JP2020163586A - Decorative sheet - Google Patents

Abstract

To provide a decorative sheet which is used in a fitting as a decorative plate and can prevent warpage of a fitting due to a difference in temperatures and humidities of a surface and a rear face of the fitting, and has stain resistance against greasy stains that are considered in actual line.SOLUTION: A decorative sheet 10 has a printing pattern layer 9 and a top coat layer 4 provided in this order on one surface of a sheet base material 1, and has a barrier film 7 layered on the other surface of the sheet base material 1, an oil-resistant sheet is used in the sheet base material 1, the top coat layer 4 containing a curable transparent resin is provided on the printing pattern layer 9, the barrier film 7 includes a plastic film 5 having an inorganic compound layer, the sheet base material 1 and the barrier film 7 are stuck to each other through an adhesive layer 8, and the oil-resistant sheet contains a thermoplastic resin, an inorganic material and a fluorine-based oil-resistant agent.SELECTED DRAWING: Figure 1

Description

The present invention relates to a decorative sheet.

After printing on the decorative sheet using paper as a base material, resin processing and design expression are added to the surface according to the intended use, design, and required quality. Those bonded to a wooden base material are also called decorative boards and decorative plywood, and are widely used as interior materials for houses and buildings, and as surface materials for furniture and fittings.
In recent years, there have been increasing demands from various fields for improving functionality and environmental compatibility, not just for design and design expression, and it is an important issue to develop new applications and improve functionality of cosmetic sheets. It has become.

For example, in fittings such as interior doors, kitchen doors, storage doors, and sliding doors, warpage may occur due to differences in temperature and humidity between the front and back of the doors or the indoor and outdoor areas. This is especially due to the penetration of humidity into the wood substrate inside the fittings.
In order to prevent this warpage, a metal support is put in the frame of the fitting to reinforce it, or a sheet with a moisture-proof layer is attached to 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 mass of the fittings, and also requires a review of the manufacturing process and costs of the fittings.
Further, as the moisture-proof layer, a metal thin film or a metal oxide thin film may be used, and an aluminum vapor-deposited film or an aluminum foil may be used. Further, a vapor-deposited film of an inorganic compound can be formed on a plastic film and used.
As the base material of the decorative sheet, a paper base material such as inter-paper reinforced paper is used to provide a pattern printing layer, and then a resin coat layer is provided to serve as a surface protective layer. If necessary, it is also laminated with other films or paper materials.

As the surface protective layer, for example, a polyol prepolymer such as a polyester-based, acrylic-based, polyether-based, or partially saponified ethylene-vinyl acetate copolymer having a hydroxyl group and an isocyanate compound are mixed and cross-cured before use. can do.
This surface protective layer imparts stain resistance and scratch resistance to the decorative sheet, but it is not always universal, and it is oil-based, especially when there are minute defects in the coating film such as cracks and pinholes. There is a risk that stains on the paper will penetrate into the paper substrate and create stains.

Patent Document 1 proposes an attempt to prevent warpage of fittings by using a decorative sheet having a front surface protective layer and a back surface moisture-proof paper using inter-paper reinforced paper, but prevention of warpage of fittings. Although a certain effect can be expected, the stain resistance to oily stains that may occur in daily life was not taken into consideration.
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 inter-paper reinforced paper. It did not take into consideration both the prevention of warpage and the stain resistance against oily stains that may occur in daily life.

JP-A-9-174767A JP-A-9-248882

The present invention has been made in view of such a situation, and can be used as a decorative board for fittings and the like to prevent the fittings from warping due to the difference in temperature and humidity between the front and back of the fittings, and also to be considered in real life. It is intended to provide a decorative sheet having stain resistance to greasy stains.

The decorative sheet according to one aspect of the present invention is a decorative sheet in which a printed pattern layer and a top coat layer are provided in this order on one surface of a sheet base material, and a barrier film is laminated on the other surface of the sheet base material. An oil-resistant sheet is used as the sheet base material, the top coat layer containing a curable transparent resin is provided on the printed pattern layer, and the barrier film is a plastic film having an inorganic compound layer. The sheet base material and the barrier film are bonded to each other via an adhesive layer, and the oil-resistant sheet contains a thermoplastic resin, an inorganic material, and a fluorine-based oil-resistant agent.

According to one aspect of the present invention, it can be used as a decorative board for fittings and the like to prevent the fittings from warping due to the difference in temperature and humidity between the front and back of the fittings, and also to withstand contamination against oil and fat stains, which is considered in real life. It is possible to provide a decorative sheet having sex.

It is a partial cross-sectional schematic diagram for demonstrating an example of the decorative sheet which concerns on embodiment of this invention. It is a partial cross-sectional schematic diagram for demonstrating Comparative Example 1 among the Examples of this invention. It is a partial cross-sectional schematic diagram for demonstrating Comparative Example 2 among the Examples of this invention.

Hereinafter, a more detailed description will be added with reference to the drawings of the configuration of the decorative sheet according to the embodiment of the present invention.
Here, the drawings are schematic, and the relationship between the thickness and the plane dimension, the ratio of the thickness of each layer, and the like are different from the actual ones. Further, the embodiments shown below exemplify a configuration for embodying the technical idea of the present invention, and the technical idea of the present invention describes the materials, shapes, structures, etc. of the constituent parts as follows. It is not something that is specific to something. The technical idea of the present invention may be modified in various ways within the technical scope specified by the claims stated in the claims.

The content of various materials described later means the content ratio (mass%) with respect to the mass of the entire corresponding member in the dry state. For example, the content of the inorganic material of the present embodiment, which will be described later, means the content ratio (mass%) with respect to the total mass of the oil resistant sheet 1 in the dry state. Further, the content of the urethane resin containing vinyl acetate or the acrylic resin containing vinyl acetate in the surface anchor layer (first anchor layer) 14a described later is the mass of the entire surface anchor layer 14a in a dry state. It means the content ratio (mass%) with respect to. Further, the content of the urethane resin containing salt and vinegar or the acrylic resin containing salt and vinegar in the back surface anchor layer (second anchor layer) 14b, which will be described later, is the mass of the entire back surface anchor layer 14b in a dry state. It means the content ratio (mass%) with respect to.

