JP7115659B2 - Decorative sheets and decorative resin moldings - Google Patents

Description

The present disclosure relates to decorative sheets and decorative resin molded products.

2. Description of the Related Art Conventionally, a decorative resin molded product obtained by laminating a decorative sheet on the surface of a resin molded product is used for interior and exterior parts of vehicles, interior materials for building materials, home appliance housings, and the like. In the production of such a decorative resin molded article, a molding method or the like is used in which a decorative sheet provided with a design in advance is integrated with a resin by injection molding. As a representative example of such a molding method, a decorative sheet is formed into a three-dimensional shape in advance using a vacuum forming mold, the decorative sheet is inserted into an injection mold, and a resin in a fluid state is injected into the mold. The insert molding method, which integrates the resin and the decorative sheet by means of injection molding, and the simultaneous injection molding method, which integrates the decorative sheet inserted into the mold during injection molding, with the molten resin injected into the cavity. A decoration method is mentioned. In addition to the injection molding method, the decorative sheet is also used in a decorative method such as a vacuum pressure bonding method, in which a decorative sheet is adhered onto a pre-formed molded body while being heated or pressurized.

As a technique for imparting a high texture to a decorative resin molded product, a method of providing a resin layer containing a delustering agent on a decorative sheet, a method of providing an uneven shape on the surface of a decorative sheet, and the like are known. For example, in Patent Document 1, on a base material layer, a first resin layer containing a matting agent, a second resin layer partially provided on the first resin layer, and on the second resin layer describes a decorative sheet having a raised layer containing a resin and organic particles provided in this order. In the decorative sheet described in Patent Document 1, the second resin layer is partially laminated on the first resin layer containing the delustering agent, and the area laminated with the second resin layer is laminated. A difference in luster occurs between the non-stained area and high designability (gloss matte expression). Furthermore, by laminating the raised layer containing the resin and the organic particles on the second resin layer, it is possible to exhibit an excellent tactile sensation without impairing the gloss mat expression.

JP 2017-65261 A

The decorative sheet described in Patent Literature 1 has a high designability and exhibits an excellent tactile feel.

On the other hand, when producing a decorative resin molded product using a decorative sheet having an uneven shape, the uneven shape is deformed by heat and pressure when the decorative sheet is subjected to injection molding or preforming (vacuum molding) prior to injection molding. There is a problem that the difference between the uneven shape formed on the decorative sheet and the uneven shape of the decorative resin molded product after molding tends to increase, such as disappearance.

Under such circumstances, the main object of the present disclosure is to provide a decorative sheet in which changes in uneven shape due to molding are suppressed. Another object of the present disclosure is to provide a decorative resin molded product.

The present disclosure provides inventions in the following aspects.
Section 1. A decorative sheet having an uneven surface,
At least a substrate layer and a plurality of unevenness forming members arranged on one side of the substrate layer,
The one-side surface of the base layer has an uneven shape,
The decorative sheet, wherein the concave-convex shape of the base layer is formed by the concave-convex forming member.
Section 2. Item 2. The decorative sheet according to Item 1, having a first resin layer at least partly between the base material layer and the unevenness forming member.
Item 3. Item 3. The decorative sheet according to Item 2, wherein the first resin layer is present at a position corresponding to a position where the unevenness forming member is present.
Section 4. Item 4. The decorative sheet according to Item 2 or 3, wherein a region including the unevenness forming member and the first resin layer forms one collective protrusion.
Item 5. Item 5. The decorative sheet according to any one of Items 2 to 4, having a pattern layer between the base material layer and the first resin layer.
Item 6. Item 6. The decorative sheet according to any one of Items 1 to 5, which has a second resin layer on at least part of the side opposite to the base layer side of the unevenness forming member.
Item 7. 7. The decorative sheet according to item 6, which has a third resin layer on at least part of the second resin layer.
Item 8. 8. The decorative sheet according to any one of Items 1 to 7, wherein the irregularities on the surface of the decorative sheet are formed by the irregularity forming member.
Item 9. 9. The decorative sheet according to any one of Items 1 to 8, wherein the unevenness forming member is not exposed on the surface of the decorative sheet.
Item 10. Item 10. The decorative sheet according to any one of Items 1 to 9, wherein the unevenness forming member is a particle.
Item 11. A decorative resin molded article having an uneven surface,
having at least a molded resin layer, a substrate layer, and a plurality of unevenness-forming members arranged on one side of the substrate layer in this order;
The one-side surface of the base layer has an uneven shape,
A decorative resin molded article, wherein the uneven shape of the base material layer is formed by the unevenness forming member.

Advantageous Effects of Invention According to the present disclosure, it is possible to provide a decorative sheet in which changes in uneven shape due to molding are suppressed. Furthermore, according to the present disclosure, it is also possible to provide a decorative resin molded product.

1 is a schematic cross-sectional view of an example of a decorative sheet of the present disclosure; FIG. 1 is a schematic cross-sectional view of an example of a decorative sheet of the present disclosure; FIG. 1 is a schematic cross-sectional view of an example of a decorative sheet of the present disclosure; FIG. 1 is a schematic cross-sectional view of an example of a decorative sheet of the present disclosure; FIG. 1 is a schematic cross-sectional view of an example of a decorative sheet of the present disclosure; FIG. 1 is a schematic cross-sectional view of an example of a decorative resin molded product using the decorative sheet of the present disclosure; FIG.

1. Decorative sheet The decorative sheet of the present disclosure is a decorative sheet having an uneven shape on its surface, and has at least a base layer and a plurality of uneven forming members arranged on one side of the base layer. The one-side surface of the base material layer has an uneven shape, and the uneven shape of the base material layer is formed by the unevenness forming member. Since the decorative sheet of the present disclosure has such a configuration, it is possible to suppress changes in the uneven shape due to molding. It is possible to achieve both excellent tactile sensation and designability.

The decorative sheet of the present disclosure will be described in detail below. In this specification, numerical ranges indicated by "-" mean "above" and "below", except where "above" and "below" are specified. For example, the notation of 2 to 15 mm means 2 mm or more and 15 mm or less. Further, in this specification, "(meth)acrylate" means "acrylate or methacrylate", and other similar terms have the same meaning.

Laminated Structure of Decorative Sheet As shown in FIGS. 2. The unevenness forming member 2 is partially provided on the base material layer 1 . Moreover, a plurality of unevenness forming members 2 are provided on the base material layer 1 . In addition, one surface of the substrate layer 1 (the surface on the side where the unevenness forming member 2 is present) has an uneven shape, and the uneven shape of the substrate layer 1 is formed by the unevenness forming member 2. be. In addition, the uneven shape of the substrate layer 1 is formed by the unevenness forming member 2 means that the uneven shape of the substrate layer 1 is formed along the uneven shape formed by the presence of the plurality of unevenness forming members 2. For example, as described later, by pressing the unevenness forming member 2 arranged on the base material layer 1, such an uneven shape can be formed on the base material layer 1. .

The uneven shape of the surface of the decorative sheet 10 of the present disclosure (the surface opposite to the base material layer 1 ) is preferably formed by the unevenness forming member 2 . That is, it is preferable that the irregularities on the surface of the decorative sheet 10 are also formed by the presence of the plurality of irregularity forming members 2 . All of the uneven shapes on the surface of the decorative sheet 10 shown in FIGS. 1 to 5 are schematic diagrams formed by the existence of the unevenness forming member 2 .

In the decorative sheet 10 of the present disclosure, as shown in FIGS. 1 to 5, it is preferable to have the first resin layer 11 at least partly between the base material layer 1 and the unevenness forming member 2 . In the manufacturing process of the decorative sheet of the present disclosure, it is preferable to perform the lamination of the unevenness forming member 2 on the base material layer 1 and the lamination of the first resin layer 11 collectively, for example, the first resin layer 11 A composition (ink) obtained by mixing a resin that forms the . By (printing), the substrate layer 1, the first resin layer 11, and the uneven forming member 2 can be laminated in the order of lamination. In addition, when laminating the first resin layer 11 in such a manufacturing process, not only between the substrate layer 1 and the unevenness forming member 2 but also on the opposite side of the substrate layer 1 of the unevenness forming member 2. Also, a part of the first resin layer 11 is laminated. That is, as shown in the schematic diagrams of FIGS. 2 to 5, the first resin layer 11 is present on both the base layer 1 side of the unevenness forming member 2 and the side opposite to the base layer 1 side. good too.

The decorative sheet of the present disclosure preferably has a second resin layer 12 as shown in FIGS. 2-5. 2, 4 and 5, the second resin layer 12 can be provided on at least part of the side opposite to the substrate layer 1 side of the unevenness forming member 2, and as shown in FIG. It can be provided on the substrate layer 1 side of the forming member 2 . The second resin layer 12 may be provided on part of the unevenness forming member 2 or may be provided on the entire surface. Also, the second resin layer 12 may be provided on a portion of one side of the decorative sheet 10 or may be provided on the entire surface. In addition, FIGS. 2 to 5 illustrate a mode in which the second resin layer 12 is provided on the entire surface of one side of the decorative sheet 10 .

In the decorative sheet 10 of the present disclosure, when the second resin layer 12 is provided on the side of the unevenness forming member 2 opposite to the base layer 1 side, the side of the second resin layer 12 opposite to the unevenness forming member 2 side is It is preferable that the third resin layer 13 is provided at the end. Further, when the second resin layer 12 is provided on the base material layer 1 side of the unevenness forming member 2, the second resin layer 12 on the side of the unevenness forming member 2 (when the first resin layer 11 exists, the first resin layer 11 and the second resin layer), a third resin layer 13 is preferably provided. The third resin layer 13 can be provided on at least part of the second resin layer 12 . As shown in the schematic diagram of FIG. 5, the third resin layer 13 is preferably provided on part of the second resin layer 12, and it is particularly preferable to synchronize the patterns of the second resin layer and the design layer. . For example, the third resin layer 13 is provided on the entire surface of the second resin layer 12 and on the entire surface of the decorative sheet. Also, between the unevenness forming member 2 and the substrate layer 1 (when the first resin layer 11 exists and the second resin layer 12 is provided on the opposite side of the unevenness forming member 2 from the substrate layer 1 side) , between the first resin layer 1 and the substrate layer 1), a third resin layer 13 may be provided.

As shown in FIGS. 4 and 5, in the decorative sheet 10 of the present disclosure, a pattern layer 3 may be provided as necessary. The pattern layer 3 may be provided on the substrate layer 1 side of the unevenness forming member 2 (under the first resin layer 11 when the first resin layer 11 is provided), or the substrate layer of the unevenness forming member 2. Although it may be provided on the side opposite to 1, it is preferably provided on the substrate layer 1 side of the unevenness forming member 2 . Further, the unevenness forming member 2 and the pattern layer 3 may be in contact with each other, or may be laminated via the first resin layer 11, a primer layer described later, or the like. In the decorative sheet 10, a primer layer may be provided at an arbitrary position between each layer, a concealing layer or the like may be provided between the base material layer 1 and the pattern layer 3, A back surface adhesive layer or the like may be provided on the back surface of the base material layer (the side opposite to the concave-convex forming member 2 side), or another layer may be provided at an arbitrary position.

