Decorative sheets and decorative resin molded products

Abstract

To provide a decorative sheet having excellent tactile feeling and designability and also excellent interlayer adhesion.SOLUTION: A decorative sheet includes a substrate layer 3, and a first resin layer 1 formed on an entire surface of one side of the substrate layer 3. The first resin layer 1 contains a first particle 1a and a second particle 1b being a particle of a kind different from the first particle 1a and relatively larger than the first particle 1a. The first resin layer 1 includes a plurality of raised parts 11 protruding on a side opposite to the substrate layer 3 side. The second particle 1b is not having contact with a layer positioned on the substrate layer 3 side of the first resin layer 1.SELECTED DRAWING: Figure 1

Description

[Technical field]

[0001] The present disclosure relates to a decorative sheet and a decorated resin molded product. [Background technology]

[0002] Conventionally, decorative resin molded products in which a decorative sheet is laminated on the surface of a resin molded product are used for vehicle interior and exterior parts, building material interior materials, home appliance housings, etc. In the manufacture of such decorative resin molded products, a molding method is used in which a decorative sheet to which a design has been previously applied is integrated with a resin by injection molding. Representative examples of such molding methods include an insert molding method in which a decorative sheet is previously molded into a three-dimensional shape using a vacuum molding mold, the decorative sheet is inserted into an injection mold, and a resin in a fluid state is injected into the mold to integrate the resin and the decorative sheet, and an injection molding simultaneous decoration method in which a decorative sheet inserted into a mold during injection molding is integrated with molten resin injected into the cavity. In addition to the molding method using injection molding, a decorative sheet is also used in a decoration method in which a decorative sheet is attached to a previously molded molded body while being heated and pressurized, such as a vacuum pressure bonding method.

[0003] Known methods for imparting high texture to a decorated resin molded product include providing a resin layer containing a matting agent on a decorative sheet and providing an uneven surface on the surface of the decorative sheet. For example, Patent Document 1 describes a decorative sheet having, on a base layer, a first resin layer containing a matting agent, a second resin layer partially provided on the first resin layer, and a raised layer containing resin and organic particles provided on the second resin layer 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 a matting agent, and a difference in gloss occurs between the area where the second resin layer is laminated and the area where it is not laminated, resulting in high designability (gloss matte expression). Furthermore, by laminating a raised layer containing resin and organic particles on the second resin layer, it is possible to provide an excellent tactile feel without impairing the gloss matte expression. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] JP 2017-65261 A Summary of the Invention [Problem to be solved by the invention]

[0005] The decorative sheet described in Patent Document 1 has high designability and also provides an excellent feel.

[0006] On the other hand, if a raised layer is partially placed on top of the layer that imparts gloss difference in order to provide an uneven surface to the decorative sheet to give it a tactile feel, the effect of the gloss caused by the raised layer must also be taken into consideration, and in order to approximate the gloss of the layer that imparts gloss difference and the raised layer, restrictions are placed on the choice of materials (there is a risk of reducing the freedom of material selection), so a new technology is needed that will allow the decorative sheet to have both an excellent tactile feel and a sense of design.

[0007] Furthermore, if the raised layer is formed by blending a large amount of particles into the ink used to form the raised layer in order to improve the tactile feel of the surface of the decorative sheet, there is a problem in that the interlayer adhesion strength between the raised layer and the layer below it decreases.

[0008] In view of the above circumstances, the present disclosure has an object to provide a decorative sheet that has both excellent tactile feel and designability and also has excellent interlayer adhesion. Another object of the present disclosure is to provide a decorated resin molded product. [Means for solving the problem]

[0009] The present disclosure provides the following aspects of the invention. Item 1. A heat-resistant insulating film comprising at least a base layer and a first resin layer formed on the entire surface of one side of the base layer, the first resin layer includes first particles and second particles that are different in type from the first particles and are relatively larger than the first particles; the first resin layer includes a plurality of raised portions protruding from a surface opposite to the base layer side, A decorative sheet, wherein the second particles are not in contact with a layer located on the base material layer side of the first resin layer. Item 2. The decorative sheet according to item 1, wherein the first particles are dispersed throughout the first resin layer. Item 3. The decorative sheet according to item 1 or 2, wherein the second particles are unevenly distributed in the protruding portion of the first resin layer. Item 4. The decorative sheet according to any one of Items 1 to 3, wherein the average height of the raised portion is 5 μm or more. Item 5. The raised portion forms an uneven shape on the surface of the decorative sheet, 5. The decorative sheet according to any one of items 1 to 4, wherein the proportion of the area of ​​the portion on the surface of the decorative sheet where the uneven shape is formed is 1% or more and 50% or less, with the area of ​​the surface of the decorative sheet being 100%. Item 6. The decorative sheet according to any one of Items 1 to 5, wherein the first resin layer contains a cured product of an ionizing radiation curable resin. Item 7. The decorative sheet according to any one of items 1 to 6, further comprising a second resin layer having a different luster from that of the first resin layer, on the opposite side of the first resin layer from the base material layer side. Item 8. The decorative sheet according to any one of Items 1 to 7, wherein the first resin layer has a thickness of 2 μm or more and 80 μm or less. Item 9. The decorative sheet according to any one of Items 1 to 8, wherein the first particles are inorganic particles. Item 10. The decorative sheet according to any one of items 1 to 9, wherein the second particles are organic particles. Item 11. The decorative sheet according to any one of Items 1 to 10, wherein the second particles have an average particle size of 10 μm or more. Item 12. The decorative sheet according to any one of items 1 to 11, further comprising a pattern layer between the base layer and the first resin layer. Item 13. A pressure-sensitive adhesive sheet comprising at least a molded resin layer, a base layer, and a first resin layer formed on the entire surface of one side of the base layer, the first resin layer includes first particles and second particles that are different in type from the first particles and are relatively larger than the first particles; the first resin layer includes a plurality of raised portions protruding from a surface opposite to the base layer side, The second particles are not in contact with a layer located on the base material layer side of the first resin layer. Effect of the Invention

[0010] According to the present disclosure, it is possible to provide a decorative sheet that has both excellent tactile feel and design properties and also has excellent interlayer adhesion. Furthermore, according to the present disclosure, it is also possible to provide a decorated resin molded product. [Brief description of the drawings]

[0011] [Figure 1] 1 is a schematic cross-sectional view of an example of a decorative sheet according to the present disclosure. [Diagram 2] 1 is a schematic cross-sectional view of an example of a decorative sheet according to the present disclosure. [Diagram 3] 1 is a schematic cross-sectional view of an example of a decorative sheet according to the present disclosure. [Figure 4] 1 is a schematic cross-sectional view of an example of a decorative sheet according to the present disclosure. [Diagram 5] 1 is a schematic cross-sectional view of an example of a decorated resin molded product using the decorative sheet of the present disclosure. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0012] 1.Decorative sheet The decorative sheet of the present disclosure includes at least a base layer and a first resin layer formed on the entire surface of one side of the base layer, the first resin layer including first particles and second particles that are different from the first particles and are relatively larger than the first particles, the first resin layer including a plurality of raised portions protruding from the surface opposite to the base layer side, and the second particles not in contact with the layer located on the base layer side of the first resin layer. The decorative sheet of the present disclosure includes such a configuration, and thus achieves both excellent tactile sensation and designability, and can further exhibit excellent interlayer adhesion. More specifically, a first resin layer including relatively small first particles and relatively large second particles is provided on the base layer, and the uneven shape of the decorative sheet surface formed by the raised portions of the first resin layer provides excellent tactile sensation and designability, and further, the relatively large second particles are not in contact with the layer located on the base layer side of the first resin layer, thereby enhancing the interlayer adhesion between the first resin layer and the layer located thereunder.

[0013] The decorative sheet of the present disclosure will be described in detail below. In this specification, the numerical range indicated by "~" means "more than or equal to" or "less than or equal to", except where it is clearly stated as "more than or equal to". For example, the expression "2 to 15 mm" means 2 mm or more and 15 mm or less. In this specification, "(meth)acrylate" means "acrylate or methacrylate", and other similar terms have the same meaning.

[0014] Laminated structure of decorative sheet 1 to 4, the decorative sheet 10 of the present disclosure has a laminated structure in which at least a base layer 3 and a first resin layer 1 are laminated. The first resin layer 1 includes a plurality of raised portions 11 protruding from the surface opposite to the base layer 3. In the decorative sheet 10 of the present disclosure, the plurality of raised portions 11 are formed so as to protrude from the surface opposite to the base layer 3, so that the surface has an uneven shape.

[0015] As shown in FIGS. 1 to 4, the first resin layer 1 is provided on the entire surface of one surface side of the base layer 3.

