative layer between the substrate and the adhesive layer. 7. The stainable decorative sheet according to claim 6, wherein the decorative layer exhibits a wood grain pattern. 8. The stainable decorative sheet according to any one of the above 1 to 7, wherein the thermoplastic urethane resin and the nonwoven fabric layer have a wet tension of 70 mN / m or more. 9. A method for coloring a decorative sheet, comprising applying a colorant to the surface layer side of the stainable decorative sheet according to any one of 1 to 8 above, thereby coloring the nonwoven fabric layer. [Effects of the Invention]

[0012] According to the present invention, it is possible to provide a stainable decorative sheet that has extremely excellent stainability, is inexpensive, and has a small environmental impact, and a method for coloring a decorative sheet using said stainable decorative sheet. [Brief explanation of the drawings]

[0013] [Figure 1] 1 is a schematic cross-sectional view showing one embodiment of the stainable decorative sheet of the present embodiment. [Figure 2] 1 is a schematic cross-sectional view showing one embodiment of the stainable decorative sheet of the present embodiment. DETAILED DESCRIPTION OF THE INVENTION

[0014] Hereinafter, an embodiment of the present invention (hereinafter, sometimes referred to as "the present embodiment") will be described. In this specification, the numerical values associated with "greater than or equal to," "less than or equal to," and "to" in describing a numerical range can be arbitrarily combined, and the numerical values in the examples are numerical values that can be used as the upper and lower limits of the numerical range.

[0015] [Stainable decorative sheet] The stainable decorative sheet of this embodiment comprises a substrate, an adhesive layer provided on at least one side of the substrate, and a nonwoven fabric layer provided on the other side of the adhesive layer opposite the side on which the substrate is provided, wherein the nonwoven fabric layer has a filled portion A on the side on which the adhesive layer is provided in the thickness direction of the layer, where the resin forming the adhesive layer fills some of the voids in the fibers constituting the nonwoven fabric layer, and the resin forming the adhesive layer is a thermoplastic urethane resin, and the contact angle of the thermoplastic urethane resin is 90.0° or less. The stainable decorative sheet of this embodiment may also be one in which the thermoplastic urethane resin and the nonwoven fabric layer have a wet tension of 70 mN / m or more.

[0016] The stainable decorative sheet of this embodiment, having the above-described configuration, exhibits the effects of being extremely excellent in stainability, inexpensive, and having a small environmental impact. In achieving these effects, the contact angle, which is an indicator of the wettability of the resin and nonwoven fabric layer that form the adhesive layer, and in some cases the wetting tension, the filled portion A formed by the adhesive layer and the nonwoven fabric layer, and, if a surface layer is provided, the filled portion B formed by the adhesive layer and the surface layer in addition to the filled portion A, play an important role. The nonwoven fabric layer can be considered a layer having two filling portions, A and B, in relation to the adhesive layer and the optional surface layer. Filling portion A is formed by at least a portion of the resin forming the adhesive layer penetrating into the nonwoven fabric layer. Therefore, when a substrate, particularly a paper substrate, is used, excellent adhesion between the paper substrate and the nonwoven fabric layer is obtained. Furthermore, by using a thermoplastic urethane resin as the resin forming the adhesive layer, the contact angle of the adhesive layer is within a specific range. Furthermore, by selecting a nonwoven fabric layer having a specific contact angle, the adhesion between the adhesive layer and the nonwoven fabric layer is improved, resulting in excellent adhesion between the substrate, the adhesive layer, and the nonwoven fabric layer. Regarding the relationship between the adhesive layer and the nonwoven fabric layer and the stain paint, the specific contact angles between these layers improve the ink-receiving ability of the stain paint and provide excellent stainability. Furthermore, as mentioned above, it is preferable to set the wetting tension of the resin forming the adhesive layer and the nonwoven fabric layer within a specific range, as this further improves the ink-receiving ability of the stain paint and provides even better stainability. When a surface layer is provided, the filling portion B is formed by at least a portion of the resin forming the surface layer penetrating into the nonwoven fabric layer. Therefore, by maintaining good fuzziness of the nonwoven fabric layer together with the surface layer, the filling portion B imparts a pleasant feel and stainability, while suppressing the loss of transparency due to the fuzziness (surface irregularities) of the nonwoven fabric layer and the refractive index caused by voids, thereby improving the design.

[0017] The stainable decorative sheet of this embodiment will be described below with reference to the drawings. In the following description of the drawings, identical or similar parts are represented by identical or similar symbols. However, the drawings are schematic, and the relationship between thickness and planar dimensions, the thickness ratio of each layer, etc., differ from reality. Therefore, specific thicknesses and dimensions should be determined in light of the following description. Furthermore, it goes without saying that the drawings also include parts with different dimensional relationships and ratios.

[0018] 1 shows that the stainable decorative sheet 1 comprises a substrate 10, an adhesive layer 20 provided on at least one surface 11 of the substrate 10, and a nonwoven fabric layer 30 provided on the adhesive layer 20 opposite the surface on which the substrate 10 is provided. The nonwoven fabric layer 30 of the stainable decorative sheet 1 of this embodiment is shown to have, on the surface 30a on which the adhesive layer 20 is provided in the thickness direction within the layer, a partially filled portion A31 in which the resin that forms the adhesive layer 20 fills some of the voids in the fibers that make up the nonwoven fabric layer 30.

[0019] 2 shows that the stainable decorative sheet 1 shown in FIG. 1 further includes a decorative layer 50 composed of a surface layer 40, an all-over colored layer 51, and a pattern layer 52. The surface layer 40 is provided on the side of the nonwoven fabric layer 30 opposite the side on which the adhesive layer 20 is provided, and the nonwoven fabric layer 30 is shown to partially include a filled portion A31 on the side on which the adhesive layer 20 is provided in the thickness direction of the layer, and a filled portion B33 on the side on which the surface layer 40 is provided in the thickness direction of the layer, formed by filling some of the voids in the fibers constituting the nonwoven fabric layer 30 with the resin that forms the surface layer 40. The nonwoven fabric layer 30 partially includes the filled portion A31 and the filled portion B33, and the portion other than these filled portions includes a fiber portion 32 in which the nonwoven fabric that forms the nonwoven fabric layer 30 remains intact, and the nonwoven fabric layer 30 is a layer having the filled portion A31, the fiber portion 32, and the filled portion B33.

