JP2018187877A - Decorative sheet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a decorative sheet configured to be used for a fitting as a decorative laminate and capable of preventing a warp of the fitting caused by differences of temperature and humidity at a front and a back of the fitting, the decorative sheet having a stain resistance against oil stains conceivable in actual life.SOLUTION: A decorative sheet 10 includes, on a paper substrate 1, a printed pattern layer 3 and a top coat layer 4 in this order, with a barrier film 7 laminated on a rear face of the paper substrate. In the decorative sheet 10, oil-resistant paper is used for the paper substrate 1, and the top coat layer 4 composed of a curable transparent resin is disposed on the printed pattern layer 3. The barrier film 7 includes a plastic film 5 having an inorganic compound layer 6, and is bonded interposing the rear face of the paper substrate 1 and an adhesive agent 8. In the decorative sheet 10, the oil-resistant paper contains a fluorine-based oil resistant agent.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a decorative sheet. In particular, the present invention relates to a decorative sheet that is excellent in moisture resistance and oil resistance, and that is excellent in anti-contamination and moisture resistance against warpage when used in joinery and oily stains that can occur in daily life.

  The decorative sheet is subjected to printing using paper as a base material, and then resin processing or design expression is added to the surface according to the intended use, designability, and required quality. What is bonded to a wooden base material is also called a decorative board or a decorative plywood, and is widely used as an interior material for a house or a building, or as a surface material for furniture or fittings.

  In recent years, there has been a widespread demand not only for design and design expression, but also for improvements in functionality and environmental compatibility, and it is important to develop new applications and improve functionality of decorative sheets. It has become.

  For example, in fittings such as indoor doors, kitchen doors, storage doors, and baskets, warpage may occur due to differences in temperature and humidity between the front and back of the doors or indoors and outdoors. This is particularly due to the penetration of humidity into the wood base inside the joinery.

  In order to prevent this warpage, a metal support is inserted into the frame of the joinery to reinforce it, or sheets with a moisture barrier layer are pasted on the front and back surfaces of the decorative board to reduce the influence of humidity. At the same time, the stress may be balanced.

  As a matter of course, this method increases the weight of the joinery and requires a review of the manufacturing process and cost of the joinery.

  In addition, as the moisture-proof layer, a metal thin film or a metal oxide thin film may be used, and an aluminum vapor deposition film or an aluminum foil may be used. Further, a vapor deposition film of an inorganic compound can be formed on a plastic film and used.

  In a decorative sheet, after a pattern printing layer is provided using a paper base material such as an inter-paper reinforced paper as a base material, a resin coat layer is provided as a surface protective layer. If necessary, lamination with other films or paper materials is also performed.

  As the surface protective layer, for example, a polyol prepolymer such as polyester-based, acrylic-based, polyether-based, or partially saponified ethylene-vinyl acetate copolymer having a hydroxyl group and an isocyanate compound are mixed and cured by crosslinking. can do.

  This surface protective layer imparts stain resistance, scratch resistance, etc. to the decorative sheet, but it is not necessarily all-purpose, especially if there are cracks or pinholes or other small defects in the coating. Such dirt may penetrate into the paper base and create a stain.

  Patent Document 1 proposes an attempt to prevent warping of joinery using a decorative sheet having a surface protective layer and back moisture-proof paper using inter-paper reinforced paper, but preventing warpage of the joinery. Although a certain effect can be expected, the anti-fouling property against oily soil that may occur in daily life has not been considered.

  Further, Patent Document 2 proposes a decorative sheet in which a decorative sheet having a surface protective layer and a synthetic resin film having a moisture-proof layer containing an inorganic substance are laminated using an inter-paper reinforced paper. This was not a consideration of both the prevention of sledding and the contamination resistance against oily soil that could occur in daily life.

JP-A-9-174767 Japanese Patent Laid-Open No. 9-248882

  The present invention has been made in view of such a situation, and can be used as a decorative plate for a joinery, etc., and can prevent warpage of the joinery due to a difference in temperature and humidity between the front and back of the joinery and is considered in real life. It is an object of the present invention to provide a decorative sheet having stain resistance against oil and fat stains.

