JP2016190398A - Coating sheet, decorative sheet and decorative material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a coating sheet, a decorative sheet and a decorative material extremely good in abrasion resistance.SOLUTION: There is provided a coating sheet 100 having a coating layer 50 containing a binder resin 52 and a particle 51 on a substance 10 and having Dand T satisfying the following condition (1), where P is a peak value of existence ratio of particle diameter distribution based on volume of the particle 51, Dis a particle diameter in a larger side of particle diameter exhibiting the existence ratio of the particle diameter distribution of 1/4P and T is thickness of the coating layer 50. 3.0T≤D(1).SELECTED DRAWING: Figure 2

Description

  The present invention relates to a coating sheet, a decorative sheet, and a decorative material.

  Conventionally, interior materials for buildings such as walls, ceilings and floors; fittings such as window frames, doors and handrails; furniture; housings for home appliances, OA equipment, etc .; adherends such as exterior materials such as entrance doors In order to impart wear resistance, a coating sheet in which a cured film is formed on a substrate is bonded to the surface of the adherend.

  The cured film of the coating sheet contains an ionizing radiation curable resin having excellent hardness or particles having excellent hardness such as alumina or silica in order to improve wear resistance.

  For example, Patent Documents 1 and 2 are disclosed as coating sheets for imparting wear resistance as described above.

Japanese Patent Laid-Open No. 11-302578 JP 2000-43204 A

The coating sheets of Patent Documents 1 and 2 are characterized in that, when the thickness of the cured film is t, particles satisfying the condition of 0.5t to 1.5t are 60% by weight or more of all particles. . In other words, the coating sheets of Patent Documents 1 and 2 are characterized by imparting wear resistance by not using extremely large particles or extremely small particles as much as possible with respect to the thickness of the cured film.
The coating sheets of Patent Documents 1 and 2 show good test results in the Taber abrasion test, which is an evaluation item of the Examples of Patent Documents 1 and 2. However, when the coating sheets of Patent Documents 1 and 2 are attached to the surface of the adherend, the surface is gradually damaged in daily life, and the wear resistance cannot be satisfied.

  An object of the present invention is to provide a coating sheet, a decorative sheet, and a decorative material having extremely good wear resistance.

As a result of diligent research, the present inventors have found that the result of the Taber abrasion test, which is the mainstream as a wear resistance evaluation method, does not correlate with the wear resistance in daily life, and has solved the above problems.
That is, the present invention provides the following [1] to [11] coating sheets, decorative sheets and decorative materials.

[1] A coating sheet provided with a coating layer containing a binder resin and particles on a substrate, wherein the peak value of the volume-based particle size distribution of the particles is P, and the presence of the particle size distribution A coating in which D _{+ 1 / 4P} and T satisfy the following condition (1), where D _{+ 1 / 4P} is the particle diameter on the larger side of the particle diameter with a ratio of 1 / 4P and the thickness of the coating layer is T Sheet.
3.0T ≦ D _{+ 1 / 4P} (1)
[2] The coating sheet according to [1], wherein the condition (1) is 3.0T ≦ D _{+ 1 / 4P} ≦ 6.0T.
[3] When the particle diameter on the larger side among the particle diameters having an abundance ratio of the particle diameter distribution of 2 / 4P is D _{+ 2 / 4P} , D _{+ 2 / 4P} and T satisfy the following condition (2): The coating sheet according to [1] or [2] above.
2.3T ≦ D _{+ 2 / 4P} (2)
[4] D _{+ 3 / 4P} and T satisfy the following condition (3) when the particle diameter on the larger side among the particle diameters having an abundance ratio of the particle diameter distribution of _{3 / 4P} is D _{+ 3 / 4P} . The coating sheet according to any one of [1] to [3].
1.7T ≦ D _{+ 3 / 4P} (3)
[5] when the existence ratio of the particle diameter distribution has a particle size showing the P and D _P, D _P and T satisfy the following condition (4), according to any one of [1] to [4] Coating sheet.
1.5T ≦ D _P (4)
[6] The coating sheet according to any one of [1] to [5], wherein the thickness T of the coating layer is 5 to 15 μm.
[7] The coating sheet according to any one of [1] to [6], wherein the particles are inorganic particles having a Mohs hardness of 4 to 8.
[8] The coating sheet according to any one of [1] to [7], wherein the binder resin is a cured product of an ionizing radiation curable resin composition containing a polyfunctional urethane (meth) acrylate oligomer.
[9] The coating sheet according to any one of the above [1] to [8], which has a design layer between the base material and the coat layer or on the opposite side of the base material from the coat layer. .
[10] A decorative sheet comprising the coating sheet according to any one of [1] to [9].
[11] A decorative material obtained by laminating and integrating an adherend and a surface opposite to the coat layer of the decorative sheet according to [10].

  Since the coating sheet, the decorative sheet and the decorative material of the present invention are extremely excellent in wear resistance, it is possible to greatly suppress the surface from being gradually damaged in daily life and to suppress the deterioration of the design.

A particle size distribution based on volume of any particle is a diagram particles of _{D + 1 / 4P, D +} 2 / 4P and _{D + 3} / 4P, the _{D P} is described. It is sectional drawing which shows one Embodiment of the coating sheet of this invention. It is sectional drawing which shows other embodiment of the coating sheet of this invention.