[0020] (Base material 10) The substrate of the stainable decorative sheet 1 of this embodiment functions as a support for providing other layers. The substrate used for the substrate 10 can be a paper substrate, a resin substrate, or the like, without any restrictions. From the viewpoints of cost reduction and environmental concerns, a paper substrate is preferably used. Examples of paper substrates that can be used include fine paper, tissue paper, linter paper, kraft paper, reinforced paper between sheets, resin-impregnated paper, wallpaper backing paper, and flame-retardant paper obtained by mixing or impregnating these papers with a flame retardant. These materials may be used alone or may be laminated in any combination, such as a laminate of papers. The 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] The thickness of the substrate 10 is evaluated and displayed in terms of basis weight (mass per unit area). There are no particular restrictions on the thickness (i.e., basis weight), but taking into consideration the durability and ease of handling of the decorative sheet, a basis weight of 20 g / m 2 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] (adhesive layer 20) The adhesive layer 20 is a layer provided on at least one surface 11 of the substrate 10, and is provided to bond the substrate 10 to the nonwoven fabric layer 30, and is a layer that fills in some of the fibers that make up the nonwoven fabric layer 30 to form the filling portion A. The adhesive used to form the adhesive layer 20 is a resin containing a thermoplastic urethane resin with a contact angle of 90.0° or less. The thermoplastic urethane resin may have a wet tension of 70 mN / m or more. By using such a resin, excellent adhesion between the substrate 10 and the nonwoven fabric layer 30 is obtained, and excellent stainability is also obtained.

[0023] In this embodiment, the contact angle of the thermoplastic urethane resin forming the adhesive layer is 90.0° or less. As mentioned above, the contact angle is an index of wettability, and a contact angle of 90.0° means that the resin has the property of being easily wetted (good compatibility between resins). Therefore, the smaller the contact angle, the better the adhesion to other layers (i.e., the substrate and nonwoven fabric layer) and the better the compatibility with stain paint, which also contributes to improving the ink-receiving ability of the stain paint. From this perspective, the contact angle is preferably 88.0° or less, and more preferably 86.0° or less. There is no particular lower limit, but considering the balance between adhesion to other layers and the ink-receiving ability of the stain paint, it is preferably 70.0° or more, and more preferably 75.0° or more. In this specification, the contact angle is measured based on the measurement method in the examples.

[0024] In this embodiment, the wetting tension of the thermoplastic urethane resin forming the adhesive layer may be 70 mN / m or more, as described above. As described above, the wetting tension is an indicator of wettability, similar to the contact angle, and a wetting tension of 70 mN / m or more indicates that the resin is easily wetted (has good compatibility with other resins). Therefore, a wetting tension of 70 mN / m or more further improves adhesion to other layers (i.e., the substrate and nonwoven fabric layer), and also provides excellent compatibility with stain paint, further improving the adhesion of the stain paint. In this specification, the wetting tension is measured based on the measurement method in the examples.

[0025] 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.

[0026] 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.

[0027] The resin forming the adhesive layer 20 may contain a thermoplastic urethane resin with a contact angle of 90.0° or less, and may also contain other resins. 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. In particular, from the viewpoint of improving stainability, the content of the thermoplastic urethane resin contained in the resin forming the adhesive layer 20 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 preferable to use only a thermoplastic urethane resin. This also facilitates a wetting tension of 70 mN / m or more. From the viewpoint of achieving a contact angle of 90.0° or less and improving stainability, it is preferable to adjust the thermoplastic urethane resin to the desired contact angle by adjusting properties that are likely to affect the contact angle, such as the number of functional groups and the proportion of urethane bonds in the molecule, and by selecting a polyol that constitutes the urethane resin, taking into consideration the hydroxyl value (for example, the hydroxyl value that a resin containing a large amount of hydroxyl groups, as described below, has). From a similar viewpoint, the thermoplastic urethane resin preferably has a glass transition point of −60°C or higher and 50°C or lower, more preferably −55°C or higher and 45°C or lower, even more preferably −50°C or higher and 35°C or lower, and even more preferably −48°C or higher and 20°C or lower. This also facilitates a wetting tension of 70 mN / m or higher.

[0028] In this embodiment, the resin forming the adhesive layer 20 can be used as a resin composition containing an appropriate amount 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 20 can be formed from a resin composition containing additives in addition to the resin.

[0029] The thickness of the adhesive layer 20 cannot be specified as a specific value because it can vary depending on the materials of the paper base material 10 and the nonwoven fabric layer 30, the thickness of the nonwoven fabric layer 30, etc. However, for example, from the viewpoint of achieving a balanced adhesion between the base material 10 and the nonwoven fabric layer 30, a balanced formation of the filling section A31 and the fiber section 32, and, if the surface layer 40 is provided, a balanced formation of the filling section A31, the filling section B33 and the fiber section 32, thereby improving stainability and transparency in a balanced manner, and further from the viewpoint of imparting water resistance and solvent resistance, the total thickness of the adhesive layer 20 and the filling section A31 is preferably 2 μm or more, more preferably 3 μm or more, and even more preferably 5 μm or more, with the upper limit being less than the thickness of the nonwoven fabric layer 30, and preferably 25 μm or less, more preferably 20 μm or less, and even more preferably 15 μm or less. The total thickness of the adhesive layer 20 and the filling portion A31 is the average value of the thicknesses measured 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).