[0016] As shown in FIG. 2 to FIG. 4, in the decorative sheet 10 of the present disclosure, a second resin layer 2 having a different luster from that of the first resin layer 1 may be provided on the opposite side of the first resin layer 1 to the base layer 3, if necessary. The second resin layer 2 may be provided on the entire surface of the opposite side of the first resin layer 1 to the base layer 3 (see FIG. 2), or may be provided partially (see FIG. 3 and FIG. 4). The second resin layer 2 may be provided on the entire surface of the raised portion 11 of the first resin layer 1, may be provided partially on the raised portion 11, or may not be provided on the raised portion 11. FIGS. 3 and 4 show an embodiment in which the second resin layer 2 is provided partially on the raised portion 11 of the first resin layer 1, and this embodiment is preferable from the viewpoint of design. As will be described later, the second resin layer 2 is provided partially on the raised portion 11 of the first resin layer 1, and the position where the second resin layer 2 is provided is made to coincide with the pattern of the picture layer (for example, FIG. 4), thereby improving design.

[0017] 4, in the decorative sheet 10 of the present disclosure, a pattern layer 4 may be provided between the base layer 3 and the first resin layer 1, if necessary. Although not shown, the decorative sheet 10 may have a primer layer or the like provided between the first resin layer 1 and the pattern layer 4, a concealing layer or the like provided between the base layer 3 and the pattern layer 4, a back adhesive layer or the like provided on the back surface of the base layer 3 (the side opposite to the first resin layer 1 side), or other layers may be provided at any position.

[0018] Examples of the laminated structure of the decorative sheet of the present disclosure include a laminated structure in which the substrate layer 3 / the first resin layer 1 are laminated in this order; a laminated structure in which the substrate layer 3 / the first resin layer 1 / the second resin layer 2 are laminated in this order; a laminated structure in which the substrate layer 3 / the pattern layer 4 / the first resin layer 1 are laminated in this order; a laminated structure in which the substrate layer 3 / the pattern layer 4 / the first resin layer 1 / the second resin layer 2 are laminated in this order; a laminated structure in which the substrate layer 3 / the concealing layer / the pattern layer 4 / the first resin layer 1 / the second resin layer 2 are laminated in this order; a laminated structure in which the substrate layer 3 / the concealing layer / the pattern layer 4 / the primer layer / the first resin layer 1 / the second resin layer 2 are laminated in this order; a laminated structure in which the adhesive layer / the substrate layer 3 / the concealing layer / the pattern layer 4 / the primer layer / the first resin layer 1 / the second resin layer 2 are laminated in this order, and the like. FIG. 1 shows a schematic cross-sectional view of an example of a decorative sheet in which the substrate layer 3 / the first resin layer 1 are laminated, as one embodiment of the laminated structure of the decorative sheet of the present disclosure. 2 and 3 show schematic cross-sectional views of an example of a decorative sheet in which a base layer 3 / a first resin layer 1 / a second resin layer 2 are laminated in this order, as one embodiment of the laminate structure of the decorative sheet of the present disclosure. FIG. 4 shows a schematic cross-sectional view of an example of a decorative sheet in which a base layer 3 / a pattern layer 4 / a first resin layer 1 / a second resin layer 2 are laminated in this order, as one embodiment of the laminate structure of the decorative sheet of the present disclosure. Note that " / " means a separator between layers.

[0019] Composition of each layer that forms the decorative sheet [Base material layer 3] The substrate layer 3 is a resin sheet (resin film) that serves as a support in the decorative sheet of the present disclosure. The resin component used in the substrate layer 3 is not particularly limited and may be appropriately selected depending on formability and compatibility with the molded resin, but preferably includes a resin film made of a thermoplastic resin. Specific examples of the thermoplastic resin include acrylonitrile-butadiene-styrene resin (hereinafter sometimes referred to as "ABS resin"), acrylonitrile-styrene-acrylic acid ester resin (hereinafter sometimes referred to as "ASA resin"), acrylic resin, polyolefin resin such as polypropylene and polyethylene, polycarbonate resin, vinyl chloride resin, polyethylene terephthalate (PET), and the like. Among these, ABS resin and acrylic resin are preferred from the viewpoint of formability. The substrate layer 3 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.

[0020] The flexural modulus of the base layer 3 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 flexural modulus of the base layer 3 in the decorative sheet of the present disclosure at 25°C is 500 to 4,000 MPa, preferably 750 to 3,000 MPa. Here, the flexural modulus at 25°C is a value measured in accordance with JIS K7171:2016. When the flexural modulus at 25°C is 500 MPa or more, the decorative sheet has sufficient rigidity, and even when subjected to an insert molding method, the surface characteristics and moldability become even better. In addition, when the flexural modulus at 25°C is 4,000 MPa or less, sufficient tension can be applied when manufactured by roll-to-roll, and sagging is unlikely to occur, so that the pattern can be printed in layers without misalignment, resulting in good pattern registration.

[0021] The substrate layer 3 may be surface-treated on one or both sides in order to improve adhesion with a layer provided thereon. Examples of the surface treatment include chemical surface treatment such as oxidation and physical surface treatment such as roughening. Examples of the oxidation method include corona discharge treatment, chromium oxidation treatment, flame treatment, hot air treatment, ozone ultraviolet treatment, etc. Examples of the roughening method include sandblasting and solvent treatment. These surface treatments are appropriately selected depending on the type of resin component constituting the substrate layer 3, but from the viewpoints of effect and operability, etc., corona discharge treatment is preferred.

[0022] The base layer 3 may be subjected to a known treatment such as forming an adhesive layer.

[0023] Furthermore, the base layer 3 may be colored with a colorant or may not be colored. The base layer 3 may be opaque, colorless and transparent, colored and transparent, or translucent. The colorant used in the base layer 3 is not particularly limited, but is preferably a colorant that does not discolor even at temperatures of 150° C. or higher, and specific examples thereof include existing dry colors, paste colors, masterbatch resin compositions, and the like.

[0024] The thickness of the base layer 3 is appropriately set depending on the application of the decorative sheet, the molding method for integrating it with a molding resin, etc., but is usually about 25 to 1000 μm, and 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 layer 3 is usually about 50 to 1000 μm, preferably about 100 to 700 μm, and more preferably about 100 to 500 μm. When the decorative sheet of the present disclosure is subjected to an injection molding simultaneous decoration method, the thickness of the base layer 3 is usually about 25 to 200 μm, preferably about 50 to 200 μm, and more preferably about 70 to 200 μm.

[0025] [First resin layer 1] In the decorative sheet 10 of the present disclosure, a first resin layer 1 is formed on the entire surface of one side of the base layer 3. The first resin layer 1 includes first particles 1a and second particles 1b, which are different from the first particles 1a and are relatively larger than the first particles. Furthermore, the first resin layer 1 includes a plurality of raised portions 11 protruding from the surface of the decorative sheet 10 opposite to the base layer 3 side. That is, the first resin layer 1 includes relatively large second particles 1b, so that the raised portions 11 are formed in the decorative sheet 10, and at least the raised portions 11 include the second particles 1b. The second particles 1b may be included in a position different from the raised portions 11 of the first resin layer 1, but it is preferable that the second particles 1b are unevenly distributed in the raised portions 11 of the first resin layer 1.

[0026] In the first resin layer 1, the second particles 1b are different from the first particles 1a in kind and are relatively larger than the first particles, meaning that, among the two or more kinds of particles contained in the first resin layer 1, the second particles 1b have a relatively larger average particle size, and the first particles 1a have a relatively smaller average particle size. As described below, the average particle size of the second particles 1b is preferably 10 μm or more, whereas the average particle size of the first particles 1a is preferably less than 10 μm.

[0027] The decorative sheet 10 of the present disclosure has a plurality of raised portions 11 protruding from the surface of the first resin layer 1 opposite the base layer 3, thereby forming an uneven shape on the surface of the decorative sheet 10.

[0028] As will be described later in the examples, in the present disclosure, the first resin layer 1 can be suitably formed by, for example, applying a resin composition A (not including second particles 1b) containing the first particles 1a and the second particles 1b in a semi-dried state, partially applying a resin composition B (not including second particles 1b) containing the first particles 1a from above by raised printing, and then applying a resin composition A (not including second particles 1b) containing the first particles 1a from above in a semi-dried state, and then curing these resin compositions. By adopting this method, it is possible to suitably form the raised portion 11 in the first resin layer 1 so that the second particles 1b do not come into contact with the layer (lower layer) located on the base layer 3 side of the first resin layer 1. In addition, in this method, by forming the first resin layer 1 by repeatedly printing while semi-drying, the formation of an interface inside the first resin layer 1 is suppressed, and the interlayer adhesion can be improved. That is, it is preferable that there is no interface inside the first resin layer 1 due to multiple printings. In particular, it is preferable that there is no interface between the raised portions 11 and between the raised portions 12.

[0029] Furthermore, in the decorative sheet 10 of the present disclosure, the relatively large second particles 1b are not in contact with a layer (such as the base layer 3, the pattern layer 4, or the primer layer) located on the base layer 3 side of the first resin layer 1, and therefore excellent interlayer adhesion can be exhibited. More specifically, in the raised portion 11 formed by containing the relatively large second particles 1b, the second particles 1b are not in contact with a layer (lower layer) located on the base layer 3 side of the first resin layer 1, and therefore a decrease in interlayer adhesion caused by an interface between the second particles 1b and the lower layer is suppressed.