Hereinafter, embodiments of the coating sheet, the decorative sheet, and the decorative material of the present invention will be described.
[Coating sheet]
The coating sheet of the present invention is a coating sheet provided with a coating layer containing a binder resin and particles on a substrate, wherein the peak value of the abundance ratio of the volume-based particle size distribution of the particles is P, the particles When the particle diameter on the larger side of the particle diameter in which the existence ratio of the diameter distribution is 1 / 4P is D _{+ 1 / 4P} and the thickness of the coating layer is T, D _{+ 1 / 4P} and T satisfy the following condition (1) It satisfies.
3.0T ≦ D _{+ 1 / 4P} (1)

FIG. 1 is a volume-based particle size distribution of an arbitrary particle. In Figure 1, P is the peak value of the existence ratio of the particle size distribution of the particles on a volume basis, D _P is present ratio is the particle diameter at the time showing a P. Moreover, 1 / 4P is the value of the abundance ratio that becomes 1/4 of the peak value, and D _{+ 1 / 4P} is the particle diameter on the larger side of the particle diameter when the abundance ratio indicates 1 / 4P. 2 / 4P is the value of the abundance ratio that is 2/4 of the peak value, and D _{+ 2 / 4P} is the larger particle diameter of the particle diameters when the abundance ratio is 2 / 4P. 3 / 4P is the value of the abundance ratio that is 3/4 of the peak value, and D _{+ 3 / 4P} is the larger particle diameter of the particle diameters when the abundance ratio is 3 / 4P.

In the coating sheet of the present invention, the peak value of the abundance ratio of the particle size distribution based on the volume of the particles is P, and the particle diameter on the larger side of the particle diameters where the abundance ratio of the particle diameter distribution is 1 / 4P is D _{+ 1 / 4P.} When the thickness of the coating layer is T, D _{+ 1 / 4P} and T satisfy the following condition (1).
3.0T ≦ D _{+ 1 / 4P} (1)

If condition (1) is not satisfied, even if good results are shown in the Taber abrasion test, which is the mainstream as a wear resistance evaluation method, it is not possible to prevent the surface from being gradually damaged in daily life, and wear resistance is reduced. Cannot be good.
As described above, the reason why the result of the Taber abrasion test does not correlate with the wear resistance in daily life is considered as follows.
First, it is considered that the reason why the coating sheet is scratched is that the friction material reaches a portion where the particles of the coating layer do not exist and the portion is worn. In the Taber abrasion test, abrasive paper or wear wheels are used as the friction material. Abrasive paper or wear ring has low flexibility and does not follow the surface shape of the coating sheet, so it is difficult for the abrasive paper or wear ring that is a friction material to reach the location where the particles of the coat layer do not exist, and the test result becomes good Conceivable.
On the other hand, in daily life, various adherends (interior materials for buildings such as walls, ceilings, floors; fittings such as window frames, doors, handrails; furniture; housings for home appliances, OA equipment, etc .; entrance doors, etc. When cleaning exterior materials, etc., cleaning tools such as rags, mops, dry sheets, and wet sheets are used. These cleaning tools are more flexible than abrasive paper and can easily follow the surface shape of the coating sheet. End up.
Further, since the Taber abrasion test is a simple rotational motion, a force is always applied from a certain direction at any location on the coating sheet. For this reason, in an arbitrary location on the coating sheet in the Taber abrasion test, scratches are generated only in a certain direction. On the other hand, the movement of the cleaning tool during cleaning is random. For this reason, in cleaning, scratches are gradually generated in various directions at arbitrary locations on the coating sheet, and the scratches are easily noticeable.
Furthermore, many cleaning tools are formed from fibers. And since the length of a fiber is various, a friction material (fiber of a cleaning tool) tends to reach | attain the location where the particle | grains of a coat layer do not exist, and a damage | wound will arise gradually.
As described above, even if the test result of the Taber abrasion test is good, it may not be possible to prevent the surface of the adherend from being gradually damaged in daily life, and the wear resistance may not be improved. .

On the other hand, when the coating sheet of the present invention satisfies the condition (1), the surface can be greatly prevented from being gradually damaged in daily life, and the wear resistance can be extremely improved.
Satisfying the condition (1) means having particles having a large particle diameter of 3 times or more the thickness of the coat layer at a high abundance ratio of 1 / 4P. That is, the coating sheet of the present invention has a high abundance ratio of particles having a particle size that is three times or more the thickness of the coat layer, thereby preventing the friction material from reaching a portion where no particles of the coat layer are present. . For this reason, the coating sheet of this invention can suppress significantly that the surface is gradually damaged in daily life, can make abrasion resistance very favorable, and can suppress the fall of the designability by extension.
Examples of the test method having a high correlation with the wear resistance in daily life include the E method (Martindale method) of JIS L1096: 2010. The abrasion test by the Martindale method uses a flexible material such as cloth or polyurethane foam as a friction material, and the movement method is a Lissajous figure movement that wears from various directions. The correlation is high.

In addition, when D _{+ 1 / 4P} is too large, particles are easily lost from the coat layer. Further, if D _{+ 1 / 4P} is too large, the particle diameter of the particles in the coat layer increases as a whole, and therefore, a portion where no particles are present is likely to occur on the surface of the coat layer, and scratches are likely to occur. .
For this reason, the condition (1) is preferably 3.0T ≦ D _{+ 1 / 4P} ≦ 6.0T, more preferably 3.5T ≦ D _{+ 1 / 4P} ≦ 5.0T, and 3.5T ≦ More preferably, D _{+ 1 / 4P} ≦ 4.5T.

In the present invention, the particle size distribution and the average particle size are measured by a laser diffraction scattering method.
Further, in the present invention, the thickness T of the coat layer is an average value when the thickness of the portion where no particles of the coat layer are present is measured at 20 locations. The thickness of the portion of the coating layer where no particles are present can be measured from a cross-sectional photograph of the coating sheet.

