JP2021186980A - Decorative sheet and method for manufacturing the same, and decorative board using the same - Google Patents

Abstract

To provide a decorative sheet capable of preventing weather resistance deterioration of a colored ink layer, a method for manufacturing the same, and a decorative board using the same.SOLUTION: There is provided a decorative sheet, comprising: a base material 11; a colored ink layer 12 formed by directly applying a mixed solution containing a coloring ink and 20 pts.wt. or more and 50 pts.wt. or less of titanium oxide based on 100 pts.wt. of the coloring ink to a surface of the base material 11; and a surface protective layer 13 directly applied to the surface of the colored ink layer 12 to protect the surface. Thickness of the colored ink layer 12 may be 3 μm or more and 10 μm or less, the base material 11 is a thermoplastic resin, and embossing may be formed on the surface of the base material between the same and the colored ink layer 12, and a primer layer may be formed on a back surface of the base material 11 to increase adhesion to the base material to be attached to the back surface.SELECTED DRAWING: Figure 1

Description

The present invention relates to a decorative sheet capable of preventing weather resistance deterioration of a colored ink layer, a method for producing the same, and a decorative board using the same.

Conventionally, a colored ink layer is formed on the surface of a base material, and a surface protective layer is further formed on the surface of the colored ink layer to protect the colored ink layer.
However, if the coating film of the surface protective layer has pinholes such as slight omissions, the colored ink layer is directly exposed to light or moisture, and the colored ink layer is embrittled and the cohesive force is reduced, resulting in significant deterioration. rice field.

Further, conventionally, a polyolefin-based decorative sheet in which a transparent resin coating layer is laminated on a pattern layer is known (see paragraph [0020] of Patent Document 1 and FIG. 2).

Japanese Unexamined Patent Publication No. 2000-21179

However, in order to prevent deterioration of the colored ink layer with respect to the conventional surface protective layer, a thermoplastic transparent PP layer can be laminated on the surface side of the colored ink layer. There was a problem that the cost was high.
In addition, since the surface protective layer is coated without removing pinholes, etc., it is possible to take measures by applying a smoothing roll, but the smoothing roll is productive because agglomerates of the resin to be coated accumulate or streaks. There was a problem with it, and it was impossible to paint it completely.

On the other hand, in Patent Document 1, a colored solid printing layer is formed under the pattern layer, and 20 parts by weight of titanium oxide is added to the colored solid printing layer with respect to 100 parts by weight of the resin content of the ink. (See paragraph 1 of Patent Document 1 and FIG. 2).
However, the colored solid printing layer of Patent Document 1 is located above the primer layer, that is, between the primer layer and the pattern layer, and adheres by preventing harmful light rays from reaching the place where the primer is located. The purpose is to ensure long-term stability of sex (see paragraph [0007] of Patent Document 1 and FIG. 2). In that sense, in Patent Document 1, the present invention attempts to improve the weather resistance of the colored ink layer, whereas the two have different problems.
Therefore, one aspect of the present invention is to provide a decorative sheet capable of preventing weather resistance deterioration of the colored ink layer, a method for producing the same, and a decorative board using the decorative sheet in order to solve the above problems.

The decorative sheet according to one aspect of the present invention comprises a base material, a colored ink, and a mixed solution containing 20 parts by weight or more and 50 parts by weight or less of titanium oxide with respect to 100 parts by weight of the colored ink. It is characterized by comprising a colored ink layer formed by being directly applied to a surface and a surface protective layer formed by being directly applied to the surface of the colored ink layer to protect the surface.
Further, the decorative sheet according to one aspect of the present invention is characterized in that the thickness of the colored ink layer is 3 μm or more and 10 μm or less.

The decorative sheet according to one aspect of the present invention is characterized in that the base material is a thermoplastic resin, and the surface thereof is embossed with the colored ink layer.
The decorative sheet according to one aspect of the present invention is characterized in that a primer layer for enhancing adhesion to a substrate to be attached to the back surface is formed on the back surface of the base material.
In the decorative sheet according to one aspect of the present invention, the surface protective layer is one of three resins, a thermosetting resin, an ultraviolet curable resin, or an electron beam curable resin, or two of the three resins. It is characterized by being composed of a mixture of the above resins.

In the method for producing a decorative sheet according to one aspect of the present invention, a colored ink and a mixed solution containing 20 parts by weight or more of titanium oxide with respect to 100 parts by weight of the colored ink are directly applied to the surface of the base material. The colored ink layer is formed, and a surface protective layer that protects the surface is directly formed on the surface of the colored ink layer.
The decorative board according to one aspect of the present invention is characterized by comprising a substrate and a decorative sheet attached to the substrate via a primer layer.