[0030] (Nonwoven fabric layer 30) The nonwoven fabric layer 30 is a layer that ensures the ink-receiving ability of colorants such as water-based stain paints and oil-based stain paints to penetrate into the voids in the fibers that form the nonwoven fabric layer 30, i.e., the fiber portion 32, and thereby exhibits stainability.The nonwoven fabric layer 30 partially has a filled portion A31 on the side 30a in the thickness direction of the layer where the adhesive layer 20 is provided, where the resin that forms the adhesive layer 20 has filled some of the voids in the fibers that form the nonwoven fabric layer 30, and if a surface layer 40 is provided, the layer partially has the filled portion A31 and a filled portion B33 on the side 30b in the thickness direction of the layer where the surface layer 40 is provided, where the resin that forms the surface layer 40 has filled some of the voids in the fibers that form the nonwoven fabric layer 30.

[0031] Furthermore, the nonwoven fabric layer 30 preferably has a wet tension of 70 mN / m or more. By combining it with the adhesive layer 20 formed from a resin containing the thermoplastic urethane resin having a contact angle of 90.0° or less, excellent adhesion and stainability can be obtained.

[0032] The fibers constituting the nonwoven fabric layer 30 are not particularly limited, and examples thereof include thermoplastic resin fibers, natural fibers, recycled fibers, and semi-synthetic fibers. From the viewpoint of improving adhesion and stainability when combined with the adhesive layer 20 formed of a resin containing a thermoplastic urethane resin, which tends to have a wet tension of 70 mN / m or more and a contact angle of 90.0° or less, thermoplastic resin fibers and recycled fibers are preferred, and recycled fibers are more preferred. In this embodiment, the fibers can be used alone or in combination of multiple types.

[0033] 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.

[0034] 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.

[0035] 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. As mentioned above, among the above fibers, fibers with many hydroxyl groups are preferred, for example, recycled fibers are preferred, and rayon fibers are particularly preferred. Fibers with many hydroxyl groups have high wet tension (specifically, 70 mN / m or more), which makes it easy to increase the wet tension of the nonwoven fabric layer, thereby improving the adhesion of stain paint and thereby improving stainability.

[0036] There are no particular restrictions on the fiber diameter of the fibers constituting the nonwoven fabric layer 30, but considering that wet tension can be easily achieved at 70 mN / m or more, improving stainability, and also taking into consideration touch, etc., it is preferable that the nonwoven fabric have an average fiber diameter of preferably 0.5 μm or more, more preferably 1 μm or more, with an upper limit of 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 have a touch that closely resembles 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.

[0037] The fibers constituting the nonwoven fabric layer 30 can be formed, for example, by forming fleece using a spunbonding method and then bonding the formed fleece using a thermal bonding method, a spunlace method (hydroentanglement method), etc. Furthermore, the nonwoven fabric layer 30 formed by these methods tends to have a texture very similar to that of wood.

[0038] The basis weight of the fibers constituting the nonwoven fabric layer 30 is not particularly limited, but from the viewpoint of improving the stainability and the strength of the nonwoven fabric layer 30, it 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 2 The following is the result.

[0039] There are no particular restrictions on the thickness of the nonwoven fabric layer 30, but taking into consideration the physical properties of the stainable decorative sheet 1 such as strength, mass, and flexibility, it is preferably 20 μm or more, more preferably 25 μm or more, and even more preferably 30 μm or more, with the upper limit being preferably 250 μm or less, more preferably 200 μm or less, even more preferably 150 μm or less, and even more preferably 100 μm or less.

[0040] (Filling section) The nonwoven fabric layer 30 has a surface 30a in the thickness direction on which the adhesive layer 20 is provided, which is provided with a filled portion A31 in which some of the voids in the fibers are filled with the resin that forms the adhesive layer 20. By having the filled portion A31, the stainable decorative sheet 10 of this embodiment can improve the adhesion between the paper substrate 10 and the nonwoven fabric layer 30 and can also contribute to improving transparency.

[0041] The filled portion A31 is a portion in which the resin that forms the adhesive layer 20 is filled into the voids in the fibers that form the nonwoven fabric layer 30, leaving no voids, and therefore does not have the ability to absorb colorants such as water-based stain paint and oil-based stain paint.

[0042] Furthermore, when the nonwoven fabric layer 30 has the surface layer 40, the surface 30b side in the thickness direction of the nonwoven fabric layer 30 on which the surface layer 40 is provided has a filled portion B33 in which some of the voids in the fibers are filled with the resin that forms the surface layer 40. The presence of the filled portion B33 suppresses a decrease in transparency due to the refractive index caused by the voids in the fibers, and allows for excellent design properties to be achieved. Like filled portion A31, filled portion B33 is a portion in which the resin that forms the surface layer 40 is filled into the voids in the fibers that form the nonwoven fabric layer 30, leaving no voids, and therefore does not have the ability to accept colorants such as water-based stain paint and oil-based stain paint.

[0043] In the stainable decorative sheet of this embodiment, the nonwoven fabric layer 30 partially has the above-mentioned filled portion A31, and if it has a surface layer 40, it partially has filled portion A31 and filled portion B33. In other words, the nonwoven fabric layer 30 needs to have the fibrous portion 32 described below, which is the portion other than filled portion A31 and filled portion B33. Without the fibrous portion 32, which is the portion other than the filled portions, these filled portions will have no voids remaining, and will not have the ink-receptivity to allow colorants such as water-based stain paint and oil-based stain paint to penetrate, and therefore stainability will not be achieved. 1 and 2, which are schematic cross-sectional views (conceptual diagrams), for the sake of simplicity and convenience in explaining the layer structure concept, the filled portions A31 and B33 are shown as if they existed in a continuous layer covering the entire surface, but in reality, they are not considered to be uniform layers as shown in the figures. Considering that coloring agents such as water-based stain paint and oil-based stain paint penetrate and color the nonwoven fabric layer 30, it is considered that within a certain range in the thickness direction of the nonwoven fabric layer 30, shown as filled portions A31 and B33 in Figures 1 and 2, for example, the voids between the fibers that form the nonwoven fabric layer 30 are filled with the resin that forms the adhesive layer 20 and the resin that forms the surface layer 40, and numerous minute regions of filled portions A31 and B33 are discontinuously present or scattered, with trace regions of unfilled fiber portions 32 interposed between them. Furthermore, in both filling section A and filling section B, the resin gradually penetrates from the outer surface of the nonwoven fabric layer 30 into the interior of the nonwoven fabric layer 30. Therefore, depending on how the processing conditions are adjusted, the nonwoven fabric layer 30 may have a three-layer structure, as shown in Figure 3, consisting of filling section A31 (consisting of multiple minute regions of filling section A interspersed with fiber sections 32) located on the side closer to the paper substrate 20, filling section B33 (consisting of multiple minute regions of filling section B interspersed with fiber sections 32) located on the opposite side from the paper substrate 20, and fiber sections 32 sandwiched between filling section A31 and filling section B33 (the gaps between the fibers are unfilled).