In the present invention, when calculating the existence ratio of the particle size distribution, the width of one section in which the ratio is integrated is determined by the following methods (1) to (4).
(1) The minimum particle size is 0.03 μm and the maximum particle size is 1000 μm.
(2) Taking a logarithm with the bottom of the maximum particle diameter as 10 and a logarithm with the bottom of the minimum particle diameter as 10, calculate the difference, and further divide the difference by 100.
(3) When the lower limit value and the upper limit value of the particle diameter of an arbitrary section are R _n and R _{n + 1} (n is an integer of 1 to 100, R ₁ = 0.03 μm, R ₁₀₁ = 1000 μm), and the base 10 logarithm of R _{n + 1,} the difference between the logarithm to the base 10 of the _{R n} is, as always the same as the divisor determines the _{R n} and _{R n + 1.} (1) to (3) can be represented by the following formula (A).
log ₁₀ R _{n + 1} -log ₁₀ R _n = [log ₁₀ 1000−log ₁₀ 0.03] / 100 (A)
(4) the width of any one section _may be represented by _{R n} + 1 -R _n.

The coating sheet of the present invention has the following condition when D _{+ 2 / 4P} and T are the following conditions when the particle diameter on the larger side of the particle diameter having a particle diameter distribution of _{2 / 4P} is D _{+ 2 / 4P} ( It is preferable to satisfy 2).
2.3T ≦ D _{+ 2 / 4P} (2)

The coating sheet of the present invention has D _{+ 3 / 4P} and T satisfying the following conditions when the particle diameter on the larger side of the particle diameter having a particle diameter distribution of _{3 / 4P} is set to D _{+ 3 / 4P} ( It is preferable to satisfy 3).
1.7T ≦ D _{+ 3 / 4P} (3)

Satisfying the condition (2) means having particles having a large particle diameter of 2.3 times or more the thickness of the coat layer at a high abundance ratio of 2 / 4P. Moreover, satisfying the condition (3) means that particles having a large particle diameter of 1.7 times or more the thickness of the coat layer are contained at a high abundance ratio of 3 / 4P.
Therefore, by satisfying the condition (2) and / or the condition (3), it is possible to more easily block the friction material from reaching the portion where the particles of the coat layer do not exist. Further, when the coating layer is subjected to friction, it tends to be lost in order from particles having a larger particle diameter. Therefore, by satisfying the condition (2) and / or the condition (3), even if a large particle that satisfies the condition (1) is missing, the particles satisfying the condition (2) and / or the condition (3) By being present, it is possible to easily block the friction material from reaching the portion where the particles of the coat layer do not exist.
Therefore, by satisfying the condition (2) and / or the condition (3), the wear resistance of the coating sheet can be further improved.

In addition, when D _{+ 2 / 4P} or D _{+ 3 / 4P} is too large, particles are easily lost from the coat layer.
For this reason, the condition (2) is more preferably 2.5T ≦ D _{+ 2 / 4P} ≦ 5.0T, further preferably 2.8T ≦ D _{+ 2 / 4P} ≦ 4.5T, 3.0T More preferably, ≦ D _{+ 2 / 4P} ≦ 4.0T.
The condition (3) is more preferably 2.0T ≦ D _{+ 3 / 4P} ≦ 4.0T, more preferably 2.0T ≦ D _{+ 3 / 4P} ≦ 3.5T, and 2.1T ≦ It is even more preferable that D _{+ 3 / 4P} ≦ 3.0T.

Further, the coating sheet of the present invention, when the existence ratio of the particle size distribution has a particle diameter D _P indicating the P, it is preferable that D _P and T satisfy the following condition (4).
1.5T ≦ D _P (4)

Condition (4) means that the particle diameter of the particles having the highest abundance ratio is 1.5 times or more the thickness of the coat layer.
Therefore, when the condition (4) is satisfied, most of the particles protrude from the surface of the coat layer, and the basic performance of wear resistance can be easily satisfied.

Incidentally, D _P is too large the particles from the coating layer is easily lost.
For this reason, the condition (4) is more preferably 1.5T ≦ D _P ≦ 2.5T, and more preferably 1.6T ≦ D _P ≦ 2.3T.

Further, the coating sheet of the present _{invention, D + 1 / 4P, D} + 2 / 4P, it is preferable that the difference between _{D + 3 / 4P} and _{D P} satisfies one or more of the following conditions (5) to (7).
Conditions (5) to (7) mean that the particle size distribution of the particles is neither too narrow nor too wide.
If the particle size distribution is too uniform, particles may be lost at once during friction. For this reason, by satisfying the conditions (5) to (7) so that the particle size distribution is not too narrow, particles are gradually lost during friction, and the friction material reaches a portion where no particles of the coat layer exist. This can be blocked to improve wear resistance, increase the filling rate of particles in the coat layer, and increase the hardness of the coating film.
Moreover, in order to block the friction material having arbitrary flexibility from reaching the surface of the coat layer, it is preferable to have a certain amount of particles having a size capable of blocking the friction material. If the particle size distribution is too wide, the amount of particles of individual sizes may be reduced, and the friction material may not be sufficiently blocked. For this reason, wear resistance can be made more favorable by satisfy | filling conditions (5)-(7) and making particle size distribution not too wide.

0.3T ≦ D _{+ 1 / 4P−} D _{+ 2 / 4P} ≦ 1.5T (5)
Condition (5) is more preferably _{0.4T ≦ D + 1 / 4P -D} + 2 / 4P ≦ 1.3T, it is _{0.4T ≦ D + 1 / 4P -D} + 2 / 4P ≦ 1.1T Is more preferable.