As the laminated structure of the decorative sheet of the present disclosure,
Laminated structure in which base material layer 1/concavo-convex forming member 2 are laminated in this order;
Laminated structure in which substrate layer 1/first resin layer 11/concavo-convex forming member 2 are laminated in this order;
Laminated structure in which substrate layer 1/first resin layer 11/concave-convex forming member 2/first resin layer 11 are laminated in this order;
Laminated structure in which substrate layer 1/first resin layer 11/concave-convex forming member 2/second resin layer 12 are laminated in this order;
Laminated structure in which base material layer 1/first resin layer 11/concavo-convex forming member 2/first resin layer 11/second resin layer 12 are laminated in this order;
Laminated structure in which substrate layer 1/second resin layer 12/first resin layer 11/concavo-convex forming member 2/first resin layer 11 are laminated in this order;
Laminated structure in which substrate layer 1/pattern layer 3/first resin layer 11/concave-convex forming member 2/second resin layer 12 are laminated in this order;
Laminated structure in which substrate layer 1/pattern layer 3/first resin layer 11/concave-convex forming member 2/first resin layer 11/second resin layer 12 are laminated in this order;
Laminated structure in which substrate layer 1/pattern layer 3/second resin layer 12/first resin layer 11/concave-convex forming member 2/first resin layer 11 are laminated in this order;
Laminated structure in which substrate layer 1/pattern layer 3/second resin layer 12/first resin layer 11/concavo-convex forming member 2/first resin layer 11/second resin layer 12 are laminated in this order;
Laminated structure in which base material layer 1/first resin layer 11/concavo-convex forming member 2/second resin layer 12/third resin layer 13 are laminated in this order;
Laminated structure in which substrate layer 1/first resin layer 11/concavo-convex forming member 2/first resin layer 11/second resin layer 12/third resin layer 13 are laminated in this order;
Laminated structure in which substrate layer 1/pattern layer 3/first resin layer 11/convex-concave forming member 2/second resin layer 12/third resin layer 13 are laminated in this order;
Laminated structure in which substrate layer 1/pattern layer 3/first resin layer 11/concave-convex forming member 2/first resin layer 11/second resin layer 12/third resin layer 13 are laminated in this order;
Laminated structure in which substrate layer 1/pattern layer 3/primer layer/first resin layer 11/concave-convex forming member 2/second resin layer 12/third resin layer 13 are laminated in this order;
Laminated structure in which substrate layer 1/pattern layer 3/primer layer/first resin layer 11/concave-convex forming member 2/first resin layer 11/second resin layer 12/third resin layer 13 are laminated in this order;
Laminated structure in which substrate layer 1/second resin layer 12/third resin layer 13/first resin layer 11/concave-convex forming member 2/first resin layer 11 are laminated in this order;
Laminated structure in which substrate layer 1/pattern layer 3/second resin layer 12/third resin layer 13/first resin layer 11/concavo-convex forming member 2/first resin layer 11 are laminated in this order;
Laminated structure in which substrate layer 1/pattern layer 3/second resin layer 12/first resin layer 11/concave-convex forming member 2/first resin layer 11/second resin layer 12 are laminated in this order;
Laminated structure in which substrate layer 1/pattern layer 3/second resin layer 12/first resin layer 11/concave-convex forming member 2/second resin layer 12/third resin layer 13 are laminated in this order; and substrate layer A laminated structure in which 1/pattern layer 3/second resin layer 12/first resin layer 11/concave-convex forming member 2/first resin layer 11/second resin layer 12/third resin layer 13 are laminated in this order. mentioned.

FIG. 1 is a schematic cross-sectional view of an example of a decorative sheet in which base layer 1/first resin layer 11/concavo-convex forming member 2 are laminated in this order, as one aspect of the laminated structure of the decorative sheet of the present disclosure. show. In FIG. 2, as one aspect of the laminated structure of the decorative sheet of the present disclosure, base layer 1/first resin layer 11/concavo-convex forming member 2/first resin layer 11/second resin layer 12 are laminated in this order. 1 shows a schematic cross-sectional view of an example of a decorative sheet. In FIG. 3, as one aspect of the laminated structure of the decorative sheet of the present disclosure, base layer 1/second resin layer 12/first resin layer 11/concavo-convex forming member 2/first resin layer 11 are laminated in this order. 1 shows a schematic cross-sectional view of an example of a decorative sheet. FIG. 4 shows, as one aspect of the laminated structure of the decorative sheet of the present disclosure, base layer 1/pattern layer 3/second resin layer 12/first resin layer 11/concave-convex forming member 2/first resin layer 11/ The schematic sectional drawing of an example of the decorative sheet in which the 2nd resin layer 12 was laminated|stacked in this order is shown. FIG. 5 shows, as one aspect of the laminated structure of the decorative sheet of the present disclosure, base layer 1/pattern layer 3/second resin layer 12/first resin layer 11/convexity forming member 2/first resin layer 11/ The schematic-drawing sectional drawing of an example of the decorative sheet in which the 2nd resin layer 12/3rd resin layer 13 were laminated|stacked in this order is shown. Note that "/" means a separator between layers.

In the decorative sheet of the present disclosure, the height of the projections of the uneven surface is preferably 5 μm or more, more preferably 10 μm or more, from the viewpoint of expressing excellent tactile sensation. Moreover, the upper limit of the height of the protrusions is preferably 50 μm or less, more preferably 40 μm or less. By setting the height of the projections within the above range, the tactile sensation and design of the decorative sheet can be more preferably enhanced. In the present specification, the height of the uneven protrusions on the surface of the decorative sheet is calculated as the average value of 10 measured values obtained by observing the cross section of the decorative sheet with a scanning electron microscope (SEM). is the value

In the decorative sheet of the present disclosure, it is also possible to express a design by utilizing the gloss difference of each layer. That is, the first resin layer 11, the second resin layer 12, the third resin layer 13, the pattern layer 3, the primer layer, etc., which are provided as necessary, are each relatively glossy or low gloss, and further, By providing the decorative sheet entirely or partially, it is possible to exhibit a design such as a three-dimensional effect due to the gloss difference when the decorative sheet is observed from the observation side (the side opposite to the base layer 1 side).

Each layer forming the decorative sheet [base layer 1]
The base material layer 1 is a resin sheet (resin film) that serves as a support in the decorative sheet of the present disclosure.

One surface of the base material layer 1 (the surface on which the unevenness forming member 2 is present) has an uneven shape. Moreover, the uneven shape of the base material layer 1 is formed by the unevenness forming member 2 . As described above, the uneven shape of the substrate layer 1 is formed by the unevenness forming member 2 means that the unevenness of the substrate layer 1 is formed along the uneven shape formed by the presence of the plurality of unevenness forming members 2 . It means that a shape is formed. For example, as described later, by pressing an unevenness forming member 2 arranged on the base material layer 1, such an uneven shape is formed on the base material layer 1. can be formed.

The depth of the uneven recesses of the base material layer 1 (the average depth of the uneven recesses of the base material layer 1) is such that the unevenness forming member 2 is not completely embedded in the base material layer 1 (preferably is not particularly limited as long as the height of at least half of the unevenness forming member 2 is not embedded in the base material layer 1 in the cross section in the thickness direction of the decorative sheet 10, but is, for example, 2 to 20 μm. about 5 to 15 μm, more preferably about 5 to 10 μm. The depth of the recesses of the uneven shape of the substrate layer 1 may be about 5 to 50% of the particle diameter of the uneven-forming member 2 . More specifically, the average ratio (%) of the maximum depth of the recesses of the substrate layer to the average particle diameter of the unevenness-forming member is preferably about 5 to 50%, more preferably about 10 to 40%. More preferably, it is about 20 to 40%.

The resin component used in the base material layer 1 is not particularly limited, and may be appropriately selected according to moldability, compatibility with the molding resin, etc., but a resin film made of a thermoplastic resin is preferable. . Specific examples of the thermoplastic resin include acrylonitrile-butadiene-styrene resin (hereinafter sometimes referred to as "ABS resin") and acrylonitrile-styrene-acrylic acid ester resin (hereinafter referred to as "ASA resin"). polyolefin resins such as acrylic resins, polypropylene and polyethylene, polycarbonate resins, vinyl chloride resins, and polyethylene terephthalate (PET). Among these, ABS resin and acrylic resin are preferable from the viewpoint of moldability. Further, the substrate layer 1 may be formed of a single-layer sheet of these resins, or may be formed of a multi-layer sheet of the same or different resins.

The bending elastic modulus of the base material layer 1 is not particularly limited. For example, when the decorative sheet of the present disclosure is integrated with a molding resin by an insert molding method, the bending elastic modulus at 25 ° C. of the base layer 1 in the decorative sheet of the present disclosure is 500 to 4,000 MPa, preferably 750 to 3,000 MPa can be mentioned. Here, the flexural modulus at 25°C is a value measured according to JIS K7171:2016. If the flexural modulus at 25° C. is 500 MPa or more, the decorative sheet will have sufficient rigidity, and even if it is subjected to the insert molding method, the surface properties and moldability will be much better. In addition, when the flexural modulus at 25° C. is 4,000 MPa or less, sufficient tension can be applied in the case of roll-to-roll production, and slack is less likely to occur. The so-called pattern registration becomes good.

The substrate layer 1 may be surface-treated on one side or both sides in order to improve the adhesion with the layer provided thereon. Surface treatments include chemical surface treatments such as oxidation methods and physical surface treatments such as roughening methods. Examples include corona discharge treatment, chromium oxidation treatment, flame treatment, hot air treatment, ozone ultraviolet treatment, and the like. In addition, examples of the roughening method include a sandblasting method, a solvent treatment method, and the like. These surface treatments are appropriately selected according to the type of the resin component that constitutes the substrate layer 1, but from the viewpoint of effects, operability, and the like, a corona discharge treatment method is preferred.

Further, the substrate layer 1 may be subjected to a treatment such as forming a known adhesive layer.

Furthermore, the base material layer 1 may be colored using a coloring agent, or may be uncolored. Moreover, the base material layer 1 may be in any mode of opaque, colorless and transparent, colored and transparent, and translucent. The coloring agent used for the substrate layer 1 is not particularly limited, but preferably includes a coloring agent that does not change color even under temperature conditions of 150° C. or higher. Specifically, existing dry colors, paste colors, and masterbatch resins. composition and the like.

The thickness of the base material layer 1 is appropriately set according to the application of the decorative sheet, the molding method for integration with the molding resin, and the like, and is usually about 25 to 1000 μm and about 50 to 700 μm. More specifically, when the decorative sheet of the present disclosure is subjected to an insert molding method, the thickness of the base material layer 1 is usually about 50 to 1000 μm, preferably about 100 to 700 μm, more preferably 100 to 500 μm. degree. Further, when the decorative sheet of the present disclosure is subjected to the simultaneous injection molding decoration method, the thickness of the base material layer 1 is usually about 25 to 200 μm, preferably about 50 to 200 μm, more preferably about 70 to 200 μm. are mentioned. In addition, the thickness of the base material layer 1 is the thickness at the position where the uneven|corrugated-shaped recessed part is not formed.

[Unevenness forming member 2]
In the decorative sheet of the present disclosure, a plurality of uneven forming members 2 are present on the base material layer 1 . Further, as described above, the unevenness forming member 2 forms unevenness on the surface of the base material layer 1 .

