JP2021160361A - Decorative sheet for recoat and coloring method of decorative sheet therewith - Google Patents

Abstract

To provide a decorative sheet for recoat that has excellent staynability and is excellent also in surface characteristics such as water resistance, and a coloring method of the decorative sheet therewith.SOLUTION: A decorative sheet for recoat comprises a paper substrate, an adhesive layer, a non-woven fabric layer, and a surface layer constituted of a cured material of a composition containing a polyol compound having a hydroxyl group in one molecule and an isocyanate curing agent in this order, in which the non-woven fabric layer partially has, on a surface side on which the adhesive layer is provided in a thickness direction in the layer is provided, a filling layer A formed by filling a resin that forms the adhesive layer on a part of voids of fibers constituting the non-woven fabric, and on a surface side provided with the surface layer in the thickness direction in the layer, a filling part B formed by filling the cured material in a part of void of fibers constituting the non-woven fabric, in which a content of remaining hydroxyl groups contained in the surface layer and a ratio of an amount of isocyanate groups in the isocyanate curing agent, and an amount of hydroxyl groups in the polyol compound are in a predetermined range, and a coloring method of the decorative sheet therewith is also provided.SELECTED DRAWING: Figure 1

Description

The present invention relates to a decorative sheet for recoating and a method for coloring a decorative sheet using the same.

Mainly in Europe and the United States, general consumers themselves use colored paints such as water-based or oil-based stain paints to paint the surface of building interior materials and furniture surface materials made of wood. Painting the surface of furniture or the like (DIY: Do It Yourself) is generally performed. Such stain paint penetrates into the wood and colors it, and since it does not cover the wood grain of the wood itself and does not form a film on the surface, it is unique to wood such as wood grain and shine (pearly luster). It has the feature of making the best use of the design appearance of.

In recent years, as a building interior material, a furniture surface material, etc., a form in which a decorative sheet made by printing wood grain imitation on the surface of a sheet-like base material is laminated instead of natural wood has come to be used. , Decorative sheets that can be used for stain coating using the above stain paint have been manufactured. Specifically, on the assumption that the purchaser himself coats the stain paint to obtain a desired texture, the recoating decorative sheet is subjected to a surface treatment that ensures the onset property of the stain paint.

As such a decorative sheet, a decorative sheet for recoating (see, for example, Patent Document 1) in which a pattern layer is printed on a polyvinyl chloride (PVC) resin base material and then heat-sealed with a non-woven fabric, a paper base material, and the like. Stability decorative sheets using non-woven fabrics (see, for example, Patent Document 2) and the like have been proposed. These recoatable and sustainable decorative sheets can be recoated, and the surface is provided with fine irregularities by a non-woven fabric, which is favorable to consumers in that they can obtain a tactile sensation very similar to wood. It is rare.

Japanese Unexamined Patent Publication No. 9-262934 JP-A-2019-64131

However, when a PVC base material is used as the base material, there is a problem that the price of the decorative sheet becomes high. Further, when a PVC base material is used as a base material, an environmental problem may occur in which a gas containing chlorine atoms such as hydrogen chloride (HCl) is generated when incineration is attempted for disposal.

Therefore, in response to the above problem, it is considered to change to a paper base material as a base material, but it is expected that various problems will occur due to the change.
For example, when laminating a non-woven fabric on a paper base material, the paper base material and the non-woven fabric do not adhere to each other, so that the method of adhering the paper base material and the non-woven fabric becomes a problem. When an adhesive layer is provided between the paper base material and the non-woven fabric to bond the non-woven fabric, the unevenness of the non-woven fabric may be lost, which may cause a problem that the tactile sensation very similar to that of wood is lost. On the other hand, if the unevenness of the non-woven fabric is used too much, the tactile sensation is lost due to the fluffing of the non-woven fabric. In some cases, the problem of reduced transparency and reduced designability may occur.

For suppressing the decrease in transparency caused by the refractive index and the decrease in tactile sensation due to fluffing, for example, it is conceivable to provide a surface layer. However, if the surface layer is provided, the permeability and the inking property of the colored paint such as the stain paint may be lowered, and on the other hand, the affinity with the colored paint such as the stain paint is improved in order to improve the permeability and the inking property. If a material having high properties is used, the surface layer may be deteriorated by a solvent (water, solvent, alcohol, etc.) contained in a colored paint such as a stain paint and whitened, which may cause an appearance problem. And this problem is a problem that can occur not only in colored paints such as stain paints but also outdoors, for example, exposed to wind and rain.

Therefore, the application suitability (referred to as "stainability" in English) that ensures the permeability and fillability of colored paints such as stain paints, but the term "stainability" is also used as a noun in this specification. It is difficult to achieve both surface characteristics (water resistance, etc.) that suppress deterioration (whitening, etc.) due to colored paints such as stain paints.

In view of the above problems, an object of the present invention is to provide a decorative sheet for recoating, which has excellent sustainability and also excellent surface properties such as water resistance, and a method for coloring the decorative sheet using the same.

As a result of diligent research in order to solve the above-mentioned problems, the present inventors have found that the above-mentioned problems can be solved by a decorative sheet for recoating having the following constitution.

1. 1. A paper base material, an adhesive layer, a non-woven layer, and a surface layer composed of a cured product of a composition containing a polyol compound having a hydroxyl group in the molecule and an isocyanate curing agent are provided in order, and the non-woven layer has a thickness within the layer. On the surface side where the adhesive layer is provided in the direction, a filling portion A formed by filling a part of the voids of the fibers constituting the non-woven layer with the resin forming the adhesive layer, and the thickness direction in the layer. On the surface side where the surface layer is provided, a filling portion B in which a part of the voids of the fibers constituting the non-woven layer is filled with the cured product is partially provided, and the residue contained in the surface layer. The content of hydroxyl groups is 0.25% by mass or more and 1.10% by mass or less, and the amount of isocyanate groups _CNCO (mmol) in the isocyanate curing agent and the amount of hydroxyl groups C _OH (mmol) in the polyol compound. , ( _CNCO / C _OH ) is 0.20 or more, a decorative sheet for recoating.
2. The decorative sheet for recoating according to 1 above, wherein the fiber is at least one fiber selected from a thermoplastic resin fiber and a regenerated fiber.
3. 3. The decorative sheet for recoating according to 1 or 2 above, wherein the fiber is a cellulose resin fiber.
4. The decorative sheet for recoating according to any one of 1 to 3 above, wherein the resin forming the adhesive layer is at least one resin selected from urethane resin and polyolefin resin.
5. 6. The decorative sheet for recoating according to any one of 1 to 4 above, wherein the polyol compound is one or more selected from acrylic polyols, polyester polyols, polyether polyols and polycarbonate polyols. The decorative sheet for recoating according to any one of 1 to 5 above, wherein the isocyanate curing agent is a multivalent isocyanate compound.
7. The decorative sheet for recoating according to any one of 1 to 6 above, further comprising a decorative layer between the paper base material and the adhesive layer.
8. The recoating decorative sheet according to 7 above, wherein the decorative layer exhibits a wood grain pattern.
9. A method for coloring a decorative sheet, wherein a colored paint is applied to the surface of the decorative sheet for recoating according to any one of 1 to 8 to color the non-woven fabric layer.

According to the present invention, it is possible to provide a decorative sheet for recoating, which has excellent sustainability and also has excellent surface characteristics such as water resistance, and a method for coloring the decorative sheet using the same.

It is a schematic cross-sectional view which shows one Embodiment of the decorative sheet for recoating of this embodiment. It is a schematic cross-sectional view which shows one Embodiment of the decorative sheet for recoating of this embodiment.

Hereinafter, embodiments of the present invention (hereinafter, may be referred to as “the present embodiment”) will be described. In addition, in this specification, the numerical values relating to "greater than or equal to", "less than or equal to" and "to" relating to the description of the numerical range are numerical values that can be arbitrarily combined, and the numerical values of Examples are numerical values that can be used for the upper and lower limits of the numerical range. Is.