0.3T ≦ D _{+ 2 / 4P−} D _{+ 3 / 4P} ≦ 1.5T (6)
Condition (6) is more preferably _{0.4T ≦ D + 2 / 4P -D} + 3 / 4P ≦ 1.3T, it is _{0.4T ≦ D + 2 / 4P -D} + 3 / 4P ≦ 1.1T Is more preferable.

0.3T ≦ D _{+ 3 / 4P−} D _P ≦ 1.5T (7)
Condition (7) is more preferably _{0.4T ≦ D + 3 / 4P -D} P ≦ 1.3T, more preferably a _{0.5T ≦ D + 3 / 4P -D} P ≦ 1.1T.

Further, particles having a particle diameter smaller than the thickness of the coat layer are less likely to contribute to the improvement of wear resistance. On the other hand, particles having a particle diameter smaller than the thickness of the coat layer contribute to the development of internal noise. When scratches occur on the surface of the coat layer, there is a difference in the external noise between the damaged area and the other areas, but by applying the internal noise, the damaged area and other areas It is possible to reduce the difference between the total haze (external noise + internal noise), and the scratched area can be made inconspicuous.
From the above viewpoints, the smaller particle size of the particle size distribution having a particle diameter distribution ratio of 1 / 4P is D _{−1 / 4P} , and the particle diameter distribution ratio of the particle diameter distribution being smaller than 2 / 4P. When the particle diameter on the side is D _{−2 / 4P} and the particle diameter on the smaller side is D _{−3 / 4P} among the particle diameters in which the abundance ratio of the particle size distribution is 3 / 4P, D _{−1 / 4P} , D _{-2 / 4P} and D- _{3 / 4P} preferably satisfy one or more of the following conditions (8) to (10).

0.3T ≦ D _{−1 / 4P} (8)
Condition (8) preferably satisfies 0.3T ≦ D _{−1 / 4P} ≦ 1.0T, and more preferably satisfies 0.4T ≦ D _{−1 / 4P} ≦ 0.9T.

0.6T ≦ D _{−2 / 4P} (9)
Condition (9) is more preferably _{0.6T ≦ D -2 / 4P ≦ 1.3T} , yet more preferably _{0.7T ≦ D -2 / 4P ≦ 1.2T} .

0.8T ≦ D _{−3 / 4P} (10)
Condition (10) is more preferably _{0.8T ≦ D -3 / 4P ≦ 1.3T} , yet more preferably _{0.7T ≦ D -3 / 4P ≦ 1.2T} .

<Base material>
The substrate is not particularly limited, and examples thereof include plastic films such as polyester, polyolefin, and polyvinyl chloride, papers, and composites thereof. When a plastic film is used as the substrate, a polyester film is preferable from the viewpoint of the substrate strength against scratches.
The base material may be colored from the viewpoint of design.
When the substrate is a plastic film or a composite of plastic film and paper, the thickness is preferably 20 to 200 μm, more preferably 40 to 160 μm, and even more preferably 40 to 100 μm from the viewpoint of mechanical strength and handleability. preferable. Further, when the substrate is of paper, from the same viewpoint, it is preferable that a basis weight of 20 to 80 g / ^{m 2,} further preferably 30 to 50 g / ^{m 2.}

Examples of papers used for the substrate include thin paper, kraft paper, and titanium paper. These paper base materials are used to reinforce the interlaminar strength between the fibers of the paper base material or between the other layers and the paper base material, and to prevent the occurrence of scuffing, in addition to these paper base materials, acrylic resin, styrene butadiene rubber, A resin such as a melamine resin or a urethane resin may be added (resin impregnation after paper making or embedded during paper making). For example, inter-paper reinforced paper, resin-impregnated paper and the like.
In addition to these, various papers often used in the field of building materials such as linter paper, paperboard, base paper for gypsum board, or a vinyl wallpaper raw material in which a vinyl chloride resin layer is provided on the surface of the paper can be mentioned. Furthermore, coated paper, art paper, sulfate paper, glassine paper, parchment paper, paraffin paper, Japanese paper, or the like used in the office field or normal printing and packaging can also be used. Moreover, although distinguished from these papers, woven fabrics and non-woven fabrics of various fibers having an appearance and properties similar to paper can be used as the base material. Examples of various fibers include inorganic fibers such as glass fibers, asbestos fibers, potassium titanate fibers, alumina fibers, silica fibers, and carbon fibers, or synthetic resin fibers such as polyester fibers, acrylic fibers, and vinylon fibers.

<Coat layer>
The coat layer contains a binder resin and particles. The coat layer is located on the outermost surface of the coating sheet.
The thickness of the coat layer is preferably from 5 to 15 μm, more preferably from 8 to 13 μm, from the viewpoints of particle retention, abrasion resistance and cost effectiveness.

(Binder resin)
The binder resin of the coating layer is not particularly limited, but a curable resin composition such as a thermosetting resin composition or an ionizing radiation curable resin composition in order to improve wear resistance and suppress particle dropping. Of these, it is preferable to include a cured product of an ionizing radiation curable resin composition, and it is more preferable to include a cured product of an electron beam curable resin composition.
The cured product of the curable resin composition in the coat layer is preferably 80% by mass or more, and more preferably 90% by mass or more with respect to the total amount of the binder resin.

The thermosetting resin composition is a composition containing at least a thermosetting resin, and is a resin composition that is cured by heating.
Examples of the thermosetting resin include acrylic resin, urethane resin, phenol resin, urea melamine resin, epoxy resin, unsaturated polyester resin, and silicone resin. In the thermosetting resin composition, a curing agent is added to these curable resins as necessary.

