JP2019209499A - Decorative sheet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a decorative sheet which is excellent in stain resistance and design, and has a visual three-dimensional effect while maintaining a three-dimensional effect by touch. A decorative sheet (8) is a transparent thermoplastic resin having a pattern layer (2) formed on a base sheet (1), a transparent adhesive layer (3) formed on the pattern layer (2), and an uneven pattern by embossing. A layer 4, a first surface protection layer 5, and a second surface protection layer 6 partially formed on the first surface protection layer 5 are provided, and the second surface protection layer 6 is The average particle size was measured according to JIS B0601: 2001, which contained a filler composed of a filler A having a particle size of 1.5 to 5 μm and a filler B having a particle size of 8 μm to 20 μm and was equivalent to the maximum height of the second surface protective layer. The maximum height Rmax value is 30 μm or more. [Selection diagram] Figure 1

Description

  The present invention relates to a decorative sheet, and particularly relates to a decorative sheet that is excellent in surface three-dimensional design and feel.

  2. Description of the Related Art Conventionally, as a decorative sheet used for interior decoration of buildings, furniture, cabinets, or interior decoration of vehicles, and particularly for having a three-dimensional design and a feel on the surface, there is a technique described in Patent Document 1, for example. .

In the technique described in Patent Document 1,
A pattern layer formed on the substrate sheet, a first surface protective layer formed on the pattern layer, and a second surface protective layer formed on the first surface protective layer; The second surface protective layer includes synthetic resin beads protruding from the second surface protective layer. Thereby, the unevenness | corrugation is provided in the surface of a decorative sheet and it is made to feel a three-dimensional effect by tactile sense.
Further, in such a decorative sheet, in order to obtain a three-dimensional effect by visual observation, the gloss of the outermost layer (gloss of the second surface protective layer) and the gloss of the layer inside the outermost layer (first surface protective layer) ).

Japanese Patent Laying-Open No. 2015-77709

  However, in the technique described in Patent Document 1, when the glossiness of the decorative sheet is to be lowered, the designability can be lowered due to the cloudiness of the protective layer.

  The present invention focuses on the above points, and provides a decorative sheet that is excellent in design by suppressing the white turbidity of the protective layer while maintaining the three-dimensional effect by tactile sensation, and further has a visual three-dimensional effect. It is aimed.

In order to solve the above problems, the first aspect of the decorative sheet in the present invention is:
On the base sheet, a pattern layer, a transparent adhesive layer, a transparent thermoplastic resin layer provided with an uneven pattern by embossing, and a surface protective layer are formed in this order,
The surface protective layer comprises a first surface protective layer formed on the transparent thermoplastic resin layer and a second surface protective layer partially formed on the first surface protective layer,
The second surface protective layer includes a filler composed of a mixture of a filler A having an average particle diameter of 1.5 to 5 μm and a filler B having an average particle diameter of 8 to 20 μm,
The decorative sheet is characterized in that the maximum height Rmax measured in accordance with JIS B0601: 2001, which corresponds to the maximum height of the second surface protective layer, is 30 μm or more.

The second aspect of the present invention is
The decorative sheet according to claim 1, wherein the second surface protective layer is formed in a pattern synchronized with a pattern of the pattern pattern layer.

The third aspect of the present invention is
The decorative sheet is characterized in that the filler A contained in the second surface protective layer is made of an acrylic resin, and the filler B is made of silica.

The fourth aspect of the present invention is
The second surface protective layer is a decorative sheet made of an ionizing radiation curable resin.

According to the present invention, the second surface protective layer is a filler made of a mixture of filler A having an average particle diameter of 1.5 to 5 μm and filler B having an average particle size of 8 to 20 μm. The filler A can be mainly responsible for adjusting the glossiness, and the coating height of the protective layer and imparting scratch resistance can be mainly assigned to the filler B.
Therefore, while adjusting the gloss of the first surface protective layer and the second surface protective layer within a range in which a visual three-dimensional effect can be expressed, the white turbidity of the protective layer is suppressed, and the bulk height of the second protective layer is 30 μm or more. Therefore, it is possible to provide a decoratively good decorative sheet having excellent scratch resistance and a visual three-dimensional effect while maintaining a three-dimensional effect by tactile sensation.