[0044] (Fiber part 32) As described above, the stainable decorative sheet of this embodiment is a layer that partially contains filled portion A31 and filled portion B33, and therefore naturally contains the portion other than these filled portions, i.e., fiber portion 32. As shown in Figures 1 and 2, fiber portion 32 is the portion of nonwoven fabric layer 30 that is not filled with the resin that forms adhesive layer 20 and surface layer 40, and where the fibers of the nonwoven fabric that form fiber portion 32 remain, leaving voids. By having fiber portion 32, the stainable decorative sheet of this embodiment ensures ink-receptivity, allowing colorants such as water-based stain paints and oil-based stain paints to penetrate into the voids in the fibers, thereby exhibiting stainability.

[0045] The form of the fiber portion 32 is not particularly limited as long as it is an embodiment in which the resin forming the adhesive layer 20 is not filled in and voids remain, or, if the surface layer 40 is present, an embodiment in which the resin forming the adhesive layer 20 and the surface layer 40 is not filled in and voids remain, but examples include an embodiment in which the resin forming the adhesive layer 20 and the surface layer 40 does not penetrate at all into the voids of the fibers forming the nonwoven fabric layer 30, leaving the fibers as they are and having voids in the fibers, as shown in Figure 2, or an embodiment in which the resin forming the adhesive layer 20 and the surface layer 40 penetrates to some extent, but the fibers are merely coated with these resins and have voids in the coated resin. In the stainable decorative sheet of this embodiment, the form of the fiber portion 32 may be any one of these. When the fiber portion 32 is in an embodiment in which the fibers are present as they are, excellent stain receptivity can be achieved by using a thermoplastic urethane resin with a contact angle of 90.0° or less, which is the resin forming the adhesive layer 20. In this case, the thermoplastic urethane resin may have a wet tension of 70 mN / m or more. Furthermore, by using a nonwoven fabric layer 30 with a wet tension of 70 mN / m or more, for example, excellent stain receptivity can be achieved. Thus, regardless of the embodiment of the fiber portion 32, excellent stainability can be achieved by using a thermoplastic urethane resin with a contact angle of 90.0° or less and a wet tension of 70 mN / m or more, which is the adhesive layer 20. Furthermore, by using a nonwoven fabric layer 30 with a wet tension of 70 mN / m or more, for example, excellent stain receptivity can be achieved, further improving stainability.

[0046] Methods for partially providing the nonwoven fabric layer 30 with the filled portion A31 and the filled portion B33 include, for example, adjusting the amount of resin composition applied when forming the adhesive layer 20, or, if the surface layer 40 is provided, adjusting the amount of resin composition applied when forming the adhesive layer 20, or the amount of resin composition applied when forming the surface layer 40. For example, increasing the amount of resin composition applied when forming the adhesive layer 20 increases the proportion of filled portions A31 in the nonwoven fabric layer 30, while increasing the amount of resin composition applied when forming the surface layer 40 increases the proportion of filled portions B33 in the nonwoven fabric layer 30. Furthermore, increasing the amount of resin composition applied when forming the adhesive layer 20 and the surface layer 40 decreases the proportion of fiber portions 32 in the nonwoven fabric layer 30, while decreasing the amount applied increases the proportion of fiber portions 32 in the nonwoven fabric layer 30. In this embodiment, the desired state of the nonwoven fabric layer 30 can be obtained by adjusting the amount of application, for example.

[0047] (Surface layer 40) The surface layer 40 is a layer provided on the surface 30b of the nonwoven fabric layer 30 opposite the surface 30a on which the adhesive layer 20 is provided (i.e., the surface side of the decorative sheet 1), and is an optional layer. By providing the surface layer 40, it is possible to adjust the fuzzing of the nonwoven fabric layer 30, and by reducing the fuzzing (surface irregularities) while maintaining stainability, it is possible to suppress deterioration in the tactile feel due to the fuzzing. Furthermore, the surface layer 40 reduces the difference in refractive index between the voids and the constituent fibers of the nonwoven fabric layer 30, thereby improving the transparency of the nonwoven fabric layer 30 when observed from the other surface 30b and reducing haze. As a result, not only is the transparency of the stainable decorative sheet of this embodiment improved, but it is also possible to impart a tactile feel.

[0048] The resin forming the surface layer 40 may be either a thermoplastic resin or a curable resin, and preferred examples include acrylic resin, styrene resin, polyester resin, urethane resin, epoxy resin, and cellulose-based resin. Of these, acrylic resin, acrylic polyol resin, and urethane resin are preferred, and acrylic resin and acrylic polyol resin are more preferred, from the viewpoint of improving design due to improved transparency. When using an acrylic polyol resin, it is preferable to use it in combination with an isocyanate-based curing agent (for example, the polyisocyanates exemplified above). In addition, in the case of a curable resin, it may be a one-component curing type or a two-component curing type, but from the viewpoint of improving stainability, the amount of curing agent added is preferably 10 parts by mass or less, more preferably 8 parts by mass or less, per 100 parts by mass of the base resin. These resins may be used alone or in combination. Considering the environmental impact of burning, vinyl chloride resins are not preferred.