As means for solving the above problems, the invention according to claim 1
On the paper substrate, a printed pattern layer and a topcoat layer are provided in this order.
A decorative sheet with a barrier film laminated on the back side of the paper substrate,
Use oil-resistant paper for the paper substrate,
The top coat layer made of a curable transparent resin is provided on the printed pattern layer,
The barrier film comprises a plastic film having an inorganic compound layer,
A decorative sheet characterized in that it is bonded to the back surface of the paper base material via an adhesive.

The invention according to claim 2
2. The decorative sheet according to claim 1, wherein the oil resistant paper contains a fluorine-based oil resistant agent.

The invention according to claim 3
The fluorine-based oilproofing agent does not contain perfluorooctane sulfonic acid (PFOS) or perfluorooctanoic acid (PFOA),
The molecular weight of the fluororesin including the functional group is 3000 or more and 80000 or less,
And the carbon number in a fluorine site | part is less than eight, The decorative sheet of Claim 1 or Claim 2 characterized by the above-mentioned.

The invention according to claim 4
The makeup according to any one of claims 1 to 3, wherein the oil-resistant paper has a value measured by the JAPAN TAPPI paper pulp test method, N0.41: 2000, as oil resistance, of 2 or more. It is a sheet.

  ADVANTAGE OF THE INVENTION According to this invention, it can use for a joinery etc. as a decorative board, and can prevent the curvature of the joinery by the difference of the temperature of the front and back of the joinery, and humidity difference, and has the contamination | pollution resistance with respect to fat and oil stain considered in real life. It is possible to provide a decorative sheet.

In particular, according to the invention described in claim 2, it can be used as a decorative panel for a joinery, and can prevent warpage of the joinery due to a difference in temperature and humidity between the front and back of the joinery, and can be considered in real life. It is possible to provide a decorative sheet having more effective anti-staining properties against water.

  In particular, according to the invention described in claim 3, it can be used as a decorative board for a joinery, etc., and can prevent warpage of the joinery due to a difference in temperature and humidity between the front and back of the joinery, and can be considered in real life. It is possible to provide a decorative sheet having stain resistance by using a more environmentally-friendly material while suppressing permeation of the material.

  In particular, according to the invention described in claim 4, it can be used as a decorative plate for a joinery, and can prevent warpage of the joinery due to a difference in temperature and humidity between the front and back of the joinery, and can be considered in real life. It is possible to provide a decorative sheet in the form of a method capable of quantifying or impartially judging the stain resistance against the contamination.

FIG. 1 is a partial cross-sectional schematic view for explaining one embodiment of a decorative sheet according to the present invention. FIG. 2 is a partial cross-sectional schematic diagram for explaining the comparative example 1 among the examples. FIG. 3 is a partial schematic cross-sectional view for explaining the comparative example 2 among the examples.

  Hereinafter, the present invention will be described in more detail with reference to the drawings. However, the present invention is not limited to the examples shown here. The invention is limited only by the following claims.

  FIG. 1 is a partial cross-sectional schematic view for explaining one embodiment of a decorative sheet according to the present invention.

  A decorative sheet (10) according to the present invention comprises a paper base (1), a paper base (1), in addition to a decorative paper (20) provided with a printed pattern layer (9) and a topcoat layer (4) in this order. ) Has a barrier film (7). In the example shown here, the printed picture layer (9) is composed of a solid ink layer (2) and a picture ink layer (3).

  In the present invention, oil-resistant paper is used for the paper substrate (1). The top coat layer (4) made of a curable transparent resin is provided on the printed picture layer (9).

  Moreover, the plastic film (5) which has an inorganic compound layer (6), ie, the barrier film (7), is bonded to the back surface of the paper substrate (1) through the adhesive layer (8).

  Each material which comprises the decorative sheet (10) by this invention is demonstrated individually.

(Paper substrate)
As described above, in the present invention, oil-resistant paper is used for the paper substrate (1). By using oil-resistant paper, the oil resistance of the decorative sheet (10) can be improved, and even if the top coat layer (4) has minute defects such as cracks and pinholes, it is stained by oil and fat stains. It becomes possible to prevent the rest.