[Cosmetic sheet for recoating]
The decorative sheet for recoating of the present embodiment comprises, in order, a paper base material, an adhesive layer, a non-woven layer, and a surface layer composed of a cured product of a composition containing a polyol compound having a hydroxyl group in the molecule and an isocyanate curing agent. The non-woven layer has a filling portion A formed by filling a part of the voids of the fibers constituting the non-woven layer with a resin forming the adhesive layer on the surface side of the layer in which the adhesive layer is provided in the thickness direction. On the surface side of the layer where the surface layer is provided in the thickness direction, a filling portion B formed by filling a part of the voids of the fibers constituting the non-woven layer with the cured product is partially provided. The content of residual hydroxyl groups contained in the surface layer is 0.25% by mass or more and 1.10% by mass or less, and the amount of isocyanate groups _CNCO (mmol) in the isocyanate curing agent and the polyol compound. It is characterized in that the ratio ( _CNCO / C _OH ) of the amount of hydroxyl groups C _{OH (mmol) is 0.20 or more.}

By having the above-mentioned structure, the decorative sheet for recoating of the present embodiment has excellent sustainability and also has excellent surface properties such as water resistance.
In general, if a surface layer is provided in order to improve surface properties such as water resistance and scratch resistance, the sustainability tends to decrease. In order to improve the surface characteristics, the affinity with the colored paint such as stain paint is lowered, that is, by using a material having a low affinity, the colored paint, mainly the solvent contained in the colored paint (water, solvent, alcohol). It becomes easier to prevent whitening by suppressing the deterioration of the material due to (etc.), but with a material that has a low affinity for the colored paint, the coating suitability that ensures the permeability and carving property of the colored paint, that is, the sustainability, is This is because it becomes difficult to obtain.

The polyol compound having a hydroxyl group in the molecule adopted in the present embodiment (hereinafter, may be simply referred to as “polyol compound”) originally has a high affinity with a colored coating material such as a stain coating material, that is, coloring. Since it has a high affinity with the solvent (water, solvent, alcohol, etc.) contained in the paint, it is easy to obtain excellent sustainability, but the property of having a high affinity with the colored paint promotes the deterioration of the polyol compound. It is a material having a property that surface characteristics such as water resistance are likely to be deteriorated, such as whitening.

In the decorative sheet for recoating of the present embodiment, the surface layer is composed of a cured product of a composition containing a polyol compound and an isocyanate curing agent while obtaining excellent sustainability by using a polyol compound having such properties. The content of the residual hydroxyl group contained in the surface layer is in the range of 0.25% by mass or more and 1.10% by mass or less, and the isocyanate group amount _CNCO (mmol) in the isocyanate curing agent and the polyol compound. _{The ratio (CNCO} / C _OH ) to the amount of hydroxyl group C _OH (mmol) is 0.20 or more, that is, a polyol is obtained while obtaining a good cured state by using an isocyanate curing agent in a certain amount or more. By leaving a part of the hydroxyl group of the compound, it is possible to achieve both the contradictory performances of sustainability and surface characteristics such as water resistance at a high level.

Conflicting performance by a relatively easy method of adjusting _{the content and ratio of residual hydroxyl groups (CNCO} / C _OH ) according to the type of polyol compound and isocyanate curing agent as the main agent and the amount used according to the type. It can be said that it is a surprising effect to be able to achieve both sustainability and surface properties such as water resistance at a high level. Such an effect is due to the fact that a polyol compound is selected as the main agent and a urethane resin (cured product) using an isocyanate curing agent is used as the material for forming the surface layer.
Also, as with the base material, when a resin composition using a PVC-based resin is used to form a layer, a gas containing chlorine atoms such as hydrogen chloride (HCl) is generated when incineration is attempted for disposal. , Environmental problems may occur. Therefore, one of the effects of using urethane resin (cured product) for forming the surface layer is to reduce the burden on the environment. It is preferable not to use the PVC resin not only in the base material and the surface layer but also in the formation of other layers.

The recoating decorative sheet of the present embodiment will be described below with reference to the drawings. In the description of the drawings below, the same or similar parts are represented by the same or similar reference numerals. However, the drawings are schematic, and the relationship between the thickness and the plane dimensions, the ratio of the thickness of each layer, etc. are different from the actual ones. Therefore, the specific thickness and dimensions should be determined in light of the following explanations. In addition, it goes without saying that the drawings include parts having different dimensional relationships and ratios from each other.

The decorative sheet 1 for recoating shown in FIG. 1 includes a paper base material 10, an adhesive layer 20, a non-woven fabric layer 30, and a surface layer 40 in this order, and the adhesive layer 20 is provided on at least one surface 11 side of the paper base material 10. It is provided. Then, the non-woven fabric layer 30 constitutes the non-woven fabric layer 30 on the surface 30a (hereinafter, also referred to as “the surface provided with the adhesive layer of the non-woven fabric layer”) in which the adhesive layer 20 in the thickness direction is provided in the layer. A surface 30b provided with a filling portion A31 formed by filling a part of the fiber voids with a resin forming the adhesive layer 20 and a surface layer 40 in the thickness direction in the layer (hereinafter, “a surface layer of a non-woven fabric layer is provided”). It is shown that a part of the voids of the fibers constituting the non-woven fabric layer 30 is partially filled with a filling portion B33 formed by filling the voids of the fibers constituting the non-woven fabric layer 30 with the composition forming the surface layer 40. Has been done. It is also shown that the non-woven fabric layer 30 has a fiber portion 32 as a portion other than the filling portion A31 and the filling portion B32 between the filling portion A31 and the filling portion B33.

Further, the recoating sheet 1 shown in FIG. 2 is a decorative layer composed of a fully colored layer 51 and a pattern layer 52 between the paper base material 10 and the adhesive layer 20 in the recoating sheet 1 shown in FIG. It has 50.
Hereinafter, each layer constituting the recoating decorative sheet of the present embodiment will be described with reference to FIGS. 1 and 2.

[Surface layer 40]
The surface layer 40 of the decorative sheet for recoating of the present embodiment is composed of a cured product of a composition containing a polyol compound having a hydroxyl group in the molecule and an isocyanate curing agent, and the content of residual hydroxyl groups contained in the surface layer is 0. It is a layer of .25% by mass or more and 1.10% by mass or less. By having the surface layer 40, as described above, it is possible to achieve both surface characteristics such as water resistance and sustainability at a high level.

(Content of residual hydroxyl group)
The surface layer 40 is composed of a cured product of a composition containing a polyol compound and an isocyanate curing agent (hereinafter, may be simply referred to as “curing agent”), and has a residual hydroxyl group of 0.25% by mass or more and 1.10% by mass. It is contained in a content of% or less. If the content of the residual hydroxyl group is less than 0.25% by mass, the affinity with the colored paint such as the stain paint cannot be obtained, so that the sustainability cannot be obtained. On the other hand, when the content of the residual hydroxyl group is more than 1.10% by mass, the surface layer 40 has an excessively high affinity with the solvent (water, solvent, alcohol, etc.), particularly water, and the deterioration of the surface layer is promoted. As a result, whitening and the like are likely to occur, so that surface characteristics such as water resistance and scratch resistance cannot be obtained.

From the viewpoint of improving the surface characteristics as well as the sustainability, the content of the residual hydroxyl group contained in the surface layer 40 is preferably 0.30% by mass or more, more preferably 0.35% by mass or more, still more preferably 0.40. By mass% or more, more preferably 0.45% by mass or more, and as an upper limit, preferably 1.05% by mass or less, more preferably 1.00% by mass or less, still more preferably 0.95% by mass or less, further. It is preferably 0.90% by mass or less. The content of the residual hydroxyl groups contained in the surface layer 40 is substantially the same as the content of the residual hydroxyl groups contained in the cured product because the surface layer 40 is composed of the cured product.