FIG. 1 is a schematic partial cross-sectional view for explaining an example of a decorative sheet according to an embodiment of the present invention.
The decorative sheet 10 of the present embodiment has a decorative paper 20 provided with a printed pattern layer 9 and a top coat layer 4 in this order on one surface (surface) of the sheet base material 1, and the other surface (surface) of the sheet base material 1. The back surface) has a barrier film 7. Further, in the example shown here, the printed pattern layer 9 is a layer including the solid ink layer 2 and the pattern ink layer 3.
In the present embodiment, an oil resistant sheet is used as the sheet base material 1. Further, a top coat layer 4 containing a curable transparent resin is provided on the printed pattern layer 9.
Further, a plastic film 5 having an inorganic compound layer 6, that is, a barrier film 7, is attached to the back surface of the sheet base material 1 via an adhesive layer 8.
Each material constituting the decorative sheet 10 according to the present embodiment will be individually described.

(Sheet base material)
As described above, in the present embodiment, an oil resistant sheet is used as the sheet base material 1. By using the oil resistant sheet, 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, stain residue due to oil stains can be prevented. Will be possible.
As the sheet base material 1, an oil-resistant sheet having improved oil resistance by containing a thermoplastic resin, an inorganic material, and a fluorine-based oil-resistant agent can be used.
The fluorine-based oil resistant agent does not contain both perfluorooctanesulfonic acid (PFOS) and perfluorooctanoic acid (PFOA), and the molecular weight of the fluororesin including the functional group is in the range of 3000 or more and 80,000 or less, and at the fluorine moiety. When the number of carbon atoms is less than 8, it is possible to eliminate the infiltration of oil and fat stains and to obtain an environment-friendly material composition.

In general, fluorine compounds exhibit excellent performance in heat resistance, chemical resistance, low friction resistance, flame retardancy, water repellency and oil repellency. In the decorative sheet 10 of the present embodiment, the ability to prevent stain residue due to oil stains is derived from this water-repellent / oil-repellent effect. On the other hand, since fluorine compounds are extremely stable substances, it has been pointed out that they may accumulate or have an environmental impact without being decomposed even when they are released into the natural world.
Specifically, it is a concern about ozone layer depletion, a concern about global warming, a concern about depletion of fluorine resources, and a concern about residual and accumulation in the living body including human beings, which are still unknown. The risk cannot be said to be zero.

As a result of diligent studies and investigations, the fluorine compound contained in the oil resistant sheet does not contain both perfluorooctanesulfonic acid (PFOS) and perfluorooctanoic acid (PFOA), and the molecular weight of the fluororesin including the functional group. It was found that the risk of biopersistence is particularly low when the number of carbon atoms is in the range of 3000 or more and 80,000 or less and the number of carbon atoms in the fluorine moiety is less than 8.
Examples of the fluorine compound include perfluoroheptane sulfonic acid (PFHpS), perfluorononane sulfonic acid (PFNS), perfluorodecane sulfonic acid (PFDS), perfluoroheptanic acid (PFHpA), perfluorononanoic acid (PFNA), and perfluorodecanoic acid (PFNA). PFDA), perfluoroundecanoic acid (PFUnDA), perfluorododecanoic acid (PFDoDA), perfluorotridecanoic acid (PFTrDA), perfluorotetradecanoic acid (PFTeDA) and the like.

Therefore, when the above-mentioned fluorine compound is used in the decorative sheet 10 according to the present embodiment, the decorative sheet 10 having stain resistance by suppressing the penetration into oil and fat stains, which is considered in real life, is more environmentally friendly. It is possible to provide using the material of the mold.
Further, when the value measured by the JAPAN TAPPI pulp and paper test method, N0.41: 20000 as a standard of oil resistance is 2 or more, it is possible to obtain a practical decorative paper 20 having more excellent oil resistance.

The sheet base material 1 in the present embodiment has an inorganic material content in the range of 15% by mass or more and 90% by mass or less with respect to the mass of the sheet base material 1, and the content of the fluorine-based oil resistant agent is the sheet base. The material used is in the range of more than 0% by mass and 10% by mass or less with respect to the mass of the material 1.
The content of the inorganic material of the present embodiment may be in the range of 15% by mass or more and 90% by mass or less, and in the range of 20% by mass or more and 80% by mass or less with respect to the mass of the sheet base material 1. More preferably, it is more preferable if it is in the range of 60% by mass or more and 80% by mass or less. If the content of the inorganic material is less than 15% by mass with respect to the mass of the sheet base material 1, the proportion of the thermoplastic resin is relatively large, so that it tends to be difficult to obtain sufficient mechanical strength to withstand use. is there. Further, when the surface of the sheet base material 1 is scratched with a Hoffman scratch tester, it may be scratched to the extent that it can be visually recognized, that is, sufficient surface hardness may not be obtained. On the other hand, when the content of the inorganic material exceeds 90% by mass with respect to the mass of the sheet base material 1, the proportion of the thermoplastic resin becomes relatively small. Therefore, when the surface of the sheet base material 1 is coated with an anchor layer described later, so-called "powder blowing" may occur on the surface of the sheet base material 1. Here, "powder blowing" means that the inorganic material contained in the sheet base material 1 emerges on the surface of the sheet base material 1. Further, when the content of the inorganic material exceeds 90% by mass with respect to the mass of the sheet base material 1, when the sheet base material 1 is bent and reopened, cracks occur from the bent portion or the inorganic material becomes It may fall.