  The ionizing radiation curable resin composition is a resin composition that is cured by irradiation with ionizing radiation. The ionizing radiation means an electromagnetic wave or a charged particle beam having an energy quantum capable of polymerizing or cross-linking molecules, and usually ultraviolet (UV) or electron beam (EB) is used. Electromagnetic waves such as γ rays, and charged particle beams such as α rays and ion rays can also be used.

The ionizing radiation curable resin can be appropriately selected from conventionally used polymerizable monomers and polymerizable oligomers or prepolymers.
As the polymerizable monomer, a (meth) acrylate monomer having a radical polymerizable unsaturated group in the molecule is suitable, and among them, a polyfunctional (meth) acrylate monomer is preferred.
The polyfunctional (meth) acrylate monomer may be a (meth) acrylate monomer having two or more ethylenically unsaturated bonds in the molecule, such as diethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, Preferable examples include trimethylolpropane tri (meth) acrylate, trimethylolpropane ethylene oxide tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate and the like. It is done. These (meth) acrylate monomers may be used individually by 1 type, and may be used in combination of 2 or more type.
In addition, (meth) acrylate means an acrylate or a methacrylate.

  The number of functional groups of the polyfunctional (meth) acrylate monomer is preferably 2 or more, and from the viewpoint of obtaining excellent surface protection properties, 2 to 8 is preferable, and 3 to 6 is more preferable.

Next, as the polymerizable oligomer, an oligomer having a radical polymerizable unsaturated group in the molecule, for example, a urethane (meth) acrylate oligomer, an epoxy (meth) acrylate oligomer, a polyester (meth) acrylate oligomer, a polyether (meth) acrylate. Preferred are (meth) acrylate oligomers such as oligomers and acrylic (meth) acrylate oligomers, and these oligomers can be used alone or in combination of two or more.
Of the above polymerizable (meth) acrylate oligomers, polyfunctional urethane (meth) acrylate oligomers are preferable, and polyfunctional urethane acrylate oligomers are more preferable. This is because the polyfunctional urethane (meth) acrylate-based oligomer can impart excellent surface protection properties and can suppress shrinkage of the coating sheet during the production process.
The number of functional groups of the polyfunctional (meth) acrylate oligomer is not particularly limited as long as it is 2 or more, but 2 to 8 is preferable and 2 to 6 is more preferable from the viewpoint of surface protection characteristics and suppression of shrinkage during production.

  The weight average molecular weight (polystyrene equivalent weight average molecular weight measured by GPC method) of the polyfunctional (meth) acrylate oligomer is preferably 1,000 to 20,000, and preferably 1,000 to 10,000. It is more preferable.

As the ionizing radiation curable resin, a monofunctional (meth) acrylate may be used in order to adjust the hardness and the viscosity of the ionizing radiation curable resin composition.
Examples of the monofunctional (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, and cyclohexyl (meth) ) Acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, isobornyl (meth) acrylate, and the like. These monofunctional (meth) acrylates may be used alone or in combination of two or more.

When an ultraviolet curable resin is used as the ionizing radiation curable resin, it is desirable to add about 0.1 to 5 parts by mass of a photopolymerization initiator with respect to 100 parts by mass of the ultraviolet curable resin.
The initiator for photopolymerization can be appropriately selected from those conventionally used, and is not particularly limited. For example, the initiator for photopolymerization such as benzoin, acetophenone, phenylketone, benzophenone, and anthraquinone An agent is preferably mentioned.
Moreover, as a photosensitizer, p-dimethylbenzoic acid ester, tertiary amines, a thiol type sensitizer, etc. can be used, for example.

(particle)
As long as the particles satisfy the above condition (1), both organic particles and inorganic particles can be used, but inorganic particles are preferred from the viewpoint of wear resistance.
Examples of the inorganic particles include particles made of silica, alumina, zirconia, titania and the like. Among these inorganic particles, inorganic particles having a Mohs hardness of 4 to 8 are preferable, and inorganic particles having a Mohs hardness of 5 to 7 are more preferable, from the viewpoint of wear resistance and suppression of deterioration of the coating machine and the printing plate. In the Examples, the coating sheets of Patent Documents 1 and 2 are intended to obtain wear resistance by containing alumina in a cured film. However, since alumina has a Mohs hardness of 9 and is extremely hard, a coating machine or a printing plate is used. It is easy to cause deterioration. On the other hand, in the present invention, by satisfying the condition (1), good wear resistance can be obtained without using ultra-hard particles such as alumina, which is advantageous in production. In particular, silica satisfying the Mohs hardness range has a low refractive index and can suppress whitening of the coating layer. Therefore, when the coating sheet has a design layer described later, it is preferable in that the appearance of the design layer can be easily maintained.
Examples of the organic particles include resin beads made of acrylic resin, urethane resin, styrene resin, polyester resin, nylon resin, and the like.

  Examples of the shape of the particles include a sphere, an ellipse, and an indefinite shape. Among these, the amorphous shape is preferable from the viewpoint of preventing the particles from falling off the coat layer.

  The average particle diameter of the particles is not particularly limited as long as the above condition (1) is satisfied, but from the viewpoint of handleability, it is preferably 7 to 25 μm, and more preferably 12 to 20 μm.

  The content of the particles in the coating layer is preferably 5 to 30% by mass, and 10 to 20% by mass in the total solid content forming the layer, from the viewpoint of the balance between wear resistance and coating strength. More preferably it is.

<Design layer>
The design layer is provided as necessary for the purpose of enhancing the design properties of the coating sheet. The design layer is provided, for example, between the base material and the coat layer or on the opposite side of the base material from the coat layer.
Examples of the design layer include a colored layer and a pattern layer. These layers may be used in appropriate combination by stacking the same kind or different kinds of layers.