[0030] It is preferable that one or more second particles 1b are contained in one raised portion 11, and more preferably two or more second particles 1b are contained in one raised portion 11. That is, in the first resin layer 1, a plurality of second particles 1b are gathered together to suitably form one raised portion 11. The number of second particles 1b contained in one raised portion 11 may be, for example, about 1 to 10.

[0031] In the first resin layer 1, the shortest distance between the second particles 1b and the layer (lower layer) located on the base layer 3 side of the first resin layer 1 is preferably about 1 μm or more, more preferably about 2 μm or more. The shortest distance is preferably about 10 μm or less, more preferably about 5 μm or less, and even more preferably about 2 μm or less. Preferred ranges for the shortest distance include about 1 to 10 μm, about 1 to 5 μm, about 1 to 2 μm, about 2 to 10 μm, and about 2 to 5 μm.

[0032] On the other hand, the first particles 1a, which are relatively smaller than the second particles 1b, are preferably dispersed throughout the first resin layer 1. In other words, it is preferable that both the first particles 1a and the second particles 1b are contained in the raised portion 11. The decorative sheet 10 of the present disclosure can favorably exhibit a matte finish and a design with an uneven surface due to the presence of the first particles 1a and the second particles 1b.

[0033] The first particles 1a are not particularly limited as long as they are a different type of particle from the second particles 1b and are relatively smaller than the second particles 1b, and may be either organic particles or inorganic particles. From the viewpoint of appropriately imparting a matte design to the decorative sheet 10, however, inorganic particles are preferred.

[0034] The inorganic particles are not particularly limited as long as they are particles formed from an inorganic compound, and examples thereof include silica particles, calcium carbonate particles, barium sulfate particles, alumina particles, and glass balloon particles, and among these, silica particles are preferred. The inorganic particles may be used alone or in combination of two or more kinds.

[0035] The average particle size of the first particles 1a is preferably less than 10 μm, more preferably 5 μm or less. The average particle size of the first particles 1a is preferably 0.5 μm or more, more preferably 1 μm or more. The preferred average particle size range of the first particles 1a is about 0.5 μm or more and less than 10 μm, about 0.5 to 5 μm, about 1 μm or more and less than 10 μm, or about 1 to 5 μm.

[0036] In the present disclosure, the average particle size of the particles means the average particle size (arithmetic mean diameter) measured for non-aggregated particles of 100 randomly selected particles when a cross section in the thickness direction of the layer is observed with a scanning electron microscope (SEM) under conditions of an accelerating voltage of 3.0 kV and a magnification of 50,000 times.

[0037] The content of the first particles 1a in the first resin layer 1 is not particularly limited, but is preferably about 1 to 60 parts by mass, and more preferably about 1 to 40 parts by mass, relative to 100 parts by mass of the resin contained in the first resin layer 1. The first particles 1a may be used alone or in combination of two or more types.

[0038] The type of second particles 1b is not particularly limited and may be either organic or inorganic particles. However, from the viewpoint of being relatively larger than the first particles 1a and achieving both excellent tactile feel and design, organic particles are particularly preferred.

[0039] The organic particles are not particularly limited, and resin beads are usually used. Examples of the resin beads include acrylic beads, urethane beads, nylon beads, and styrene beads. Among these, it is preferable to use acrylic beads or urethane beads from the viewpoint of suppressing the whitening of the raised portion 11, imparting an excellent touch, and improving the scratch resistance of the decorative sheet. In particular, it is preferable to use acrylic beads or urethane beads from the viewpoint of suppressing the whitening of the raised portion 11, and it is preferable to use urethane beads from the viewpoint of improving the scratch resistance. In addition, it is preferable to use crosslinked resin beads from the viewpoint of imparting an excellent touch and improving the scratch resistance of the raised portion 11. Specific examples of the crosslinked resin beads include crosslinked acrylic beads and crosslinked urethane beads.

[0040] From the viewpoint of providing an excellent touch in the decorative sheet of the present disclosure, the average particle size of the second particles 1b is preferably about 10 μm or more, more preferably about 15 μm or more, and even more preferably about 20 μm or more. The preferred upper limit of the average particle size is preferably about 60 μm or less, more preferably about 50 μm or less, even more preferably less than about 50 μm, even more preferably about 40 μm or less, and particularly preferably about 35 μm or less. Preferred average particle sizes of the second particles 1b include about 10 to 60 μm, about 10 to 50 μm, about 10 to 40 μm, about 10 to 35 μm, about 15 to 60 μm, about 15 to 50 μm, about 15 to 40 μm, about 15 to 35 μm, about 20 to 60 μm, about 20 to 50 μm, about 20 to 40 μm, and about 20 to 35 μm. By setting the average particle size of the second particles 1b contained in the raised portion 11 within the above range, the texture and design of the decorative sheet can be more suitably improved. The average height of the raised portion 11 and the average particle size of the second particles 1b can be made approximately the same.

[0041] It is preferable from the viewpoint of optimally achieving the effects of the present disclosure that at least 90% or more of the second particles 1b contained in the raised portion 11 satisfy these particle diameters on a number basis. If the average particle diameter of the second particles 1b is less than 10 μm, there is a risk that an excellent tactile feel cannot be obtained. If the average particle diameter of the second particles 1b exceeds 60 μm, there is a risk that production stability decreases and it becomes difficult to form the raised portion 11 of the desired shape with good reproducibility. In forming the first resin layer 1, when the raised portion 11 is formed by raised printing, it is preferable that the average particle diameter of the second particles 1b is ½ or less of the plate depth from the viewpoint of ink transfer stability.

[0042] In the decorative sheet 10 of the present disclosure, the second particles 1b are preferably contained in a proportion of 50% by mass or less, more preferably 40% by mass or less, based on the solid content of the resin composition forming the raised portion 11. When the content of the second particles 1b is 50% by mass or less, the second particles 1b are uniformly distributed in the coating film (raised portion 11), so that the touch is stable. When the content of the second particles 1b exceeds 50% by mass, the organic particles may aggregate, the average thickness of the raised portion may be unstable, and the transparency of the raised portion 11 may be impaired, so that the design may be deteriorated. The content of the second particles 1b is preferably 2% by mass or more, more preferably 10% by mass or more. When the content of the second particles 1b is less than 2% by mass, the touch may be insufficient, and the thixotropy of the resin composition forming the raised portion may be insufficient, so that it may be difficult to form the raised portion 11 by raised printing.

[0043] From the viewpoint of achieving excellent tactile sensation and design, the average height (average thickness) of the raised portion 11 is preferably about 5 μm or more, more preferably about 10 μm or more, and even more preferably about 15 μm or more. The average height (average thickness) of the raised portion 11 is preferably about 60 μm or less, more preferably about 50 μm or less, and even more preferably about 40 μm or less. Preferred ranges for the height of the raised portion 11 include about 5 to 60 μm, about 5 to 50 μm, about 5 to 40 μm, about 10 to 60 μm, about 10 to 50 μm, about 10 to 40 μm, about 15 to 60 μm, about 15 to 50 μm, and about 15 to 40 μm. By setting the average thickness of the raised portion 11 within the above range, the tactile sensation and design of the decorative sheet can be more suitably improved. In this specification, the average height (average thickness) of the raised portions 11 refers to the vertical distance in the thickness direction from the position between the raised portions 11 and the apex of the raised portions 11, based on the position of the gap 12 between the raised portions 11. The average height (average thickness) of the raised portions 11 is a value calculated as the average of measured values ​​at 10 points when the cross section of the decorative sheet is observed with a scanning electron microscope (SEM). Observation with the scanning electron microscope (SEM) is performed under conditions of an accelerating voltage of 3.0 kV and a magnification of 50,000 times.

[0044] The raised portion 11 of the first resin layer 1 is preferably formed by raised printing when the first resin layer 1 is formed, so as to impart a desired tactile feel based on the uneven shape to the surface of the decorative sheet. In the present disclosure, the raised portion 11 refers to a form shown as a convex shape in the schematic cross-sectional views shown in Figs. 1 to 5, and includes not only a form in which conical or cylindrical protrusions are formed on the surface of the decorative sheet, but also a form in which protrusions are formed linearly, such as a duct pattern.

[0045] From the viewpoint of excellent tactile sensation and design, in the decorative sheet 10 of the present disclosure, the raised portion 11 forms an uneven shape on the surface of the decorative sheet 10, and the ratio of the area of ​​the portion on the surface of the decorative sheet 10 where the uneven shape is formed is preferably about 1 to 50%, more preferably about 3 to 50%, even more preferably about 5 to 50%, even more preferably about 5 to 40%, and even more preferably about 6 to 30%, based on the area of ​​the surface of the decorative sheet 10 being 100%. By providing the uneven shape within the above range, a decorative sheet with a better tactile sensation can be obtained. Here, when the cross section of the raised portion 11 is trapezoidal or conical, etc., and the area of ​​the upper surface and the lower surface of the raised portion 11 differs, the area of ​​the uneven shape formed by the raised portion 11 is the area of ​​the region where the uneven shape is formed on the surface on the base layer 3 side.