It is a cross-sectional schematic diagram showing the decorative sheet which concerns on embodiment of this invention.

Next, embodiments of the present invention will be described with reference to the drawings.
Here, the drawings are schematic, and the relationship between the thickness and the planar dimensions, the ratio of the thickness of each layer, and the like are different from the actual ones. Further, the embodiment described below exemplifies a configuration for embodying the technical idea of the present invention, and the technical idea of the present invention is that the material, shape, structure, etc. of the component parts are as follows. It is not something specific. The technical idea of the present invention can be variously modified within the technical scope defined by the claims described in the claims.

As shown in FIG. 1, the decorative sheet 8 of the present embodiment has a pattern layer 2, a transparent adhesive layer 3, and a transparent thermoplastic resin layer 4 laminated on one surface (front surface) side of the base sheet 1, Further, a first surface protective layer 5 and a second surface protective layer 6 are laminated.
Moreover, the back surface resin coat layer 7 which comprises a resin layer is provided in the surface (back surface) on the opposite side to the design pattern layer 2 in the base material sheet 1.

(Substrate sheet)
The base sheet 1 is made of, for example, a colored thermoplastic resin. As the thermoplastic resin, for example, vinyl chloride resin, acrylic resin, polyolefin-based polypropylene resin or polyethylene resin can be used. Among these, polyolefin resins can be preferably used in terms of environmental compatibility, processability, and cost.
In addition, the grade and composition of the resin can be selected in consideration of ease of sheeting, printability and suitability for bending.

  When the base material sheet 1 is colored, the base material to which the decorative sheet is bonded is concealed, and the hue can be appropriately selected as the background color of the pattern pattern layer 2. For example, when a thermoplastic resin is sheeted, it can be colored by mixing and kneading a colorant such as a pigment. Alternatively, a colored layer can be provided under the pattern layer 2 by using a coating or printing technique as a solid ink layer before the pattern layer 2 is provided.

(Pattern pattern layer)
The pattern layer 2 is a layer for forming a pattern for imparting design properties, which is formed on the base sheet 1 by a known printing technique. The printing method is not particularly limited, but for example, a gravure printing method can be used in consideration of productivity and picture quality.
As the pattern, for example, a pattern suitable for a place where the decorative sheet 8 is used, such as wood grain, cork, stone, tile, pottery, and abstract pattern, can be selected.

  The printing ink that forms the pattern of the pattern layer 2 is not particularly limited, but an ink corresponding to the printing method can be selected as appropriate. In particular, it is preferable to select in consideration of adhesion to the substrate sheet 1 made of resin, printability, or weather resistance as a decorative material.

  If necessary, an adhesive layer (not shown) is formed on the pattern layer 2 for the purpose of improving the adhesion between the pattern layer 2 and the transparent adhesive layer 3 and between the transparent adhesive layer 3 and the transparent thermoplastic resin layer 4. May be provided. The resin used for the adhesive layer (not shown) is not particularly limited. For example, a two-component curable urethane resin can be used, and for example, it can be provided using a coating apparatus, a gravure printing apparatus, or the like.