Further, the uneven shape of the surface of the decorative sheet 10 of the present disclosure (the surface opposite to the base material layer 1 ) is preferably formed by the unevenness forming member 2 . That is, it is preferable that the irregularities on the surface of the decorative sheet 10 are also formed by the presence of the plurality of irregularity forming members 2 . All of the uneven shapes on the surface of the decorative sheet 10 shown in FIGS. 1 to 5 are schematic shapes formed by the existence of the uneven forming member 2 .

An aggregate of a plurality of unevenness forming members 2 can form one convexity of the unevenness on the surface of the decorative sheet, or each individual unevenness forming member 2 can form one convexity of the unevenness on the surface of the decorative sheet. You can also form a part. As shown in the schematic diagrams of FIGS. 1 to 5, usually, the projections of the individual unevenness forming members 2 and the projections of the assembly of the plurality of unevenness forming members 2 are combined to form the uneven shape of the decorative sheet. shape. In the present disclosure, the concave-convex forming member 2 has a form shown in a convex shape in schematic cross-sectional views as shown in FIGS. 1 to 5 . The protrusions formed by the unevenness forming member 2 may be, for example, not only conical or cylindrical protrusions formed on the surface of the decorative sheet, but also protrusions extending linearly, such as a conduit pattern. Also includes forms that In addition, within a range that does not impair the effects of the present disclosure, a form in which the top part protrudes from a layer when there is another layer on the unevenness forming member 2 is also included.

In the decorative sheet 10 of the present disclosure, the concave-convex forming member 2 is exposed on the surface of the decorative sheet 10 from the viewpoint of ease of manufacture and suppression of detachment of the concave-convex forming member 2 from the decorative sheet 10. preferably not.

The concave-convex forming member 2 in the present disclosure is preferably formed by printing together with the formation of the first resin layer 11, which will be described later, so as to give the surface of the decorative sheet a desired tactile sensation based on the concave-convex shape. That is, in the manufacturing process of the decorative sheet, a composition (ink) obtained by mixing the resin forming the first resin layer 11 and the plurality of uneven forming members 2 is applied to the base layer 1 (the pattern layer 3 described later, etc.). By laminating (printing) on the other layer when the layer of (2) is provided, the substrate layer 1, the first resin layer 11, and the unevenness forming member 2 can be laminated in the order of lamination.

The unevenness forming member 2 is preferably particles. Since the unevenness-forming member 2 is particles, the unevenness-forming member 2 can suitably contribute to both excellent tactile sensation and designability of the decorative sheet without forming the unevenness-forming member 2 thickly. The average particle diameter of the particles is preferably 5 μm or more, more preferably 10 μm or more, still more preferably 15 μm or more, and still more preferably 20 μm or more, from the viewpoint of expressing excellent tactile sensation in the decorative sheet of the present disclosure. Further, the preferred upper limit of the average particle size is preferably 60 µm or less, more preferably 50 µm or less, still more preferably less than 50 µm, still more preferably 40 µm or less, and particularly preferably 35 µm or less. . By setting the average particle diameter of the particles within the above range, the tactile sensation and design of the decorative sheet can be more suitably enhanced.

The particles are not particularly limited and may be either organic particles or inorganic particles, but organic particles are preferred. That is, at least one of organic particles and inorganic particles should be used as the unevenness forming member 2, and organic particles are preferably used.

The organic particles are not particularly limited, and usually resin beads are used. Examples of resin beads include acrylic beads, urethane beads, nylon beads, styrene beads, and the like. Among these, it is preferable to use acrylic beads or urethane beads from the viewpoint of suppressing whitening of the irregularity forming member 2, imparting an excellent tactile feel, and improving the scratch resistance of the decorative sheet. In particular, acrylic beads or urethane beads are preferably used from the viewpoint of suppressing whitening of the decorative sheet, and urethane beads are preferably used from the viewpoint of improving the scratch resistance of the decorative sheet. In addition, from the viewpoint of imparting an excellent tactile sensation and improving the scratch resistance of the decorative sheet, it is preferable to use crosslinked resin beads. Specific examples of crosslinked resin beads include crosslinked acrylic beads and crosslinked urethane beads.

When the unevenness forming member 2 is organic particles, the average particle diameter is preferably 15 μm or more, more preferably 20 μm or more. Further, the preferred upper limit of the average particle size is preferably 60 µm or less, more preferably 50 µm or less, still more preferably less than 50 µm, still more preferably 40 µm or less, and particularly preferably 35 µm or less. . The preferred range of the particle size of the organic particles is 15 to 60 μm, 15 to 50 μm, 15 to 50 μm, 15 to 40 μm, 15 to 35 μm, 20 to 60 μm, 20 to 50 μm, 20 to 50 μm, 20 to 40 μm, 20 to 40 μm. For example, 35 μm. It is preferable that at least 90% or more of the organic particles, on a number basis, satisfy these particle diameters, from the viewpoint of favorably exhibiting the effects of the present disclosure. If the average particle size of the organic particles is less than 15 μm, it may not be possible to obtain an excellent tactile sensation due to the uneven shape of the decorative sheet. Further, if the average particle diameter of the organic particles exceeds 60 μm, production stability may decrease, and it may become difficult to form the unevenness forming member 2 having a desired shape with good reproducibility. When the unevenness forming member 2 is made of a resin composition (ink) together with a resin that forms the first resin layer 11 described later and is laminated on the base material layer 1 by printing, from the viewpoint of ink transfer stability, The average particle size of the organic particles is preferably 1/2 or less of the plate depth. In the present disclosure, the average particle size is obtained by observing the cross section in the thickness direction of the layer with a scanning electron microscope (SEM) under the conditions of an acceleration voltage of 3.0 kV and a magnification of 50,000 times, and randomly selected. means the average value (arithmetic mean diameter) of the particle diameters measured for non-aggregates of 100 particles.

When the organic particles as the unevenness forming member 2 are made into a resin composition together with a resin that forms the first resin layer 11 described later and are laminated on the base material layer 1 by printing, the unevenness forming member 2 is made of the resin It is preferably contained in a proportion of 50% by mass or less, more preferably 40% by mass or less in the solid content of the composition. When the content of the organic particles is 50% by mass or less, the organic particles are uniformly distributed in the coating film (unevenness-forming member 2), so that the tactile sensation is stable. If the content of the organic particles exceeds 50% by mass, the organic particles may aggregate, the height of the unevenness forming member may not be stable, and the transparency of the unevenness forming member 2 may be impaired, thereby degrading the design. There is a risk. The content of the organic particles is preferably 2% by mass, more preferably 10% by mass or more. If the content of the organic particles is less than 2% by mass, the tactile sensation may be insufficient, and the thixotropic properties of the ink may be insufficient, making it difficult to form the concave-convex forming member 2 by thick embossing printing.

The inorganic particles are not particularly limited as long as they are particles formed from an inorganic compound. Examples thereof include silica particles, calcium carbonate particles, barium sulfate particles, alumina particles, and glass balloon particles. Among these, silica particles are preferred. particles. One type of inorganic particles may be used alone, or two or more types may be used in combination. The average particle diameter of the inorganic particles is, for example, about 0.5 to 20 μm, preferably about 1 to 10 μm. As described above, the average particle diameter of the inorganic particles is obtained by observing the cross section in the thickness direction of the layer with a scanning electron microscope (SEM) under the conditions of an acceleration voltage of 3.0 kV and a magnification of 50,000 times, and randomly It means the average particle diameter (arithmetic mean diameter) measured for non-aggregates of 100 selected particles.

[First resin layer 11]
In the decorative sheet 10 of the present disclosure, as shown in FIGS. 1 to 5, it is preferable to have the first resin layer 11 at least partly between the base material layer 1 and the unevenness forming member 2 . The first resin layer 11 may be formed on the entire surface of the decorative sheet 10, or may be formed partially. In the manufacturing process of the decorative sheet, it is preferable that the lamination of the unevenness forming member 2 on the base material layer 1 and the lamination of the first resin layer 11 are performed collectively. A composition (ink) obtained by mixing a resin and a plurality of irregularity forming members 2 is laminated (printed) on the base material layer 1 (another layer if it has other layers such as the pattern layer 3 described later). By doing so, the substrate layer 1, the first resin layer 11, and the unevenness forming member 2 can be stacked in the order of stacking. In addition, when laminating the first resin layer 11 in such a manufacturing process, not only between the substrate layer 1 and the unevenness forming member 2 but also on the opposite side of the substrate layer 1 of the unevenness forming member 2. Also, a part of the first resin layer 11 is laminated. That is, as shown in the schematic diagrams of FIGS. 2 to 5, the first resin layer 11 is present on both the base layer 1 side of the unevenness forming member 2 and the side opposite to the base layer 1 side. good too. When printing a composition (ink) in which the resin forming the first resin layer 11 and the plurality of unevenness forming members 2 are mixed, the first resin layer 11 is Since it is not separated by the unevenness forming member 2, it is a single layer. The first resin layer 11 is preferably present at a position corresponding to the position where the unevenness forming member 2 is present. As described above, since the first resin layer 11 is suitably used for arranging the concave-convex forming member 2 on the base material layer 1, in the decorative sheet 10 of the present disclosure, the concave-convex forming member 2 and the second It is also preferable that the region (ridged portion) including one resin layer 11 forms one collective convex portion.

In the decorative sheet 10 of the present disclosure, when the raised portion forms at least part of the uneven shape of the surface of the decorative sheet, the total ratio of the area where the plurality of raised portions are provided is the base material Taking the area of one side of the layer 1 as 100%, it is preferably 3 to 80%, more preferably 3 to 50%, even more preferably 5 to 50%, and 5 to 40%. and more preferably 6 to 30%. By providing the raised portion within the range described above, it is possible to obtain a decorative sheet with a more excellent tactile feel. Here, when the cross section of the ridge is trapezoidal, conical, or the like, and the area of the upper side and the lower side of the ridge is different, the area where the ridge is provided is the base material layer of the ridge. It is the area of the surface on the 1 side.

In the decorative sheet of the present disclosure, the average thickness (height) of the raised portion is preferably 5 μm or more, more preferably 10 μm or more, still more preferably 15 μm or more, and particularly preferably 20 μm or more, from the viewpoint of expressing excellent tactile sensation. is. Further, the upper limit of the average thickness of the raised portion is preferably 50 µm or less, preferably less than 50 µm, and more preferably 40 µm or less. By setting the average thickness of the raised portion within the above range, the tactile sensation and design of the decorative sheet can be more preferably enhanced. In this specification, the average thickness of the raised portion is a value calculated as an average value of 10 measured values obtained by observing the cross section of the decorative sheet with a scanning electron microscope (SEM). Observation with a scanning electron microscope (SEM) was performed under the conditions of an acceleration voltage of 3.0 kV and a magnification of 1,500 times.

The resin forming the first resin layer 11 is preferably a curable resin such as a thermosetting resin or an ionizing radiation curable resin (for example, an electron beam curable resin) from the viewpoint of favorably exhibiting the effects of the present disclosure. In particular, ionizing radiation-curable resins are preferable from the viewpoint of high surface hardness, productivity, and the like.

Thermosetting resins include, for example, unsaturated polyester resins, polyurethane resins (including two-component curing polyurethanes), epoxy resins, aminoalkyd resins, phenolic resins, urea resins, diallyl phthalate resins, melamine resins, guanamine resins, melamine - urea co-condensation resin, silicone resin, polysiloxane resin and the like.