[0046] The resin forming the first resin layer 1 is preferably a curable resin such as a thermosetting resin or an ionizing radiation curable resin (e.g., an electron beam curable resin) from the viewpoint of suppressing deformation of the raised portion 11 and forming a desired shape. In particular, an ionizing radiation curable resin is preferable from the viewpoints of high surface hardness, productivity, etc.

[0047] Examples of thermosetting resins include 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 resins, silicon resins, and polysiloxane resins.

[0048] A crosslinking agent, a curing agent such as a polymerization initiator, and a polymerization accelerator can be added to the resin. For example, curing agents such as isocyanate and organic sulfonate can be added to unsaturated polyester resin and polyurethane resin, and organic amine can be added to epoxy resin. Peroxides such as methyl ethyl ketone peroxide and radical initiators such as azoisobutylnitrile can be added to unsaturated polyester resin.

[0049] Methods for forming the first resin layer 1 using a thermosetting resin include, for example, applying a solution of a thermosetting resin by a coating method such as roll coating, gravure coating, gravure printing, or silk screen printing, and then drying and curing the solution.

[0050] The ionizing radiation curable resin is a resin that is crosslinked and cured by irradiation with ionizing radiation. Specifically, it is a suitable mixture of at least one of prepolymers, oligomers, and monomers having polymerizable unsaturated bonds or epoxy groups in the molecule. Here, the ionizing radiation means electromagnetic waves or charged particle beams that have an energy quantum capable of polymerizing or crosslinking molecules, and usually ultraviolet rays (UV) or electron beams (EB) are used, but also includes electromagnetic waves such as X-rays and γ-rays, α-rays, ion beams, and other charged particle beams. Among the ionizing radiation curable resins, electron beam curable resins are preferably used in the formation of the first resin layer 1 because they can be made solvent-free, do not require a photopolymerization initiator, and have stable curing properties.

[0051] <Ionizing radiation curable resin> The monomer used as the ionizing radiation curable resin is preferably a (meth)acrylate monomer having a radical polymerizable unsaturated group in the molecule, and among them, a polyfunctional (meth)acrylate monomer is preferable. The polyfunctional (meth)acrylate monomer may be a (meth)acrylate monomer having two or more (bifunctional or more), preferably three or more (trifunctional or more), polymerizable unsaturated bonds in the molecule. Specific examples of polyfunctional (meth)acrylate monomers include ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, hydroxypivalic acid neopentyl glycol di(meth)acrylate, dicyclopentanyl di(meth)acrylate, caprolactone-modified dicyclopentenyl di(meth)acrylate, ethylene oxide-modified phosphoric acid di(meth)acrylate, allylated cyclohexyl di(meth)acrylate, isocyanurate di(meth)acrylate, and trimethylol. Examples of the monomer include propane 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, etc. These monomers may be used alone or in combination of two or more.

[0052] As the oligomer used as the ionizing radiation curable resin, a (meth)acrylate oligomer having a radical polymerizable unsaturated group in the molecule is preferable, and among them, a polyfunctional (meth)acrylate oligomer having two or more (two or more functional) polymerizable unsaturated bonds in the molecule is preferable. Examples of the polyfunctional (meth)acrylate oligomer 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, and oligomers having a cationic polymerizable functional group in the molecule (e.g., novolac type epoxy resin, bisphenol type epoxy resin, aliphatic vinyl ether, aromatic vinyl ether, 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 at the end or side chain, and can be obtained, for example, by esterifying a polycarbonate polyol with (meth)acrylic acid. The polycarbonate (meth)acrylate may be, for example, a urethane (meth)acrylate having a polycarbonate skeleton. The urethane (meth)acrylate having a polycarbonate skeleton can be obtained, for example, by reacting a polycarbonate polyol with a polyvalent isocyanate compound and a hydroxy (meth)acrylate. The acrylic silicone (meth)acrylate can be obtained by radical copolymerization of a silicone macromonomer with a (meth)acrylate monomer. The urethane (meth)acrylate can be obtained, for example, by esterifying a polyurethane oligomer obtained by the reaction of a polyether polyol or a polyester polyol with a polyisocyanate compound with (meth)acrylic acid. Epoxy (meth)acrylates can be obtained, for example, by reacting an oxirane ring of a relatively low molecular weight bisphenol type epoxy resin or novolac type epoxy resin with (meth)acrylic acid to effect esterification.In addition, a carboxyl-modified epoxy (meth)acrylate obtained by partially modifying this epoxy (meth)acrylate with a dibasic carboxylic anhydride can also be used. The polyester (meth)acrylate can be obtained, for example, by esterifying the hydroxyl group of a polyester oligomer having hydroxyl groups at both ends obtained by condensation of a polyvalent carboxylic acid and a polyhydric alcohol with (meth)acrylic acid, or by esterifying the terminal hydroxyl group of an oligomer obtained by adding an alkylene oxide to a polyvalent carboxylic acid with (meth)acrylic acid. The polyether (meth)acrylate can be obtained by esterifying the hydroxyl group of a polyether polyol with (meth)acrylic acid. The polybutadiene (meth)acrylate can be obtained by adding (meth)acrylic acid to the side chain of a polybutadiene oligomer. The silicone (meth)acrylate can be obtained by adding (meth)acrylic acid to the end or side chain of a silicone having a polysiloxane bond in the main chain. Among these, particularly preferred polyfunctional (meth)acrylate oligomers are polycarbonate (meth)acrylate, urethane (meth)acrylate, etc. These oligomers may be used alone or in combination of two or more.

[0053] When the decorative sheet is required to have three-dimensional moldability, such as when it is used to manufacture a decorated resin molded product, it is preferable to use a multifunctional polycarbonate (meth)acrylate from the viewpoint of obtaining excellent three-dimensional moldability among the above-mentioned ionizing radiation curable resins. Moreover, from the viewpoint of achieving both three-dimensional moldability and scratch resistance, it is more preferable to use a combination of a multifunctional polycarbonate (meth)acrylate and a multifunctional (meth)acrylate other than the multifunctional polycarbonate (meth)acrylate. Moreover, when a multifunctional (meth)acrylate monomer is used as the 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, and it is more preferable to set the mass ratio of the multifunctional (meth)acrylate monomer to the thermoplastic resin in the ionizing radiation curable resin composition to 25:75 to 75:25 from the viewpoint of achieving both three-dimensional moldability and scratch resistance. Hereinafter, the multifunctional polycarbonate (meth)acrylate and the multifunctional (meth)acrylate used in combination will be described in detail.

[0054] <Multifunctional polycarbonate (meth)acrylate> The multifunctional polycarbonate (meth)acrylate is not particularly limited as long as it has a carbonate bond in the polymer main chain and has two or more (meth)acrylates at the end or side chain. In addition, the (meth)acrylate preferably has 2 to 6 functional groups per molecule from the viewpoint of improving crosslinking and curing. The multifunctional polycarbonate (meth)acrylate may be used alone or in combination of two or more.

[0055] Multifunctional polycarbonate (meth)acrylates can be obtained, for example, by converting a part or all of the hydroxyl groups of a polycarbonate polyol to (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 with an acrylic acid halide or a methacrylic acid halide in the presence of a base, 2) a method of condensing a polycarbonate polyol with an acrylic acid anhydride or a methacrylic acid anhydride in the presence of a catalyst, or 3) a method of condensing a polycarbonate polyol with an acrylic acid or a methacrylic acid in the presence of an acid catalyst can be mentioned.

[0056] Polycarbonate polyol is a polymer having a carbonate bond in the polymer main chain and having 2 or more, preferably 2 to 50, and more preferably 3 to 50 hydroxyl groups at the terminal or side chain. A representative method for producing the polycarbonate polyol includes a method by polycondensation reaction of a diol compound (A), a trihydric or higher polyhydric alcohol (B), and a compound (C) serving as a carbonyl component.

[0057] The diol compound (A) used as a raw material for polycarbonate polyol is represented by the general formula HO-R 1 -OH, where R 1 R is a divalent hydrocarbon group having 2 to 20 carbon atoms, which may contain an ether bond. 1 is, for example, a linear or branched alkylene group, a cyclohexylene group, or a phenylene group.

[0058] Specific examples of the diol compound 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, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, etc. These diols may be used alone or in combination of two or more.

[0059] Examples of the trihydric or higher polyhydric alcohol (B) used as a raw material for polycarbonate polyol include alcohols such as trimethylolpropane, trimethylolethane, pentaerythritol, ditrimethylolpropane, dipentaerythritol, glycerin, and sorbitol. The trihydric or higher polyhydric alcohol may be an alcohol having a hydroxyl group in which 1 to 5 equivalents of ethylene oxide, propylene oxide, or other alkylene oxide are added to the hydroxyl group of the polyhydric alcohol. These polyhydric alcohols may be used alone or in combination of two or more.

[0060] The compound (C) serving as the carbonyl component used as a raw material for polycarbonate polyol is any compound selected from among carbonic acid diesters, phosgene, or 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; and halogenated formates such as methyl chloroformate, ethyl chloroformate, and phenyl chloroformate. These compounds may be used alone or in combination of two or more.