As the paper substrate (1), one having improved oil resistance by containing a fluorine-based oil resistant agent can be used. Furthermore, the fluorine-based oil proofing agent does not contain perfluorooctane sulfonic acid (PFOS) or perfluorooctanoic acid (PFOA), the molecular weight of the fluororesin including the functional group is 3000 or more and 80000 or less, and carbon in the fluorine site. When the number is less than 8, it is possible to eliminate the contamination of fat and oil stains and to have an environmentally compatible material configuration.

  In general, fluorine compounds exhibit excellent performance in heat resistance, chemical resistance, low friction, flame retardancy, water repellency and oil repellency. In the decorative sheet (10) of the present invention, the ability to prevent stain residue due to oil stains is derived from this water / oil repellency effect. On the other hand, since the fluorine compound is a very stable substance, it has been pointed out that the fluorine compound may be accumulated without being decomposed even when released into the natural world or may have an environmental impact.

  Specifically, it is a concern about the destruction of the ozone layer, a concern about global warming, a concern about the depletion of fluorine resources, and a concern about the persistence and accumulation in the body including human beings. The risk is not zero.

  As a result of intensive research and investigation, the fluorine compound contained in the oil-resistant paper does not contain perfluorooctane sulfonic acid (PFOS) or perfluorooctanoic acid (PFOA), and the molecular weight of the fluororesin including functional groups is It has been found that the risk of biological persistence is particularly low when it is 3000 or more and 80000 or less and the number of carbon atoms in the fluorine moiety is less than 8.

  Therefore, in the decorative sheet (10) according to the present invention, when the above-described fluorine compound is used, the decorative sheet (10) having stain resistance can be suppressed by suppressing permeation of oil and fat stains, which is considered in actual life. It can be provided using a more environmentally friendly material.

  Moreover, when the value measured by the JAPAN TAPPI paper pulp test method, N0.41: 20000 is 2 or more as a standard of oil resistance, it is possible to obtain a practical decorative paper (20) having more excellent oil resistance. It is.

(Print pattern layer)
The printed picture layer (9) consists of a solid ink layer (2) and a picture ink layer (3). The solid ink layer (2) serves to conceal the paper substrate (1) and expresses the color tone of the entire printed pattern layer (9).

  The pattern ink layer (3) is configured by using a plurality of plates in addition to a single color, and can express a more complicated pattern of the decorative paper (20) such as a wood grain pattern or an abstract pattern.

  As the printing method, an existing printing method may be used. For example, a gravure printing method, an offset printing method, a flexographic printing method, a silk screen printing method, an ink jet printing method, or the like can be selected as appropriate. In particular, the gravure printing method is more suitable in terms of printing definition and productivity.

  The ink used for the printed pattern layer (9) is not particularly limited, and can be appropriately selected in consideration of adhesion to a paper substrate, color tone, light resistance, and the like.

  For example, nitrified cotton-based ink can be used for the solid ink layer (2) and the pattern ink layer (3). In particular, the solid ink layer (2) has a role of hiding the paper substrate (1). An opaque layer containing titanium dioxide in the pigment is preferable.

(Topcoat layer)
In the present invention, the top coat layer (4) made of a curable transparent resin is provided on the printed pattern layer (9). The topcoat layer (4) can improve the scratch resistance and antifouling property of the decorative sheet surface and is effective as a surface protective layer.

  The resin system of the topcoat layer (4) may be appropriately selected from curable transparent resins. For example, a urethane resin made of acrylic polyol can be used. Further, for the purpose of improving the designability, it is also possible to provide a gloss matte effect by providing a difference in gloss partially using repelling ink or the like.

(Barrier film)
The barrier film (7) includes an inorganic compound layer (6) and a plastic film (5). An anchor coat can be provided for the purpose of further strengthening the adhesion between the inorganic compound layer (6) and the plastic film (5).

When the decorative sheet (10) according to the present invention is used as a decorative sheet for a joinery, the barrier film (7) can eliminate the temperature difference between the front and back of the joinery, the difference in humidity, particularly the influence of the humidity on the wooden substrate, The plastic film (5) which can prevent warping of joinery is a film made of a polymer resin composition, for example, polyolefin (polyethylene, polypropylene, etc.), polyester (polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, etc.) Polyamide (Nylon-6, Nylon-66, etc.), polyimide, and the like can be used and are appropriately selected depending on the application. In particular, when polypropylene or polyethylene terephthalate is used as a base film, it is more preferable in terms of film strength and price.