According to one aspect of the present invention, it is possible to provide a decorative sheet capable of preventing weather resistance deterioration of a colored ink layer, a method for producing the same, and a decorative board using the same.

It is sectional drawing of the decorative sheet which concerns on 1st Embodiment.

(Cosmetic sheet 10)
In FIG. 1, reference numeral 10 denotes a decorative sheet according to the first embodiment, which is for an interior, is mainly a single color, and is a white color.
Although a single color is exemplified, the present invention is not limited to this, and a plurality of colors may be used, and a white system is exemplified as the single color, but other color systems may be used.

The decorative sheet 10 is formed from the following layers.
The following (1) to (4) will be described later.
(1) Base material 11
(2) Colored ink layer 12
(3) Surface protective layer 13
(4) Primer layer 14
The layer of the decorative sheet 10 is not limited to the four layers (1) to (4) described above, and for example, although not shown, the back surface side of the base material 11 is fixed to the substrate via the primer layer 14. It may be used as a 5-layer decorative board.

(Base material 11)
The base material 11 is a sheet containing a thermoplastic resin. As the thermoplastic resin, a polyester resin can be used. Specifically, polyethylene terephthalate, polybutylene terephthalate, polycyclohexylene methylene terephthalate, polyethylene naphthalate, polylactic acid and the like are used.

Further, although not shown, embossing is provided on the surface side of the base material 11, and for example, a satin-like embossing is formed.
The embossing is provided as necessary in order to give a three-dimensional design feeling to the surface side of the base material 11. The embossing is not limited to the satin finish, and any uneven shape can be used. For example, wood grain conduit shape, stone grain shape, cloth grain shape, abstract pattern shape, Japanese paper shape, suede shape, leather shape, sand grain shape can be used. , Hairline shape, parallel straight line group, parallel curve group or a combination thereof and the like can be used. Further, as a method for forming the embossing, for example, a doubling embossing method, an extrusion laminating simultaneous embossing method, or the like, which is performed before, after, or at the same time as laminating the thermoplastic resin layer on the surface of the base material 11, can be used.

(Colored ink layer 12)
The colored ink layer 12 is formed by directly applying a mixed solution containing 20 parts by weight or more of titanium oxide to 100 parts by weight of the colored ink and the colored ink directly on the surface side of the base material 11.
The blending amount of titanium oxide is preferably 20 parts by weight or more, 50 parts by weight or less, and preferably 25 parts by weight or more.
The thickness of the colored ink layer 12 is preferably, for example, 3 μm or more and 10 μm or less, and 5 μm or more and 7 μm or less in actual operation.

As the titanium oxide, for example, ^{a white pigment made of titanium dioxide TiO 2} having an average particle size of about 0.1 to 0.5 μm can be adopted. For example, KR-310 manufactured by Titanium Kogyo Co., Ltd. and Teikoku Kako Co., Ltd. Commercial products such as JR, FR-41 manufactured by Furukawa Mining Co., Ltd., CR-50 manufactured by Ishihara Sangyo Co., Ltd. can be adopted. Titanium oxide has anatase type (also known as anatase) and rutile type (also known as rutile), and has a refractive index of 2.45 to 2.55 and 2.61 to 2.90, respectively. The mold is preferable because it has a high refractive index and therefore has excellent concealing properties, as well as excellent chemical stability and light resistance.
Further, in addition to the above-mentioned effects of imparting concealment and coloring, these titanium oxides also have the effect of improving the adhesion to the base material 11 by the anchoring effect.

As for materials other than titanium oxide, opaque ink such as carbon black can be expected to be effective, but in the case of a single color sheet, it is often a white color, so titanium oxide was selected.
Further, the colored ink layer 12 is assumed to be a single color (ivory), and when the base material 11 has, for example, satin embossing, unevenness becomes conspicuous unless the coating amount is high and titanium oxide is highly filled. Thought it was even tougher.

In addition to the titanium oxide pigment described in detail above, a small amount of another pigment (for example, a concealing or non-concealing inorganic pigment or an organic pigment) is used in combination with the colored ink layer 12 for the purpose of adjusting the color tone. You may. However, it is important to mainly use titanium oxide pigments until it gets tired, and the amount of other pigments used is preferably 20% by mass or less based on the total amount of the pigments. Further, as the pigment to be used in combination, it is preferable to select a pigment having high light resistance, and among the inorganic pigments, cobalt blue, carbon black and the like, and among the organic pigments, a phthalocyanine pigment such as phthalocyanine blue is more preferable. .. Further, if necessary, an extender pigment such as silica, calcium carbonate, barium sulfate and the like can be used in combination.