(Transparent adhesive layer and transparent thermoplastic resin layer)
The transparent adhesive layer 3 covers the design pattern of the design pattern layer 2 as shown in FIG. 1 for the purpose of strengthening the adhesion between the base sheet 1 and the design pattern layer 2 and the transparent thermoplastic resin layer 4. Is provided. When this adhesion is strong, it is possible to give the decorative sheet 8 bending workability that follows a curved surface or a right-angled surface.
For the transparent adhesive layer 3, any material can be selected as the adhesion method, and there are lamination methods such as thermal lamination, extrusion lamination, and dry lamination, and the adhesive is acrylic, polyester, polyurethane, epoxy, or the like. It can be selected as appropriate. In general, it is desirable to use a urethane-based material obtained by a reaction with a polyol using an isocyanate as a two-component curing type because of its cohesive strength.
In addition, you may abbreviate | omit the transparent contact bonding layer 3, when the adhesive strength of the transparent thermoplastic resin layer 4 and the pattern pattern layer 2 is fully obtained.

  For the transparent thermoplastic resin layer 4, for example, a vinyl chloride resin, an acrylic resin, a polyolefin-based polypropylene resin, or a polyethylene resin can be used. Of these, polyolefin resins can be preferably used in terms of environmental compatibility, processability, and cost. It is important to select the grade and composition of the resin in consideration of the ease of sheeting and printability, as well as the bendability that does not cause whitening or cracking in the bending processability.

  The transparent thermoplastic resin layer 4 has an effect that the decorative sheet has a thickness and depth that are designed to increase, and can improve the weather resistance and wear resistance of the decorative sheet.

(First surface protective layer)
The first surface protective layer 5 is a sheet-like layer that is formed on the transparent thermoplastic resin layer 4 and covers the entire transparent thermoplastic resin layer 4. The first surface protective layer 5 is formed of a material (resin) that is transparent or translucent to such an extent that the pattern of the pattern layer 2 can be seen through the first surface protective layer 5. The first surface protective layer 5 may be a single layer, or a plurality of layers may be stacked to form the surface protective layer 5.

As a material of the first surface protective layer 5, for example, an ionizing radiation curable resin, a thermosetting resin, or a mixed resin thereof can be used. Here, the ionizing radiation means an electromagnetic wave and a charged particle beam that can crosslink the organic resin constituting the protective layer directly or indirectly through activation of a reaction initiator. Ultraviolet rays or electron beams are used.
As the ionizing radiation curable resin, an ultraviolet curable resin that can widely select the introduction cost of the equipment and the resin to be used can be preferably used. As the ultraviolet curable resin, for example, (meth) acrylic resin, silicone resin, polyester resin, urethane resin, amide resin, epoxy resin, and polycarbonate resin can be used.

The thermosetting resin has a urethane bond such as a two-component curable urethane resin in consideration of, for example, adhesion to the second surface protective layer 6, deformation followability of the decorative sheet 8, and scratch resistance. It is preferable to use a thermosetting resin (binder). A matting agent such as silica particles may be added to the thermosetting resin.
As the two-component curable urethane resin, for example, a urethane resin mainly containing a polyol and having an isocyanate as a crosslinking agent (curing agent) can be used. The polyol has two or more hydroxyl groups in the molecule, and for example, polyethylene glycol, polypropylene glycol, acrylic polyol, polyester polyol, polyether polyol, polycarbonate polyol, and polyurethane polyol can be used.

As the isocyanate, a polyvalent isocyanate having two or more isocyanate groups in the molecule can be used. For example, aromatic isocyanate such as 2,4-tolylene diisocyanate, xylene diisocyanate, 4,4'-diphenylmethane diisocyanate, or 1,6-hexamethylene diisocyanate, isophorone diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated diphenylmethane diisocyanate, etc. Aliphatic (or alicyclic) isocyanates can be used.
Also, adducts or multimers of the above various isocyanates can be used. For example, there are tolylene diisocyanate adducts, tolylene diisocyanate trimers, and the like. In the above isocyanate, an aliphatic (or alicyclic) isocyanate is preferable in that weather resistance and heat-resistant yellowing can be improved, and for example, 1,6-hexamethylene diisocyanate can be used.

  Scratch resistance and stain resistance of the decorative sheet 8 can be obtained by the first surface protective layer 5 exposed on the surface.