A crosslinking agent, a curing agent such as a polymerization initiator, and a polymerization accelerator can be added to the above resin. For example, as curing agents, isocyanates, organic sulfonates, etc. can be added to unsaturated polyester resins, polyurethane resins, etc., and organic amines, etc. can be added to epoxy resins. Peroxides such as methyl ethyl ketone peroxide and radical initiators such as azoisobutylnitrile can be added to the unsaturated polyester resin.

As a method for forming the first resin layer 11 with a thermosetting resin, for example, a thermosetting resin solution is applied by a coating method such as a roll coating method, a gravure coating method, a gravure printing method, a silk screen printing method, and dried. and curing methods.

The ionizing radiation curable resin is a resin that crosslinks and cures when exposed to ionizing radiation. Specifically, prepolymers, oligomers, and monomers having polymerizable unsaturated bonds or epoxy groups in the molecule. and the like are appropriately mixed. Here, the ionizing radiation means, among electromagnetic waves or charged particle beams, those having energy quanta capable of polymerizing or cross-linking molecules, and usually ultraviolet rays (UV) or electron beams (EB) are used. ray, electromagnetic waves such as γ-rays, and charged particle beams such as α-rays and ion beams. Among the ionizing radiation curable resins, the electron beam curable resin can be solvent-free, does not require a photopolymerization initiator, and provides stable curing properties. preferably used.

<Ionizing radiation curable resin>
As the monomer used as the ionizing radiation-curable resin, a (meth)acrylate monomer having a radically polymerizable unsaturated group in the molecule is suitable, and a polyfunctional (meth)acrylate monomer is particularly preferable. The polyfunctional (meth)acrylate monomer may be a (meth)acrylate monomer having two or more (difunctional or more), preferably three or more (trifunctional or more) polymerizable unsaturated bonds in the molecule. Specific examples of polyfunctional (meth)acrylates include ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate. ) acrylate, neopentyl glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, neopentyl glycol hydroxypivalate di(meth)acrylate, dicyclopentanyl di(meth)acrylate, caprolactone-modified dicyclopentenyl di(meth)acrylate ) acrylate, ethylene oxide-modified phosphate di(meth)acrylate, allylated cyclohexyl di(meth)acrylate, isocyanurate di(meth)acrylate, trimethylolpropane tri(meth)acrylate, ethylene oxide-modified trimethylolpropane tri(meth)acrylate, dipentaerythritol tri(meth)acrylate, propionic acid-modified dipentaerythritol tri(meth)acrylate, pentaerythritol tri(meth)acrylate, propylene oxide-modified trimethylolpropane tri(meth)acrylate, tris(acryloxyethyl) isocyanurate, Propionic acid-modified dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, ethylene oxide-modified dipentaerythritol hexa(meth)acrylate, caprolactone-modified dipentaerythritol hexa(meth)acrylate and the like. These monomers may be used singly or in combination of two or more.

In addition, as the oligomer used as the ionizing radiation-curable resin, a (meth)acrylate oligomer having a radically polymerizable unsaturated group in the molecule is suitable, and among them, two or more polymerizable unsaturated bonds in the molecule. A polyfunctional (meth)acrylate oligomer having (2 or more functionalities) is preferred. Examples of polyfunctional (meth)acrylate oligomers include polycarbonate (meth)acrylate, acrylic silicone (meth)acrylate, urethane (meth)acrylate, epoxy (meth)acrylate, polyester (meth)acrylate, polyether (meth)acrylate, Polybutadiene (meth)acrylate, silicone (meth)acrylate, oligomers having cationic polymerizable functional groups in the molecule (e.g., novolac epoxy resins, bisphenol epoxy resins, aliphatic vinyl ethers, aromatic vinyl ethers, etc.). Here, the polycarbonate (meth)acrylate is not particularly limited as long as it has a carbonate bond in the polymer main chain and a (meth)acrylate group in the terminal or side chain. It can be obtained by esterification with acrylic acid. Polycarbonate (meth)acrylate may be, for example, urethane (meth)acrylate having a polycarbonate skeleton. A urethane (meth)acrylate having a polycarbonate skeleton can be obtained, for example, by reacting a polycarbonate polyol, a polyvalent isocyanate compound, and a hydroxy (meth)acrylate. Acrylic silicone (meth)acrylates can be obtained by radically copolymerizing silicone macromonomers with (meth)acrylate monomers. Urethane (meth)acrylate can be obtained, for example, by esterifying a polyurethane oligomer obtained by reacting a polyether polyol or polyester polyol with a polyisocyanate compound with (meth)acrylic acid. Epoxy (meth)acrylate can be obtained, for example, by reacting (meth)acrylic acid with an oxirane ring of a relatively low-molecular-weight bisphenol-type epoxy resin or novolac-type epoxy resin for esterification. A carboxyl-modified epoxy (meth)acrylate obtained by partially modifying this epoxy (meth)acrylate with a dibasic carboxylic acid anhydride can also be used. Polyester (meth)acrylate is obtained, for example, by esterifying the hydroxyl groups of a polyester oligomer having hydroxyl groups at both ends obtained by condensation of polyhydric carboxylic acid and polyhydric alcohol with (meth)acrylic acid, or to polyhydric carboxylic acid. It can be obtained by esterifying the terminal hydroxyl group of the oligomer obtained by adding alkylene oxide with (meth)acrylic acid. Polyether (meth)acrylate can be obtained by esterifying the hydroxyl groups of polyether polyol with (meth)acrylic acid. Polybutadiene (meth)acrylate can be obtained by adding (meth)acrylic acid to the side chain of polybutadiene oligomer. A silicone (meth)acrylate can be obtained by adding (meth)acrylic acid to the terminal or side chain of a silicone having a polysiloxane bond in its main chain. Among these, polycarbonate (meth)acrylate, urethane (meth)acrylate and the like are particularly preferable as polyfunctional (meth)acrylate oligomers. These oligomers may be used singly or in combination of two or more.

When the decorative sheet is required to have three-dimensional moldability, such as when it is used in the production of a decorative resin molded product, from the viewpoint of obtaining excellent three-dimensional moldability among the ionizing radiation-curable resins described above, It is preferred to use polyfunctional polycarbonate (meth)acrylates. Moreover, from the viewpoint of achieving both three-dimensional moldability and scratch resistance, it is more preferable to use a combination of a polyfunctional polycarbonate (meth)acrylate and a polyfunctional (meth)acrylate. When using a polyfunctional (meth)acrylate monomer as an ionizing radiation-curable resin, it is preferable to use it in combination with a thermoplastic resin such as an acrylic resin from the viewpoint of obtaining excellent three-dimensional moldability. From the viewpoint of achieving both performance and scratch resistance, it is more preferable that the mass ratio of the polyfunctional (meth)acrylate monomer and the thermoplastic resin in the ionizing radiation-curable resin composition is 25:75 to 75:25. . The polyfunctional polycarbonate (meth)acrylate and the polyfunctional (meth)acrylate are described in detail below.

<Polyfunctional polycarbonate (meth)acrylate>
The polyfunctional polycarbonate (meth)acrylate is not particularly limited as long as it has a carbonate bond in the polymer main chain and two or more (meth)acrylates in the terminal or side chain. Further, the (meth)acrylate preferably has 2 to 6 functional groups per molecule from the viewpoint of improving cross-linking and curing. One type of polyfunctional polycarbonate (meth)acrylate may be used alone, or two or more types may be used in combination.

Polyfunctional polycarbonate (meth)acrylates are obtained, for example, by converting some or all of the hydroxyl groups of polycarbonate polyols into (meth)acrylates (acrylic acid esters or methacrylic acid esters). This esterification reaction can be carried out by a normal esterification reaction. For example, 1) a method of condensing a polycarbonate polyol and an acrylic acid halide or a methacrylic acid halide in the presence of a base, 2) a method of condensing a polycarbonate polyol and an acrylic anhydride or a methacrylic acid anhydride in the presence of a catalyst, Alternatively, 3) a method of condensing a polycarbonate polyol and acrylic acid or methacrylic acid in the presence of an acid catalyst.

Polycarbonate polyols are polymers having carbonate bonds in the polymer main chain and 2 or more, preferably 2 to 50, more preferably 3 to 50 hydroxyl groups in terminal or side chains. A representative method for producing the polycarbonate polyol includes a method by a polycondensation reaction from a diol compound (A), a polyhydric alcohol (B) having a valence of 3 or more, and a compound (C) serving as a carbonyl component.

The diol compound (A) used as a starting material for polycarbonate polyol is represented by the general formula HO--R ¹ --OH. Here, R ¹ is a divalent hydrocarbon group having 2 to 20 carbon atoms and may contain an ether bond in the group. R ¹ is, for example, a linear or branched alkylene group, cyclohexylene group or phenylene group.

Specific examples of diol compounds include ethylene glycol, 1,2-propylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, polyethylene glycol, neopentyl glycol, 1,3-propanediol, 1,4-butanediol, 1 ,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,3-bis(2-hydroxyethoxy)benzene, 1,4-bis(2 -hydroxyethoxy)benzene, neopentyl glycol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol and the like. These diols may be used singly or in combination of two or more.

Examples of polyhydric alcohols (B) having a valence of 3 or more to be used as raw materials for polycarbonate polyols include alcohols such as trimethylolpropane, trimethylolethane, pentaerythritol, ditrimethylolpropane, dipentaerythritol, glycerin, and sorbitol. are mentioned. In addition, the trihydric or higher polyhydric alcohol is an alcohol having a hydroxyl group obtained by adding 1 to 5 equivalents of ethylene oxide, propylene oxide, or other alkylene oxide to the hydroxyl group of the polyhydric alcohol. good. These polyhydric alcohols may be used singly or in combination of two or more.

The carbonyl component compound (C) used as a starting material for the polycarbonate polyol is any compound selected from diester carbonate, phosgene, and equivalents thereof. Specific examples of the compound include carbonic acid diesters such as dimethyl carbonate, diethyl carbonate, diisopropyl carbonate, diphenyl carbonate, ethylene carbonate, and propylene carbonate; phosgene; halogenated formic acids such as methyl chloroformate, ethyl chloroformate, and phenyl chloroformate. Esters etc. are mentioned. These compounds may be used individually by 1 type, and may be used in combination of 2 or more type.

The polycarbonate polyol is synthesized by subjecting the diol compound (A), the polyhydric alcohol (B) having a valence of 3 or more, and the compound (C) serving as a carbonyl component to a polycondensation reaction under general conditions. The charged molar ratio of the diol compound (A) and the polyhydric alcohol (B) may be set, for example, within the range of 50:50 to 99:1. Further, the charged molar ratio of the compound (C) to be the carbonyl component with respect to the diol compound (A) and the polyhydric alcohol (B) is, for example, 0.2 to 2 with respect to the hydroxyl groups of the diol compound and the polyhydric alcohol. It should be set within the equivalent range.

The number of equivalents (eq./mol) of hydroxyl groups present in the polycarbonate polyol after the polycondensation reaction at the above charging ratio is, for example, an average of 3 or more, preferably 3 to 50, more preferably 3 to 50 per molecule. is 3 to 20. When such an equivalent number is satisfied, the necessary amount of (meth)acrylate groups are formed by the esterification reaction described below, and the polyfunctional polycarbonate (meth)acrylate resin is imparted with appropriate flexibility. The terminal functional groups of this polycarbonate polyol are usually OH groups, but part of them may be carbonate groups.