The colored layer is a solid layer on the entire surface, and has a purpose of mainly providing concealability. The colored layer can be formed by printing or the like.
As the ink used for forming the colored layer, an ink obtained by appropriately mixing a binder, a colorant such as a pigment or a dye, an extender pigment, a solvent, a stabilizer, a plasticizer, a catalyst, or a curing agent is used.
The binder is not particularly limited. For example, acrylic resin, styrene resin, polyester resin, urethane resin, chlorinated polyolefin resin, vinyl chloride-vinyl acetate copolymer resin, polyvinyl butyral resin, alkyd resin, Examples include petroleum resins, ketone resins, epoxy resins, melamine resins, fluorine resins, silicone resins, fiber derivatives, rubber resins, and the like. These resins can be used alone or in admixture of two or more.
The colorant may be appropriately selected from the application of the coating sheet and the color compatibility with the pattern layer. For example, carbon black (black), iron black, titanium white, antimony white, yellow lead, titanium yellow, and petal , Inorganic pigments such as cadmium red, ultramarine, and cobalt blue, organic pigments or dyes such as quinacridone red, isoindolinone yellow, and phthalocyanine blue, metal pigments made of scaly foil pieces such as aluminum and brass, titanium dioxide-coated mica, base And nacreous (pearl) pigments composed of scaly foil pieces such as conductive lead carbonate.

  The pattern layer is formed by printing or the like. Pattern patterns (pattern patterns) include wood grain patterns, marble patterns (for example, travertine marble patterns), stone patterns that simulate the surface of rocks, fabric patterns that simulate cloth and cloth-like patterns, tiled patterns, There are brickwork patterns, etc., and there are also patterns such as marquetry and patchwork that combine these. In the present invention, a wood grain pattern is preferable from the viewpoint of a synergistic effect with the effect of the uneven surface. These patterns are formed by multicolor printing with the usual yellow, red, blue and black process colors, as well as by multicolor printing with special colors prepared by preparing the individual color plates that make up the pattern. Is done. As the ink using the pattern layer, the same ink as the colored layer can be used.

  The thickness of the design layer can be appropriately adjusted within a range of about 0.1 to 20 μm in consideration of the form of the design layer and the target design properties. The design layer may contain additives such as an antioxidant and an ultraviolet absorber as long as the effects of the present invention are not impaired.

<Sealer layer>
When using an impregnating base material such as paper as the base material, it may have a sealer layer between the base material and the coating layer in order to prevent the base material from being impregnated with the coating layer coating liquid. preferable.
When it has the design layer mentioned above between the base material and the coat layer, the sealer layer may be located between the base material and the design layer, or may be located between the design layer and the coat layer. Good.

The sealer layer preferably contains a cured product of a curable resin composition such as a thermosetting resin composition or an ionizing radiation curable resin composition, and includes a cured product of the thermosetting resin composition among them. Is more preferable.
The content of the cured product of the curable resin composition is preferably 50% by mass or more, more preferably 65 to 95% by mass of the total solid content of the sealer layer.
Examples of the thermosetting resin composition and the ionizing radiation curable resin composition of the sealer layer are the same as those exemplified for the coat layer. Moreover, as a thermosetting resin composition, 2 liquid curable resin of a polyol and isocyanate is preferable, and 2 liquid curable resin of an acrylic polyol and hexamethylene diisocyanate is more preferable.

The sealer layer preferably contains particles from the viewpoint of drying suitability and viscosity adjustment. The content of the particles is preferably 5 to 50% by mass, more preferably 5 to 35% by mass, based on the total solid content of the sealer layer.
The particles of the sealer layer may be the same as those exemplified for the coat layer. The particles are preferably inorganic particles, and silica is particularly preferable.
The particles preferably have an average particle size of 0.1 to 2.0 μm, and more preferably 0.2 to 1.5 μm.

  The thickness of the sealer layer is preferably 0.5 to 5 μm, and more preferably 1 to 3 μm, from the viewpoint of preventing impregnation and cost effectiveness.

<Upper part>
The coating sheet of the present invention may have a raised portion on the base material or on any layer positioned between the base material and the coating layer. When a coating sheet has a design layer between a base material and a coat layer, it is preferable to have a raised portion on the design layer as shown in FIG.
The raised portion gives the coating sheet a tactile sensation (for example, a tactile sensation of wood if it is a wood grain pattern), and has a role of enhancing a high-class feeling.

Although the height of the raised portion varies depending on the thickness of the coat layer and the like, it cannot be generally stated, but is usually in the range of 20 to 50 μm.
Moreover, it is preferable that the occupied area ratio of the upper part is in the range of 2 to 25%, more preferably in the range of 5 to 25% with respect to the area of the plane of the coating sheet.
By selecting the range of the height and the occupied area ratio, it is possible to give a particularly suitable tactile sensation to the coating sheet. For example, in the case of a wood grain pattern, it approaches the tactile sensation of a real tree. be able to.
In addition, the occupation area ratio of the upper portion means a ratio represented by [area of the bottom surface of the upper portion / area of the plane of the decorative sheet] × 100.

The shape of the raised portion is not particularly limited, and may be a regular shape such as a regular array of circles, squares, or hexagons, or an irregular pattern. In particular, an irregular pattern is preferable because it is excellent in touch, matte, gloss and design.
Moreover, it does not specifically limit as a material of the upper part, A thermosetting resin composition, an ionizing radiation curable resin composition, etc. can be used. Among these, in particular, as a vehicle component, polyisocyanate is added as a curing agent to a resin having a functional group such as a hydroxyl group, a carboxyl group, or an amino group as an acrylic, polyester, acrylic urethane, or urethane resin. A liquid curable resin is desirable from the viewpoint of maintaining surface performance and cost.