[0049] The resin forming the surface layer 40 may be selected from the resins exemplified above, but it is preferable to select one with a wetting tension of 70 mN / m or more, as this improves the adhesion of the stain paint and thereby improves stainability. From this perspective, the resins exemplified above are preferable, and acrylic polyol resins and combinations of acrylic polyol resins with isocyanate-based curing agents are preferred. Therefore, with a particular focus on improving stainability, it is preferable that the wetting tension of the surface layer (the wetting tension of the resin forming the surface layer) be 70 mN / m or more. Resins containing many hydroxyl groups tend to have a wet tension of 70 mN / m or more. From this perspective, suitable resins have a hydroxyl value of, for example, 5 mgKOH / g or more, more preferably 10 mgKOH / g or more, even more preferably 15 mgKOH / g or more, even more preferably 20 mgKOH / g or more, with the upper limit preferably being 60 mgKOH / g or less, more preferably 55 mgKOH / g or less, even more preferably 50 mgKOH / g or less, and even more preferably 45 mgKOH / g or less. In this specification, the hydroxyl value is measured according to JIS K1557-1:2007 (Plastics - Test methods for polyurethane raw polyols - Part 1: Determination of hydroxyl value). This hydroxyl value can also be applied to the above-mentioned thermoplastic urethane resins. As for the type of resin, among the above resins, an acrylic polyol resin is preferred, and it is preferable to use an acrylic polyol resin in combination with an isocyanate curing agent.

[0050] Furthermore, the resin forming the surface layer 40 in this embodiment can be used as a resin composition containing an appropriate amount of additives, such as colorants such as pigments and dyes, ultraviolet absorbers, weather resistance agents such as light stabilizers, extender pigments, solvents, stabilizers, plasticizers, catalysts, and curing agents. That is, the surface layer 40 can be formed from a resin composition containing additives in addition to the resin.

[0051] 1 and 2, the surface layer 40 may be present in the form of a layer with a certain thickness on the surface 30b, or may be present so as to cover the outermost fibers along the surface 30b of the nonwoven fabric layer 30. Either form is acceptable, but from the standpoint of improving stainability as well as transparency and tactile feel, it is sufficient that the surface layer 40 is present on at least a portion of the surface on the front side of the decorative sheet, and it may be present so as to cover at least a portion of the outermost fibers, or so as to cover the entire surface.

[0052] When the surface layer 40 is present in a layered form, it is preferably present on a portion of the surface of the stainable decorative sheet of this embodiment, from the viewpoint of ensuring ink receptivity for colorants such as water-based stain paints and oil-based stain paints and obtaining excellent stainability. Furthermore, when it is present so as to cover the fibers on the outermost surface, it is preferable that voids formed by the fibers on the outermost surface and nearby (nearby in the thickness direction within the nonwoven fabric layer 30) are at least partially present, from the viewpoint of ensuring ink receptivity and obtaining excellent stainability. Thus, regardless of the form in which the surface layer 40 exists, in order to ensure the ink-receiving ability of colorants such as water-based stain paints and oil-based stain paints to penetrate and to obtain excellent stainability, it is preferable that there are voids formed between fibers, at least in part of which the surfaces of which may be coated with resin, at the outermost surface and its vicinity (nearby in the thickness direction within the layer of the nonwoven fabric layer 30).

[0053] The thickness of the surface layer 40 can be determined mainly by considering the thickness of the surface layer 40 as well as the balance between the filler B33, the fiber portion 32, and the filler A31 in the nonwoven fabric layer 30. From the viewpoint of forming the filler A31, the filler B33, and the fiber portion 32 in a balanced manner and improving the tactile feel and transparency of the surface as well as the stainability in a balanced manner, the total thickness of the surface layer 40 and the filler B33 is usually 0.5 μm or more, preferably 1 μm or more, more preferably 2 μm or more, and even more preferably 5 μm or more, with the upper limit being preferably 20 μm or less, more preferably 16 μm or less, and even more preferably 12 μm or less. The total thickness of the surface layer 40 and the filler B33 is the average value of measurements measured using the same method as for the total thickness of the adhesive layer 20 and the filler A31.

[0054] (Decorative layer 50) From the viewpoint of improving design, the stainable decorative sheet of this embodiment preferably has a decorative layer 50. The decorative layer 50 may be provided between the substrate 10 and the nonwoven fabric layer 30, and is preferably provided between the substrate 10 and the adhesive layer 20. The decorative layer 50 may be a layer consisting of only an all-over colored layer 51 provided to cover the entire front surface, or a layer consisting of only a patterned layer 52 provided to cover a portion of the all-over colored layer 51 and form a pattern, or a layer combining the all-over colored layer 51 and the patterned layer 52. These layer configurations may be determined according to the desired pattern.

[0055] The pattern imparted by the decorative layer 50 is not particularly limited and may be selected as desired, and examples thereof include wood grain patterns, marble patterns (e.g., travertine marble patterns), stone patterns imitating the surface of rock such as the cleavage plane of a granite slab, fabric patterns imitating cloth grain or fabric-like patterns, leather (leather grain) patterns expressing leather grain, tiled patterns, brickwork patterns, hairline patterns, linear grooves, pear-skin patterns, sand patterns, letters, symbols, geometric patterns, and patterns combining these, such as marquetry and patchwork.Further examples of patterns combining these include artificial stone patterns made by mixing crushed stone such as marble with white cement, hardening it, and polishing it to resemble marble, i.e., so-called artificial marble patterns. Although consumer demands for designs change with trends, etc., wood grain patterns remain popular, and therefore wood grain patterns are preferred for the pattern of the stainable decorative sheet of this embodiment. Wood grain patterns include straight grain patterns, cross grain patterns, figured grain patterns, end grain patterns, etc., and any of these may be used.

[0056] To form the decorative layer 50, it is preferable to use a resin composition containing at least a binder resin and a colorant such as a pigment or dye, and an appropriate mixture of 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, can be used. In other words, the decorative layer is a layer that contains at least a binder resin and a colorant such as a pigment or dye, and can also contain other components used as desired.

[0057] 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.