As described above, the content of the inorganic material of the present embodiment is 15% by mass or more and 90% by mass or less, preferably 20% by mass or more and 80% by mass or less, and more preferably 60% by mass with respect to the mass of the sheet base material 1. Within the range of 80% by mass or more, the occurrence of powder blowing can be reduced, the occurrence of cracks at the bent portion of the sheet can be reduced, and a sufficient surface hardness can be obtained.
Further, if the content of the fluorine-based oil resistant agent is within the range of more than 0% by mass and 10% by mass or less with respect to the mass of the sheet base material 1, sufficient oil resistance can be surely obtained.

Further, the inorganic material of the present embodiment is preferably in a powder shape (powder shape), and its average particle diameter is preferably in the range of 1 μm or more and 3 μm or less, and the maximum particle diameter is preferably 50 μm or less. .. When the average particle size and the maximum particle size of the inorganic material are within the above numerical ranges, the flatness of the surface of the sheet base material 1 can be maintained while improving the dispersibility of the inorganic material with respect to the thermoplastic resin. If the average particle size of the inorganic material is less than 1 μm, the cohesive force between the inorganic materials may increase, and the dispersibility in the thermoplastic resin described later may decrease. Further, when the average particle size of the inorganic material exceeds 3 μm, the flatness of the surface of the sheet base material 1 is lowered, and the thickness of the front surface anchor layer 14a or the back surface anchor layer 14b, which will be described later, becomes uneven, or unevenness or chipping occurs. It may occur. Further, when the maximum particle size of the inorganic material exceeds 50 μm, the flatness of the surface of the sheet base material 1 is lowered, and the thickness of the front surface anchor layer 14a or the back surface anchor layer 14b, which will be described later, becomes uneven, or unevenness or chipping occurs. It may occur. In this embodiment, the "average particle size" means the mode diameter. The particles having the maximum particle diameter are preferably in the range of 5% by mass or more and 30% by mass or less of the entire inorganic material.

The inorganic material is, for example, a powder containing at least one of calcium carbonate and calcium carbonate salt. The powder containing at least one of calcium carbonate and calcium carbonate salt is preferably contained in the range of 50% by mass or more and 100% by mass or less. That is, the purity of the powder containing at least one of calcium carbonate and calcium carbonate salt is preferably in the range of 50% by mass or more and 100% by mass or less of calcium carbonate or the like. A powder containing at least one of calcium carbonate and a calcium carbonate salt containing 50% by mass or more of calcium carbonate or the like can impart sufficient mechanical strength to the sheet base material 1.

As the inorganic material, in addition to the powder containing at least one of the calcium carbonate and the calcium carbonate salt, for example, zirconium such as silica (particularly hollow silica), alumina, antimony trioxide, antimony soda, zircon silicate, and zircon oxide. Antimony trioxide and silica complex, antimony trioxide, such as compounds, magnesium hydroxide, aluminum hydroxide, basic magnesium carbonate, borosand, zinc borate, molybdenum trioxide or antimony dimolybate and aluminum hydroxide At least one such as a complex of aluminum hydroxide with zinc hydroxide, silicic acid of aluminum hydroxide, a complex of a zirconium compound with antimony trioxide, and salts thereof. In particular, calcium carbonate and calcium carbonate salt are easy to control the particle size and compatibility with the thermoplastic resin by the manufacturing method, and the material cost is low, so from the viewpoint of reducing the cost of the sheet base material. Is also suitable.

Further, the inorganic material may be a powder material having crystallinity, so-called crystalline powder, or a powder material having no crystallinity, so-called amorphous type powder material. If the inorganic material is a crystalline powder material, the powder itself is homogeneous and hasotropic, so that the mechanical strength of the powder itself is improved, and the scratch resistance and durability of the sheet base material 1 tend to be improved. .. Further, if the inorganic material is an amorphous type powder material, the electrical conductivity and thermal conductivity of the powder itself, or the light transmittance and light absorption rate can be appropriately adjusted, so that there are variations in tactile sensation and luster. It is possible to give abundant design.

The thermoplastic resin of the present embodiment preferably contains at least one of polypropylene, polyethylene and polyester, and more preferably polypropylene. By using at least one of polypropylene, polyethylene and polyester as the thermoplastic resin, the dispersibility of the inorganic material is improved. Further, by using polypropylene as the thermoplastic resin, the dispersibility of the inorganic material is further improved.
Further, the total content of the thermoplastic resin and the inorganic material is preferably in the range of 90% by mass or more and 95% by mass or less with respect to the mass of the sheet base material 1. When the total content of the thermoplastic resin and the inorganic material is within the above numerical range, cracks generated in the bent portion of the sheet can be reduced. If the total content of the thermoplastic resin and the inorganic material is less than 90% by mass with respect to the mass of the sheet base material 1, cracks may occur in the bent portion of the sheet.

When the total content of the thermoplastic resin and the inorganic material is 95% by mass with respect to the mass of the sheet base material 1, the content of the thermoplastic resin is 10% by mass or more and 80% by mass or less. It is preferably within the range, and the content of the inorganic material is preferably within the range of 15% by mass or more and 85% by mass or less. Further, it is more preferable that the content of the thermoplastic resin is in the range of 20% by mass or more and 75% by mass or less, and the content of the inorganic material is in the range of 20% by mass or more and 75% by mass or less. Further, it is more preferable that the content of the thermoplastic resin is in the range of 20% by mass or more and 35% by mass or less, and the content of the inorganic material is in the range of 60% by mass or more and 75% by mass or less. When the total content of the thermoplastic resin and the inorganic material is within the above numerical range, cracks generated in the bent portion of the sheet can be reliably reduced.