<Backside primer layer>
The back primer layer is a layer that is preferably provided for the purpose of improving adhesion to various adherends, and is provided on the outermost surface on the side opposite to the coat layer of the coating sheet.
The material used for forming the back primer layer is not particularly limited, and examples thereof include urethane resin, acrylic resin, polyester resin, vinyl chloride / vinyl acetate copolymer, chlorinated polypropylene resin, and chlorinated polyethylene resin. What is necessary is just to select suitably according to the material of a material.
Moreover, it is preferable that the thickness of a back surface primer layer is 1-5 micrometers, and it is more preferable that it is 1-3 micrometers.

<Physical properties of coating sheet>
As described above, the coating sheet of the present invention is extremely excellent in wear resistance.
In general, an object having a high gloss or an object having a high blackness is prone to scratches when the surface is damaged by abrasion. For this reason, the effect of the coating sheet of the present invention is more conspicuous when the gloss is high or the blackness is high.
Specifically, the coating sheet of the present invention preferably has a specular gloss of 2% or more at 60 ° of JIS Z8741: 1997 on the surface of the coating layer side, more preferably 3% or more. Note that the upper limit of the specular gloss is about 30%.
The specular glossiness means an average value when measurements are made at 20 arbitrary locations.

[Decorative sheet]
The decorative sheet of the present invention comprises the above-described coating sheet of the present invention.
Such decorative sheets include, for example, interior materials for buildings such as walls, ceilings, and floors; fittings such as window frames, doors, and handrails; furniture; housings for home appliances and OA equipment; exterior materials such as entrance doors By using as a surface material (decorative sheet) of the adherend, extremely good wear resistance can be imparted to the adherend. In particular, it is preferably used as a surface material (decorative sheet) of an adherend that is frequently cleaned, such as interior materials, joinery, and furniture.

[Cosmetic materials]
The decorative material of the present invention is formed by laminating an adherend and a surface opposite to the above-described coating layer of the decorative sheet of the present invention.
The material of the adherend is, for example, wood veneer, wood plywood, particle board, MDF (medium density fiber board), etc .; gypsum board such as gypsum board, gypsum slag board; calcium silicate board, asbestos slate board, Cement boards such as lightweight foamed concrete board and hollow extruded cement board; fiber cement boards such as pulp cement board, asbestos cement board and wood chip cement board; ceramic boards such as earthenware, porcelain, earthenware, glass and firewood; iron board, galvanized steel sheet Metal plates such as steel sheets coated with polyvinyl chloride sol, aluminum plates, copper plates; thermoplastic resin plates such as polyolefin resin plates, acrylic resin plates, ABS plates, polycarbonate plates; phenol resin plates, urea resin plates, unsaturated polyester resin plates, Thermosetting resin plates such as polyurethane resin plates, epoxy resin plates, melamine resin plates; phenol resins, urea resins, unsaturated polymers Examples include so-called FRP plates in which resins such as ester resins, polyurethane resins, epoxy resins, melamine resins, diallyl phthalate resins, etc. are impregnated and cured on glass fiber nonwoven fabrics, fabrics, papers, and other various fibrous base materials. These may be used alone, or may be used as a composite substrate in which two or more of these are laminated.

The method for laminating the decorative sheet on the various adherends is not particularly limited, and examples thereof include means for laminating via the back primer layer described above or laminating via an adhesive.
What is necessary is just to select an adhesive agent suitably from well-known adhesive agents according to the kind etc. of to-be-adhered material. Examples include polyvinyl acetate, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, ethylene-acrylic acid copolymer, ionomer, butadiene-acrylonitrile rubber, neoprene rubber, natural rubber, and the like.

  For example, decorative materials are preferably used as interior materials for buildings such as walls, ceilings and floors; fittings such as window frames, doors and handrails; furniture; housings for home appliances and OA equipment; exterior materials such as entrance doors. be able to. Among them, it is preferable to use it as an interior material for buildings, and it is preferable to use it for floors.

  EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited at all by this example. “Part” is based on mass unless otherwise specified.

1. Measurement and Evaluation The following measurements and evaluations were performed on the coating sheets prepared in Examples and Comparative Examples. The results are shown in Table 1.

1-1. Measurement of particle size distribution Using a particle size distribution measuring device (manufactured by Shimadzu Corporation, trade name SALD-2200, measurement method: laser diffraction scattering method), the silica of the coating layer used in Examples and Comparative Examples under the following conditions the particle size distribution and average particle diameter on a volume basis is measured, the measurement results from _{D + 1 / 4P, D +} 2 / 4P and _{D + 3 / 4P, D P} , D -1 / 4P, D -2 / 4P and D _{- 3 / 4P} led. In addition, the width of one section when calculating the existence ratio of the particle size distribution complies with the above definition.

1-2. Taber abrasion test A coating sheet was fixed horizontally on a rotating disk of a Taber abrasion tester, and an abrasion test was performed under the following conditions. The case where the residual rate of the grain pattern after the test was 50% or more was indicated as “◯”, and the case where the residual rate of the grain pattern after the test was less than 50% was indicated as “x”.
(Test conditions)
Turntable material: JAS special plywood wear base material: Two rubber discs (those specified in JIS A1453: 1973) wrapped with wear paper (S42) Use load: 500g including the weight of the wear base material (250g x 2)
Test time: Until 50 rotations are completed

1-3. Martindale Test Using a Martindale tester, an abrasion test was performed under the following conditions in accordance with JIS L1096: 2010 E method (Martindale method). “◎” indicates that there is almost no change in the surface after the test, “○” indicates a slight change in gloss on the surface after the test, but it is not noticeable for practical use, and scratches on the surface after the test. “×” was confirmed.
(Test conditions)
Wear base material: Product name Scotch Bright 7446 manufactured by 3M
Load: 6N
Friction table motion method: Lissajous circular motion test time: Until the number of friction is 100 times

1-4. Specular Glossiness Based on JIS Z8741: 1997, the 60-degree specular glossiness of the coating layer side surface of the coating sheet was measured.