  In addition to the vapor deposition layer of an inorganic compound, the inorganic compound layer (6) can be formed by overlapping a coating layer. After the anchor coat is provided on the plastic film (5), the vapor deposition layer and the coating layer are sequentially provided. .

  For the anchor coat layer of the barrier film (7), for example, urethane acrylate can be used. For the formation of the anchor coat layer, a coating method using a printing technique such as gravure coating with a paint in which a resin is dissolved in a solvent can be used, and a coating film can be formed using a generally known coating method.

  As a method of forming the inorganic compound layer (6), an inorganic compound such as SiO or AlO is coated on a base film provided with an anchor coat layer using a vacuum deposition method, and an inorganic compound layer is formed by a vacuum deposition method. Can be formed. The thickness of the vapor deposition layer is preferably 15 nm to 30 nm.

  Further, as a method for forming the coating layer, an aqueous solution containing at least one of water-soluble polymer, (a) one or more alkoxides or hydrolysates thereof, or (b) tin chloride, or water / A coating agent mainly composed of an alcohol-mixed aqueous solution can be applied on a film and dried by heating to form an inorganic compound layer by a coating method to form a coating layer. At this time, the adhesion with the anchor coat layer can be improved by adding a silane monomer to the coating agent.

  An inorganic compound layer has a barrier property only by a coating film formed by a vacuum deposition method, but a coating layer, which is an inorganic compound layer formed by a coating method, is formed so as to overlap with a deposited layer that is an inorganic compound layer formed by a vacuum deposition method. be able to.

By combining these two layers, a reaction layer of both layers is formed at the interface between the inorganic compound layer by the vacuum deposition method and the inorganic compound layer by the coating method, or the inorganic compound layer by the coating method becomes an inorganic compound layer by the vacuum deposition method. A dense structure is formed by filling and reinforcing defects such as pinholes, cracks, and grain boundaries, or by reinforcing them, so that high gas barrier properties, moisture resistance, and water resistance are achieved, and flexibility that can withstand deformation is achieved. Since it has the property, it can also have the suitability for lamination to base materials, such as joinery.

(Adhesive layer)
The adhesive layer (8) laminates and bonds the decorative paper (2) and the barrier film (7). Lamination and adhesion can be performed using dry lamination. For example, a polyester-based dry lamination adhesive can be used.
As described above, according to the present invention, it is possible to prevent the warpage of the joinery due to the difference in temperature and humidity between the front and back surfaces of the joinery by using it as a decorative board for the joinery and the like, and the resistance to oil and dirt that can be considered in real life. It is possible to provide a decorative sheet having contamination.

  Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to the examples shown here. The invention is limited only by the claims.

  The decorative sheet of the material structure shown in the following Example 1, Comparative Example 1, and Comparative Example 2 was created, and evaluation was carried out by setting evaluation items.

<Example 1>
The description of the first embodiment is based on FIG.
The material structure of the decorative sheet (10) is as follows.
Paper base material (1): Oil-resistant paper containing a fluorine-based oil-proofing agent was used. (Basis weight 30g / m ² )
Solid ink layer (2): Nitrified cotton-based ink containing 70% titanium dioxide was applied by a gravure printing method.
Pattern ink layer (3): The pattern ink was printed with a gravure printing method using nitrified cotton-based ink.
Topcoat layer (4): A urethane resin made of acrylic polyol was used. (Application amount 7 g / m ² ). In addition, the surface has a gloss mat pattern.
Inorganic compound layer (6): An inorganic compound layer was formed on a plastic film by using a vacuum vapor deposition method using SiO as an inorganic compound.
Plastic film (5): A polyethylene terephthalate film (thickness: 12 μm) was used.
Adhesive layer (8): The back surface of the paper substrate (1) and the inorganic compound layer (6) side of the barrier film (7) were laminated and bonded via the adhesive layer (8). A polyester dry lamination adhesive (amount applied: 3 g / m ² ) was used.

<Comparative Example 1>
The description of Comparative Example 1 is based on FIG.
The material structure of the decorative sheet (30) is as follows.
Paper base material (11): An inter-paper reinforcing paper was used. (Basis weight 30g / m ² )
The material configuration other than the paper substrate (11) is the same as that of Example 1.