[0061] The polycarbonate polyol is synthesized by polycondensation reaction of the diol compound (A), a trihydric or higher polyhydric alcohol (B), and a compound (C) serving as a carbonyl component under general conditions. The molar ratio of the diol compound (A) to the polyhydric alcohol (B) may be set, for example, in the range of 50:50 to 99:1. The molar ratio of the compound (C) serving as a carbonyl component to the diol compound (A) and the polyhydric alcohol (B) may be set, for example, in the range of 0.2 to 2 equivalents relative to the hydroxyl groups of the diol compound and the polyhydric alcohol.

[0062] The equivalent number (eq. / mol) of hydroxyl groups present in the polycarbonate polyol after polycondensation reaction at the above-mentioned charging ratio is, for example, 3 or more, preferably 3 to 50, and more preferably 3 to 20 on average per molecule. When such an equivalent number is satisfied, a necessary amount of (meth)acrylate groups are formed by the esterification reaction described later, and suitable flexibility is imparted to the multifunctional polycarbonate (meth)acrylate resin. The terminal functional group of this polycarbonate polyol is usually an OH group, but a part of it may be a carbonate group.

[0063] The method for producing the polycarbonate polyol described above is described, for example, in JP-A-64-1726. The polycarbonate polyol can also be produced by transesterification of a polycarbonate diol with a trihydric or higher polyhydric alcohol, as described in JP-A-3-181517.

[0064] The molecular weight of the multifunctional polycarbonate (meth)acrylate is not particularly limited, but may be, for example, a weight average molecular weight of 5,000 or more, preferably 10,000 or more. The upper limit of the weight average molecular weight of the multifunctional polycarbonate (meth)acrylate is not particularly limited, but from the viewpoint of controlling the viscosity not to be too high, may be, for example, 100,000 or less, preferably 50,000 or less. The weight average molecular weight of the multifunctional polycarbonate (meth)acrylate is preferably 10,000 to 50,000, more preferably 10,000 to 20,000.

[0065] In this specification, the weight average molecular weight of the polyfunctional polycarbonate (meth)acrylate is a value measured by gel permeation chromatography using polystyrene as a standard substance.

[0066] The content of polyfunctional polycarbonate (meth)acrylate in the ionizing radiation curable resin composition used to form the first resin layer 1 is not particularly limited, as long as the effects of the present disclosure are achieved. However, from the viewpoint of maintaining the uneven shape formed by the raised portion 11 even under heat and pressure during injection molding, etc., and more effectively suppressing deterioration of the high quality texture expressed in the decorative sheet, the content is preferably 50 mass % or more, more preferably 80 mass % or more, and even more preferably 85 mass % or more.

[0067] <Polyfunctional (meth)acrylate> The polyfunctional (meth)acrylate other than the polyfunctional polycarbonate (meth)acrylate used in combination with the polyfunctional polycarbonate (meth)acrylate is not particularly limited, but is preferably a polyfunctional urethane (meth)acrylate. The polyfunctional urethane (meth)acrylate is not particularly limited as long as it has a urethane bond in the polymer main chain and has two or more (meth)acrylates at the end or side chain. Such a polyfunctional urethane (meth)acrylate can be obtained, for example, by esterifying a polyurethane oligomer obtained by the reaction of a polyether polyol or a polyester polyol with a polyisocyanate with (meth)acrylic acid. In addition, the polyfunctional urethane (meth)acrylate preferably has 2 to 12 functional groups per molecule from the viewpoint of improving crosslinking and curing. In addition, the polyfunctional (meth)acrylate may be silicone-modified. The polyfunctional (meth)acrylate may be used alone or in combination of two or more.

[0068] The molecular weight of the polyfunctional (meth)acrylate used in combination with the polyfunctional polycarbonate (meth)acrylate is not particularly limited, but may be, for example, a weight average molecular weight of 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 may be, for example, 30,000 or less, preferably 10,000 or less, from the viewpoint of controlling the viscosity so as not to become too high.

[0069] In this specification, the weight average molecular weight of the polyfunctional (meth)acrylate is a value measured by gel permeation chromatography using polystyrene as a standard substance.

[0070] The content of polyfunctional (meth)acrylate in the ionizing radiation curable resin composition used to form the first resin layer 1 is not particularly limited, as long as the effects of the present disclosure are achieved. However, from the viewpoint of maintaining the uneven shape formed by the raised portion 11 even under heat and pressure during injection molding, etc., and more effectively suppressing deterioration of the high quality texture expressed in the decorative sheet, the content is preferably 50 mass % or less, more preferably 20 mass % or less, and even more preferably 15 mass % or less.

[0071] In the ionizing radiation curable resin composition used to form the first resin layer 1, when a multifunctional polycarbonate (meth)acrylate is used in combination with a multifunctional (meth)acrylate other than the multifunctional polycarbonate (meth)acrylate, the mass ratio thereof (multifunctional polycarbonate (meth)acrylate:multifunctional (meth)acrylate) is preferably about 50:50 to 99:1, more preferably about 80:20 to 99:1, and even more preferably about 85:15 to 99:1.

[0072] The first resin layer 1 is formed, for example, by preparing the above-mentioned ionizing radiation curable resin composition, applying the composition, and crosslinking and curing it. The viscosity of the ionizing radiation curable resin composition may be any viscosity that allows an uncured resin layer to be formed on the layer adjacent to the first resin layer 1 by the coating method described below. In the present disclosure, the prepared coating liquid is applied to the layer adjacent to the first resin layer 1 to the above thickness by a known method such as gravure coating, bar coating, roll coating, reverse roll coating, comma coating, etc., preferably gravure coating, to form an uncured resin layer. The uncured resin layer thus formed is irradiated with ionizing radiation such as electron beams or ultraviolet rays to cure the uncured resin layer, thereby forming the first resin layer 1. Here, when an electron beam is used as the ionizing radiation, the acceleration voltage can be appropriately selected depending on the resin used and the thickness of the layer, but the acceleration voltage is usually about 70 to 300 kV.

[0073] In addition, in the case of electron beam irradiation, the higher the acceleration voltage, the greater the penetration ability. Therefore, when a resin that is easily deteriorated by electron beam irradiation is used under the first resin layer 1, the acceleration voltage is selected so that the penetration depth of the electron beam and the thickness of the first resin layer 1 are substantially equal. This makes it possible to suppress the irradiation of excess electron beams to the layer located under the first resin layer 1, and to minimize the deterioration of each layer due to excess electron beams. In addition, the irradiation dose is preferably an amount at which the crosslink density of the first resin layer 1 is saturated, and is usually selected within the range of 5 to 300 kGy (0.5 to 30 Mrad), preferably 10 to 50 kGy (1 to 5 Mrad). Furthermore, there is no particular limitation on the electron beam source, and various electron beam accelerators such as Cockroft-Walton type, Van de Graft type, resonant transformer type, insulating core transformer type, linear type, dynamitron type, and high frequency type can be used. When ultraviolet light is used as the ionizing radiation, light containing ultraviolet light with a wavelength of 190 to 380 nm may be emitted. The ultraviolet light source is not particularly limited, but examples thereof include high pressure mercury lamps, low pressure mercury lamps, metal halide lamps, and carbon arc lamps.

[0074] Various additives can be blended into the first resin layer 1 according to the desired physical properties to be provided to the first resin layer 1. Examples of the additives include weather resistance improvers such as ultraviolet absorbers and light stabilizers, abrasion resistance improvers, polymerization inhibitors, crosslinking agents, infrared absorbers, antistatic agents, adhesion improvers, leveling agents, thixotropic agents, coupling agents, plasticizers, defoamers, fillers, solvents, colorants, and the like. These additives can be appropriately selected from those commonly used. In addition, reactive ultraviolet absorbers and light stabilizers having a polymerizable group such as a (meth)acryloyl group in the molecule can also be used as the ultraviolet absorbers and light stabilizers.

[0075] 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 11, forming the desired shape, and achieving good three-dimensional formability, it is preferable to use polycarbonate (meth)acrylate as the ionizing radiation curable resin constituting the first resin layer 1.

[0076] Furthermore, 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 while improving three-dimensional formability, it is also preferable to configure the first resin layer 1 with a mixture of an ionizing radiation 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 can be the same as those explained for the second resin layer 2 described later.

[0077] It is preferable that the thickness of the first resin layer 1 is adjusted to have a tactile feel based on the uneven shape, taking into consideration the average thickness of the raised portions 11, etc. From this viewpoint, the thickness of the first resin layer 1 is preferably about 2 to 80 μm, more preferably about 2 to 60 μm, even more preferably about 2 to 50 μm, and even more preferably about 2 to 40 μm. The thickness range of the first resin layer 1 is a thickness range including positions where the raised portions 11 are present and positions where they are not present.

[0078] [Second resin layer 2] The second resin layer 2 is a layer that is provided on the side of the first resin layer 1 opposite to the base layer 3 side, as necessary, for the purpose of adjusting the gloss of the decorative sheet 10. The second resin layer 2 has a gloss different from that of the first resin layer 1.