The thickness of the sheet base material 1 may be in the range of 50 μm or more and 1000 μm or less, preferably in the range of 50 μm or more and 250 μm or less, and more preferably in the range of 70 μm or more and 200 μm or less. When the thickness of the sheet base material 1 is within the above numerical range, cracks generated in the bent portion of the sheet can be reduced. If the thickness of the sheet base material 1 is less than 50 μm, it tends to be difficult to obtain sufficient mechanical strength that can withstand use. Further, if the thickness of the sheet base material 1 exceeds 250 μm, cracks may occur in the bent portion of the sheet.
Further, the sheet base material 1 is preferably a uniaxially stretched or biaxially stretched sheet base material. If the sheet base material 1 is a uniaxially stretched or biaxially stretched sheet base material, the versatility of the sheet base material 1 can be enhanced.

On at least one of the front surface (first surface) and the back surface (second surface) of the sheet base material 1, for example, the front surface anchor layer (first anchor layer) 14a and the back surface anchor layer (second anchor layer) described later ) It is preferable to perform surface treatment such as corona treatment and plasma treatment before forming 14b. Here, the "surface (first surface) of the sheet base material 1" means the surface on the side of the printed pattern layer 9. Here, the "back surface (second surface) of the sheet base material 1" means a surface opposite to the printed pattern layer 9, that is, a surface on the barrier film 7 side. Further, by applying surface treatment such as corona treatment or plasma treatment to at least one of the front surface and the back surface of the sheet base material 1, the front surface anchor layer 14a and the sheet base material 1 and the back surface anchor layer 14b and the sheet base material 1 are adhered to each other. The properties (adhesion) are improved respectively.
Further, before forming the front surface anchor layer 14a and the back surface anchor layer 14b, for example, at least one of the front surface and the back surface of the sheet base material 1 is brushed and powder-blown inorganic material, for example, at least calcium carbonate and calcium carbonate salt. The powder containing one of them may be dropped in advance.

(Surface anchor layer 14a)
The surface anchor layer 14a is a layer formed so as to cover the entire surface of the sheet base material 1, and is a layer for preventing powder falling off of the inorganic material contained in the sheet base material 1. When the printed pattern layer 9 is printed on the sheet base material 1, if the inorganic material contained in the sheet base material 1 falls off in the printing system, specifically, in the printing apparatus, the inside of the printing system may be contaminated. ..
The surface anchor layer 14a preferably contains a urethane-based resin containing vinyl acetate or an acrylic resin containing vinyl acetate. Here, "salt vinegar bi" means a copolymer of vinyl chloride and vinyl acetate. The "urethane resin containing salt vinegar" is a composition containing salt vinegar and urethane resin, and the ratio of the content of salt vinegar to the content of urethane resin (salt vinegar). The bi content (mass) / urethane resin content (mass)) may be in the range of 80/20 to 1/99, preferably in the range of 50/50 to 5/95, 20 It is more preferable if it is in the range of / 80 to 10/90.

Further, the "urethane-based resin containing vinyl acetate" may contain a curing agent in addition to the above-mentioned vinyl acetate and urethane-based resin. This curing agent is added to reliably cure the urethane-based resin containing vinyl acetate, and the content thereof is not particularly limited. For example, the ratio of the content of the urethane resin containing vinyl acetate to the content of the curing agent (content of urethane resin containing vinyl acetate (mass) / content of curing agent (mass)) is 99. It may be in the range of / 1 to 1/99, preferably in the range of 99/1 to 50/50, and more preferably in the range of 95/5 to 90/10.

The content of the urethane resin containing salt and vinegar or the acrylic resin containing salt and vinegar in the surface anchor layer 14a is in the range of 15% by mass or more and 100% by mass or less with respect to the mass of the surface anchor layer 14a. It is more preferably in the range of 80% by mass or more and 100% by mass or less, and further preferably in the range of 85% by mass or more and 95% by mass or less. When the content of the urethane resin containing salt and vinegar or the acrylic resin containing salt and vinegar in the surface anchor layer 14a is within the above numerical range, the interlayer strength between the surface anchor layer 14a and the sheet base material 1 is increased. It is possible to form a uniform surface anchor layer 14a without unevenness or chipping while making the surface anchor layer sufficient. When the content of the urethane resin containing vinyl acetate or the acrylic resin containing vinyl acetate in the surface anchor layer 14a is less than 15% by mass with respect to the mass of the surface anchor layer 14a, the surface anchor layer 14a and The interlayer strength with the sheet base material 1 may be insufficient. Further, if the content of the urethane resin containing salt and vinegar or the acrylic resin containing salt and vinegar in the surface anchor layer 14a is less than 80% by mass with respect to the mass of the surface anchor layer 14a, there is no problem in use. Although there is no problem, the ratio of the surface anchor layer 14a to the sheet base material 1 is lowered, and the interlayer strength between the surface anchor layer 14a and the sheet base material 1 is slightly lowered. If the content of the urethane resin containing salt and vinegar or the acrylic resin containing salt and vinegar in the surface anchor layer 14a is 100% by mass or less with respect to the mass of the surface anchor layer 14a, there is no problem in use. However, if it exceeds 95% by mass, or more accurately 98% by mass, the surface anchor layer 14a may be chipped due to insufficient curing, or the interlayer strength between the surface anchor layer 14a and the sheet base material 1 may decrease. Sometimes.

The content of the urethane resin containing vinyl acetate or the acrylic resin containing vinyl acetate in the front surface anchor layer 14a is the urethane resin containing vinyl acetate or the vinyl acetate in the back surface anchor layer 14b, which will be described later. It may be the same as the content of the acrylic resin containing. That is, the content of the urethane-based resin containing vinyl acetate or the acrylic resin containing vinyl acetate in the front surface anchor layer 14a includes the urethane-based resin containing vinyl acetate or the vinyl acetate in the back surface anchor layer 14b. It may be 1.0 times (within the range of 0.95 times or more and 1.04 times or less) the content of the acrylic resin. The content of the urethane resin containing salt and vinegar in the front anchor layer 14a or the acrylic resin containing salt and vinegar is the urethane resin containing salt and vinegar or the acrylic resin containing salt and vinegar in the back surface anchor layer 14b. When the content is the same as the resin content, the physical properties of the front surface anchor layer 14a and the physical properties of the back surface anchor layer 14b are almost the same, so that the sheet base material 1 is provided with the front surface anchor layer 14a and the back surface anchor layer 14b. In, the occurrence of distortion, warpage, etc. can be reduced. Therefore, it is possible to reduce the occurrence of distortion, warpage, etc. of the entire sheet base material 1. Further, since the coating liquid for forming the front surface anchor layer 14a and the coating liquid for forming the back surface anchor layer 14b can be shared, the manufacturing cost can be reduced and the work efficiency can be improved. be able to.