[0058] 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, and the like; and pearlescent pigments consisting of scaly foil flakes of titanium dioxide-coated mica, basic lead carbonate, and the like.

[0059] Furthermore, from the viewpoint of further improving the design, the decorative layer 50 may contain a matting agent among the other components that may be used as desired. Examples of the matting agent include inorganic fillers such as silica, clay, heavy calcium carbonate, light calcium carbonate, precipitated barium sulfate, calcium silicate, synthetic silicate, and silicate fine powder; and organic fillers such as acrylic resin, urethane resin, nylon resin, polypropylene resin, and urea resin.

[0060] By including a matting agent in the decorative layer 50, the decorative layer has a lower gloss, which makes it possible to create a design that has a visually uneven appearance due to differences in gloss. For example, in the wood grain pattern exemplified as a preferred pattern, the wood grain pattern includes a lower gloss (matte or low gloss) vessel portion, a higher gloss (glossy or high gloss) spring wood portion, and an even higher gloss autumn wood portion (shiny portion). In the decorative layer 50, a highly decorative pattern can be formed by combining multiple pattern layers 52, such as a pattern layer forming a lower gloss vessel portion, a pattern layer forming a higher gloss spring wood portion, and a pattern layer forming an even higher gloss autumn wood portion. In this case, for example, by not including a matting agent in the full-colored layer 51 or by including a lower matting agent content than in the pattern layer 52, the difference in gloss from the pattern layer 52 can be increased, thereby improving the design.

[0061] The thickness of the decorative layer 50 is not particularly limited, but from the viewpoint of improving 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 50 is formed from two or more layers, it is preferable that the total thickness of the layers be within the above range.

[0062] (Method for manufacturing stainable decorative sheet) The method for producing the stainable decorative sheet 1 of this embodiment will be explained using the stainable decorative sheet 1 shown in FIG. 2, which is one of the preferred embodiments of the stainable decorative sheet 1 of this embodiment, as an example. The stainable decorative sheet 1 of this embodiment shown in Figure 2 can be manufactured through step 1 of providing a decorative layer 50 on a substrate 10, step 2 of providing an adhesive layer 20 on the decorative layer 50, step 3 of providing a nonwoven fabric layer 30 and a filling portion A31 on the adhesive layer 20, and step 4 of applying a resin composition that forms a surface layer 40 to the surface of the nonwoven fabric layer 30, and forming a filling portion B33 together with the surface layer 40.

[0063] Step 1 is to provide a decorative layer 50 on the substrate 10 . The decorative layer 50 is preferably formed by printing the resin composition used to form the decorative layer 50 using gravure printing, silk screen printing, gravure offset printing, flexographic printing, ink jet printing, etc., and it is more preferable to use gravure printing for large lots and ink jet printing for small lots.

[0064] Step 2 is a step of providing an adhesive layer 20 on the decorative layer 50 . For example, a resin composition, preferably containing a urethane resin, is appropriately selected from the resins exemplified as resins capable of forming the adhesive layer 20 and is applied onto the decorative layer 50 to form the adhesive layer 20. In this case, the method for applying the resin composition may be selected from any of the known methods exemplified as the method for applying the resin composition to the decorative layer 50 described above.

[0065] In this case, the coating amount (dry base) of the resin composition forming the adhesive layer 20 is preferably 2 g / m from the viewpoint of obtaining excellent adhesiveness, forming the filler A 31, the filler B 33, and the fiber portion 32 in a balanced manner, and improving the stainability and transparency in a balanced manner. 2 More preferably, 3 g / m 2 More preferably, 5 g / m 2 The upper limit is preferably 45 g / m 2Less than 40 g / m 2 More preferably, 30 g / m or less 2 The following is the result.

[0066] Step 3 is a step of providing the nonwoven fabric layer 30 and the filling portion A31 on the adhesive layer 20. The nonwoven fabric layer 30 and the filling portion A31 are formed, for example, by forming an adhesive layer 20 by applying a resin composition, placing a nonwoven fabric on top of it, and then forming the nonwoven fabric layer 30 by extrusion lamination (sand lamination), dry lamination, thermocompression bonding, etc., and filling the resin composition used to form the adhesive layer into some of the voids in the nonwoven fabric to form the filling portion A31.

[0067] The nonwoven fabric layer 30 and the filling portion A31 can also be formed together with the adhesive layer 20. For example, the adhesive layer 20 can be appropriately selected from the resins exemplified as those capable of forming the adhesive layer 20, and preferably a thermoplastic urethane resin can be melt-extruded to form the adhesive layer-forming resin, and then a nonwoven fabric can be placed on top of this, and then extrusion lamination (sand lamination) or the like can be used to form a filling portion A31 in which the adhesive layer-forming resin has filled some of the voids in the nonwoven fabric, together with the adhesive layer 20, and a nonwoven fabric layer 30.

[0068] In this case, the thickness of the adhesive layer-forming resin is preferably 5% or more, more preferably 10% or more, and even more preferably 12% or more of the thickness of the nonwoven fabric layer 30, from the viewpoint of obtaining excellent adhesion between the paper base material 10 and the nonwoven fabric layer 30, and from the viewpoint of forming the filling portion A31, the filling portion B33, and the fiber portion 32 in a balanced manner and improving the stainability and transparency in a balanced manner, and the upper limit is preferably 25% or less, more preferably 23% or less, and even more preferably 20% or less.

[0069] Step 4 is a step of applying a resin composition for forming the surface layer 40 to the surface of the nonwoven fabric layer 30, thereby forming the surface layer 40 and the filling portion B33. The resin composition for forming the surface layer 40 may be applied by selecting any of the known methods exemplified above as methods for applying the resin composition for the decorative layer 50. When forming the surface layer 40, the amount of resin composition to be applied may be determined mainly in consideration of the thickness of the surface layer 40 as well as the balance between the filler B33, the fiber portion 32, and the filler A31 in the nonwoven fabric layer 30. From the viewpoint of forming the filler A31, the filler B33, and the fiber portion 32 in a balanced manner and improving the tactile feel, stainability, and transparency of the surface in a balanced manner, an amount of resin composition to be applied is usually 1 g / m 2 More than 2g / m 2 More than 5g / m 2 The upper limit is preferably 20 g / m 2 or less, more preferably 16 g / m 2 More preferably, 12 g / m or less 2 The following is the result.