[0079] The second resin layer 2 may be provided on the entire surface of the first resin layer 1 on the side opposite to the base layer 3 (see FIG. 2), or may be provided partially (see FIGS. 3 and 4). The second resin layer 2 may be provided on the entire surface of the protruding portion 11 of the first resin layer 1, may be provided partially on the protruding portion 11, or may not be provided on the protruding portion 11. FIGS. 3 and 4 show an embodiment in which the second resin layer 2 is provided partially on the protruding portion 11 of the first resin layer 1, and this embodiment is preferable from the viewpoint of design.

[0080] When the decorative sheet 10 has the second resin layer 2, the first resin layer 1 is preferably in contact with the second resin layer 2.

[0081] Examples of resins constituting the second resin layer 2 include phenolic resin, urea resin, diallyl phthalate, melamine resin, guanamine resin, unsaturated polyester resin, polyurethane resin, epoxy resin, aminoalkyd resin, melamine-urea co-condensate, silicone resin, polysiloxane, polyethylene terephthalate, polybutylene terephthalate, polyamide, polyethylene, polypropylene, ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, ethylene-acrylic acid ester copolymer, ionomer, polymethylpentene, acrylic acid ester, methacryl ester, polycarbonate, cellulose triacetate, and the like.

[0082] Moreover, an ionizing radiation curable resin may be used to form the second resin layer 2. Details of the ionizing radiation curable resin include the same resins as those described in detail in the section [First resin layer 1].

[0083] The second resin layer 2 preferably contains a matting agent. The matting agent is not particularly limited, and a wide variety of known matting agents can be used. Examples of the matting agent include inorganic particles and organic particles exemplified in the section of [First resin layer 1], and preferably include inorganic particles such as silica, alumina, calcium carbonate, magnesium carbonate, aluminosilicate, and barium sulfate; and resin (organic) particles such as acrylic beads, polyethylene, urethane resin, polycarbonate, and polyamide (nylon). The average particle size of the particles is preferably 0.5 to 20 μm, and more preferably 0.5 to 10 μm. The amount of the matting agent added is preferably 2 to 40 mass %, and more preferably 5 to 30 mass %, based on the resin composition (excluding the solvent) forming the second resin layer 2. The shape of the particles is polyhedral, spherical, scaly, and the like. Of the inorganic particles and organic particles described above, silica is preferred.

[0084] It is preferable that the thickness of the second resin layer 2 is adjusted to have a tactile feel based on the uneven shape, taking into consideration the average height of the raised portions 11. From this viewpoint, the thickness of the second resin layer 2 is preferably about 0.1 to 20 μm, more preferably about 0.3 to 10 μm, and even more preferably about 0.5 to 5 μm.

[0085] When the decorative sheet of the present disclosure is used for injection molding or vacuum molding applications, from the viewpoint of improving the scratch resistance of the decorative sheet while improving three-dimensional formability, it is preferable to use the above-mentioned polycarbonate (meth)acrylate as the ionizing radiation curable resin constituting the second resin layer 2.

[0086] When the decorative sheet of the present disclosure is used for injection molding or vacuum molding, it is also preferable to configure the second resin layer 2 with a mixture of an ionizing radiation curable resin and a thermoplastic resin from the viewpoint of improving the scratch resistance of the decorative sheet while improving three-dimensional formability. Examples of the thermoplastic resin include acrylic resin, urethane resin, and olefin resin, and acrylic resin is particularly preferable. The mixing ratio of the ionizing radiation curable resin and the thermoplastic resin is preferably about 10:90 to 75:25 by mass, and more preferably about 25:75 to 50:50.

[0087] In the case where the decorative sheet 10 of the present disclosure includes a pattern layer 4 described later, it is preferable that the second resin layer 2 is provided in harmony with the pattern of the pattern layer 4. By configuring the pattern of the pattern layer 4 and the pattern of the second resin layer 2 to be in harmony with each other, a decorative sheet with better design can be obtained. In the present disclosure, the synchronization between the pattern of the pattern layer 4 and the second resin layer 2 can be, for example, a mode in which the position of the pattern of the pattern layer 4 corresponds to the position where the second resin layer 2 is formed when the decorative sheet is observed in plan view (so-called positive), or a mode in which the position of the pattern of the pattern layer 4 corresponds to the position where the second resin layer 2 is not formed (so-called negative). FIG. 4 illustrates a negative mode as an example of the synchronization between the pattern of the pattern layer 4 and the second resin layer 2.

[0088] In the decorative sheet 10 of the present disclosure, it is preferable that the picture layer 4 has a wood grain pattern, and a second resin layer 2 having a higher gloss than the first resin layer 1 is provided on the portion other than at least one of the winter grain pattern and the vascular pattern of the wood grain. This reduces the gloss of the winter grain pattern and / or the vascular pattern portion of the wood grain, so that an excellent design similar to that of natural wood can be obtained. In order to form the second resin layer 2 as described above, it is preferable to use a plate in a state in which the same winter grain pattern and / or vascular pattern of the wood grain as the picture layer 4 is inverted (i.e., in a negative state) and printed using a known printing method. As the printing method, gravure printing, screen printing, etc. are preferable.

[0089] The second resin layer 2 may be colored, but it is preferable not to mix a colorant therein.

[0090] [Pattern layer 4] The pattern layer 4 is a layer that is provided, as necessary, under the first resin layer 1 for the purpose of imparting decorativeness to the decorative sheet. The first resin layer 1 and the pattern layer 4 may be in contact with each other, or may be laminated via a primer layer, which will be described later.

[0091] The design layer 4 can be a layer in which a desired design is formed using, for example, an ink composition. The ink composition used to form the design layer 4 is a suitable mixture of a binder, a colorant such as a pigment or dye, an extender pigment, a solvent, a stabilizer, a plasticizer, a catalyst, a hardener, and the like.

[0092] The binder used in the ink composition is not particularly limited, but examples thereof include polyurethane resin, vinyl chloride-vinyl acetate copolymer, vinyl chloride-vinyl acetate-acrylic copolymer, chlorinated polypropylene resin, acrylic resin, polyester resin, polyamide resin, butyral resin, polystyrene resin, nitrocellulose resin, cellulose acetate resin, etc. These binders may be used alone or in combination of two or more.

[0093] The colorant used in the ink composition is not particularly limited, but examples thereof include inorganic pigments such as carbon black, 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 scaly foil flakes of aluminum, brass, and the like; and pearlescent pigments consisting of scaly foil flakes of titanium dioxide-coated mica, basic lead carbonate, and the like.

[0094] The pattern formed by the pattern layer 4 is not particularly limited, and examples thereof include a wood grain pattern, a marble pattern (e.g., a travertine marble pattern) or other stone pattern that imitates the surface of rock, a fabric pattern that imitates a cloth or fabric-like pattern, a tiled pattern, a brickwork pattern, etc., and may also be a combination of these patterns such as marquetry or patchwork, or may be a single plain color (so-called solid color on the entire surface). These patterns are formed by multi-color printing using normal process colors of yellow, red, blue, and black, but can also be formed by multi-color printing using special colors by preparing plates of each color that constitutes the pattern.

[0095] The thickness of the design layer 4 is not particularly limited, but may be, for example, 1 to 30 μm, and preferably 1 to 20 μm.

[0096] The pattern layer 4 may also be a metal thin film layer. Examples of metals that form the metal thin film layer include tin, indium, chromium, aluminum, nickel, copper, silver, gold, platinum, zinc, and alloys containing at least one of these metals. The method of forming the metal thin film layer is not particularly limited, and examples of the method include deposition methods such as vacuum deposition, sputtering, and ion plating using the above metals. The metal thin film layer may be provided on the entire surface or on a part of the surface. In order to improve adhesion to adjacent layers, a primer layer using a known resin may be provided on the front or back surface of the metal thin film layer.

[0097] [Primer layer] The primer layer is provided under the first resin layer 1 as necessary for the purpose of improving the adhesion of the first resin layer 1, etc.

[0098] From the viewpoint of improving adhesion between the first resin layer 1 and the layer located thereunder, it is preferable to provide a primer layer directly under the first resin layer 1. The primer layer is provided, for example, between the first resin layer 1 and the design layer 4.

[0099] As the primer composition constituting the primer layer, those containing urethane resin, (meth)acrylic resin, (meth)acrylic-urethane copolymer, vinyl chloride-vinyl acetate copolymer, polyester resin, butyral resin, chlorinated polypropylene, chlorinated polyethylene, etc. as a binder resin are preferably used, and these resins can be used alone or in combination of two or more. Among these, urethane resin, (meth)acrylic resin, and (meth)acrylic-urethane copolymer are preferred.

[0100] As the urethane resin, polyurethane containing polyol (polyhydric alcohol) as a main component and isocyanate as a crosslinking agent (curing agent) can be used. As the polyol, one having two or more hydroxyl groups in the molecule, such as polyester polyol, polyethylene glycol, polypropylene glycol, acrylic polyol, polyether polyol, etc. can be used. As the isocyanate, a polyvalent isocyanate having two or more isocyanate groups in the molecule, an aromatic isocyanate such as 4,4-diphenylmethane diisocyanate, or an aliphatic (or alicyclic) isocyanate such as hexamethylene diisocyanate, isophorone diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated diphenylmethane diisocyanate, etc. can also be used to form the resin by mixing the urethane resin and the butyral resin.