The content of the urethane-based resin containing vinyl acetate or the acrylic resin containing vinyl acetate in the front surface anchor layer 14a includes the urethane-based resin containing vinyl acetate or the vinyl acetate in the back surface anchor layer 14b. It may be higher or lower than the content of the acrylic resin. The content of the urethane resin containing salt and vinegar in the front anchor layer 14a or the acrylic resin containing salt and vinegar is the urethane resin containing salt and vinegar or the acrylic resin containing salt and vinegar in the back surface anchor layer 14b. When the content is higher or lower than the resin content, the physical properties of the front surface anchor layer 14a and the back surface anchor layer 14b are different, so that the sheet base material 1 provided with the front surface anchor layer 14a and the back surface anchor layer 14b is distorted. And warpage can be added. In this way, by imparting distortion, warpage, etc. to the sheet base material 1 provided with the front surface anchor layer 14a and the back surface anchor layer 14b, the sheet base material 1 is attached to the base material or the like having a curved surface without gaps. be able to. For example, the content of the urethane-based resin containing vinyl acetate or the acrylic resin containing vinyl acetate in the front surface anchor layer 14a includes the urethane-based resin containing vinyl acetate or the vinyl acetate in the back surface anchor layer 14b. The content of the acrylic resin may be 1.1 times or more and 10 times or less, or 0.1 times or more and 0.9 times or less.

The thickness of the surface anchor layer 14a is, for example, in the range of 0.5 μm or more and 20 μm or less, preferably in the range of 0.5 μm or more and 10 μm or less. Further, the thickness of the front surface anchor layer 14a may be the same as the thickness of the back surface anchor layer 14b. When the thickness of the front surface anchor layer 14a is the same as the thickness of the back surface anchor layer 14b, the physical properties of the front surface anchor layer 14a and the physical properties of the back surface anchor layer 14b are substantially the same, so that the sheet base material 1 is the surface anchor layer 14a. In the state where the back surface anchor layer 14b is provided, it is possible to reduce the occurrence of distortion, warpage, and the like.

Further, the thickness of the front surface anchor layer 14a may be thicker or thinner than the thickness of the back surface anchor layer 14b. By making the thickness of the front surface anchor layer 14a different from the thickness of the back surface anchor layer 14b, a difference in gloss is generated, so that the front surface side and the back surface side of the sheet base material 1 can be easily visually recognized. By doing so, the printed pattern layer 9 can be printed without forming, for example, an identification mark indicating that it is a printed surface on the surface of the printed pattern layer 9. As a result, product loss caused by laminating the printed pattern layer 9 on the back surface (non-printing surface) side of the sheet base material 1 can be reduced.

(Back surface anchor layer 14b)
The back surface anchor layer 14b is a layer formed so as to cover the entire back surface of the sheet base material 1, and is a layer for preventing powder falling off of the inorganic material contained in the sheet base material 1. When the adhesive layer 8 for laminating (adhering) the barrier film 7 on the sheet base material 1 is coated, the inorganic material contained in the sheet base material 1 is powdered in the coating system, specifically, in the printing coating apparatus. If it falls, it may contaminate the inside of the coating system.
The back surface anchor layer 14b preferably contains a urethane resin containing vinyl acetate or an acrylic resin containing vinyl acetate.

The content of the urethane resin containing salt and vinegar or the acrylic resin containing salt and vinegar in the back surface anchor layer 14b is, for example, in the range of 15% by mass or more and 100% by mass or less with respect to the mass of the back surface anchor layer 14b. Is preferable, the range of 80% by mass or more and 100% by mass or less is more preferable, and the range of 85% by mass or more and 95% by mass or less is further preferable. If the content of the urethane resin containing salt and vinegar or the acrylic resin containing salt and vinegar in the back surface anchor layer 14b is within the above numerical range, a uniform back surface anchor layer 14b without unevenness or chipping is formed. be able to. When the content of the urethane resin containing vinyl acetate or the acrylic resin containing vinyl acetate in the back surface anchor layer 14b is less than 15% by mass with respect to the mass of the back surface anchor layer 14b, powder falling can be prevented. It may not be enough. Further, if the content of the urethane resin containing salt and vinegar or the acrylic resin containing salt and vinegar in the back surface anchor layer 14b is less than 80% by mass with respect to the mass of the back surface anchor layer 14b, there is no problem in use. Although there is no problem, the ratio of the back surface anchor layer 14b to the sheet base material 1 is reduced, and the interlayer strength between the back surface anchor layer 14b and the sheet base material 1 is slightly reduced. If the content of the urethane resin containing salt and vinegar or the acrylic resin containing salt and vinegar in the back surface anchor layer 14b is 100% by mass or less with respect to the mass of the back surface anchor layer 14b, there is no problem in use. However, if it exceeds 95% by mass, or more accurately 98% by mass, the back surface anchor layer 14b may be chipped due to insufficient curing, or the interlayer strength between the back surface anchor layer 14b and the sheet base material 1 may decrease. Sometimes.