The method for producing the polycarbonate polyol described above is described, for example, in JP-A-64-1726. Further, this polycarbonate polyol can also be produced by transesterification reaction between a polycarbonate diol and a polyhydric alcohol having a valence of 3 or more, as described in JP-A-3-181517.

Although the molecular weight of the polyfunctional polycarbonate (meth)acrylate is not particularly limited, for example, the weight average molecular weight is 55,000 or more, preferably 10,000 or more. The upper limit of the weight average molecular weight of the polyfunctional polycarbonate (meth)acrylate is not particularly limited, but from the viewpoint of controlling the viscosity not to become too high, for example, 100,000 or less, preferably 50,000,000 or less. be done. The weight average molecular weight of the polyfunctional polycarbonate (meth)acrylate is preferably 10,000 to 50,000, more preferably 10,000 to 20,000.

In addition, the weight average molecular weight of polyfunctional polycarbonate (meth)acrylate in this specification is a value measured by gel permeation chromatography using polystyrene as a standard substance.

The content of the polyfunctional polycarbonate (meth)acrylate in the ionizing radiation curable resin composition used to form the first resin layer 11 is not particularly limited as long as the effects of the present disclosure are achieved, but injection molding From the viewpoint of maintaining the irregular shape of the surface of the decorative sheet and more effectively suppressing the deterioration of the high texture expressed on the decorative sheet, it is preferably 50% by mass or more. , more preferably 80% by mass or more, and still more preferably 85% by mass or more.

<Polyfunctional (meth)acrylate>
Polyfunctional (meth)acrylates are not particularly limited, but polyfunctional urethane (meth)acrylates are preferred. The polyfunctional urethane (meth)acrylate is not particularly limited as long as it has a urethane bond in its polymer main chain and two or more (meth)acrylates in its terminals or side chains. Such a polyfunctional urethane (meth)acrylate can be obtained, for example, by esterifying a polyurethane oligomer obtained by reacting a polyether polyol or polyester polyol with a polyisocyanate with (meth)acrylic acid. Moreover, the number of functional groups per molecule of the polyfunctional urethane (meth)acrylate is preferably 2 to 12 from the viewpoint of good cross-linking and curing. Moreover, the polyfunctional (meth)acrylate may be silicone-modified. Polyfunctional (meth)acrylate may be used individually by 1 type, and may be used in combination of 2 or more types.

Although the molecular weight of the polyfunctional (meth)acrylate is not particularly limited, for example, the weight average molecular weight is 2,000 or more, preferably 5,000 or more. The upper limit of the weight average molecular weight of the polyfunctional (meth)acrylate is not particularly limited, but from the viewpoint of controlling the viscosity so as not to become too high, it is, for example, 30,000 or less, preferably 10,000 or less.

In addition, the weight average molecular weight of the polyfunctional (meth)acrylate in this specification is a value measured by gel permeation chromatography using polystyrene as a standard substance.

The content of the polyfunctional (meth)acrylate in the ionizing radiation curable resin composition used to form the first resin layer 11 is not particularly limited as long as the effects of the present disclosure are achieved, but injection molding From the viewpoint of maintaining the uneven shape of the surface of the decorative sheet and more effectively suppressing the deterioration of the high texture expressed on the decorative sheet, the content is preferably 50% by mass or less. , more preferably 20% by mass or less, and still more preferably 15% by mass or less.

In the ionizing radiation-curable resin composition used to form the first resin layer 11, when a polyfunctional polycarbonate (meth)acrylate and a polyfunctional (meth)acrylate are used in combination, the mass ratio of these (polyfunctional polycarbonate (meth) ) acrylate: Polyfunctional (meth)acrylate preferably has a ratio of about 50:50 to 99:1, more preferably about 80:20 to 99:1, still more preferably about 85:15 to 99:1.

Formation of the first resin layer 11 is performed by, for example, preparing the above-described ionizing radiation-curable resin composition, applying it, and cross-linking and curing it. The viscosity of the ionizing radiation-curable resin composition may be any viscosity that allows the formation of an uncured resin layer on a layer adjacent to the first resin layer 11 by a coating method described below. In the present disclosure, the prepared coating liquid is coated on a layer adjacent to the first resin layer 11 so as to have the thickness described above, using known methods such as gravure coating, bar coating, roll coating, reverse roll coating, and comma coating. It is applied by a method, preferably gravure coating, to form an uncured resin layer. The uncured resin layer thus formed is irradiated with ionizing radiation such as electron beams and ultraviolet rays to cure the uncured resin layer, thereby forming the first resin layer 11 . Here, when an electron beam is used as the ionizing radiation, the acceleration voltage can be appropriately selected according to the thickness of the resin and the layer used, but the acceleration voltage is usually about 70 to 300 kV.

In electron beam irradiation, the higher the acceleration voltage, the higher the penetration ability. The acceleration voltage is selected so that the thickness of one resin layer 11 is substantially uniform. This makes it possible to suppress the irradiation of excess electron beams to the layers located under the first resin layer 11, and minimize the deterioration of each layer due to the excess electron beams. The irradiation dose is preferably an amount that saturates the crosslink density of the first resin layer 11, and is usually selected in the range of 5 to 300 kGy (0.5 to 30 Mrad), preferably 10 to 50 kGy (1 to 5 Mrad). Furthermore, the electron beam source is not particularly limited, and various electron beam accelerators such as Cockroft-Walton type, Vandegraft type, resonance transformer type, insulated core transformer type, linear type, dynamitron type, and high frequency type can be used. can be used. When ultraviolet rays are used as the ionizing radiation, rays containing ultraviolet rays having a wavelength of 190 to 380 nm may be emitted. Examples of ultraviolet light sources include, but are not limited to, high-pressure mercury lamps, low-pressure mercury lamps, metal halide lamps, and carbon arc lamps.

Various additives can be blended into the first resin layer 11 according to the desired physical properties of the first resin layer 11 . Examples of such additives include weather resistance improvers such as ultraviolet absorbers and light stabilizers, abrasion resistance improvers, polymerization inhibitors, cross-linking agents, infrared absorbers, antistatic agents, adhesion improvers, leveling agents, Examples include thixotropic agents, coupling agents, plasticizers, antifoaming agents, fillers, solvents, colorants and the like. These additives can be appropriately selected and used from commonly used ones. As the ultraviolet absorber or light stabilizer, a reactive ultraviolet absorber or light stabilizer having a polymerizable group such as a (meth)acryloyl group in the molecule can also be used.

As described above, when the decorative sheet of the present disclosure is used for injection molding or vacuum molding, from the viewpoint of suppressing deformation of the raised portion and achieving a desired shape while improving three-dimensional moldability, the first resin As the ionizing radiation-curable resin forming the layer 11, polycarbonate (meth)acrylate is preferably used.

In addition, when the decorative sheet of the present disclosure is used for injection molding or vacuum molding, the first resin layer 11 is made of an ionizing radiation-curable resin from the viewpoint of improving the scratch resistance of the decorative sheet and improving the three-dimensional moldability. It is also preferable to configure with a mixture of a resin and a thermoplastic resin. The type of thermoplastic resin and the preferred mixing ratio of the ionizing radiation-curable resin and the thermoplastic resin can be the same as those described for the second resin layer 12, which will be described later.

[Second resin layer 12]
The decorative sheet 10 of the present disclosure preferably has the second resin layer 12 . The second resin layer 12 may be provided on part of the unevenness forming member 2 or may be provided on the entire surface. Also, the second resin layer 12 may be provided on a part of the decorative sheet 10 or may be provided on the entire surface. From the viewpoint of protecting the layer closer to the base material layer 1 than the second resin layer 12 , the second resin layer 12 is preferably provided over the entire surface of the unevenness forming member 2 , and is preferably provided over the entire surface of the decorative sheet 10 . More preferred. The second resin layer 12 may be provided on the substrate layer 1 side of the unevenness forming member 2 , or may be provided on the opposite side of the unevenness forming member 2 from the substrate layer 1 .

The second resin layer 12 is preferably in contact with the unevenness forming member 2 or the first resin layer 11 .

The second resin layer 12 can contain a delustering agent for the purpose of adjusting the luster of the decorative sheet 10, for example.

Examples of resins constituting the second resin layer 12 include phenol resins, urea resins, diallyl phthalate, melamine resins, guanamine resins, unsaturated polyester resins, polyurethane resins, epoxy resins, aminoalkyd resins, and melamine-urea cocondensates. , silicone resin, polysiloxane, polyethylene terephthalate, polybutylene terephthalate, polyamide, polyethylene, polypropylene, ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, ethylene-acrylate copolymer, ionomer, polymethylpentene , acrylic acid ester, methacrylic acid ester, polycarbonate, cellulose triacetate, and the like.

Alternatively, the second resin layer 12 may be formed using an ionizing radiation curable resin. The details of the ionizing radiation curable resin are the same as those described in detail in the section [First resin layer 11].

When the second resin layer 12 contains a matting agent, the matting agent is not particularly limited, and a wide range of known matting agents can be used. Examples of matting agents include inorganic particles such as silica, alumina, calcium carbonate, magnesium carbonate, aluminosilicate, and barium sulfate; resin (organic) particles such as acrylic beads, polyethylene, urethane resin, polycarbonate, polyamide (nylon), and the like. mentioned. The average particle size of the particles is preferably 0.5-20 μm, more preferably 0.5-10 μm. The amount of the matting agent added is preferably 2 to 40% by mass, more preferably 5 to 30% by mass based on the resin composition (excluding the solvent) forming the second resin layer 12 . The shape of the particles may be polyhedral, spherical, scaly, or the like. Among the above inorganic particles and organic particles, silica is preferred.

It is preferable to adjust the thickness of the second resin layer 12 in consideration of the size of the irregularity forming member 2, the irregular shape of the decorative sheet, and the like. From this point of view, the thickness of the second resin layer 12 is preferably about 2 to 10 μm, more preferably about 0.1 to 20 μm, even more preferably about 0.3 to 10 μm, still more preferably 0.5 to 5 μm. degree. The thickness of the second resin layer 12 means the thickness of the second resin layer 12 that is not located on the unevenness forming member 2 .

When the decorative sheet of the present disclosure is used for injection molding or vacuum molding, from the viewpoint of improving the scratch resistance of the decorative sheet and improving the three-dimensional moldability, the ionizing radiation curable forming the second resin layer 12 As the resin, it is preferable to use the aforementioned polycarbonate (meth)acrylate.

In addition, when the decorative sheet of the present disclosure is used for injection molding or vacuum molding, the second resin layer 12 is made of an ionizing radiation-curable material from the viewpoint of improving the scratch resistance of the decorative sheet and improving the three-dimensional moldability. It is also preferable to configure with a mixture of a resin and a thermoplastic resin. Examples of thermoplastic resins include acrylic resins, urethane resins, and olefin resins, with acrylic resins being particularly preferred. The mixing ratio of the ionizing radiation curable resin and the thermoplastic resin is preferably about 10:90 to 75:25, more preferably about 25:75 to 50:50 in mass ratio.