(Surface protection layer 13)
The surface protective layer 13 is provided on the surface side of the colored ink layer 12 and is a layer for protecting the colored ink layer 12 and imparting good surface physical properties such as abrasion resistance and solvent resistance. As the material of the surface protective layer 13, for example, a resin having high transparency is preferable, but at least a resin having transparency enough to allow the embossing of the base material 11 to be seen through the colored ink layer 12 may be used. As long as it is, it may be a translucent or colored transparent resin.

(Primer layer 14)
The primer layer 14 is applied as necessary in order to improve the adhesion to the adhesive used for adhesion to the substrate (not shown) to which the base material 11 is attached.
For example, when the substrate is made of a wood-based material, an adhesive such as a vinyl acetate emulsion type or a two-component curable urethane type is used as the adhesive, so that the primer layer 14 is an adhesive thereof. It is desirable to design the resin according to the above. For example, urethane-based, acrylic-based, ethylene-vinyl acetate copolymer, vinyl chloride-vinyl acetate copolymer-based, polyester-based, and the like can be used. In particular, a two-component curable urethane-based primer or the like obtained by blending a polyester polyol and a polyisocyanate is preferable. Further, for example, adding an inorganic powder such as silica, barium sulfate, or calcium carbonate is effective in preventing blocking during winding and storage and improving the adhesive strength due to the anchoring effect.

(Production method)
The decorative sheet 10 having the above configuration is provided in the following order.
(1) Primer layer 14
(2) Base material 11
(3) Colored ink layer 12
(4) Surface protective layer 13

(Effect of the first embodiment)
The effects of the first embodiment are as follows.
First, according to the first embodiment, the colored ink layer 12 contains 20 parts by weight to 50 parts by weight of titanium oxide, which will be described later, in the adhesion test of cellophane tape (registered trademark) after the weather resistance test. Ink peeling can be suppressed, and embrittlement and deterioration of adhesion due to weather resistance deterioration can be prevented.
Secondly, according to the first embodiment, the thermoplastic transparent PP layer provided on the surface side of the colored ink layer 12 can be commercialized at a low cost.
Third, according to the first embodiment, when the base material 11 has embossing such as satin finish, it is difficult to apply the colored ink uniformly and it may become uneven, but it contains titanium oxide. By doing so, it has a concealing property and can make unevenness inconspicuous.

(Veneer)
Although not shown, the decorative board according to the second embodiment will be described.
Although not shown, the decorative board has a substrate attached to the back surface side of the primer layer 14 of the decorative sheet 10 having the above-described configuration.
The substrate is a plate-shaped member attached via an adhesive. As the substrate, for example, a substrate made of a wood-based material, a metal-based material, or a synthetic resin material can be used. As the substrate made of wood-based material, for example, wood veneer, wood plywood, laminated wood, particle board, medium density fiberboard, and hardboard can be adopted. Further, as the substrate made of a metal-based material, for example, a steel plate, a brass plate, an aluminum plate, a duralumin plate, or a stainless steel plate can be adopted. Further, as the substrate made of the synthetic resin material, for example, a vinyl chloride resin plate, an acrylic resin plate, or a polyolefin-based resin plate (polypropylene resin plate, polyethylene resin plate, etc.) can be adopted.

Hereinafter, Examples 1 and 2 and Comparative Examples 1 and 2 of the wood base material according to the first embodiment of the present invention will be described. The present invention is not limited to the following Examples 1 and 2.

(Example 1)
In Example 1, a decorative sheet was prepared with the following materials and procedures.
A pigment-blended random polypropylene sheet (manufactured by Riken Technos) with a thickness of 100 μm and an embossing depth of 25 μm is used as the base material, and a single color (ivory color) is used as a colored ink layer using urethane ink (Lamister manufactured by Toyo Ink Mfg. Co., Ltd.) by gravure printing. Formed.
The urethane ink contained 20 parts by weight of titanium oxide.
Further, the colored ink layer was formed so that the thickness was 5 to 7 μm.
Further, a thermosetting resin (urethane acrylate resin manufactured by DIC Graphic Corporation) was applied as a surface protective layer to a thickness of 5 μm to form a surface protective layer.

(Example 2)
Example 2 is the same as that of Example 1 except that the titanium oxide of the urethane ink is 50 parts by weight.
(Example 3)
Example 3 is the same as that of Example 1 except that titanium oxide of the urethane ink is 25 parts by weight.

(Example 4)
In Example 4, titanium oxide of the urethane ink is 25 parts by weight, and the colored ink layer is formed so as to have a thickness of 3 μm, and other than that, the same as in Example 1.
(Example 5)
In Example 5, titanium oxide of the urethane ink is 25 parts by weight, and the colored ink layer is formed so as to have a thickness of 10 μm, and other than that, the same as in Example 1.