(Second surface protective layer)
The second surface protective layer 6 is partially formed on the first surface protective layer 5 and covers a part of the first surface protective layer 5 (for example, a portion facing the printing ink of the pattern layer 2). It is a layer to do. Thereby, the design of the decorative sheet 8 can be expressed by both the vision derived from the pattern layer 2 and the tactile sensation derived from the unevenness of the surface protective layer 6.

  For example, the second surface protective layer 6 may be formed in an area of 0.1% or more on the first surface protective layer 5. In the present embodiment, since the first surface protective layer 5 has high scratch resistance and stain resistance, the decorative sheet 8 can be made scratch resistant and stain resistant even if the area of the second surface protective layer 6 is small. It can be excellent.

The second surface protective layer 6 is formed of a material (resin) that is transparent or translucent so that the pattern of the pattern layer 2 can be seen through the second surface protective layer 6 and the first surface protective layer 5. Has been.
As a material for the second surface protective layer 6, an ionizing radiation curable resin is preferable. As the ionizing radiation curable resin, the aforementioned resin composition can be used. In consideration of the adhesiveness with the first surface protective layer 5 and the like, a thermosetting resin having a urethane bond such as a two-component curable urethane resin can be added to adjust the hardness and flexibility. .

The surface of the second surface protective layer 6 can give a three-dimensional effect due to a tactile sensation by setting the maximum height Rmax measured with a contact roughness meter based on JIS B0601: 2001 to 30 μm or more.
In order to effectively obtain the tactile sensation, the value indicated by the ratio H / L between the length L in the width direction and the maximum height H of the partially formed second surface protective layer 6 is preferably 0.25 or more, preferably Is 0.33 or more, and is preferably formed of an independent region as appropriate.

  Even when the area of the second surface protective layer 6 is large, the distance of 100 μm from the formation end of the surface protective layer 6 is regarded as L, and the rising of the height falls within the above range, so that the boundary stereoscopic effect is tactile. Can be made to feel properly.

  Further, by appropriately adding a filler as a matting agent, the gloss (gloss) of the first surface protective layer 5 and the gloss of the second surface protective layer 6 can be made different. The gloss value is arbitrarily selected from the design requirements under the conditions of use of the decorative sheet, and is used in the range of about 4 to 60. The difference in gloss value between the two layers is the difference in visual observation even at low gloss. It is preferably 3 or more so that it can be felt, and in high gloss, it is difficult to feel a change when the difference in gloss is small, so that it is preferable that there is a contrast of about 50% of the background gloss value. In practice, if there is a difference of up to about 15, an excellent design effect can be obtained. Therefore, the difference in gloss is in the range of 0-30, preferably 3-15.

  In this way, by forming the second surface protective layer 6 with a gloss different from that of the first surface protective layer 5, the second surface protective layer 6 and the first surface protective layer 5 provide a visual stereoscopic effect. Can be expressed appropriately. Further, by using an ionizing radiation resin, even if the protective layer is thickened when the maximum height Rmax of the second surface protective layer 6 is set to 30 μm or more, the shape can be maintained by curing in a short time. The sheet can be continuously processed by winding the sheet on a roll.

The filler contained in the second surface protective layer 6 includes a filler made of a mixture of filler A having an average particle diameter of 1.5 to 5 μm and filler B having an average particle diameter of 8 to 20 μm. The intent is to balance gloss with coating height and scratch resistance.
In order to obtain the above-described coating height and gloss, the filler A mainly functions as a matting agent, and the filler B mainly functions as imparting scratch resistance and maintaining the coating height. At this time, the filler A has an average particle size as small as 1.5 to 5 μm, and since the light reflection area is increased by forming fine irregularities on the surface of the surface protective layer 6, the filler A is efficiently glossy with respect to the addition amount. Adjustments can be made. On the other hand, since the filler B has a large average particle size of 8 μm to 20 μm, it acts as a resin support for the second surface protective layer 6 and has the effect of suppressing the flow of the uncured resin immediately after coating and the scratch resistance after curing. Can be improved.