In the present specification, the content of the residual hydroxyl group contained in the surface layer 40 forms a urethane bond by reacting with the isocyanate group (-NCO) in the curing agent among the hydroxyl groups in the polyol compound contained in the resin composition. It is the content (% by mass) of the hydroxyl groups remaining without being added to the total amount of the cured product constituting the surface layer 40, strictly speaking, the polyol compound and the curing agent. Specifically, it is a content that can be calculated by the following method.
Based on JIS K1557-1: 2007 (Plastic-Polyurethane Raw Material Polyol Test Method-Part 1: How to Obtain Hydroxylity Value), the hydroxyl value X _OH (mgKOH / g) of a polyol compound having a hydroxyl group in the molecule is determined. Using the obtained hydroxyl group value X _OH and each of the following amounts, the content of the residual hydroxyl group is calculated by the following mathematical formula (1).

Content of residual hydroxyl groups (% by mass) = (Amount of residual hydroxyl groups) / (Amount of polyol compound used + Amount of curing agent used) x 100 (1)
Hydroxyl group content of residual hydroxyl group amount = the polyol compound - hydroxyl group content of the isocyanate group-weight polyol compound in the curing agent _{(g) = X OH /56.1×A P} × 17.0
Isocyanate content in the curing agent _{(g) = X NCO × A} C × 42.0
A _P (g): The amount of polyol compound A _C (g): amount X _NCO curing agent (mmol / g): The content of isocyanate groups in the curing agent

(Ratio of isocyanate group amount to hydroxyl group amount)
In the surface layer 40, the ratio ( _CNCO / C _{OH ) of the isocyanate group amount CNCO} (mmol) in the isocyanate curing agent and the hydroxyl group amount C _OH (mmol) in the polyol compound is 0.20 or more. Needs. If the ratio is less than 0.20, the cross-linking ratio due to the isocyanate group is reduced, so that excellent surface characteristics cannot be obtained.

The isocyanate content _C NCO in the curing agent (mmol), and hydroxyl group content _C OH in polyol compound (mmol), the ratio _(C NCO _/ C _OH) of, from the viewpoint of improving the Suteinaburu resistance and surface properties, preferably Is 0.25 or more, more preferably 0.30 or more. The upper limit is not particularly limited, but is preferably 0.90 or less, more preferably 0.80 or less, still more preferably 0.60 or less, still more preferably 0.45 or less in order to improve sustainability.

Here, the amount of hydroxyl groups _C OH isocyanate group amount _C NCO (mmol) and the polyol compound in the curing agent (mmol) is the value calculated by the following equation (2) and (3).
Isocyanate content _C NCO in the curing agent _{(mmol) = X NCO × A} C (2)
Hydroxyl group content _C OH of the polyol compound _{(mmol) = X OH /56.1×A P} (3)

(Polyol compound)
The surface layer 40 is composed of a cured product of a composition containing a polyol compound having a hydroxyl group in the molecule and an isocyanate curing agent.
Preferred examples of the polyol compound include acrylic polyols, polyester polyols, polyether polyols, polycarbonate polyols, and the like, and these can be used alone or in combination of two or more. Acrylic polyols are particularly preferable from the viewpoint of improving surface properties as well as sustainability.

As a specific example of the acrylic polyol, a plurality of (meth) acrylic acid alkyl esters such as ethyl (meth) acrylate are copolymerized with hydroxy acrylates such as 2-hydroxyethyl acrylate and 2-hydroxy-3-phenoxypropyl acrylate. Examples thereof include those in which the hydroxyl group of the above is introduced.
Specific examples of polyester polyols include poly (ethylene adipate), poly (butylene adipate), poly (neopentyl adipate), poly (hexamethylene adipate), poly (butylene azelaate), poly (butylene caproate), and poly. Caprolactone and the like can be mentioned.

Specific examples of the polyether polyol include those having an alkyleneoxy group as a repeating unit, for example, polyoxyethylene monomethyl ether, polyethylene glycol, polyoxyethylene glycerol ether, polyoxyethylene trimetyl propane ether, and polyoxyethylene neopentylglycerol ether. , Polyoxyethylene pentaelist reel ether, polypropylene glycol, polytetramethylene glycol and the like.

Specific examples of the polycarbonate polyol include one or more alkylene diols having an alkylene group having 4 to 12 carbon atoms and a low molecular weight carbonate compound (for example, a dialkyl carbonate having 1 to 6 carbon atoms in an alkyl group). More specific examples thereof include polycarbonate diols produced by condensing an alkylene carbonate having an alkylene group having 2 to 6 carbon atoms and a diaryl carbonate having an aryl group having 6 to 9 carbon atoms while conducting a dealcohol reaction. Examples thereof include polybutylene carbonate polyol, polyhexamethylene carbonate polyol, polycyclohexanedimethylene carbonate polyol and the like.

As the polyol compound, the hydroxyl value (mgKOH / g) is preferably 5 mgKOH / g or more, more preferably 10 mgKOH / g or more, still more preferably 15 mgKOH / g or more, still more preferably 20 mgKOH / g or more, and the upper limit is preferably 20 mgKOH / g or more. It is 60 mgKOH / g or less, more preferably 55 mgKOH / g or less, still more preferably 50 mgKOH / g or less, still more preferably 45 mgKOH / g or less. When the hydroxyl value of the polyol compound is within the above range, the content of the residual hydroxyl group can be easily adjusted to 0.25% by mass or more and 1.10% by mass or less, and the surface characteristics can be improved as well as the sustainability.

(Isocyanate curing agent)
The isocyanate curing agent is preferably a polyvalent isocyanate compound, and examples thereof include aliphatic diisocyanates, aromatic diisocyanates, and prepolymer-type, isocyanurate-type, urea-type, and carbodiimide-type modified products of these diisocyanates.
Examples of the aliphatic diisocyanate include isophorone diisocyanate (hereinafter, also referred to as “IPDI”), 4,4′-dicyclohexamethylene diisocyanate (hereinafter, also referred to as “DCI”), 4-methyl-1,3-cyclohexamethylene diisocyanate, and 1 , 2-Bis (isophorone methyl) cyclohexane and other alicyclic diisocyanates; hexamethylene diisocyanate (hereinafter also referred to as “HMDI”), trimethylhexamethylene diisocyanate and other linear or branched chain aliphatic diisocyanates can be mentioned. ..
Examples of the aromatic diisocyanate include 4,4'-diphenylmethane diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, and 1,3-xylylene diisocyanate. Examples thereof include isocyanate, 1,4-xylylene diisocyanate, 1,5-naphthalenediocyanate, and 3,3'-dimethyl-4,4'-biphenylenediocyanate.

The content of the isocyanate group (-NCO) contained in the isocyanate curing agent is preferably 5% by mass or more, more preferably 10% by mass or more, still more preferably 15% by mass or more, and the upper limit is preferably 30% by mass or less. , More preferably 25% by mass or less, still more preferably 20% by mass or less. When the content of the isocyanate group contained in the isocyanate curing agent is within the above range, the content of the residual hydroxyl group can be easily adjusted to 0.25% by mass or more and 1.10% by mass or less, and the surface characteristics are improved as well as the sustainability. Can be made to.

Among the above isocyanate curing agents, chain aliphatic diisocyanates are preferable, and hexamethylene diisocyanates are particularly preferable, from the viewpoint of improving surface properties as well as sustainability.

The content of the residual hydroxyl group contained in the surface layer 40 can be adjusted by the type of the polyol compound and the isocyanate curing agent contained in the composition used for forming the surface layer, the content thereof, and the like.
The content of the polyol compound and the isocyanate curing agent in the composition is not particularly limited as long as the content of the residual hydroxyl group is 0.25% by mass or more and 1.10% by mass or less. For example, the amount of isocyanate groups in the curing agent. The ratio ( _CNCO / C _OH ) of C _NCO (mmol) and the amount of hydroxyl groups C _OH (mmol) in the polyol compound is preferably set to be within the above preferable range.