(Comparative Example 1)
Comparative Example 1 is the same as that of Example 1 except that the content of titanium oxide is 15 parts by weight.
(Comparative Example 2)
Comparative Example 2 is the same as that of Example 1 except that the content of titanium oxide is 55 parts by weight.
(Comparative Example 3)
In Comparative Example 3, the content of titanium oxide is 25 parts by weight, and the colored ink layer is formed so as to have a thickness of 2 μm, and other than that, it is the same as that of Example 1.

(Evaluation method and evaluation criteria)
The physical properties of the decorative sheet were evaluated on the following two points: (1) SWOM2000h post-adhesion and (2) unevenness evaluation.
(Adhesion after SWOM2000h)
In the evaluation method of adhesion after SWOM2000h, the decorative sheets described in Examples 1 and 2 and Comparative Examples 1 and 2 were subjected to a sunshine weather meter test, taken out from the testing machine after 2,000 hours had passed, and cellophane tape was adhered to the covering portion. Then, it was vigorously peeled off in the direction of 45 °, and the presence and amount of ink and agglomerates of the surface protective layer attached to the cellophane tape side were observed.
The evaluation criteria for close contact after SWOM2000h were three grades of "○", "△", and "×", and "○" was evaluated as passing, and "△" and "×" below it were evaluated as failing.

(Evaluation of unevenness)
In the evaluation method of unevenness evaluation, the state of unevenness of the colored ink layer was visually judged.
The evaluation criteria for unevenness evaluation are four grades of "◎", "○", "△", and "×", and "◎" and "○" are passed, and "△" and "×" below that are rejected. I evaluated it.

(Evaluation results)
The evaluation results of the decorative sheet are shown in Table 1 below.

(Comparative Example 1)
In Comparative Example 1, since the content of titanium oxide was low, the weather resistance of the ink binder deteriorated, and the evaluation after SWOM 2000h was “Δ”, which was unacceptable.
As a result, it was speculated that the higher the content of titanium oxide, the less likely it is to deteriorate in weather resistance because it is an inorganic substance.
Further, in Comparative Example 1, when printing is performed on the embossed satin finish of the base material, it is difficult to apply a uniform film thickness to the unevenness. ", And it was a failure.
As a result, it was presumed that if the content of titanium oxide, which is opaque, is high, even if the film thickness is uneven, it cannot be seen as color tone unevenness.

(Comparative Example 2)
In Comparative Example 2, since the content of titanium oxide is high, the influence of weather resistance deterioration of the ink binder is small, but since the content of titanium oxide is high, the cohesive force is originally weak, and the evaluation of adhesion after SWOM2000h is "×". ", And it was a failure.
(Comparative Example 3)
In Comparative Example 3, the unevenness evaluation was “Δ” and the result was unacceptable. As a result, it was presumed that the thickness of the colored ink layer was too thin.

(Examples 1 to 5)
In Examples 1 to 5, both of the two physical property evaluations were "passed".
As a result, it was estimated that the suitable content range of titanium oxide was 20 parts by weight or more and 50 parts by weight or less.
In particular, in Examples 2 and 3, there was no unevenness in film thickness and color tone, and it was estimated that the content of titanium oxide was preferably 25 parts by weight or more and 50 parts by weight or less.

10 Decorative sheet 11 Base material 12 Colored ink layer 13 Surface protective layer 14 Primer layer

Claims (7)

With the base material
A colored ink layer formed by directly applying a mixed solution containing 20 parts by weight or more and 50 parts by weight or less of titanium oxide to the surface of the base material with respect to 100 parts by weight of the colored ink and the colored ink.
A decorative sheet characterized by comprising a surface protective layer formed by directly applying to the surface of the colored ink layer and protecting the surface. The decorative sheet according to claim 1, wherein the thickness of the colored ink layer is 3 μm or more and 10 μm or less. The base material is
It is a thermoplastic resin
The decorative sheet according to claim 1 or 2, wherein the surface is embossed with the colored ink layer. On the back surface of the base material,
The decorative sheet according to any one of claims 1 to 3, wherein a primer layer for enhancing adhesion to a substrate to be attached to the back surface is formed. The surface protective layer is
Claims 1 to 4 comprising a mixture of any one of the three resins of a thermosetting resin, an ultraviolet curable resin or an electron beam curable resin, or two or more of the three resins. The decorative sheet according to any one of the above items. A colored ink layer is formed by directly applying a colored ink and a mixed solution containing 20 parts by weight or more of titanium oxide to 100 parts by weight of the colored ink on the surface of the base material.
A method for producing a decorative sheet, which comprises directly forming a surface protective layer for protecting the surface on the surface of the colored ink layer. With the board
The decorative board according to any one of claims 1 to 5, comprising the decorative sheet according to any one of claims 1 to 5, which is attached to the substrate via a primer layer.

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