[0070] By the above steps, a stainable decorative sheet 1 having a preferred embodiment shown in Figure 2 can be produced, which has, in order, a paper base material 10, a decorative layer 50, an adhesive layer 20, a nonwoven fabric layer 30 (filler A31, fiber portion 32, filler B33), and a surface layer 40.

[0071] [Method for coloring stainable decorative sheet] The method for coloring the stainable decorative sheet of this embodiment is characterized by applying a colorant to the surface layer side of the stainable decorative sheet of this embodiment, thereby coloring the nonwoven fabric layer. The stainable decorative sheet 1 of this embodiment has a nonwoven fabric layer 30, which ensures ink-receptivity by allowing colorants such as water-based stain paint and oil-based stain paint to penetrate into the voids in the fibers. In addition, the stainable decorative sheet 1 has an adhesive layer 20 between the paper substrate 10 and the nonwoven fabric layer 30, and the adhesive layer 20 provides water resistance and solvent resistance, so that even when applied to the nonwoven fabric layer 30, the physical properties of the paper substrate 10 are not affected. [Example]

[0072] Next, the present invention will be described in more detail by way of examples, but the present invention is not limited to these examples in any way.

[0073] (Evaluation method) The decorative sheets obtained in each of the Examples and Comparative Examples were evaluated as follows. <Evaluation of Steadiness> The decorative sheets obtained in each of the Examples and Comparative Examples were coated on the surface layer side with an oil-based stain paint, and stainability was evaluated. In this evaluation, a rating of B or higher was considered to be acceptable. A: Excellent coloring with oil-based stain paint, with little or no deterioration in the physical properties of the decorative sheet. B: The coloring of the oil-based stain paint was good, and there was almost no deterioration in the physical properties of the decorative sheet. C: The coloring of the oil-based stain paint was slightly inferior, but there was almost no deterioration in the physical properties of the decorative sheet. D: Oil-based stain paint could not be colored, and / or the physical properties of the decorative sheet were deteriorated.

[0074] <Evaluation of Adhesion> The decorative sheets obtained in each Example and Comparative Example were cut into 300 mm x 300 mm pieces to prepare test pieces for adhesive strength tests. A 25 mm wide cellophane adhesive tape (manufactured by Nichiban Co., Ltd., product name "Cellotape (registered trademark)") was applied to the nonwoven fabric layer side of the test piece and then peeled off to evaluate adhesiveness. In this evaluation, an A rating is a pass. A: No peeling occurred within the nonwoven fabric layer or between the nonwoven fabric layer and the adhesive layer. B: Partial peeling occurred within the nonwoven fabric layer or between the nonwoven fabric layer and the adhesive layer. C: Peeling occurred within the nonwoven fabric layer or between the nonwoven fabric layer and the adhesive layer.

[0075] <Evaluation of appearance transparency> The decorative sheets obtained in each of the Examples and Comparative Examples were evaluated for appearance according to the following criteria: In this evaluation, a rating of B or higher is considered acceptable. A: There was absolutely no deterioration in the transparency of the appearance, and the design was excellent. B: Almost no deterioration in the transparency of the appearance was observed, and there was no problem in practical use. C: A decrease in transparency of the appearance was confirmed, and the design was deteriorated.

[0076] (Measurement method) <Wetting tension measurement> The resin composition used to form the layer was applied to a support (thickness: 25 μm, material: PET resin) for measuring wet tension in an atmosphere of 23°C (relative humidity: 50%) at a coating amount of 8 g / m 2 After forming a layer, a wetting tension measuring pen ("Tension Checker TC-B-70 (dyne number: 70)" manufactured by Pacific Chemical Co., Ltd.) was applied to the layer, and the state of the liquid film after 3 seconds was visually observed to check whether the liquid film had broken or shrunk. If no break or shrinkage occurred, it indicates that the wetting tension was 70 mN / m or more. Furthermore, the wet tension of the nonwoven fabric forming the nonwoven fabric layer was measured in the same manner as above, except that a wet tension measuring pen was applied to the surface of the nonwoven fabric.

[0077] <Contact angle measurement> In the same manner as in the above <Measurement of Wet Tension>, the resin composition used to form the layer was applied to a support (thickness: 25 μm, material: PET resin) for measuring wet tension at a coating amount of 8 g / m 2 A layer was formed by coating with the solution. Thereafter, the contact angle between the layer and pure water was measured using a contact angle meter ("CA-X (model number)" manufactured by Kyowa Interface Science Co., Ltd.). The contact angle was measured at 9 random points, the maximum and minimum values were excluded, and the average value of the remaining 7 points was taken as the contact angle.