For example, the amount of the isocyanate curing agent used with respect to 100 parts by mass of the polyol compound in the composition is preferably 0.3 parts by mass or more, more preferably 1.0 part by mass or more, still more preferably 1.5 parts by mass or more. It is more preferably 2.0 parts by mass or more, particularly preferably 2.5 parts by mass or more, and the upper limit is preferably 20.0 parts by mass or less, more preferably 12.5 parts by mass or less, still more preferably 10.0. It is less than or equal to parts by mass, more preferably 7.0 parts by mass or less, and particularly preferably 5.5 parts by mass or less. When the amount of the isocyanate curing agent used is within the above range, the content of the residual hydroxyl group can be easily adjusted to 0.25% by mass or more and 1.10% by mass or less, and the surface characteristics can be improved as well as the sustainability. In addition, the isocyanate curing agent used in the formation of the surface layer can also contribute to the improvement of the adhesiveness between the paper base material and the non-woven fabric layer, which will be described later, so that the thickness of the adhesive layer can be made relatively thin. ..

(Aspect of surface layer 40)
The mode of the surface layer 40 is not particularly limited as long as it includes a filling portion B such that a part of the voids of the fibers constituting the non-woven fabric layer is filled with the cured product. For example, FIGS. 1 and 2 show. As shown, it may be layered on the surface 30b with a certain thickness, or it covers the outermost fibers along the surface 30b of the non-woven fabric layer 30, that is, the fibers constituting the non-woven fabric layer 30. The voids may be present on the outermost surface.

When the surface layer 40 has a certain thickness and exists in a layered state, the surface layer 40 of the present embodiment ensures excellent sturability by ensuring the inking property of a colored paint such as a water-based stain paint and an oil-based stain paint. It will be present on a part of the surface side of the decorative sheet for recoating.
When present so as to cover the fibers on the outermost surface, the fibers on the outermost surface and its vicinity (near the thickness direction in the layer of the non-woven fabric layer 30) from the viewpoint of ensuring inking property and obtaining excellent sustainability. It is preferable that the voids formed by the above are at least partially present. From the viewpoint of improving surface properties as well as sustainability, and further improving transparency, tactile sensation, etc., the surface layer preferably exists so as to cover the outermost fibers, and covers the entire surface thereof. More preferably present.

In this way, regardless of the mode in which the surface layer 40 is present, the outermost surface and its outermost surface and its outermost surface are ensured from the viewpoint of ensuring the inking property of colored paints such as water-based stain paints and oil-based stain paints and obtaining excellent sustainability. In the vicinity (near the thickness direction in the layer of the non-woven fabric layer 30), it is preferable that at least a part thereof has voids formed by fibers whose surfaces may be coated with a resin.

The surface layer 40 contains colorants such as pigments and dyes, weather resistant agents such as ultraviolet absorbers and light stabilizers, extender pigments, solvents, stabilizers, plasticizers, and additives such as catalysts, depending on the desired performance. You may. That is, the composition containing the polyol compound used for forming the surface layer 40 and the isocyanate curing agent may contain these additives.
In this case, the content of the additive is not particularly limited as long as it depends on the desired performance and does not hinder the curing of the polyol compound and the isocyanate curing agent. For example, the resin content of the surface layer 40 (that is, the polyol). The total amount of the additive used may be about 1 part by mass and 20 parts by mass or less, preferably 3 parts by mass or more, and more preferably 5 parts by mass with respect to 100 parts by mass of the total amount of the compound and the isocyanate curing agent. As described above, the upper limit is preferably 15 parts by mass or less, and more preferably 10 parts by mass or less.

The thickness of the surface layer 40 may be determined mainly in consideration of the thickness of the surface layer 40 and the balance of the filling portion B33, the fiber portion 32 and the filling portion A31 in the non-woven fabric layer 30, and the filling portion A31. , The total thickness of the surface layer 40 and the filling portion B33 from the viewpoint of forming the filling portion B33 and the fiber portion 32 in a well-balanced manner, improving the surface characteristics as well as the sustainability, and further improving the transparency, the tactile sensation, etc. The upper limit is preferably 0.5 μm or more, more preferably 1 μm or more, still more preferably 2 μm or more, and the upper limit is preferably 10 μm or less, more preferably 8 μm or less, still more preferably 6 μm or less. The total thickness of the surface layer 40 and the filling portion B33 is photographed using various electron microscopes such as a transmission electron microscope (TEM), a scanning electron microscope (SEM), or a scanning transmission electron microscope (STEM). The thickness at any 30 points is measured from the image of the cross section, and is the average value of the thicknesses at the 30 points.

(Non-woven fabric layer 30)
The non-woven fabric layer 30 is a layer that ensures the incarnation property in which colored paints such as water-based stain paint and oil-based stain paint enter into the voids of the fibers forming the non-woven fabric layer 30 and exhibits sustainability, and the thickness in the layer. On the side of the surface 30a provided with the adhesive layer 20 in the direction, a filling portion A31 formed by filling a part of the voids of the fibers constituting the non-woven fabric layer 30 with the resin forming the adhesive layer 20, and the thickness inside the layer. On the side of the surface 30b where the surface layer 40 is provided in the direction, a filling portion B33 formed by filling a part of the voids of the fibers constituting the non-woven fabric layer 30 with a cured product forming the surface layer 40 is partially provided. It is a layer to have.

Examples of the fibers constituting the non-woven layer 30 include thermoplastic resin fibers, natural fibers, regenerated fibers, semi-synthetic fibers, and the like, and from the viewpoint of sustainability, thermoplastic resin fibers and regenerated fibers are preferable. In the present embodiment, the fibers can be used alone or in combination of two or more.

Examples of the thermoplastic resin fiber include (meth) acrylic resin such as poly (meth) acrylic acid ester; polyvinyl acetal (butyral resin) such as polyvinyl butyral; polyester resin such as polyethylene terephthalate and polybutylene terephthalate; polyethylene and polypropylene. Polyolefin resin such as polystyrene, styrene resin such as α-methylstyrene; acetal resin such as polyoxymethylene; polyolefin-based thermoplastic elastomer, polystyrene-based thermoplastic elastomer, polydiene-based thermoplastic elastomer, polyurethane-based thermoplastic elastomer, polyester Thermoplastic elastomers such as fluororesin-based thermoplastic elastomers; fluororesins such as vinyl chloride resin, polyurethane resin, ethylene-4ethylene fluoride copolymer, polyamide resin, polyimide resin, polylactic acid resin, polycarbonate resin , A thermoplastic resin fiber composed of a thermoplastic resin such as a polyvinyl acetal resin and a liquid crystal polyester resin is preferable. Among these thermoplastic resin fibers, in consideration of morphological stability, a thermoplastic resin fiber composed of a resin such as a polyester resin, a polyolefin resin, or a polyurethane resin is preferable, and a thermoplastic resin composed of a polyester resin or a polyolefin resin is preferable. Resin fibers are preferred.

The thermoplastic resin constituting the thermoplastic resin fiber may be one kind alone or a combination of a plurality of kinds, for example, a fiber having a double structure in which the core is a polyester resin and the sheath is a polyolefin resin. It may be a composite fiber such as.

Examples of natural fibers include fibers made of natural materials such as cotton, wool and silk, examples of recycled fibers include rayon, cupra and lyocell, and examples of semi-synthetic fibers include triacetate and promix. Be done.

The fiber diameter of the fibers constituting the non-woven fabric layer 30 is not particularly limited, but the average fiber diameter is preferably 0.5 μm or more, more preferably 1 μm or more, and the upper limit is preferably 50 μm or less, particularly considering the tactile sensation. A non-woven fabric of 30 μm or less, more preferably 20 μm or less is preferable. Nonwoven fabrics made of fibers having an average fiber diameter in this range tend to have a tactile sensation very similar to that of wood.
The average fiber diameter of the fibers constituting the non-woven fabric is measured by measuring the width (diameter) of 30 fibers existing at any position on the non-woven fabric using an electron microscope (300 times), and the obtained measurement results are obtained. It can be measured by averaging the values.

The fibers constituting the non-woven fabric layer 30 can be formed, for example, by forming a fleece by a spunbond method and bonding the formed fleece by a thermal bond method, a spunlace method (water flow entanglement method) or the like. Further, the non-woven fabric layer 30 formed by these methods tends to have a tactile sensation very similar to that of wood.

The basis weight of the fibers constituting the non-woven fabric layer 30 is not particularly limited, but is preferably 10 g / m ² or more, more preferably 15 g / m ² or more, and is preferable as an upper limit from the viewpoint of obtaining the strength of the non-woven fabric layer 30. Is 40 g / m ² or less, more preferably 30 g / m ² or less, still more preferably 20 g / m ² or less.