[Third resin layer 13]
Although illustration is omitted for convenience of drawing, in the decorative sheet 10 of the present disclosure, when the second resin layer 12 is provided on the side opposite to the base layer 1 side of the unevenness forming member 2, the second resin layer 12 It is preferable that the third resin layer 13 is provided on the side opposite to the unevenness forming member 2 side. Further, when the second resin layer 12 is provided on the base material layer 1 side of the unevenness forming member 2, the second resin layer 12 on the side of the unevenness forming member 2 (when the first resin layer 11 exists, the first resin layer 11 and the second resin layer), a third resin layer 13 is preferably provided. The third resin layer 13 can be provided on at least part of the second resin layer 12 . For example, the third resin layer 13 is provided on the entire surface of the second resin layer 12 and on the entire surface of the decorative sheet. Also, between the unevenness forming member 2 and the substrate layer 1 (when the first resin layer 11 exists and the second resin layer 12 is provided on the opposite side of the unevenness forming member 2 from the substrate layer 1 side) , between the first resin layer 1 and the substrate layer 1), a third resin layer 13 may be provided.

In the decorative sheet of the present disclosure, for example, the third resin layer 13 is partially provided on the second resin layer 12, and the second resin layer 12 containing the matting agent is exposed and not exposed. The decorative sheet of the present disclosure can be given a high degree of designability by forming and creating a gloss difference between the regions. The third resin layer 13 preferably has a gloss higher than that of the second resin layer 12 from the viewpoint of obtaining a more excellent design. That is, the second resin layer 12 contains a matting agent so that it has a relatively low gloss, and the third resin layer 13 has a relatively high gloss, and between the second resin layer 12 and the third resin layer Preferably, a gloss differential is provided.

Furthermore, in the decorative sheet 10 of the present disclosure, it is preferable that the position where the concave-convex forming member 2 exists and the position where the third resin layer 13 is formed are synchronized. Synchronization here means that the position where the unevenness forming member 2 exists (particularly, the position of the raised portion) and the position where the third resin layer 13 is formed are related to each other in plan view. shall mean that it exists in Specifically, in plan view, (a) when the third resin layer 13 is present at the same position as the unevenness-forming member 2 (especially, the position of the raised portion), (b) the unevenness-forming member 2 (especially , the position of the raised portion), (c) a position apart from the unevenness forming member 2 (particularly, the position of the raised portion) by a certain distance, The case where the third resin layer 13 exists while maintaining the direction is included.

The third resin layer 13 is preferably a transparent resin layer. Note that the term “transparent” includes all of colorless transparent, colored transparent, translucent, and the like.

Examples of resins constituting the third resin layer 13 include phenol resins, urea resins, diallyl phthalate, melamine resins, guanamine resins, unsaturated polyester resins, polyurethane resins, epoxy resins, aminoalkyd resins, and melamine-urea cocondensates. , silicone resin, polysiloxane, polyethylene terephthalate, polybutylene terephthalate, polyamide, polyethylene, polypropylene, ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, ethylene-acrylate copolymer, ionomer, polymethylpentene , acrylic acid ester, methacrylic acid ester, polycarbonate, cellulose triacetate, and the like. Also, the ionizing radiation curable resin described above may be used. These resins can be used alone or in combination of two or more.

In addition, the third resin layer 13 can contain a delustering agent for luster adjustment. When the third resin layer 13 contains a matting agent, the content of the matting agent in the third resin layer 13 is preferably less than the content of the matting agent in the second resin layer 12 . For example, by making the content of the matting agent in the third resin layer 13 less than the content of the matting agent in the second resin layer 12, the glossiness of the third resin layer 13 is higher than that of the second resin layer 12. It becomes easy to obtain excellent designability.

Examples of the matting agent used for the third resin layer 13 are the same as those listed for the second resin layer 12 . The amount of the matting agent to be added is preferably 0.5 to 20 mass %, more preferably 1 to 15 mass % based on the resin composition (excluding the solvent) forming the third resin layer 13 . In addition, when the content of the matting agent in the third resin layer 13 is less than the content of the matting agent in the second resin layer 12, the solid content of the resin composition forming the third resin layer 13 per unit mass is smaller than the mass of the matting agent contained per unit mass of the solid content of the resin composition forming the second fat layer 12 .

When the decorative sheet 10 of the present disclosure has a pattern layer 3 , which will be described later, it is preferable that the third resin layer 13 is provided in synchronization with the pattern of the pattern layer 3 . By making the pattern of the pattern layer 3 and the pattern of the third resin layer 13 in harmony with each other, a decorative sheet having a more excellent design can be obtained. In the present disclosure, the synchronization between the pattern of the pattern layer 3 and the third resin layer 13 means, for example, when the decorative sheet is observed from the plane, the position of the pattern of the pattern layer 3 and the position of the pattern of the third resin layer 13 are formed (so-called positive), and the pattern position of the pattern layer 3 and the position where the third resin layer 13 is not formed correspond (so-called negative). .

In the decorative sheet 10 of the present disclosure, the pattern layer 3 has a wood grain pattern, and a third resin layer 13 having a gloss higher than that of the pattern layer 3 is provided on a portion other than the winter grain pattern and/or the conduit pattern of the wood grain. preferably. As a result, the luster of the winter grain pattern and/or vessel pattern portion of the wood grain is lowered, so that excellent design properties similar to those of natural wood can be obtained. In order to form the third resin layer 13 as described above, a plate in which the same winter grain pattern and/or conduit pattern of the pattern layer 3 is reversed (that is, a negative state) is used, and a known printing method is used. It is preferable to print using As a printing method, a gravure printing method, a screen printing method, or the like is preferable.

Although the third resin layer 13 may be colored, it is desirable not to add a coloring agent.

The thickness of the third resin layer 13 is preferably about 0.1 to 20 μm, more preferably about 0.5 to 10 μm, and even more preferably about 1 to 5 μm, from the viewpoint of achieving both excellent tactile sensation and design. .

When the decorative sheet 10 of the present disclosure is used for injection molding or vacuum molding, the third resin layer 13 is formed from the viewpoint of improving the scratch resistance of the decorative sheet 10 and improving the three-dimensional moldability. Polycarbonate (meth)acrylate is preferably used as the ionizing radiation-curable resin. The same polycarbonate (meth)acrylate as exemplified in the section [First resin layer 11] can be used.

In addition, when the decorative sheet 10 of the present disclosure is used for injection molding or vacuum molding, the third resin layer 13 is irradiated with ionizing radiation from the viewpoint of improving the scratch resistance of the decorative sheet 10 and improving the three-dimensional moldability. It is also preferable to use a mixture of a curable resin and a thermoplastic resin. The type of thermoplastic resin and the preferred mixing ratio of the ionizing radiation-curable resin and the thermoplastic resin are the same as those described in the section [First resin layer 11].

[Pattern layer 3]
The pattern layer 3 is a layer provided as necessary for the purpose of imparting decorativeness to the decorative sheet. The pattern layer 3 may be provided on the substrate layer 1 side of the unevenness forming member 2 (under the first resin layer 11 when the first resin layer 11 is provided), or the substrate layer of the unevenness forming member 2. Although it may be provided on the side opposite to 1, it is preferably provided on the substrate layer 1 side of the unevenness forming member 2 . Further, the unevenness forming member 2 and the pattern layer 3 may be in contact with each other, or may be laminated via the first resin layer 11, a primer layer described later, or the like.

The pattern layer 3 can be a layer in which a desired pattern is formed using an ink composition, for example. As the ink composition used for forming the pattern layer 3, a mixture of a binder, a coloring agent such as a pigment and a dye, an extender pigment, a solvent, a stabilizer, a plasticizer, a catalyst, a curing agent, etc. is used. .

The binder used in the ink composition is not particularly limited, but examples include polyurethane resins, vinyl chloride-vinyl acetate copolymers, vinyl chloride-vinyl acetate-acrylic copolymers, chlorinated polypropylene resins, acrylic resins, polyesters. resins, polyamide resins, butyral resins, polystyrene resins, nitrocellulose resins, cellulose acetate resins, and the like. These binders may be used singly or in combination of two or more.

Colorants used in the ink composition are not particularly limited, but examples include carbon black (ink), iron black, titanium white, antimony white, yellow lead, titanium yellow, red iron oxide, cadmium red, ultramarine blue, and cobalt blue. organic pigments or dyes such as quinacridone red, isoindolinone yellow, and phthalocyanine blue; metal pigments consisting of scale-like foil pieces such as aluminum and brass; scale-like foils such as titanium dioxide-coated mica and basic lead carbonate A pearl luster (pearl) pigment consisting of flakes and the like can be mentioned.

The pattern formed by the pattern layer 3 is also not particularly limited, but may be, for example, a wood grain pattern, a marble pattern (for example, a travertine marble pattern), a stone grain pattern imitating the surface of a rock, or a texture or cloth-like pattern. Examples include a fabric pattern, a tiled pattern, and a brickwork pattern, and may be a pattern such as a parquet or patchwork that combines these, or may be a single-color solid pattern (so-called all-over solid pattern). These patterns are formed by multi-color printing using the usual process colors of yellow, red, blue, and black, but they can also be formed by special-color multi-color printing by preparing individual color plates that make up the pattern. can be formed.

Although the thickness of the pattern layer 3 is not particularly limited, it is, for example, 1 to 30 μm, preferably 1 to 20 μm.

Also, the pattern layer 3 may be a metal thin film layer. Examples of metals forming the metal thin film layer include tin, indium, chromium, aluminum, nickel, copper, silver, gold, platinum, zinc, and alloys containing at least one of these. A method for forming the metal thin film layer is not particularly limited, and examples thereof include a vapor deposition method such as a vacuum vapor deposition method, a sputtering method, and an ion plating method using the above metals. The metal thin film layer may be provided on the entire surface or may be provided partially. Further, a primer layer using a known resin may be provided on the front surface or the back surface of the metal thin film layer in order to improve the adhesion with the adjacent layer.

[Primer layer]
The primer layer is provided at an arbitrary position between each layer as necessary for the purpose of improving the adhesion between the layers included in the decorative sheet. The primer layer is preferably provided between the pattern layer 3 and the first resin layer 11 .

Examples of the primer composition constituting the primer layer include urethane resin, (meth)acrylic resin, (meth)acrylic-urethane copolymer, vinyl chloride-vinyl acetate copolymer, polyester resin, butyral resin, chlorinated polypropylene, chlorine It is preferable to use a binder resin such as poly(ethylene terephthalate), and these resins can be used singly or in combination of two or more. Among these, urethane resins, (meth)acrylic resins, and (meth)acrylic-urethane copolymers are preferred.

As the urethane resin, a polyurethane containing polyol (polyhydric alcohol) as a main component and isocyanate as a cross-linking agent (curing agent) can be used. As the polyol, those having two or more hydroxyl groups in the molecule, for example, polyester polyol, polyethylene glycol, polypropylene glycol, acrylic polyol, polyether polyol and the like are used. Examples of the isocyanate include polyisocyanates having two or more isocyanate groups in the molecule, aromatic isocyanates such as 4,4-diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, hydrogenated tolylene diisocyanate, and hydrogenated diphenylmethane diisocyanate. Aliphatic (or alicyclic) isocyanates such as are used. It is also possible to mix urethane resin and butyral resin.

From the viewpoint of physical properties and moldability, it is preferable to combine acrylic polyol or polyester polyol as a polyol with hexamethylene diisocyanate and 4,4-diphenylmethane diisocyanate as a cross-linking agent, and in particular, acrylic polyol and hexamethylene diisocyanate are used in combination. is preferred.