2. Preparation of coating sheet [Example 1]
A colored layer having a thickness of 2 μm and a pattern layer having a grain pattern of 2 μm in thickness were sequentially formed on a white thin paper base (made by Oji F-Tex Co., Ltd., trade name T-print S30, basis weight 30 g / m ² ) by a gravure printing method. In addition, the colored layer used the mixture which mix | blended the coloring agent with the 2-component hardening urethane resin which consists of the polyol which has a polyester-type urethane as a principal chain, and a hexamethylene diisocyanate. Moreover, the mixture with which the coloring agent was mixed with the acrylic resin and the nitrocellulose type resin was used for the pattern layer.
Next, a sealer layer having a thickness of 2 μm was formed on the pattern layer. The sealer layer is a two-part cured acrylic urethane resin composed of an acrylic polyol and hexamethylene diisocyanate, and a sealer layer coating liquid containing silica (average particle size 1 μm) (mass ratio of the two-part cured acrylic urethane resin and silica = 75:25) was applied and dried.
Next, an electron beam curable resin composition comprising a urethane acrylate oligomer and a coating layer coating solution containing silica (Mohs hardness 7.0) (mass ratio of the electron beam curable resin composition to silica = 85: 15) Then, it is applied so that the thickness after drying becomes 9 μm, and an electron beam (acceleration voltage: 165 keV, irradiation amount: 3 Mrad) is irradiated to crosslink and cure the electron beam curable resin composition, and further cured at 70 ° C. for 24 hours. Thus, a coating sheet (decorative sheet) of Example 1 was obtained.

[Examples 2 to 5], [Comparative Examples 1 to 4]
A coating sheet (decorative sheet) was obtained in the same manner as in Example 1 except that the silica of the coating layer was changed to one having a particle size distribution shown in Table 1.

From the results of Table 1, it can be confirmed that the coating sheets (decorative sheets) of Examples 1 to 5 satisfying the condition (1) have extremely excellent wear resistance. Among them, the coating sheets (decorative sheets) of Examples 1 to 3 that satisfy the condition of 3.5T ≦ D _{+ 1 / 4P} ≦ 5.0 were particularly excellent in wear resistance.
On the other hand, the coating sheets (decorative sheets) of Comparative Examples 1 to 4 that do not satisfy the condition (1) show good results in the Taber abrasion test, which is the mainstream as a method for evaluating abrasion resistance, but wear resistance in daily life. In the Martindale test highly correlated with the property, scratches were generated and the wear resistance was not good.

  Since the coating sheet, decorative sheet, and decorative material of the present invention are extremely excellent in abrasion resistance, they are useful in that they can greatly suppress the gradual damage of the surface in daily life and can suppress a decrease in design.

DESCRIPTION OF SYMBOLS 10: Base material 20: Sealer layer 30: Design layer 31: Colored layer 32: Picture layer 40: Top part 50: Coat layer 51: Particle 52: Binder resin 100: Coating sheet

Claims (11)

A coating sheet comprising a coating layer containing a binder resin and particles on a substrate, wherein the peak value of the volume-based particle size distribution of the particles is P, and the particle size distribution is 1 A coating sheet in which D _{+ 1 / 4P} and T satisfy the following condition (1), where D _{+ 1 / 4P} is the particle diameter on the larger side of the particle diameter indicating _{/ 4P} , and T is the thickness of the coating layer.
3.0T ≦ D _{+ 1 / 4P} (1) The coating sheet of Claim ₁ whose said conditions (1) are 3.0T <= D _{+ 1 / 4P} <= 6.0T. _{2. When} D _{+ 2 / 4P} is used as the particle diameter on the larger side among the particle diameters in which the abundance ratio of the particle size distribution is 2 / 4P, D _{+ 2 / 4P} and T satisfy the following condition (2). Or the coating sheet of 2.
2.3T ≦ D _{+ 2 / 4P} (2) The particle size distribution having an abundance ratio of 3 / 4P, wherein D _{+ 3 / 4P} and T satisfy the following condition (3) when the larger particle size is D _{+ 3 / 4P.} The coating sheet of any one of -3.
1.7T ≦ D _{+ 3 / 4P} (3) When the existence ratio of the particle diameter distribution has a particle size showing the P and D _P, D _P and T satisfy the following condition (4), a coating sheet according to claim 1.
1.5T ≦ D _P (4)   The coating sheet according to claim 1, wherein the coating layer has a thickness T of 5 to 15 μm.   The coating sheet according to any one of claims 1 to 6, wherein the particles are inorganic particles having a Mohs hardness of 4 to 8.   The coating sheet according to any one of claims 1 to 7, wherein the binder resin is a cured product of an ionizing radiation curable resin composition containing a polyfunctional urethane (meth) acrylate oligomer.   The coating sheet of any one of Claims 1-8 which has a design layer between the said base material and the said coating layer, or the opposite side to the said coating layer of the said base material.   A decorative sheet comprising the coating sheet according to any one of claims 1 to 9.   A decorative material obtained by laminating and integrating an adherend and a surface opposite to the coat layer of the decorative sheet according to claim 10.