The thickness of the non-woven fabric layer 30 is not particularly limited, but is preferably 30 μm or more, more preferably 50 μm or more, still more preferably 60 μm or more in consideration of physical properties such as strength, mass, and flexibility of the decorative sheet 1 for recoating. , More preferably 70 μm or more, and the upper limit is preferably 250 μm or less, more preferably 200 μm or less, still more preferably 150 μm or less, still more preferably 100 μm or less.

(Filling part A31 and filling part B33)
The surface 30a side of the non-woven fabric layer 30 provided with the adhesive layer 20 in the thickness direction is provided with a filling portion A31 in which a resin forming the adhesive layer 20 is filled in a part of the fiber voids, and the other layer. On the side of the surface 30b where the surface layer 40 in the thickness direction is provided, a filling portion B33 formed by filling a part of the voids of the fibers with a cured product forming the surface layer 40 is provided.

In order to improve the effect of obtaining surface characteristics as well as sustainability, and further to improving the tactile sensation and transparency of the surface, the filling portion A formed from the adhesive layer 20 and the non-woven fabric layer 30 together with the above-mentioned structure of the surface layer 40. The filling portion B formed from the surface layer 40 and the non-woven fabric layer 30 also plays an important role. It can be said that the non-woven fabric layer 30 is a layer having two filling portions A and B in relation to the adhesive layer 20 and the surface layer 40.

Since the filling portion A31 is formed by penetrating at least a part of the resin forming the adhesive layer 20 into the non-woven fabric layer 30, excellent adhesiveness between the paper base material 10 and the non-woven fabric layer 30 can be obtained. By suppressing and protecting the penetration of solvents (water, solvent, alcohol, etc.) contained in colored paints such as stain paints into the paper substrate 10, apart from water resistance as a surface characteristic, the entire decorative sheet for recoating Water resistance is also obtained.
On the other hand, since the filling portion B33 is formed by permeating at least a part of the resin forming the surface layer 40 into the non-woven fabric layer 30, surface characteristics can be obtained as well as stability, and the fluff of the non-woven fabric layer 30 is further obtained together with the surface layer 40. Is in a good state to give a tactile sensation, and it is also possible to suppress a decrease in transparency due to fluffing (unevenness on the surface) of the non-woven fabric layer 30 and a refractive index due to voids. Can also be obtained. Further, since deterioration of the paper base material 10 due to permeation of a solvent (water, solvent, alcohol, etc.) contained in a colored paint such as a stain paint can be suppressed, water resistance of the entire decorative sheet for recoating can be obtained.

Since the filling portion A31 is in a state in which the resin forming the adhesive layer 20 is filled in the gaps of the fibers forming the non-woven fabric layer 30 and the gaps do not remain, the filling portion A31 does not have the inking property for the colored paint such as stain paint to enter. It is a part.
Similar to the filling portion A31, the filling portion B33 is in a state in which the voids of the fibers forming the non-woven fabric layer 30 are filled with the cured product forming the surface layer 40 and no voids remain. It is a part that does not have a meat-forming property to which colored paint such as paint enters.

In the recoating decorative sheet 1 of the present embodiment, the non-woven fabric layer 30 partially has the filling portion A31 and the filling portion B33. That is, the non-woven fabric layer 30 needs to have a fiber portion 32, which will be described later, which is a portion other than the filling portion A31 and the filling portion B33. If the fiber portion 32, which is a portion other than the filling portion, is not provided, the filling portion is in a state where no voids remain, and the colored paint such as a stain paint does not have a fleshing property, so that the sustainability cannot be obtained. Because.

In FIGS. 1 and 2, the filling portion A31 and the filling portion B33 are schematically shown to have layers, but the shape of the fibers constituting the non-woven fabric layer 30, the shape of the voids of the fibers, and the like are not uniform. , It is considered that the layer is not always uniform as shown in the figure. Considering that colored paint such as stain paint has entered and is colored, for example, the non-woven fabric is shown as the filling portion A31 and the filling portion B33 in a certain range in the thickness direction in the layer of the nonwoven fabric layer 30. The gaps between the fibers forming the layer 30 are dotted with the filling portions A31 and the filling portions B33 filled with the resin forming the adhesive layer 20 and the cured product forming the surface layer 40, respectively, and the remaining portions will be described later. It is considered that the fiber portions 32 are scattered.

(Fiber part 32)
As described above, the decorative sheet for recoating of the present embodiment is a layer having a filling portion A31 and a filling portion B33 partially, and therefore has a portion other than these filling portions, that is, a fiber portion 32. It becomes. By having the fiber portion 32, the decorative sheet for recoating of the present embodiment secures the inking property of the colored paint such as the stain paint entering the voids of the fiber, and exhibits the sustainability.

The aspect of the fiber portion 32 is not particularly limited as long as the cured product forming the adhesive layer 20 and the surface layer 40 is not filled and voids remain, but for example, the voids of the fibers forming the non-woven fabric layer 30 are formed. Although the resin forming the adhesive layer 20 and the surface layer 40 does not enter at all, the fibers exist as they are and the fibers have voids, and the resin forming the adhesive layer 20 and the surface layer 40 enters to some extent. Examples thereof include a mode in which the fibers are only coated with these resins and have voids in the coated resins. In the decorative sheet for recoating of the present embodiment, any aspect of the fiber portion 32 may be used.

The fiber portion 32 is a portion not filled with the resin forming the adhesive layer 20 and the surface layer 40, that is, a portion other than the filling portion A31 and the filling portion B33. In FIGS. 1 and 2, the fiber portion 32 is schematically shown to exist in a layered manner, but the filling portion A31 and the filling portion B33 are described in the thickness direction in the layer of the non-woven fabric layer 30 as described above. Since they are scattered in a certain range, it is considered that they do not exist in layers in a strict sense. Therefore, it is considered that the fiber portions 32 are scattered in a certain range in the thickness direction of the non-woven fabric layer 30 shown as the fiber portions 32 in FIGS. 1 and 2.

As a method of allowing the non-woven fabric layer 30 to partially have the filling portion A31 and the filling portion B33, for example, when the amount of the resin composition used for forming the adhesive layer 20 is applied and when the surface layer 40 is formed. Examples thereof include a method of adjusting the coating amount and the like of the resin composition to be used. For example, if the amount of the resin composition applied when forming the adhesive layer 20 is increased, the proportion of the filled portion A31 in the non-woven fabric layer 30 increases. On the other hand, when the amount of the composition used for forming the surface layer 40 is increased, the proportion of the filled portion B33 in the non-woven fabric layer 30 increases. Further, when the coating amount of the composition used for forming the adhesive layer 20 and the surface layer 40 is increased, the proportion of the fiber portion 32 in the non-woven fabric layer 30 is reduced, and when the coating amount is reduced, the fibers in the non-woven fabric layer 30 are applied. The proportion of part 32 will increase.
In the present embodiment, for example, by adjusting the coating amount and the like, it is possible to obtain a desired state of the non-woven fabric layer 30.

(Adhesive layer 20)
The adhesive layer 20 is a layer provided on at least one surface side of the paper base material 10, and is a layer provided for bonding the paper base material 10 and the non-woven fabric layer 30. Further, by providing the adhesive layer 20 so as to have the filling portion A, in addition to the adhesiveness between the paper base material 10 and the non-woven fabric layer 30, the solvent (water, solvent, solvent) contained in the stain coating material on the paper base material 10 is provided. Since it is possible to suppress and protect the permeation of (alcohol, etc.), water resistance of the entire decorative sheet for recoating can be obtained in addition to water resistance as a surface characteristic.