The (meth)acrylic resin may be a homopolymer of a (meth)acrylic acid ester, a copolymer of two or more different (meth)acrylic acid ester monomers, or a copolymer of a (meth)acrylic acid ester and another monomer. Polymers include, specifically, polymethyl (meth)acrylate, polyethyl (meth)acrylate, poly(meth)propyl acrylate, polybutyl (meth)acrylate, methyl (meth)acrylate- Butyl (meth)acrylate copolymer, ethyl (meth)acrylate-butyl (meth)acrylate copolymer, ethylene-methyl (meth)acrylate copolymer, styrene-methyl (meth)acrylate copolymer A (meth)acrylic resin comprising a homopolymer or a copolymer containing a (meth)acrylic acid ester such as is preferably used.

As the (meth)acryl-urethane copolymer, for example, an acrylic-urethane (polyester urethane) block copolymer is preferable. As the curing agent, the various isocyanates described above are used. If desired, the acrylic/urethane ratio (mass ratio) of the acrylic-urethane (polyester urethane) block copolymer is preferably adjusted in the range of 9/1 to 1/9, more preferably 8/2 to 2/8. is preferred.

Although the thickness of the primer layer is not particularly limited, it is, for example, about 0.5 to 20 μm, preferably 1 to 5 μm.

The primer layer is formed by gravure coating, gravure reverse coating, gravure offset coating, spinner coating, roll coating, reverse roll coating, kiss coating, wheel coating, dip coating, solid coating by silk screen, wire bar coating, and flow coating using the primer composition. It is formed by a normal coating method such as coating, comma coating, flow coating, brush coating, spray coating, or a transfer coating method. Here, the transfer coating method is a method in which a coating film such as a primer layer or an adhesive layer is formed on a thin sheet (film substrate), and then the target layer surface in the decorative sheet is coated.

[Hiding layer]
The concealing layer is provided between the substrate layer 1 and the unevenness forming member 2 for the purpose of suppressing color change and unevenness of the substrate layer 1. It is a layer provided as needed between.

The concealing layer is provided to prevent the base material layer 1 from adversely affecting the color tone and pattern of the decorative sheet, and is generally formed as an opaque layer.

The concealing layer is formed using an ink composition in which a coloring agent such as a pigment or a dye, an extender, a solvent, a stabilizer, a plasticizer, a catalyst, a curing agent, and the like are appropriately mixed with a binder. The ink composition for forming the masking layer is appropriately selected from those used for the pattern layer 3 described above.

The concealing layer is usually set to have a thickness of about 1 to 20 μm, and is desirably formed as a so-called solid printing layer.

The concealing layer can be formed by ordinary printing methods such as gravure printing, offset printing, silk screen printing, printing by transfer from a transfer sheet, inkjet printing; gravure coating, gravure reverse coating, gravure offset coating, spinner coating, roll coating, reverse roll. It is formed by a normal coating method such as coating.

[Back adhesive layer]
The back adhesive layer is a layer provided as necessary on the side opposite to the outer surface of the decorative sheet for the purpose of enhancing adhesion to the molding resin when molding the decorative resin molded product.

A thermoplastic resin or a curable resin is used for the back adhesive layer depending on the molding resin used for the decorative resin molded product.

Thermoplastic resins used for forming the back adhesive layer include, for example, acrylic resins, acrylic-modified polyolefin resins, chlorinated polyolefin resins, vinyl chloride/vinyl acetate copolymers, thermoplastic urethane resins, thermoplastic polyester resins, and polyamides. Resins, rubber-based resins, and the like can be mentioned. These thermoplastic resins may be used singly or in combination of two or more.

Further, examples of thermosetting resins used for forming the back adhesive layer include urethane resins and epoxy resins. These thermosetting resins may be used singly or in combination of two or more.

2. Method for manufacturing decorative sheet The above-described decorative sheet 10 of the present disclosure has at least the unevenness forming member 2 on one surface of the base material layer 1, and the uneven shape of the one side of the base material layer 1 is It can be manufactured so as to be formed by the concave-convex shaped member 2 . As described above, the decorative sheet 10 is laminated with the first resin layer 11, the second resin layer 12, the third resin layer 13, the pattern layer 3, the primer layer, the concealing layer, the back adhesive layer, etc., if necessary. You can also The components used to form each layer, the thickness, specific conditions for forming each layer, and the like are as described in the section on the composition of each layer.

The concave-convex shape of the base layer 1 in the decorative sheet 10 of the present disclosure is obtained, for example, by pressing the concave-convex forming member arranged on one side of the base layer into the base layer 1 side in the manufacturing process of the decorative sheet. can be formed by More specifically, the pattern layer 3 or the like is laminated on the base material layer 1 as necessary, and the resin composition containing the resin forming the first resin layer 11 and the unevenness forming member 2 from thereon. (ink) is applied, and if necessary, the second resin layer 12, the third resin layer 13, etc. are laminated, and while the first resin layer 11 is in an uncured state, the unevenness forming member 2 is rolled using a rubber roll or the like. By pressing into the substrate layer 1 and then curing the first resin layer 11 , the uneven shape formed by the unevenness forming member 2 can be formed on the substrate layer 1 .

3. Decorative Resin Molded Product The decorative resin molded product 20 of the present disclosure is formed by integrating molding resin with the decorative sheet of the present disclosure. That is, the decorative resin molded product 20 of the present disclosure is, as shown in the schematic diagram of FIG. 1 and a plurality of unevenness forming members 2 arranged on one side of the base material layer 1 in this order, the surface of the one side of the base material layer 1 having an uneven shape, and the unevenness of the base material layer 1 The shape is characterized by being formed by the unevenness forming member 2 . In the decorative resin molded product 20 of the present disclosure, if necessary, the first resin layer 11, the second resin layer 12, the third resin layer 13, the pattern layer 3, the primer layer, the concealing layer, the back adhesive layer, etc. may further be provided with at least one layer of

The decorative resin molded product of the present disclosure is produced, for example, using the decorative sheet of the present disclosure by various injection molding methods such as an insert molding method, an injection molding simultaneous decoration method, a blow molding method, and a gas injection molding method. be. In the present disclosure, by subjecting the decorative sheet of the present disclosure to various injection molding methods to produce a decorative resin-molded product, excellent adhesion can be exhibited between the decorative sheet and the molded resin layer. Among these injection molding methods, the insert molding method and the simultaneous injection molding decoration method are preferred.

In the insert molding method, first, in the vacuum forming process, the decorative sheet of the present disclosure is vacuum-formed (off-line preforming) in advance into the surface shape of the molded product using a vacuum forming mold, and then, if necessary, the excess portion is trimmed. Obtain a molded sheet. This molding sheet is inserted into an injection mold, the injection mold is clamped, and the resin in a fluid state is injected into the mold, solidified, and the decorative sheet is integrated with the outer surface of the resin molding at the same time as the injection molding. A decorative resin molded product is manufactured by making it harden.

More specifically, the decorative resin molded product of the present disclosure is manufactured by an insert molding method including the following steps.
A vacuum forming step of forming the decorative sheet of the present disclosure into a three-dimensional shape in advance with a vacuum forming mold;
A trimming process to obtain a molded sheet by trimming the excess part of the vacuum-formed decorative sheet, insert the molded sheet into the injection mold, close the injection mold, and inject the resin in a fluid state into the injection mold. An integration process that integrates the resin and the molded sheet.

In the vacuum forming step in the insert molding method, the decorative sheet may be heated and formed. The heating temperature at this time is not particularly limited, and may be appropriately selected depending on the type of resin constituting the decorative sheet and the thickness of the decorative sheet. If so, it can be usually set to about 120 to 200°C. In addition, in the integration step, the temperature of the resin in a fluid state is not particularly limited, but it can usually be about 180 to 320.degree.

In the simultaneous injection molding and decorating method, the decorative sheet of the present disclosure is arranged in a female mold that is also used as a vacuum molding mold provided with injection molding suction holes, and preforming (inline preforming) is performed in this female mold. After that, the injection mold is clamped, and the resin in a fluid state is injected and filled into the mold, solidified, and the decorative sheet of the present disclosure is integrated with the outer surface of the resin molding at the same time as the injection molding. Thus, a decorative resin molded product is manufactured.

More specifically, the decorated resin molded product of the present disclosure is manufactured by the simultaneous injection molding and decorating method including the following steps.
After the decorative sheet of the present disclosure is placed so that the base layer 1 side of the decorative sheet faces the molding surface of a movable mold having a molding surface of a predetermined shape, the decorative sheet is heated and softened. A preforming step of preforming the decorative sheet by vacuum suction from the movable mold side and adhering the softened decorative sheet along the molding surface of the movable mold,
After the movable mold and fixed mold having the decorative sheet adhered along the molding surface are clamped, the resin in a fluid state is injected into the cavity formed by both molds, filled and solidified. A process of integrating the resin molded body and the decorative sheet by lamination, and a resin molding in which all layers of the decorative sheet are laminated by separating the movable mold from the fixed mold. Extraction process to take out the body.

In the preforming step of the simultaneous injection molding and decorating method, the heating temperature of the decorative sheet is not particularly limited, and may be appropriately selected depending on the type of resin constituting the decorative sheet, the thickness of the decorative sheet, and the like. When a polyester resin film or an acrylic resin film is used as the base material layer 1, the temperature can be usually about 70 to 130°C. Also, in the injection molding process, the temperature of the resin in a fluid state is not particularly limited, but it can usually be about 180 to 320.degree.

In addition, the decorative resin molded product of the present disclosure is a decoration method in which the decorative sheet of the present disclosure is attached on a three-dimensional resin molded body (molded resin layer 5) prepared in advance, such as a vacuum pressure bonding method. can also be produced by In the vacuum crimping method, first, the decorative sheet and the resin molded body of the present disclosure are placed in a vacuum crimping machine consisting of a first vacuum chamber located on the upper side and a second vacuum chamber located on the lower side. It is placed in the vacuum pressure bonding machine so that the vacuum chamber side, the resin molded body is on the second vacuum chamber side, and the base layer 1 side of the decorative sheet faces the resin molded body side, and the two vacuum chambers are placed in a vacuum state. do. The resin molded body is placed on a vertically movable platform provided on the side of the second vacuum chamber. Next, while pressurizing the first vacuum chamber, the molded body is pressed against the decorative sheet using a lifting table, and the resin molded body is stretched while stretching the decorative sheet using the pressure difference between the two vacuum chambers. affixed to the surface of Finally, the two vacuum chambers are opened to the atmospheric pressure, and the excess portion of the decorative sheet is trimmed as necessary to obtain the decorated resin molded product of the present disclosure.

In the vacuum pressure bonding method, it is preferable to include a step of heating the decorative sheet in order to soften the decorative sheet and improve formability before the step of pressing the molding against the decorative sheet. A vacuum compression bonding method including the process is sometimes called a vacuum thermocompression bonding method. The heating temperature in this step may be appropriately selected depending on the type of resin constituting the decorative sheet, the thickness of the decorative sheet, and the like. For example, the temperature can be usually about 60 to 200°C.

In the decorative resin molded product of the present disclosure, the molded resin layer 5 may be formed by selecting a resin according to the application. The molding resin that forms the molding resin layer 5 may be a thermoplastic resin or a thermosetting resin.

Examples of thermoplastic resins include polyolefin resins such as polyethylene and polypropylene, ABS resins, styrene resins, polycarbonate resins, acrylic resins, vinyl chloride resins, and the like. Therefore, among these, the ABS resin is preferable. These thermoplastic resins may be used singly or in combination of two or more.