The thickness of the back surface anchor layer 14b is, for example, in the range of 0.5 μm or more and 20 μm or less, preferably in the range of 0.5 μm or more and 10 μm or less.
In the embodiment, as described above, the case where both the front surface anchor layer 14a and the back surface anchor layer 14b are provided has been described, but the present invention is not limited thereto. For example, at least one of the front surface anchor layer 14a and the back surface anchor layer 14b may be provided, or both the front surface anchor layer 14a and the back surface anchor layer 14b may not be provided.

(Printed pattern layer)
The print pattern layer 9 is composed of a solid ink layer 2 and a pattern ink layer 3. The solid ink layer 2 plays a role of hiding the sheet base material 1 and expresses the color tone of the entire printed pattern layer 9.
Further, 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, and for example, a gravure printing method, an offset printing method, a flexographic printing method, a silk screen printing method, an inkjet printing method, or the like can be appropriately selected and used. In particular, the gravure printing method is more suitable from the viewpoint of printing fineness and productivity.
Further, the ink used for the print pattern layer 9 is not particularly limited, and can be appropriately selected in consideration of adhesion to the sheet base material 1, color tone, light resistance, and the like.
For example, nitric acid cotton-based ink can be used for the solid ink layer 2 and the pattern ink layer 3, and in particular, the solid ink layer 2 has a role of concealing the sheet base material 1, so that the pigment contains titanium dioxide and is opaque. Layer is preferable.

(Top coat layer)
In the present embodiment, a top coat layer 4 containing a curable transparent resin is provided on the printed pattern layer 9. The top coat layer 4 is effective as a surface protective layer because it can improve the scratch resistance and stain resistance of the surface of the decorative sheet.
The resin system of the top coat layer 4 may be appropriately selected from the curable transparent resin, and for example, a urethane resin composed of an acrylic polyol can be used. Further, for the purpose of improving the design, it is also possible to give a gloss matte effect by partially providing a difference in gloss using a repellent ink or the like.

(Barrier film)
The barrier film 7 includes an inorganic compound layer 6 and a plastic film 5. An anchor coat layer (not shown) 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 embodiment is used as a decorative board for fittings and the like, the barrier film 7 can eliminate the difference in temperature and humidity between the front and back of the fitting, especially the influence of humidity on the wood substrate, and warp of the fitting. Can be prevented.
The plastic film 5 is a film containing a polymer resin composition, for example, polyolefin (polyethylene, polypropylene, etc.), polyester (polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, etc.), polyamide (nylon-6, nylon-66, etc.), etc. ), Polyethylene, etc. can be used and are appropriately selected according to the application. In particular, when polypropylene or polyethylene terephthalate is used as the base film, it is more preferable in terms of film strength and price.

The inorganic compound layer 6 can be formed by stacking a coating layer in addition to the thin-film deposition layer of the inorganic compound, and the thin-film deposition layer and the coating layer may be sequentially provided on the plastic film 5.
As a method for forming the inorganic compound layer 6, an inorganic compound such as SiO or AlO is coated on the sheet base material 1 provided with the back surface anchor layer 14b by a vacuum vapor deposition method, and the inorganic compound layer is formed by the vacuum vapor deposition method. Can be formed. The thickness of the vapor deposition layer is preferably 15 nm to 30 nm.

As another method for forming the inorganic compound layer, for example, at least one of a water-soluble polymer, (a) one or more alkoxides or a hydrolyzate thereof, or both, or (b) tin chloride. A coating agent containing an aqueous solution containing water or a water / alcohol mixed aqueous solution as a main component is applied onto a sheet base material 1 provided with a back surface anchor layer 14b and dried by heating to form an inorganic compound layer 6 by a coating method. can do. At this time, by adding a silane monomer to the coating agent, it is possible to improve the adhesion with the back surface anchor layer 14b.

The inorganic compound layer 6 has a barrier property only by the coating film by the vacuum vapor deposition method, but is formed by alternately stacking the coating layer which is the inorganic compound layer 6 by the coating method and the vapor deposition layer which is the inorganic compound layer by the vacuum vapor deposition method. It can be used as a barrier layer.
A dense structure is formed by the composite of these two layers. Therefore, it has high gas barrier property, moisture resistance, and water resistance, and has flexibility to withstand deformation. Therefore, it can also be suitable for laminating on a base material such as a fitting.

(Adhesive layer)
In the adhesive layer 8, the sheet base material 1 and the barrier film 7 are laminated and adhered. Lamination and adhesion can be performed using dry lamination, and for example, a polyester-based dry lamination adhesive can be used.
As described above, according to the present embodiment, it is possible to prevent the fitting from warping due to the difference in temperature and humidity between the front and back of the fitting by using it as a decorative board for fittings and the like, and to prevent greasy stains that are considered in real life. It is possible to provide a decorative sheet having stain resistance.

Hereinafter, the present invention will be described in more detail by way of examples. However, the present invention is not limited to the examples shown here. The present invention is limited only by claim.
Decorative sheets having the material composition shown in Examples 1 to 19 below, and Comparative Examples 1 and 2 were prepared, and evaluation items were determined and evaluated.

<Example 1>
The description of the first embodiment is based on FIG.
The material composition of the decorative sheet 10 is as follows.
-Sheet base material 1: An oil resistant sheet containing a fluorine-based oil resistant agent was used. (Basis weight 40 g / m ² )
As the fluorine-based oil-resistant agent, perfluoroheptane sulfonic acid (PFHpS) (content 4% by mass, oil resistance 1) was used. In this fluorine-based oil resistant agent, the molecular weight of the fluororesin including the functional group was 10,000, and the number of carbon atoms in the fluorine moiety was 7.
The inorganic material contained in the oil resistant sheet was silica (15% by mass) having an average particle diameter of 0.8 μm. The thermoplastic resin contained in the oil-resistant sheet was polystyrene. The total content of the thermoplastic resin and the inorganic material was 85% by mass.
-Solid ink layer 2: A nitrocellulose-based ink containing 70% titanium dioxide was applied by a gravure printing method.
-Pattern ink layer 3: A wood grain pattern was printed by a gravure printing method using nitric acid cotton-based ink.
-Top coat layer 4: A urethane resin made of acrylic polyol was used. (Applyance amount 7 g / m ² ). The surface has a gloss matte pattern.
-Inorganic compound layer 6: Using SiO as an inorganic compound, the inorganic compound layer 6 was formed on the plastic film 5 by a vacuum vapor deposition method.
-Plastic film 5: A polyethylene terephthalate film (thickness 12 μm) was used.
-Adhesive layer 8: The back surface of the sheet base material 1 and the inorganic compound layer 6 side of the barrier film 7 were laminated and bonded via the adhesive layer 8. A polyester-based dry lamination adhesive (coating amount: 3 g / m ² ) was used.