The adhesive used for the adhesive layer 20 is not particularly limited, and an adhesive made of various resins can be used. Examples of the resin forming the adhesive include urethane resin, polyolefin resin, acrylic resin, epoxy resin and the like, and these resins can be used alone or in combination of two or more. Of these, urethane resin and polyolefin resin are preferable, and urethane resin is more preferable. When these resins are used, while excellent adhesiveness is obtained, the penetration of the solvent (solvent, alcohol) of the stain paint applied to the non-woven fabric layer 30 into the paper base material 10 is suppressed, and the water resistance of the decorative sheet 1 for recoating 1 is suppressed. Surface characteristics such as properties can be improved, and it becomes easy to maintain physical properties such as strength, mass, and flexibility.
The non-woven fabric layer 30 includes a resin that forms the adhesive layer 20, a filling portion A31 that is filled with the resin that forms the surface layer 40, and a filling portion B33, and also includes a fiber layer 32 that is not filled with any of the resins. Also provided is a portion where the resin forming the adhesive layer and the resin forming the surface layer are in contact with each other. Therefore, if the same type of resin as the resin used for forming the surface layer 40, that is, urethane resin is used as the adhesive used for the adhesive layer 20, the adhesiveness can be further improved. From this point of view, urethane resin is particularly preferable as the adhesive used for the adhesive layer 20.

As the urethane resin, either a thermoplastic urethane resin or a curable urethane resin may be used, and it is particularly preferable to use a curable urethane resin from the viewpoint of adhesiveness.
The curable polyurethane resin may be either a two-component curable type or a one-component curable type, and a two-component curable polyurethane resin is preferable from the viewpoint of adhesiveness.
The two-component curable polyurethane resin is a polyurethane resin containing a polyol as a main component and an isocyanate as a cross-linking agent (curing agent), and the polyol and the isocyanate are the polyol compound and the isocyanate described as being used for forming the surface layer, respectively. It may be appropriately selected from the curing agents and used.
The thermoplastic polyurethane resin is a copolymer obtained by copolymerizing a monomer with a urethane bond formed by condensing an isocyanate group and a compound having a hydroxyl group such as an alcohol group.

Examples of the polyolefin resin include those containing one or more monoolefins such as ethylene, propylene, butene, penten, hexene, heptene, octene, and 4-methyl-1-pentene as the monomer unit, and further. , Cyclopentene, alicyclic olefins such as cyclohexene, chains such as 1,4-hexadiene, 1,5-hexadiene, divinylbenzene, 1,3-cyclopentadiene, 1,3-cyclohexadiene, 5-vinyl-2-norbornene, etc. Examples thereof include those containing a monomer unit other than monoolefin such as an aromatic vinyl compound such as cyclic or cyclic polyene, styrene, and substituted styrene.
The polyolefin resin is preferably a polyethylene resin containing ethylene as a monomer unit from the viewpoint of adhesion to the paper base material 10 and the non-woven fabric layer 30.

When a urethane resin or a polyolefin resin is used, the ratio of the urethane resin or the polyolefin resin to the total resin forming the adhesive layer 20 is preferably 50% by mass or more, more preferably 70% by mass or more, and 90% by mass. It is more preferably% or more, and even more preferably 100%.

In the present embodiment, the resin forming the adhesive layer 20 is used as a resin composition in which additives such as an ultraviolet absorber, a weather resistant agent such as a light stabilizer, an extender pigment, a solvent, a stabilizer, and a plasticizer are appropriately mixed. be able to. That is, the adhesive layer 20 can be formed of a resin composition containing additives in addition to the above resin.

Since the thickness of the adhesive layer 20 can vary depending on the materials of the paper base material 10 and the non-woven fabric layer 30, the thickness of the non-woven fabric layer 30, and the like, it is not possible to unconditionally specify a numerical value. The adhesive layer 20 and the filling portion A31 are formed in a well-balanced manner with the adhesiveness to the layer 30, the filling portion A31, the filling portion B33, and the fiber portion 32, and from the viewpoint of improving the surface characteristics as well as the sustainability and further improving the transparency and the like. The total thickness of the above is preferably 1 μm or more, more preferably 3 μm or more, further preferably 5 μm or more, still more preferably 8 μm or more, and the upper limit is preferably 25 μm or less, more preferably 20 μm or less, still more preferably 18 μm. Below, it is even more preferably 15 μm or less. Further, when it is within the above range, the water resistance of the entire decorative sheet for recoating is also improved.
The total thickness of the adhesive layer 20 and the filling portion A31 is the same as the total thickness of the surface layer 30 and the filling portion B33, for example, a transmission electron microscope (TEM), a scanning electron microscope (SEM), or scanning transmission. The thickness of any 30 points is measured from an image of a cross section taken with various electron microscopes such as a type electron microscope (STEM), and is an average value of the thicknesses of the 30 points.

(Paper base material 10)
For the decorative sheet 1 for recoating of the present embodiment, a paper base material is adopted from the viewpoint of reducing the environmental load and the price. The paper base material 10 functions as a support for providing another layer in the recoating decorative sheet 1 of the present embodiment.
Examples of the base material used for the paper base material 10 include high-quality paper, thin leaf paper, linter paper, kraft paper, inter-paper reinforced paper, resin-impregnated paper, backing paper for wallpaper, and these papers mixed with flame retardant or containing flame retardant. Flame-retardant paper or the like that is invaded can be used. These materials may be used alone, or may be a laminate in any combination, such as a laminate of papers.
The paper base material 10 may be appropriately added with additives such as a flame retardant, an inorganic agent, a dry paper strength enhancer, a wet paper strength enhancer, a colorant, a sizing agent, and a fixing agent, if necessary. ..

The thickness of the paper base material 10 is not particularly limited, but in consideration of the durability and ease of handling of the decorative sheet, the basis weight is preferably in the range of ^{20 g / m 2} or more and 150 g / m ^{2 or less.} It is more preferably in the range of 25 g / m ² or more and 120 g / m ^{2 or less, further preferably in the range of 35 g / m 2} or more and 100 g / m ² or less, and in the range of 40 g / m ² or more and 60 g / m ² or less. Is even more preferable.

(Decorative layer 50)
The recoating decorative sheet 1 of the present embodiment preferably has a decorative layer 50 from the viewpoint of improving the design. The decorative layer 50 may be provided between the paper base material 10 and the non-woven fabric layer 30, and is preferably provided between the paper base material 10 and the adhesive layer 20.
The decorative layer 50 may be a layer composed of only the fully colored layer 51 provided so as to cover the entire surface thereof, or the pattern layer 52 provided so as to form a pattern so as to cover a part thereof. It may be a layer composed of only, or it may be a layer in which the entire surface coloring layer 51 and the pattern layer 52 are combined. These layer configurations may be determined according to the desired pattern.

The pattern imparted by the decorative layer 50 may be selected as desired without particular limitation, and imitates the surface of a rock such as a wood grain pattern, a marble pattern (for example, a travertin marble pattern), or a cliff surface of a granite plate. Stone pattern, cloth pattern imitating cloth grain or cloth-like pattern, leather (leather grain) pattern expressing leather grain, tiled pattern, brickwork pattern, hairline, perforated groove, satin finish, sand grain, letters , Symbols, geometric patterns, etc., and patterns such as parquet, patchwork, etc., which are a combination of these. Further, as a pattern in which these are combined, for example, an artificial stone in which crushed stone of a stone material such as marble is mixed with white cement, hardened, and polished to finish like marble, that is, a pattern like so-called artificial marble can be mentioned.
Although the demand for the design of the consumer changes depending on the fashion and the like, the wood grain pattern is preferable as the pattern of the decorative sheet 1 for recoating of the present embodiment because the popularity of the wood grain pattern is deep-rooted. The wood grain pattern includes a grain pattern, a plank pattern, a heather pattern, a wood grain pattern, and the like, but any of them may be used.

A resin composition containing at least a binder resin and a colorant such as a pigment and a dye is preferably used for forming the decorative layer 50, and other components used as desired, such as a matting agent and an extender pigment, are used. A stabilizer, a solvent, an ultraviolet absorber, a weathering agent such as a light stabilizer, and the like can be appropriately mixed. That is, the decorative layer 50 is a layer containing at least a binder resin and a colorant such as a pigment and a dye, and is a layer that can contain other components that can be used as desired and optionally.