Further, examples of thermosetting resins include urethane resins and epoxy resins. These thermosetting resins may be used singly or in combination of two or more.

Decorative resin molded articles of the present disclosure include, for example, interior and exterior materials for vehicles such as automobiles; fittings such as window frames and door frames; interior materials for buildings such as walls, floors and ceilings; It can be used as a housing for home electric appliances such as machines;

EXAMPLES The present disclosure will be described in detail below with reference to examples and comparative examples. However, the present disclosure is not limited to the examples.

(Production of decorative sheet)
[Example 1]
A black ABS raw material was prepared as a substrate layer, and gravure printing was performed using an ink containing a copolymer of vinyl chloride and vinyl acetate with a coloring agent to form a 1 μm-thick full-surface colored layer (hiding layer) and a 4 μm-thick The pattern layers of the wood grain pattern were sequentially coated. The wood grain pattern was formed so that the winter wood grain portion was dark.

Next, 60% by mass of an ionizing radiation-curable resin (EB1) composed of a bifunctional urethane acrylate (weight average molecular weight: 30,000) having a polycarbonate skeleton that forms the first resin layer, and urethane that forms a plurality of irregularities forming members. An ink containing 40% by mass of beads (average particle size 20 μm, particle size 10 to 70 μm) is prepared and coated by printing using a pattern plate with a plate depth of 90 μm to form the first resin layer on the pattern layer. and a region containing a plurality of uneven forming members was printed in a pattern. In the confirmation of the cross section described later, in the region containing the first resin layer and the plurality of unevenness forming members, the first resin layer, the plurality of unevenness forming members, and the second resin layer were present in this order on the pattern layer. The pattern was a wood grain pattern, and was formed so as to have an area ratio of 25% with respect to one surface of the substrate layer.

Next, an ink containing 70% by mass of an ionizing radiation-curable resin (EB1) composed of a bifunctional urethane acrylate having a polycarbonate skeleton (weight average molecular weight of 30,000) and 30% by mass of silica particles (average particle diameter of 2 μm) as a matting agent. was used to form a second resin layer having a thickness of 5 μm by performing gravure printing (overall solid printing) on the entire area including the first resin layer and the plurality of concave-convex forming members. The glossiness of the second resin layer was set to 1.0 (60° gloss).

Next, it contains 6% by mass of silica particles (average particle size 2 μm) as a matting agent, and 94% by mass of an ionizing radiation curable resin (EB1) composed of a bifunctional urethane acrylate having a polycarbonate skeleton (weight average molecular weight 30,000). A third resin layer having a thickness of 2 μm was formed by using ink and gravure printing in a pattern excluding the winter grain portion of the wood grain pattern of the pattern layer so as to be in sync with the wood grain pattern. The glossiness of the third resin layer was set to 10.0 (60° gloss).

Further, the back side of the base material was sandwiched between a metal roll and a rubber roll (hardness 70 degrees) on the third resin layer side, and a pressure of 2 kg/cm ² was applied to push the unevenness forming member into the base material layer. Next, from the third resin layer side, an electron beam with an acceleration voltage of 165 kV and an irradiation dose of 50 kGy (5 Mrad) is applied to the ionizing radiation curable resin of the first resin layer, the second resin layer, and the third resin layer. It was cured to obtain a decorative sheet. In the obtained decorative sheet, it was confirmed that the concave-convex forming member was pushed into the base material layer.

[Example 2]
A decorative sheet was obtained in the same manner as in Example 1, except that urethane beads (average particle diameter: 10 μm, particle diameter: 3 to 40 μm) were used as the urethane beads that form the plurality of uneven forming members. In the decorative sheet obtained in Example 2 as well, it was confirmed that the concave-convex forming member was pushed into the base material layer.

[Example 3]
A decorative sheet was obtained in the same manner as in Example 1, except that urethane beads (average particle diameter: 50 μm, particle diameter: 10 to 80 μm) were used as the urethane beads for forming the plurality of irregularities forming members. Also in the decorative sheet obtained in Example 3, it was confirmed that the concave-convex forming member was pushed into the base material layer.

[Example 4]
Example except that an ink containing an ionizing radiation-curable resin made of a bifunctional urethane acrylate (weight average molecular weight: 30,000) having a polycarbonate skeleton containing no silica particles was used to form the second resin layer. A decorative sheet was obtained in the same manner as in 1. Also in the decorative sheet obtained in Example 4, it was confirmed that the concave-convex forming member was pressed into the base material layer.

[Example 5]
A decorative sheet was obtained in the same manner as in Example 1, except that the third resin layer was not provided. Also in the decorative sheet obtained in Example 5, it was confirmed that the concave-convex forming member was pushed into the base material layer.

[Example 6]
As the ionizing radiation curable resin (EB2) of the second resin layer and the third resin layer, instead of "bifunctional urethane acrylate having a polycarbonate skeleton (weight average molecular weight 30,000)", "pentaerythritol triacrylate and thermoplastic resin (Methyl methacrylate homopolymer, weight average molecular weight 100,000) "ionizing radiation curable resin (pentaerythritol triacrylate: thermoplastic resin = 30:70 (mass ratio))" A decorative sheet was obtained in the same manner as in Example 1. Also in the decorative sheet obtained in Example 6, it was confirmed that the concave-convex forming member was pressed into the base material layer.

[Comparative Example 1]
A decorative sheet was obtained in the same manner as in Example 1, except that the rubber roll was not pressed from above the third resin layer. In the decorative sheet obtained in Comparative Example 1, it was confirmed that the concave-convex forming member was not pushed into the base material layer.

[Comparative Example 2]
A decorative sheet was obtained in the same manner as in Example 5, except that the rubber roll was not pressed from above the third resin layer. In the decorative sheet obtained in Comparative Example 2, it was confirmed that the concave-convex forming member was not pushed into the base material layer.

[Comparative Example 3]
A decorative sheet was obtained in the same manner as in Example 1, except that the second resin layer and the third resin layer were not provided and the rubber roll was not pressed from above the third resin layer. In the decorative sheet obtained in Comparative Example 3, it was confirmed that the concave-convex forming member was not pushed into the base material layer.

<Cross-sectional observation of decorative sheet>
Observation of cross sections in the thickness direction of each decorative sheet obtained in Examples and Comparative Examples (10 points each) with a scanning electron microscope (accelerating voltage of 3.0 kV, magnification of 1,500 times) to form unevenness. It was confirmed whether or not the urethane beads used as the member were pressed into the base material layer (the uneven shape was formed on the surface of the base material layer by the unevenness forming member). In addition, the maximum depth of the concave portion of the base material layer was measured for 10 cross-sectional images, and the average value was calculated. In addition, the ratio (%) of the average maximum depth of the concave portions of the substrate layer to the average particle size of the concave-convex forming member was calculated. Table 1 shows the results.

<Evaluation of tactile sensation of decorative sheet>
For each decorative sheet obtained above, the surface on the side of the third resin layer (the side opposite to the base material layer) was touched with a finger, and the tactile sensation was evaluated according to the following criteria. Table 1 shows the results.
A: Unevenness is clearly felt B: Unevenness is felt C: Unevenness is felt weakly, but it can be said that it is a decorative sheet that imparts a tactile sensation D: Almost no unevenness is felt, and a decoration that imparts a tactile sensation not a sheet

<Evaluation of tactile sensation of decorative resin molded product>
Each decorative sheet obtained above was heated with an infrared heater and softened until the sheet temperature reached 160°C. Then, vacuum forming was performed using a vacuum forming mold (maximum draw ratio: 100%) to form the internal shape of the mold. After the molded decorative sheet was cooled, it was released from the mold. After that, the injection resin was injected into the cavity of the mold, and the decorative sheet and the injection resin were integrally molded. . The surface of the decorative resin molded product on the side of the third resin layer (the side opposite to the base material layer) was touched with a finger, and the tactile sensation was evaluated according to the following criteria. Table 1 shows the results.
A: Unevenness is clearly felt B: Unevenness is felt C: Unevenness is felt weakly, but it can be said that it is a decorative resin molded product with a tactile feel D: Almost no unevenness is felt and a tactile feeling is given Not a decorative resin molded product

<Evaluation of the difference in tactile sensation between the decorative sheet and the decorative resin molded product>
Based on the evaluation results of each tactile sensation described above, the difference in tactile sensation between the decorative sheet and the decorative resin molded product was evaluated according to the following criteria. Table 1 shows the results.
A: Almost no difference in tactile sensation between the decorative sheet and the decorative resin molded article.
B: The tactile sensation of the decorative resin molded product is slightly weaker than that of the decorative sheet, but the intended tactile sensation is maintained.
C: The tactile sensation of the decorative resin molded product is weaker than that of the decorative sheet, and is different from the intended tactile sensation.

In the decorative sheet of Example 1-6, one surface of the base material layer has an uneven shape, and the uneven shape is formed in the base material layer by pressing the unevenness forming member. In the decorative sheet of Example 1-6, the difference in tactile sensation between the decorative sheet and the decorative resin molded product was small, and the change in uneven shape due to molding was suppressed.

DESCRIPTION OF SYMBOLS 1... Base material layer 2... Concavo-convex forming member 11... First resin layer 12... Second resin layer 13... Third resin layer 3... Pattern layer 5... Molded resin layer 10... Decorating sheet 20... Decorating resin molding

Claims (6)

A decorative sheet having an uneven surface,
At least a substrate layer and a plurality of unevenness forming members arranged on one side of the substrate layer,
The one-side surface of the base layer has an uneven shape,
The uneven shape of the base layer is formed by the unevenness forming member,
The unevenness forming member is particles having an average particle diameter of 5 μm or more and 60 μm or less,
A second resin layer is provided on at least a portion of the concave-convex forming member opposite to the base layer side,
The second resin layer is provided on the entire surface of the unevenness forming member,
having a first resin layer at least partially between the base material layer and the unevenness forming member;
Having a pattern layer between the base material layer and the first resin layer ,
A decorative sheet having a third resin layer on at least part of the second resin layer . The decorative sheet according to claim 1, wherein the first resin layer is present at a position corresponding to a position where the unevenness forming member is present. The decorative sheet according to claim 1 or 2, wherein a region including the unevenness forming member and the first resin layer forms a single convex portion. The decorative sheet according to any one of claims 1 to 3 , wherein the concave-convex shape on the surface of the decorative sheet is formed by the concave-convex forming member. The decorative sheet according to any one of claims 1 to 4 , wherein the unevenness forming member is not exposed on the surface of the decorative sheet. A decorative resin molded article having an uneven surface,
having at least a molded resin layer, a substrate layer, and a plurality of unevenness-forming members arranged on one side of the substrate layer in this order;
The one-side surface of the base layer has an uneven shape,
The uneven shape of the base layer is formed by the unevenness forming member,
The unevenness forming member is particles having an average particle diameter of 5 μm or more and 60 μm or less,
A second resin layer is provided on at least a portion of the concave-convex forming member opposite to the base layer side,
The second resin layer is provided on the entire surface of the unevenness forming member,
having a first resin layer at least partially between the base material layer and the unevenness forming member;
Having a pattern layer between the base material layer and the first resin layer ,
A decorative resin molded article having a third resin layer on at least part of the second resin layer .

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