<Example 2>
A decorative sheet 10 of Example 2 was obtained in the same manner as in Example 1 except that the content of the inorganic material was 80% by mass.
<Example 3>
A decorative sheet 10 of Example 3 was obtained in the same manner as in Example 2 except that the oil resistance of the fluorine-based oil resistant agent was set to 2.
<Example 4>
A decorative sheet 10 of Example 4 was obtained in the same manner as in Example 2 except that the content of the fluorine-based oil resistant agent was 5% by mass.
<Example 5>
A decorative sheet 10 of Example 5 was obtained in the same manner as in Example 2 except that the content of the fluorine-based oil resistant agent was 10% by mass.

<Example 6>
A decorative sheet 10 of Example 6 was obtained in the same manner as in Example 2 except that the average particle size of the inorganic material was 1 μm.
<Example 7>
A decorative sheet 10 of Example 7 was obtained in the same manner as in Example 2 except that the average particle size of the inorganic material was 3 μm.
<Example 8>
A decorative sheet 10 of Example 8 was obtained in the same manner as in Example 2 except that the inorganic material was antimony trioxide.
<Example 9>
A decorative sheet 10 of Example 9 was obtained in the same manner as in Example 2 except that the inorganic material was zircon oxide.

<Example 10>
A decorative sheet 10 of Example 10 was obtained in the same manner as in Example 2 except that the inorganic material was calcium carbonate.
<Example 11>
A decorative sheet 10 of Example 11 was obtained in the same manner as in Example 2 except that the thermoplastic resin was polypropylene.
<Example 12>
A decorative sheet 10 of Example 12 was obtained in the same manner as in Example 2 except that the thermoplastic resin was polyethylene.
<Example 13>
A decorative sheet 10 of Example 13 was obtained in the same manner as in Example 2 except that the thermoplastic resin was polyester.

<Example 14>
A decorative sheet 10 of Example 14 was obtained in the same manner as in Example 2 except that the total content of the thermoplastic resin and the inorganic material was 90% by mass.
<Example 15>
A decorative sheet 10 of Example 15 was obtained in the same manner as in Example 2 except that the total content of the thermoplastic resin and the inorganic material was 95% by mass.
<Example 16>
The decorative sheet 10 of Example 16 was obtained in the same manner as in Example 2 except that the anchor layers were formed on both sides of the sheet base material 1 with a urethane resin containing vinyl acetate.
<Example 17>
A decorative sheet 10 of Example 17 was obtained in the same manner as in Example 2 except that anchor layers were formed on both sides of the sheet base material 1 with an acrylic resin containing vinyl acetate.

<Example 18>
The inorganic material contained in the oil-resistant sheet is calcium carbonate (80% by mass) having an average particle diameter of 2 μm, the thermoplastic resin contained in the oil-resistant sheet is polypropylene, and the total content of the thermoplastic resin and the inorganic material is 90% by mass. Examples except that the content of the fluorine-based oil-resistant agent was 10% by mass, the oil resistance of the fluorine-based oil-resistant agent was 10, and the anchor layers were formed on both sides of the oil-resistant sheet with a urethane-based resin containing calcium carbonate. In the same manner as in 2, the decorative sheet 10 of Example 18 was obtained.
<Example 19>
A decorative sheet 10 of Example 19 was obtained in the same manner as in Example 18 except that anchor layers were formed on both sides of the oil resistant sheet with an acrylic resin containing vinyl acetate.

<Comparative example 1>
The explanation of Comparative Example 1 is based on FIG.
The material composition of the decorative sheet 30 is as follows.
-Sheet base material 11: Paper-to-paper reinforced paper was used. (Basis weight 30 g / m ² )
The material composition other than the sheet base material 11 is the same as that of the first embodiment.

<Comparative example 2>
The explanation of Comparative Example 2 is based on FIG.
The material composition of the decorative sheet 40 is as follows.
-Sheet base material 1: An oil resistant sheet containing a fluorine-based oil resistant agent was used. (Basis weight 30 g / m ² ).
That is, the material composition 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 unprinted surface of the sheet base material 1 and the inter-paper reinforced paper 13, and laminated and adhered.
That is, Comparative Example 2 has a configuration in which a barrier film is not used.

The evaluation items are as follows.
-Evaluation of warpage (moisture permeability): According to JIS Z 0208.
◎: 1.0g ^/ m 2 · 24h following 〇: 1.0g ^/ m 2 · 24h ultra-~1.5g ^/ m 2 · 24h or less ×: In 1.5g ^/ m 2 · 24h super this evaluation, moisture permeability if it exceeds 1.5g ^/ m 2 · 24h was the "unacceptable (×)" as the warp may occur.

-Evaluation of stain resistance (salad oil dripping test): 1 ml of salad oil dyed with Zudan Black (C ₂₉ H ₂₄ N ₆ ) was dropped on the surface of the decorative sheet, covered with a watch glass for 8 hours, and then the salad oil was added. It was wiped off and the presence or absence of oil penetration was observed.
(Hand cream evaluation test): Hand cream (Nivea cream) (registered trademark) was dropped on the surface of the cosmetic sheet, covered with a watch glass for 8 hours, left to stand, and then the hand cream was wiped off and the presence or absence of infiltration was observed. ..
⊚: Oil infiltration cannot be visually confirmed ○: Oil infiltration can be visually confirmed slightly but there is no problem in use △: Oil infiltration can be visually confirmed but there is no problem in use X: Oil penetration can be visually confirmed and is not suitable for use.