The binder resin is not particularly limited, and for example, urethane resin, acrylic polyol resin, acrylic resin, polyester resin, alkyd resin, amide resin, butyral resin, styrene resin, urethane-acrylic copolymer, vinyl chloride-vinyl acetate common weight. Preferable examples thereof include a coalesced resin, a vinyl chloride-vinyl acetate-acrylic copolymer resin, a nitrocellulose resin (nitrated cotton), and a cellulose acetate resin. Further, for example, a curable resin such as a two-component curable resin using various polyols such as acrylic polyol as a main agent and various isocyanates as a curing agent may be used. These can be used alone or in combination of two or more.

Colorants include, for example, inorganic pigments such as titanium white, white lead, carbon black, iron black, yellow lead, titanium yellow, petals, cadmium red, ultramarine blue, cobalt blue; quinacridone red, isoindolinone yellow, nickel azo complex. , Organic pigments or dyes such as phthalocyanine blue; metal pigments composed of scaly foil pieces such as aluminum and brass; known as pearl luster (pearl) pigments composed of scaly foil pieces such as titanium dioxide-coated mica and basic lead carbonate. Can be appropriately selected and used.

Further, from the viewpoint of further improving the design, the decorative layer 50 preferably contains a matting agent among the above-mentioned other components used as desired.
Matters include inorganic fillers such as silica, clay, heavy calcium carbonate, light calcium carbonate, precipitated barium sulfate, calcium silicate, synthetic silicate, and fine powder of silicic acid; acrylic resin, urethane resin, nylon. Examples thereof include an organic filler such as a resin, a polypropylene resin, or a urea-based resin.

When the decorative layer 50 contains a matting agent, the decorative layer has a lower gloss, so that it is possible to express a design having a visual unevenness due to the difference in gloss.
For example, with respect to the wood grain pattern exemplified as a preferable pattern, the wood grain pattern has a lower gloss (matte or low gloss) conduit portion, a higher gloss (glossy or high gloss) spring wood portion, and a higher gloss autumn wood. There is a part (shining part) and the like. In the decorative layer 50, a plurality of pattern layers 52 such as a pattern layer forming a lower glossy conduit portion, a pattern layer forming a higher glossy spring lumber portion, and a pattern layer forming a higher gloss autumn lumber portion are provided. By combining them, it is possible to form a pattern with high design. Further, in this case, for example, by not including the matting agent in the entire colored layer 51 or by reducing the content thereof from the pattern layer 52, the gloss difference from the pattern layer 52 is further increased and the design is improved. It is also possible.

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, still more preferably 1 μm or more, and the upper limit is preferably 10 μm. Hereinafter, it is more preferably 9 μm or less, still more preferably 7.5 μm or less. When the decorative layer 50 is formed from two or more layers, the total thickness of each layer is preferably in the above range.

(Manufacturing method of decorative sheet for recoating)
Regarding the method for producing the recoating decorative sheet 1 of the present embodiment, the manufacturing method is described by taking as an example the recoating decorative sheet 1 shown in FIG. 2, which is one of the preferred embodiments of the recoating decorative sheet 1 of the present embodiment. explain.
In the recoating decorative sheet 1 of the present embodiment shown in FIG. 2, the step 1 of providing the decorative layer 50 on the paper base material 10, the step 2 of providing the adhesive layer 20 on the decorative layer 50, and the adhesive layer 20. Step 3 in which the non-woven fabric layer 30 and the filling portion A31 are provided on the non-woven fabric layer 30, and step 4 in which the resin composition forming the surface layer 40 is applied to the surface of the non-woven fabric layer 30 to form the filling portion B33 together with the surface layer 40. Can be manufactured via.

Step 1 is a layer for providing the decorative layer 50 on the paper base material 10.
The decorative layer 50 is preferably formed by forming the resin composition used for forming the decorative layer 50 by gravure printing, silk screen printing, gravure offset printing, flexographic printing, ink jet printing, or the like, and in the case of a large lot. It is more preferable to use gravure printing and ink jet printing in the case of small lots.

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

In this case, the coating amount (dry base) of the resin composition forming the adhesive layer 20 is from the viewpoint of obtaining excellent adhesiveness, and the filling portion A31, the filling portion B33 and the fiber portion 32 are formed in a well-balanced manner, and the sustainability and stability are improved. From the viewpoint of improving transparency, it is preferably 2 g / m ² or more, more preferably 5 g / m ² or more, further preferably 8 g / m ² or more, still more preferably 10 g / m ² or more, and the upper limit is preferably. It is 50 g / m ² or less, more preferably 45 g / m ² or less, still more preferably 40 g / m ² or less, still more preferably 30 g / m ² or less.

Step 3 is a step of providing the non-woven fabric layer 30 and the filling portion A31 on the adhesive layer 20.
The non-woven fabric layer 30 and the filling portion A31 form the non-woven fabric layer 30 by, for example, forming an adhesive layer 20 by applying a resin composition, arranging the non-woven fabric on the adhesive layer 20, and then dry laminating the non-woven fabric layer 30. The filling portion A31 is formed by filling a part of the voids of the non-woven fabric with the resin composition used for forming the adhesive layer.

In this case, the thickness of the adhesive layer forming resin is from the viewpoint of obtaining excellent adhesiveness between the paper base material 10 and the non-woven fabric layer 30, and the filling portion A31, the filling portion B33 and the fiber portion 32 are formed in a well-balanced manner, and the stability is assured. From the viewpoint of improving transparency, transparency, tactile sensation, etc., the thickness of the non-woven fabric layer 30 is preferably 10% or more, more preferably 12% or more, still more preferably 14% or more. The upper limit is preferably 25% or less, more preferably 23% or less, still more preferably 20% or less.

Step 4 is a step of applying the composition forming the surface layer 40 to the surface of the non-woven fabric layer 30 and forming the filling portion B33 together with the surface layer 40.
The composition forming the surface layer 40 may be applied by selecting any of the known methods exemplified as the method for applying the resin composition in the decorative layer 50. In forming the surface layer 40, the coating amount of the composition is determined mainly in consideration of the thickness of the surface layer 40 and the balance of the filling portion B33, the fiber portion 32 and the filling portion A31 in the non-woven fabric layer 30. ^{Usually, 2 g / m 2} or more is formed from the viewpoint of forming the filling portion A31, the filling portion B33 and the fiber portion 32 in a well-balanced manner to improve the surface characteristics as well as the sustainability, and further to improve the transparency and the tactile sensation. It is preferably 4 g / m ² or more, more preferably 6 g / m ² or more, and the upper limit is preferably 20 g / m ² or less, more preferably 15 g / m ² or less, still more preferably 12 g / m ² or less.

A preferred embodiment shown in FIG. 2 having a paper base material 10, a decorative layer 50, an adhesive layer 20, a non-woven fabric layer 30 (filling portion A31, fiber portion 32, filling portion B33) and a surface layer 40 in this order by the above steps. The recoating decorative sheet 1 having the above can be produced.

[How to color the decorative sheet]
The method for coloring the decorative sheet of the present embodiment is characterized in that a colored paint is applied to the surface layer side of the decorative sheet for recoating of the present embodiment to color the non-woven fabric layer. Examples of the coloring paint include stain paint (water-based or oil-based).
Since the decorative sheet 1 for recoating of the present embodiment has the non-woven fabric layer 30, it ensures the meat-forming property that the colored paint such as the water-based stain paint and the oil-based stain paint enters into the voids of the fibers. By applying the colored paint using the coloring method of the present embodiment, the colored paint is held on the fiber portion 32 of the non-woven fabric layer 30 together with the outermost surface of the decorative sheet for recoating, and the decorative sheet exhibiting the design by the colored paint can be obtained. can get.

Next, the present invention will be described in more detail by way of examples, but the present invention is not limited to this example.