As the material of the filler added to the surface protective layer 6, for example, highly transparent acrylic resin beads as a synthetic resin, or surface-treated inorganic fillers, preferably silica glass beads can be used. Any material can be used for both the fillers A and B, but the refractive index of the filler A is close to that of the constituent resin of the surface protective layer 6 in terms of both the gloss adjustment ability and the transmission visibility of the pattern layer 2. Acrylic resin beads are preferred.
The filler B is preferably an inorganic filler from the viewpoint of imparting scratch resistance, and silica glass beads are preferred. In consideration of the close contact with the surface protective layer 6, it is possible to select one that has been subjected to an affinity treatment by a known surface treatment technique.

The filler is preferably contained in an amount of 3% by mass or more based on the total mass of the second surface protective layer 6. Thereby, the gloss of the 2nd surface protective layer 6 can fully be reduced, and the gloss difference of the 2nd surface protective layer 6 and the 1st surface protective layer 5 can be adjusted. Therefore, even if the area of the second surface protective layer 6 is small with respect to the total area of the first surface protective layer 5, a visual stereoscopic effect can be appropriately felt. In addition, the addition upper limit of a filler shall be 35 mass% or less with respect to the total mass of a thermosetting resin. Addition of 35% by mass or more deteriorates the bending workability of the surface protective layer 6, and it is difficult to avoid design deterioration due to white turbidity after coating or foaming during coating drying.

  As described above, in the present embodiment, the second surface protective layer is made of a filler composed of a mixture of filler A having an average particle diameter of 1.5 to 5 μm and filler B having an average particle diameter of 8 to 20 μm. The filler A can be mainly responsible for adjusting the glossiness of the surface protective layer, and the coating height of the protective layer and imparting scratch resistance can be mainly assigned to the filler B. Therefore, while adjusting the gloss of the first surface protective layer and the second surface protective layer within a range in which a visual stereoscopic effect can be expressed, the white turbidity of the protective layer is suppressed, and the bulk height of the second protective layer is 30 μm. It becomes possible to provide scratch resistance while maintaining the above, and it is possible to provide a decoratively good decorative sheet having excellent scratch resistance and a visual stereoscopic effect while maintaining a three-dimensional effect by tactile sensation.

  The effects exhibited by one embodiment of the present invention will be described below using Examples and Comparative Examples.

<Example 1>
A pattern is printed on a 60 μm-thick polypropylene-based sheet using urethane / vinyl acetate ink, and a 70 μm-thickness is formed on the pattern layer via a polyurethane-based transparent adhesive layer having a thickness of 5 μm. Were laminated by melt extrusion lamination to form a transparent adhesive layer and a transparent thermoplastic resin layer.
Embossing is performed from above the transparent thermoplastic resin layer using a shaping plate having a plate depth of 20 μm, and the first surface protective layer 1 in which acrylic polyol resin and HDI (hexamethylene diisocyanate) are mixed is gravure coated to a thickness of 6 μm. Formed with. Furthermore, using a printing plate that matches the pattern layer from the top of the first surface protective layer, an ultraviolet curable resin mainly composed of urethane acrylate is stacked with a thickness of 30 μm, and cured with a high-pressure mercury lamp to form a second surface protective layer. did.
The gloss of the first surface protective layer is 10, and the gloss of the second surface protective layer is 4 by adding 3 parts by weight of acrylic beads having an average particle diameter of 2 μm and 3 parts by weight of silica glass beads having an average particle diameter of 18 μm. .

<Comparative Example 1>
It was created in the same manner as in Example 1 except that the thickness of the second surface protective layer was 20 μm.

<Comparative example 2>
It was created in the same manner as in Example 1 except that the thickness of the second surface protective layer was 10 μm.