<Comparative Example 2>
The description of Comparative Example 2 is based on FIG.
The material structure of the decorative sheet (40) is as follows.
Paper base material (1): Oil-resistant paper containing a fluorine-based oil-proofing agent was used. (Basis weight 30 g / m ² ). That is, the material configuration of the decorative paper portion is the same as that of the first embodiment.

A low-density polyethylene layer was formed as a moisture-proof layer (12) between the non-printed side of the paper substrate (1) and the inter-paper reinforced paper (13), and was laminated and adhered.
That is, Comparative Example 2 has a configuration in which no barrier film is used.

The evaluation items are as follows.
(Moisture permeability): According to JIS Z 0208.
(Oil resistance): JAPAN TAPPI paper pulp test method No. 41: 2000.
(Salad oil dripping test): 1 ml of salad oil dyed with sudan black (C ₂₉ H ₂₄ N ₆ ) is dropped on the surface of the decorative sheet, covered with a watch glass for 8 hours, left to dry, and then the salad oil is wiped off. Observe the presence or absence of.
(Hand cream evaluation test): Hand cream (Nivea cream) (registered trademark) is dropped on the surface of the decorative sheet, covered with a watch glass for 8 hours, and then left to wipe off the hand cream and observe the presence or absence of soaking. .

  The evaluation results are shown in Table 1.

  As is clear from the results shown in Table 1, it was verified that Example 1 which is a decorative sheet according to the present invention has low moisture permeability and is excellent in oil resistance, salad oil dripping and hand cream evaluation. .

  As for moisture permeability, Comparative Example 1 using a barrier film similar to Example 1 is similarly low and Comparative Example 2 is high, so that a barrier film having an inorganic compound layer is extremely effective. When the decorative sheet according to the invention is used for a joinery or the like, it can be seen that warpage of the joinery due to a difference in temperature and humidity between the front and back of the joinery can be prevented.

  Comparative Example 2 similar to Example 1 is superior in stain resistance against oil stains, which is considered to be the effect of using oil-resistant paper containing a fluorine-based oil-resistant agent in the paper substrate.

  It can be seen that the decorative sheet according to the present invention greatly improves the moisture resistance by the barrier film, and improves the oil stain resistance against oil stains by the oil resistant paper, realizing both of them.

  As described above, according to the present invention, it is possible to prevent the warpage of the joinery due to the difference in temperature and humidity between the front and back surfaces of the joinery, and to prevent contamination of oil stains, which are considered in real life, by using as a decorative plate for the joinery and the like. It is possible to provide a decorative sheet having properties.

DESCRIPTION OF SYMBOLS 1 ... Paper base material 2 ... Solid ink layer 3 ... Pattern ink layer 4 ... Topcoat layer 5 ... Plastic film layer 6 ... Inorganic compound layer 7 ... Barrier film 8 ... -Adhesive layer 9 ... Print pattern layer 10 ... Cosmetic sheet 11 ... Paper base material 12 ... Moisture-proof layer 13 ... Inter-paper reinforcing paper 20 ... Cosmetic paper 30 ... Cosmetic sheet 40 ... Cosmetic sheet

Claims (4)

On the paper base material, a printed pattern layer, a top coat layer is provided in this order, and the back surface of the paper base material is a decorative sheet in which a barrier film is laminated,
Use oil-resistant paper for the paper substrate,
The top coat layer made of a curable transparent resin is provided on the printed pattern layer,
The barrier film comprises a plastic film having an inorganic compound layer,
A decorative sheet, which is bonded to the back surface of the paper substrate via an adhesive.   The decorative sheet according to claim 1, wherein the oil resistant paper contains a fluorine-based oil resistant agent. The fluorine-based oilproofing agent is
Does not contain perfluorooctane sulfonic acid (PFOS) or perfluorooctanoic acid (PFOA)
The molecular weight of the fluororesin including the functional group is 3000 or more and 80000 or less,
And the number of carbon atoms in the fluorine site is less than 8,
The decorative sheet according to claim 1 or 2. The oil resistant paper is
A value measured by JAPAN TAPPI paper pulp test method, N0.41: 2000 as oil resistance is 2 or more,
The decorative sheet according to any one of claims 1 to 3.