[0101] In terms of adhesion to the first resin layer 1, the likelihood of interactions occurring after lamination of the first resin layer 1, physical properties, and moldability, it is preferable to combine an acrylic polyol or a polyester polyol as the polyol with hexamethylene diisocyanate or 4,4-diphenylmethane diisocyanate as the crosslinking agent, and it is particularly preferable to use a combination of an acrylic polyol and hexamethylene diisocyanate.

[0102] Examples of the (meth)acrylic resin include 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. Specifically, (meth)acrylic resins consisting of a homopolymer or copolymer containing a (meth)acrylic acid ester, such as polymethyl(meth)acrylate, polyethyl(meth)acrylate, polypropyl(meth)acrylate, polybutyl(meth)acrylate, a methyl(meth)acrylate-butyl(meth)acrylate copolymer, an ethyl(meth)acrylate-butyl(meth)acrylate copolymer, an ethylene-methyl(meth)acrylate copolymer, or a styrene-methyl(meth)acrylate copolymer, are preferably used.

[0103] As the (meth)acrylic-urethane copolymer, for example, an acrylic-urethane (polyester urethane) block copolymer is preferable. As the curing agent, the above-mentioned various isocyanates are used. As for the acrylic-urethane (polyester urethane) block copolymer, it is preferable to adjust the acrylic / urethane ratio (mass ratio) within the range of preferably 9 / 1 to 1 / 9, more preferably 8 / 2 to 2 / 8, as desired.

[0104] The thickness of the primer layer is not particularly limited, but is, for example, about 0.5 to 20 μm, and preferably 1 to 5 μm.

[0105] The primer layer is formed using a primer composition by a normal coating method such as gravure coating, gravure reverse coating, gravure offset coating, spinner coating, roll coating, reverse roll coating, kiss coating, wheeler coating, dip coating, solid coating by silk screen, wire bar coating, flow coating, comma coating, flow coating, brush coating, spray coating, or transfer coating. Here, the transfer coating method is a method in which a coating film of a primer layer or an adhesive layer is formed on a thin sheet (film substrate), and then the surface of a target layer in the decorative sheet is coated with the coating film.

[0106] [Hidden layer] The concealing layer is a layer that is provided as necessary between the base material layer 3 and the first resin layer 1, or between the base material layer 3 and the pattern layer 4 if a pattern layer 4 is provided, for the purpose of suppressing color changes and variations in the base material layer 3.

[0107] The concealing layer is provided to prevent the base layer 3 from adversely affecting the color tone and pattern of the decorative sheet, and is therefore generally formed as a layer of an opaque color.

[0108] The concealing layer is formed using an ink composition in which a binder is appropriately mixed with a colorant such as a pigment or dye, an extender pigment, a solvent, a stabilizer, a plasticizer, a catalyst, a hardener, etc. The ink composition for forming the concealing layer is appropriately selected from those used for the design layer 4 described above.

[0109] The concealing layer is usually set to a thickness of about 1 to 20 μm, and is desirably formed as a so-called solid print layer.

[0110] The concealing layer is formed by a conventional printing method such as gravure printing, offset printing, silk screen printing, printing by transfer from a transfer sheet, inkjet printing, etc.; or a conventional coating method such as gravure coating, gravure reverse coating, gravure offset coating, spinner coating, roll coating, reverse roll coating, etc.

[0111] [Back adhesive layer] The back surface adhesive layer is a layer that is provided, if necessary, on the side opposite the outer surface of the decorative sheet for the purpose of increasing adhesion with the molding resin when molding a decorated resin molded product.

[0112] The back surface adhesive layer is made of a thermoplastic resin or a curable resin depending on the molding resin used in the decorated resin molded product.

[0113] Examples of the thermoplastic resin used to form the back surface adhesive layer include acrylic resin, acrylic modified polyolefin resin, chlorinated polyolefin resin, vinyl chloride-vinyl acetate copolymer, thermoplastic urethane resin, thermoplastic polyester resin, polyamide resin, rubber resin, etc. These thermoplastic resins may be used alone or in combination of two or more.

[0114] Examples of the thermosetting resin used to form the back surface adhesive layer include urethane resin, epoxy resin, etc. These thermosetting resins may be used alone or in combination of two or more.

[0115] 2. Manufacturing method of decorative sheet The decorative sheet 10 of the present disclosure described above can be manufactured by a method including a step of laminating each layer so as to obtain a laminate in which at least the base layer 3 and the first resin layer 1 are laminated in this order on one side of the base layer 3. The components used to form each layer, the thickness, and the specific conditions of the method for forming each layer are as described in the section on the composition of each layer. In addition, as described above, the decorative sheet 10 can also be laminated with the second resin layer 2, the pattern layer 4, the primer layer, the concealing layer, the back adhesive layer, and the like, as necessary.

[0116] 3. Decorative resin moldings The decorated resin molded product 20 of the present disclosure is formed by integrating a molded resin with the decorative sheet of the present disclosure. That is, as shown in the schematic diagram of FIG. 5, the decorated resin molded product 20 of the present disclosure includes at least a molded resin layer 5, a base layer 3, and a first resin layer 1 formed on the entire surface of one side of the base layer 3, the first resin layer 1 includes a first particle 1a and a second particle 1b which is a different type of particle from the first particle 1a and is relatively larger than the first particle 1a, the first resin layer 1 includes a plurality of raised portions 11 protruding from the surface opposite to the base layer 3 side, and the second particle 1b is not in contact with the layer located on the base layer 3 side of the first resin layer 1. The surface on one side of the decorated resin molded product 20 of the present disclosure has an uneven shape. In the decorated resin molded product 20 of the present disclosure, at least one layer such as the second resin layer 2, the pattern layer 4, the primer layer, the concealing layer, and the back adhesive layer may be further provided as necessary.

[0117] The decorated resin molded product of the present disclosure is produced, for example, by various injection molding methods such as insert molding, simultaneous injection molding and decoration, blow molding, and gas injection molding using the decorative sheet of the present disclosure. In the present disclosure, the decorative sheet of the present disclosure is subjected to various injection molding methods to produce a decorated resin molded product, so that the decorative sheet and the molded resin layer can exhibit excellent adhesion. Among these injection molding methods, the insert molding method and simultaneous injection molding and decoration method are preferably used.

[0118] In the insert molding method, first, in a vacuum forming step, the decorative sheet of the present disclosure is vacuum-formed in advance into the surface shape of the molded product (offline preforming) using a vacuum forming mold, and then excess parts are trimmed as necessary to obtain a molded sheet. This molded sheet is inserted into an injection mold, the injection mold is clamped, and a fluid resin is injected into the mold and solidified, and the decorative sheet is integrated with the outer surface of the resin molded product at the same time as injection molding, thereby producing a decorated resin molded product.

[0119] More specifically, the decorated resin molded product of the present disclosure is produced by an insert molding method including the following steps. A vacuum forming process in which the decorative sheet of the present disclosure is formed into a three-dimensional shape in advance using a vacuum forming mold; A trimming step of trimming an excess portion of the vacuum-formed decorative sheet to obtain a molded sheet; and An integration process in which the molded sheet is inserted into an injection mold, the mold is closed, and fluid resin is injected into the mold to integrate the resin and the molded sheet.

[0120] 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, the thickness of the decorative sheet, etc., but for example, when an ABS resin film is used as the base layer 3, it is usually 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 is usually about 180 to 320°C.

[0121] In addition, in the simultaneous injection molding decoration method, the decorative sheet of the present disclosure is placed in a female mold that also serves as a vacuum forming mold and is provided with suction holes for injection molding, and preforming (in-line preforming) is performed using this female mold.The injection molding mold is then clamped, and a fluid resin is injected to fill the mold and solidify.The decorative sheet of the present disclosure is integrated with the outer surface of the resin molded product at the same time as injection molding to produce a decorated resin molded product.

[0122] More specifically, the decorated resin molded article of the present disclosure is produced by a simultaneous injection molding and decoration method including the following steps. a preforming step of placing the decorative sheet of the present disclosure against a molding surface of a movable mold having a predetermined shape, with the base layer 3 side of the decorative sheet facing the molding surface, and then heating and softening the decorative sheet while vacuum-suctioning the decorative sheet from the movable mold side to bring the softened decorative sheet into close contact with the molding surface of the movable mold, thereby preforming the decorative sheet; an integration process in which a movable mold and a fixed mold are clamped together, the movable mold and the fixed mold have a decorative sheet in close contact with each other along their molding surfaces, and then a resin in a fluid state is injected into a cavity formed by the two molds, filled therein, and solidified to form a resin molded body, and the resin molded body and the decorative sheet are laminated and integrated together; A removal process in which the movable mold is separated from the fixed mold to remove a resin molded body including all layers of the decorative sheet laminated thereon.

[0123] In the preforming step of the simultaneous injection molding and decoration 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, etc., but it can usually be about 70 to 130°C when a polyester resin film or an acrylic resin film is used as the base layer 3. In the injection molding step, the temperature of the resin in a fluid state is not particularly limited, but can usually be about 180 to 320°C.