<Comparative Example 3>
The second surface protective layer was prepared in the same manner as in Example 1 except that the acrylic beads of the average particle diameter were changed to 5 μm.

<Comparative example 4>
The same procedure as in Example 1 was performed except that the silica glass beads of the second surface protective layer were changed to acrylic beads having an average particle diameter of 19 μm.

<Comparative Example 5>
The printing plate of the second surface protective layer was prepared in the same manner as in Example 1 except that a solid plate having a coating thickness of 25 μm was used.

<Comparative Example 6>
The second surface protective layer was prepared in the same manner as in Example 1 except that a mixed binder resin of acrylic polyol and HDI was used and the coating was placed at 40 ° C. for 72 hours and cured after coating.

(Evaluation of three-dimensional effect)
For Example 1 and Comparative Examples 1 and 2, the three-dimensional effect was evaluated by touching the finger, and a feeling of unevenness was evaluated as ◯, a feeling of unevenness was slightly felt as Δ, and a feeling of unevenness was not felt. The thing was made into x. The results are shown in Table 1.

  In Comparative Examples 1 and 2 in which the thickness of the second surface protective layer was less than 30 μm, the unevenness due to finger touch was weakened, and the design having a three-dimensional effect was inferior.

(Scratch resistance and design evaluation)
Next, for Example 1 and Comparative Examples 3 to 5, the scratches on the surface were compared by reciprocating the surface 10 times with steel wool with a load of 20 g / cm ² as an evaluation of scratch resistance. Moreover, the designability was evaluated from the gloss and the appearance of the coated surface of the second surface protective layer.
In Comparative Example 3, the transparency of the filler was inferior to that of Example 1 and became cloudy, so the transparency of the pattern layer was poor and the design was inferior.
In Comparative Example 4, there was no problem in appearance and unevenness, but the results were poor in scratch resistance.
As for Comparative Example 5, as a result of forming a protective layer on the entire surface rather than overprinting the surface protective layer 2 corresponding to the pattern, the appearance was deteriorated by foaming, the texture was sandy, and was consistent with the pattern The result was inferior in design compared to the three-dimensional effect.
Table 2 shows the results.

For Comparative Example 6, when the sheet was wound and cured after the coating process of the second surface protective layer, the uncured resin adhered to the back surface of the sheet, causing sheet breakage or surface resin transfer, The above trouble occurred.
These troubles did not occur when the second surface protective layer was formed of an ultraviolet curable resin.

DESCRIPTION OF SYMBOLS 1 Base material sheet 2 Picture pattern layer 3 Transparent adhesive layer 4 Transparent thermoplastic resin layer 5 1st surface protective layer 6 2nd surface protective layer 7 Back surface resin coat layer 8 Cosmetic sheet

Claims (4)

On the base sheet, a pattern layer, a transparent adhesive layer, a transparent thermoplastic resin layer provided with an uneven pattern by embossing, and a surface protective layer are formed in this order,
The surface protective layer comprises a first surface protective layer formed on the transparent thermoplastic resin layer and a second surface protective layer partially formed on the first surface protective layer,
The second surface protective layer includes a filler composed of a mixture of a filler A having an average particle diameter of 1.5 to 5 μm and a filler B having an average particle diameter of 8 μm to 20 μm, and has a maximum height of the second surface protective layer. A decorative sheet characterized in that the maximum height Rmax value measured in accordance with JIS B0601: 2001 is 30 μm or more.   The decorative sheet according to claim 1, wherein the second surface protective layer is formed in a pattern synchronized with a pattern of the pattern pattern layer.   The decorative sheet according to claim 1 or 2, wherein the filler A contained in the second surface protective layer is made of an acrylic resin, and the filler B is made of silica.   The decorative sheet according to any one of claims 1 to 3, wherein the second surface protective layer is made of an ionizing radiation curable resin.