-Evaluation of oil resistance performance The oil resistance performance of the entire decorative sheet was evaluated based on the value measured by the JAPAN TAPPI pulp and paper test method, N0.41: 20000.
⊚: 4 or more ○: 2 or more and less than 4 Δ: 1 or more and less than 2 ×: 1 or less

-Evaluation of Adhesiveness After pressure-bonding Nichiban cellophane tape to the surface of the decorative sheet 10, it was strongly peeled off with a certain force, and the presence or absence of peeling between the printed pattern layer 9 and the sheet base material 1 was visually evaluated. .. The evaluation criteria are as follows.
⊚: When peeled off with a force of 15N (Newton), no peeling occurred between the layers of the printed pattern layer 9 and the sheet base material 1. ○: When peeled off with a force of 10N, the printed pattern layer 9 and No peeling occurred between the layers of the sheet base material 1 ×: The top coat layer 4 and the printed pattern layer 9 adhered to the entire surface of the cellophane tape, and remarkable peeling occurred between the printed pattern layer 9 and the sheet base material 1. In the above evaluation, "◎" and "○" were accepted.
The evaluation results are shown in Table 1.

As is clear from the results shown in Table 1, the decorative sheets according to the present embodiment, Examples 1 to 19, have low humidity permeability, so that it is possible to prevent the fittings from warping due to the difference in humidity, and the resistance to oil and fat stains. It was verified that it is also excellent in pollutability.
More specifically, it can be seen that in the decorative sheet according to the present embodiment, the moisture-proof property is greatly improved by the barrier film, and the oil-resistant stain resistance to oil and fat stains is improved by the oil-resistant sheet, and both of them are realized.
As described above, according to the present invention, it is possible to prevent the fitting from warping due to the difference in temperature and humidity between the front and back of the fitting by using it as a decorative board for fittings and the like, and it is possible to prevent the fitting from being contaminated with oil stains, which is considered in real life. It is possible to provide a decorative sheet having sex.

1 ... Sheet base material 2 ... Solid ink layer 3 ... Picture ink layer 4 ... Top coat layer 5 ... Plastic film 6 ... Inorganic compound layer 7 ... Barrier film 8 ... Adhesive layer 9 ... Printed pattern layer 10 ... Decorative sheet 11 ... Sheet base material 12 ... Moisture-proof layer 13 ... Paper-to-paper reinforced paper 14a ... Front anchor layer 14b ... Back anchor Layer 20 ... Decorative paper 30 ... Decorative sheet 40 ... Decorative sheet

Claims (9)

A decorative sheet in which a printed pattern layer and a top coat layer are provided in this order on one surface of the sheet base material, and a barrier film is laminated on the other surface of the sheet base material.
An oil resistant sheet is used as the sheet base material.
The top coat layer containing a curable transparent resin is provided on the printed pattern layer.
The barrier film comprises a plastic film having an inorganic compound layer and
The sheet base material and the barrier film are bonded to each other via an adhesive layer.
The oil-resistant sheet contains a thermoplastic resin, an inorganic material, and a fluorine-based oil-resistant agent.
The decorative sheet is characterized in that the content of the inorganic material is in the range of 15% by mass or more and 90% by mass or less with respect to the mass of the oil-resistant sheet. The fluorine-based oil resistant agent does not contain perfluorooctanesulfonic acid (PFOS) and perfluorooctanoic acid (PFOA), and the molecular weight of the fluororesin including a functional group is in the range of 3000 or more and 80,000 or less, and at the fluorine moiety. The decorative sheet according to claim 1, wherein the number of carbon atoms is less than 8. The decorative sheet according to claim 1 or 2, wherein the oil-resistant sheet has a value of 2 or more as the oil resistance measured by the JAPAN TAPPI pulp and paper test method, N0.41: 2000. The content of the fluorine-based oil-resistant agent is in the range of more than 0% by mass and 10% by mass or less with respect to the mass of the oil-resistant sheet, according to any one of claims 1 to 3. The described cosmetic sheet. Any one of claims 1 to 4, wherein the inorganic material has a powder shape, an average particle diameter in the range of 1 μm or more and 3 μm or less, and a maximum particle diameter of 50 μm or less. Cosmetic sheet described in. The inorganic materials include antimony trioxide, antimony soda, zirconium silicate, zirconium oxide, magnesium hydroxide, aluminum hydroxide, basic magnesium carbonate, borosand, zinc borate, calcium carbonate, molybdenum trioxide or antimony dimolybate and water. Contains at least one of aluminum oxide complex, antimony trioxide and silica complex, antimony trioxide and zinc flower complex, silicic acid of zirconium, zirconium compound and antimony trioxide, and salts thereof. The decorative sheet according to any one of claims 1 to 5, which is characterized by the above. The decorative sheet according to any one of claims 1 to 6, wherein the thermoplastic resin contains at least one of polypropylene, polyethylene and polyester. Claims 1 to 7 are characterized in that the total content of the thermoplastic resin and the inorganic material is in the range of 90% by mass or more and 95% by mass or less with respect to the mass of the oil-resistant sheet. The decorative sheet according to any one of the above. A first anchor layer formed on the first surface of the oil resistant sheet and
Further provided with a second anchor layer formed on a second surface which is a surface opposite to the first surface of the oil resistant sheet.
Any of claims 1 to 8, wherein the first anchor layer and the second anchor layer contain a urethane-based resin containing vinyl acetate or an acrylic resin containing vinyl acetate. Or the decorative sheet according to item 1.

Images