[0078] Example 1 The paper substrate was printing paper (HPT30 (product number), manufactured by Hokuetsu Kishu Paper Co., Ltd., thickness: 60 μm, basis weight: 45 g / m 2) was prepared, and a decorative layer with a wood grain pattern (thickness: 2-6 μm) was formed on the printing paper by gravure printing using an ink containing a pigment in a binder resin (an ink containing a 1:1 mass ratio mixture of vinyl chloride-vinyl acetate copolymer resin and acrylic resin as the binder, and carbon black as the pigment). Next, a resin composition (adjusted so that the contact angle was 85.2° and the wetting tension was 70 mN / m or more; glass transition temperature of the thermoplastic urethane resin: -45°C) was used to form an adhesive layer on the decorative layer by gravure printing at 12 g / m. 2 (dry base) to provide an adhesive layer (thickness: 12 μm). Separately, a nonwoven fabric made of rayon fiber (product number "3016", manufactured by Kinsei Paper Co., Ltd., thickness: 80 μm, basis weight: 17 g / m) was used. 2 ) was prepared, and the paper base material on which the decorative layer and adhesive layer were formed was laminated with a nonwoven fabric by thermocompression to obtain a laminate having a paper base material, a decorative layer, an adhesive layer, and a nonwoven fabric layer consisting of a filling portion A and a fiber portion. Next, a resin composition for forming a surface layer on the fiber side of the laminate, containing 100 parts by mass of acrylic polyol resin (hydroxyl value: 41 mgKOH / g) and 5 parts by mass of an isocyanate-based curing agent (hexamethylene diisocyanate, isocyanate group content: 19% by mass), was applied in an amount of 12 g / m 2 (dry base) to form the filling portion B and the surface layer, thereby obtaining a stainable decorative sheet having a paper base material, a decorative layer, an adhesive layer, the filling portion A, a nonwoven fabric layer consisting of the fiber portion and the filling portion B, and the surface layer. The stainable decorative sheet obtained was evaluated by the above-mentioned methods, and the results are shown in Table 1. Furthermore, when the wet tension of the resin composition forming the adhesive layer, the resin composition forming the surface layer, and the nonwoven fabric was measured by the above-mentioned method, all were 70 mN / m or more.

[0079] Example 2 A stainable decorative sheet was obtained in the same manner as in Example 1, except that no surface layer was provided. The obtained stainable decorative sheet was evaluated using the above method, and the results are shown in Table 1. Furthermore, when the wet tension of the resin composition forming the adhesive layer and the nonwoven fabric was measured using the above method, both were 70 mN / m or more, as in Example 1.

[0080] (Comparative Example 1) A decorative sheet was obtained in the same manner as in Example 1, except that in Example 1, polyethylene resin (adjusted to a contact angle of 97.0° and a wet tension of 38 mN / m) was melt-extruded to form an adhesive layer (thickness: 20 μm). The decorative sheet obtained was evaluated by the above-mentioned methods, and the results are shown in Table 1.

[0081] Examples 3 and 4 In Example 1, the thermoplastic urethane resin of the resin composition forming the adhesive layer was adjusted so that the contact angle and wetting tension were as shown in Table 1 (glass transition point of the thermoplastic urethane resin used in Example 3: 30°C, glass transition point of the thermoplastic urethane resin used in Example 4: 0°C). 2 Stainable decorative sheets of Examples 3 and 4 were obtained in the same manner as in Example 1, except that an adhesive layer (thickness: 12 μm) was provided by applying the coating amount (dry base). The decorative sheet obtained was evaluated by the above-mentioned methods, and the results are shown in Table 1.

[0082] [Table 1] *1, The resin used is polyester resin.

[0083] The results of the examples confirmed that the stainable decorative sheet of this embodiment has excellent stainability, adhesion, and transparency, because it uses a thermoplastic urethane resin with a contact angle of 90.0° or less as the resin that forms the adhesive layer. Furthermore, the stainable decorative sheet of this embodiment has excellent stainability, adhesion, and transparency, partly because the wet tension of the thermoplastic urethane resin and nonwoven fabric layer is greater than 70 mN / m. On the other hand, the decorative sheet of Comparative Example 1 had excellent transparency due to the presence of a surface layer, but the contact angle of the resin forming the adhesive layer was 97.0°, which was larger than 90.0°, and because it was not a thermoplastic urethane resin, it had poor stainability and slightly poor adhesion. Furthermore, the wetting tension of the resin forming the adhesive layer of Comparative Example 1 was 38 mN / m, which is less than 70 mN / m, which is also thought to be a factor in the poor stainability and adhesion. [Industrial Applicability]

[0084] The stainable decorative sheet of this embodiment has extremely excellent stainability, is inexpensive, has a small environmental impact, and also has excellent adhesion and transparency, and therefore is suitable for use as interior or exterior components of buildings such as walls, ceilings, and floors, as fittings or fixtures such as window frames, doors, handrails, baseboards, moldings, and other building components, as well as surface decorative panels for kitchen equipment, furniture, or cabinets for low-voltage and office equipment, and as layers constituting interior or exterior components of vehicles. [Explanation of symbols]

[0085] 1: Stainable decorative sheet 10:Paper base material 20: Adhesive layer 30: Non-woven fabric layer 31, 33: Filling section 32: Fiber section 40: Surface layer 50: Picture layer

Claims

1. A paper substrate, an adhesive layer provided on at least one surface of the paper substrate; a nonwoven fabric layer provided on the other side of the adhesive layer opposite to the side on which the paper substrate is provided; Equipped with the nonwoven fabric layer is made of rayon fibers, the nonwoven fabric layer has, on the surface on which the adhesive layer is provided in the thickness direction of the layer, a filled portion A in which a resin forming the adhesive layer is filled into a part of voids between fibers constituting the nonwoven fabric layer, the resin forming the adhesive layer is a thermoplastic urethane resin, The contact angle of the thermoplastic urethane resin is 90.0° or less. Stainable decorative sheet.

2. a surface layer on the side of the nonwoven fabric layer opposite to the side on which the adhesive layer is provided; the resin forming the surface layer is at least one resin selected from an acrylic resin, an acrylic polyol resin, and a urethane resin, The nonwoven fabric layer has a filling portion A on the side of the layer where the adhesive layer is provided in the thickness direction of the layer, and a filling portion B on the side of the layer where the surface layer is provided in the thickness direction of the layer, in which some of the voids of the fibers constituting the nonwoven fabric layer are filled with a resin that forms the surface layer.

3. 3. The stainable decorative sheet according to claim 1, further comprising a decorative layer between the paper substrate and the adhesive layer.

4. 4. The stainable decorative sheet according to claim 3, wherein said decorative layer exhibits a wood grain pattern.

5. The stainable decorative sheet according to any one of claims 1 to 4, wherein the wet tension of the thermoplastic urethane resin and nonwoven fabric layer is 70 mN / m or more.

6. A method for coloring a decorative sheet, comprising applying a colorant to the surface layer side of the stainable decorative sheet according to claim 2 to color the nonwoven fabric layer.

Images