(Evaluation method)
The decorative sheets obtained in each Example and Comparative Example were evaluated as follows.
<Evaluation of sustainability>
The decorative sheets obtained in each Example and Comparative Example were cut to a size of 200 mm × 300 mm, and an aqueous stain agent (“W stain (trade name)”, manufactured by Osaka Paint Industry Co., Ltd.) and an oil-based stain agent (“WOODFINISH”) were cut. (Product name) ”, manufactured by MINWAX Co., Ltd.) were uniformly applied and dried. After that, a cellophane adhesive tape with a width of 25 mm (“Cellophane Tape (registered trademark)”, manufactured by Nichiban Co., Ltd.) is attached to the stain part and then peeled off. It was evaluated. In this evaluation, the A evaluation is acceptable.
A: No peeling was confirmed for both aqueous stain and oil stain.
B: Peeling was confirmed for the aqueous stain.
C: Peeling was confirmed for both aqueous stain and oil stain.

<Evaluation of surface characteristics (water resistance)>
The decorative sheets obtained in each Example and Comparative Example were cut to a size of 100 mm × 100 mm, cotton wool soaked in water was placed on the surface of the sheet, and the cotton wool was arranged so as to be covered with a cap 24. I left it for a while. Then, the cap was removed, water was wiped off, and the appearance of the surface was visually evaluated according to the following criteria to evaluate the surface characteristics (water resistance). In this evaluation, the A evaluation is acceptable.
A: No change in appearance was confirmed.
B: Slight whitening was confirmed on the surface.
C: Significant whitening was confirmed on the surface.

(Example 1)
A printing paper (“HPT30 (product number)”, manufactured by Hokuetsu Kishu Paper Co., Ltd., thickness: 60 μm, basis weight: 45 g / m ² ) was prepared as a paper base material, and acrylic resin was used as a binder resin on the printed paper. A decorative layer having a wood grain pattern was formed by gravure printing using an ink containing a pigment (an ink containing an acrylic resin as a binder and carbon black as a pigment) (thickness: 2 to 6 μm). Next, a resin composition for forming an adhesive layer on the decorative layer (urethane resin, main agent: polyester polyol ("Seikabond E-295NTL-D50 (product name)", manufactured by Dainichiseika Kogyo Co., Ltd.), isocyanate curing agent ("Seikabond C-55 (product name)", manufactured by Dainichiseika Kogyo Co., Ltd.) was applied by gravure printing to provide an adhesive layer (thickness: 3 μm).
Separately, a non-woven fabric made of rayon fiber (“3016 (product number)”, manufactured by ^{Kinsei Seishi Co., Ltd., thickness: 80 μm, basis weight: 17 g / m 2} ) is prepared, and a paper base material on which the decorative layer and the adhesive layer are formed is formed. And the non-woven fabric were dry-laminated to obtain a laminate having a paper base material, a decorative layer, an adhesive layer, and a non-woven fabric layer composed of a filling portion A and a fiber portion.
Next, 100 g of acrylic polyol compound 1 (hydroxyl value: 41 mgKOH / g) and an isocyanate curing agent (hexamethylene diisocyanate, isocyanate group content: 19 mass) were added as a composition for forming a surface layer on the non-woven fabric layer side of the laminate. A composition containing 5 g of%) is applied at a coating amount of 12 g / m ² (dry base) to form a filling portion B and a surface layer, which is cured at 70 ° C. for 48 hours to form a paper substrate, a decorative layer, and an adhesive. A decorative sheet for recoating having a layer, a non-woven fabric layer composed of a filling portion A, a fiber portion and a filling portion B, and a surface layer was obtained.
Table 1 shows the results of evaluation of the obtained decorative sheet for recoating by the above method.

(Example 2)
In Example 1, with respect to the composition used for forming the surface layer, except that the acrylic polyol compound 1 was the acrylic polyol compound 2 (hydroxyl value: 24 mgKOH / g) and the amount of the isocyanate curing agent used was 5 g to 3 g. A decorative sheet for recoating was obtained in the same manner as in Example 1.
Table 1 shows the results of evaluation of the obtained decorative sheet for recoating by the above method.

(Comparative Examples 1 to 4)
In Example 1, the composition used for forming the surface layer was made up in the same manner as in Example 1 except that the amounts of the acrylic polyol compound 1 and the isocyanate curing agent used were changed as shown in Table 1. I got a sheet.
Table 1 shows the results of evaluation of the obtained decorative sheet by the above method.

From the results of the examples, it was confirmed that the decorative sheet for recoating of the present embodiment is excellent not only in sustainability but also in surface characteristics such as water resistance.
On the other hand, the decorative sheet of Comparative Example 1 was inferior in water resistance because the content of residual hydroxyl groups was high and the affinity of the surface layer with water was too high. The decorative sheet of Comparative Examples 2 and 3, low content of residual hydroxyl group, and because the decorative sheet of Comparative Example 3 is smaller than the molar ratio _{(C NCO /} C _OH) also 0.20, Suteinaburu properties, surface properties It was inferior in at least one of the respects.

Regarding the decorative sheet of Comparative Example 4, although the content of residual hydroxyl groups was appropriate, the molar ratio ( _CNCO / C _OH ) was smaller than 0.20, so that the surface characteristics (water resistance) were inferior. rice field.
These results, when both the content of the residual hydroxyl groups and the molar ratio _{(C NCO /} C _OH) is not satisfied, it was confirmed that not be both Suteinaburu and surface properties.

Since the decorative sheet for recoating of the present embodiment has excellent surface properties such as water resistance as well as sustainability, it is used for repainting with a colored paint such as stain paint, for example, for walls, ceilings, floors, etc. In addition to fittings and construction members for interior and exterior materials of buildings, window frames, doors, handrails, skirting boards, surrounding edges, moldings, etc., surface makeup of cabinets such as kitchen equipment, furniture or light electric appliances, OA equipment, etc. It is suitably used as a layer constituting a board, a member for interior or exterior of a vehicle.

1: Decorative sheet for recoating 10: Paper base material 20: Adhesive layer 30: Non-woven fabric layer 30a: Surface on which the adhesive layer of the non-woven fabric layer is provided 30b: Surface on which the surface layer of the non-woven fabric layer is provided 31: Filling portion A
32: Fiber part 33: Filling part B
40: Surface layer 50: Decorative layer 51: Fully colored layer 52: Pattern layer

Claims (9)

A paper base material, an adhesive layer, a non-woven fabric layer, and a surface layer composed of a cured product of a composition containing a polyol compound having a hydroxyl group in the molecule and an isocyanate curing agent are provided in this order.
The non-woven fabric layer is a filling portion A formed by filling a part of the voids of the fibers constituting the non-woven fabric layer with a resin forming the adhesive layer on the surface side of the layer in which the adhesive layer is provided in the thickness direction. And, on the surface side of the layer where the surface layer is provided in the thickness direction, a filling portion B formed by filling a part of the voids of the fibers constituting the non-woven fabric layer with the cured product is partially provided. death,
The content of residual hydroxyl groups contained in the surface layer is 0.25% by mass or more and 1.10% by mass or less.
The ratio ( _CNCO / C _OH ) of the isocyanate group amount _CNCO (mmol) in the isocyanate curing agent and the hydroxyl group amount C _OH (mmol) in the polyol compound is 0.20 or more.
Cosmetic sheet for recoating. The decorative sheet for recoating according to claim 1, wherein the fiber is at least one fiber selected from a thermoplastic resin fiber and a regenerated fiber. The decorative sheet for recoating according to claim 1 or 2, wherein the fiber is a cellulose resin fiber. The decorative sheet for recoating according to any one of claims 1 to 3, wherein the resin forming the adhesive layer is at least one resin selected from urethane resin and polyolefin resin. The decorative sheet for recoating according to any one of claims 1 to 4, wherein the polyol compound is at least one selected from an acrylic polyol, a polyester polyol, a polyether polyol, and a polycarbonate polyol. The decorative sheet for recoating according to any one of claims 1 to 5, wherein the isocyanate curing agent is a multivalent isocyanate compound. The decorative sheet for recoating according to any one of claims 1 to 6, further comprising a decorative layer between the paper base material and the adhesive layer. The decorative sheet for recoating according to claim 7, wherein the decorative layer exhibits a wood grain pattern. A method for coloring a decorative sheet, which comprises applying a coloring paint to the surface layer side of the decorative sheet for recoating according to any one of claims 1 to 8 to color the non-woven fabric layer.

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