[0124] The decorated resin molded product of the present disclosure can also be produced by a decoration method such as a vacuum pressure bonding method, in which the decorative sheet of the present disclosure is attached to a three-dimensional resin molded body (molded resin layer 5) prepared in advance. In the vacuum pressure bonding method, the decorative sheet of the present disclosure and the resin molded body are first placed in a vacuum pressure bonding machine consisting of a first vacuum chamber located on the upper side and a second vacuum chamber located on the lower side, so that the decorative sheet faces the first vacuum chamber side, the resin molded body faces the second vacuum chamber side, and the base layer 3 side of the decorative sheet faces the resin molded body side, and the two vacuum chambers are placed in a vacuum state. The resin molded body is placed on a lifting platform provided on the second vacuum chamber side, which can be raised and lowered up and down. Next, the first vacuum chamber is pressurized, and the lifting platform is used to press the molded body against the decorative sheet, and the decorative sheet is attached to the surface of the resin molded body while stretching it by utilizing the pressure difference between the two vacuum chambers. Finally, the two vacuum chambers are opened to atmospheric pressure, and excess portions of the decorative sheet are trimmed as necessary, thereby obtaining the decorated resin molded product of the present disclosure.

[0125] In the vacuum pressure bonding method, it is preferable to include a step of heating the decorative sheet before the step of pressing the above-mentioned molded body against the decorative sheet in order to soften the decorative sheet and improve its formability. A vacuum pressure bonding method including this step is sometimes called a vacuum heat and pressure bonding method. The heating temperature in this step may be appropriately selected depending on the type of resin constituting the decorative sheet and the thickness of the decorative sheet, but when a polyester resin film or an acrylic resin film is used as the base layer 3, it can usually be about 60 to 200°C.

[0126] In the decorated resin molded product of the present disclosure, the molded resin layer 5 may be formed by selecting a resin according to the application. The molded resin forming the molded resin layer 5 may be a thermoplastic resin or a thermosetting resin.

[0127] Examples of the thermoplastic resin include polyolefin resins such as polyethylene and polypropylene, ABS resin, styrene resin, polycarbonate resin, acrylic resin, vinyl chloride resin, etc., and among these, ABS resin is preferable because it has particularly excellent adhesion to the base layer 3. These thermoplastic resins may be used alone or in combination of two or more.

[0128] Examples of the thermosetting resin include urethane resin, epoxy resin, etc. These thermosetting resins may be used alone or in combination of two or more.

[0129] The decorated resin molded product of the present disclosure can be used, for example, as interior or exterior materials for vehicles such as automobiles; building fittings such as window frames and door frames; interior materials for buildings such as walls, floors, and ceilings; housings for home appliances such as television sets and air conditioners; containers, etc. EXAMPLES

[0130] 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. In the inks used to form the first resin layer in the following examples, the resin compositions A-1, A-2, B-1, and B-3 each contain silica particles as the first particles, and the resin compositions A-2 and B-1 further contain polyurethane particles as the second particles. The resin compositions A-2 and B-1 containing the second particles are each used to form the raised portion of the first resin layer.

[0131] (Production of decorative sheets) [Example 1] A black ABS sheet was prepared as the base layer, and a 1 μm thick full-colored layer (concealing layer) and a 4 μm thick wood grain pattern layer were coated in sequence by gravure printing using an ink containing a 5:5 mixture of acrylic resin and vinyl chloride-vinyl acetate copolymer with a coloring agent. The wood grain pattern was formed so that the winter wood grain parts were dark in color.

[0132] Next, a first resin layer was formed by the following three printing operations.

[0133] First, an ink consisting of resin composition A-1 "22.5% by mass of a bifunctional urethane acrylate having a polycarbonate skeleton (weight average molecular weight 30,000), 7.5% by mass of silica particles (average particle size 2 μm, matting agent) as the first particles, and 70% by mass of a dilution solvent" was applied to the entire surface over the pattern layer by gravure printing, and then dried in a drying oven at 50°C for 30 seconds.

[0134] Next, while the ink made of the resin composition A-1 was in a semi-dried state, an ink made of a resin composition B-1 "15% by mass of an ionizing radiation curable resin made of pentaerythritol triacrylate: thermoplastic resin (homopolymer of methyl methacrylate) = 30: 70 (mass ratio)", 5% by mass of silica particles (average particle size 2 μm, matting agent) as the first particles, 15% by mass of urethane particles (average particle size 20 μm, particle size 5 to 60 μm (90% of the particle sizes of all organic particles are in the range of particle size 5 to 60 μm)) as the second particles, and 65% by mass of a dilution solvent" was partially coated by raised printing using a pattern plate with a plate depth of 90 μm, and dried for 30 seconds in a drying oven at 50 ° C. to form a raised portion. The pattern of the raised portion was a wood grain pattern, and was formed so that the area ratio to one side of the base layer was 25%. Next, while the ink made of the resin composition B-1 was in a semi-dried state, the ink made of the resin composition A-1 was applied to the entire surface from above by gravure printing, and dried in a drying oven at 90°C for 3 minutes.

[0135] By performing the above three printing steps, a first resin layer having a plurality of raised portions was formed on the design layer.

[0136] The thickness of the first resin layer is 5 μm in the area where the raised portion is not formed (between the raised portions), and 10 to 50 μm in the area where the raised portion is formed. In addition, in the raised portion, the urethane particles, which are the second particles, are densely present, and the raised portion is formed by the presence of the second particles. In addition, the second particles are not present in the positions between the raised portions (areas formed by the ink made of the resin composition A-1). In addition, the silica particles, which are the first particles, are contained in all the inks forming the first resin, so the first particles are dispersed throughout the first resin layer. Furthermore, since the ink made of the resin composition A-1, which does not contain the second particles, was printed first, and then the ink made of the resin composition B-1, which contains the second particles, was printed, in the raised portion of the first resin layer, the second particles are not in contact with the pattern layer. Furthermore, in the raised portion, the ink made of the resin composition A-1 was used in the first and third printings, and the printing was performed in a semi-dried state, so that no clear interface was formed due to compatibility. The first resin layer was set to have a gloss of 1.0 (60° gloss).

[0137] Next, an ink consisting of 28% by mass of resin composition B-2 "ionizing radiation curable resin consisting of pentaerythritol triacrylate: thermoplastic resin (homopolymer of methyl methacrylate) = 30:70 (mass ratio)", 2% by mass of silica particles (average particle size 2 μm, matting agent) as first particles, and 70% by mass of dilution solvent" was gravure printed in a pattern excluding the grain part of the wood grain pattern of the picture layer in harmony with the wood grain pattern to form a second resin layer 2 μm thick. The gloss of the second resin layer was set to 10.0 (60° gloss).

[0138] Finally, the surface was irradiated with an electron beam at an acceleration voltage of 165 kV and an exposure dose of 50 kGy (5 Mrad) to cure the ionizing radiation curable resin, thereby obtaining a decorative sheet.

[0139] [Example 2] A decorative sheet was obtained in the same manner as in Example 1, except that the first resin layer was formed by the following three printing operations.

[0140] First, an ink consisting of 22.5% by mass of resin composition B-3 "an ionizing radiation curable resin consisting of pentaerythritol triacrylate:thermoplastic resin (homopolymer of methyl methacrylate) = 30:70 (mass ratio)", 7.5% by mass of silica particles (average particle size 2 μm, matting agent) as the first particles, and 70% by mass of a dilution solvent" was applied to the entire surface over the pattern layer by gravure printing, and then dried for 30 seconds in a drying oven at 50°C.

[0141] Next, while the ink made of the resin composition B-3 was in a semi-dried state, an ink made of the resin composition B-1 "ionizing radiation curable resin made of pentaerythritol triacrylate: thermoplastic resin (homopolymer of methyl methacrylate) = 30: 70 (mass ratio)" was 15 mass%, silica particles (average particle size 2 μm matting agent) as the first particles were 5 mass%, urethane particles (average particle size 20 μm, particle size 5 to 60 μm (90% of the particle sizes of all organic particles are in the range of particle size 5 to 60 μm)) as the second particles were 15 mass%, and dilution solvent was 65 mass% was partially coated by raised printing using a pattern plate with a plate depth of 90 μm, and dried for 30 seconds in a drying oven at 50 ° C. to form a raised portion. The pattern of the raised portion was a wood grain pattern, and was formed so that the area ratio to one side of the base layer was 25%.

[0142] Next, while the ink made of the resin composition B-1 was in a semi-dried state, the ink made of the resin composition B-3 was applied to the entire surface from above by gravure printing, and dried in a drying oven at 90°C for 3 minutes.

[0143] [Example 3] A decorative sheet was obtained in the same manner as in Example 1, except that the first resin layer was formed by the following three printing operations.

[0144] First, an ink consisting of resin composition A-1 "22.5% by mass of a bifunctional urethane acrylate having a polycarbonate skeleton (weight average molecular weight 30,000), 7.5% by mass of silica particles (average particle size 2 μm, matting agent) as the first particles, and 70% by mass of a dilution solvent" was applied to the entire surface over the pattern layer by gravure printing, and then dried in a drying oven at 50°C for 30 seconds.

[0145] Next, while the ink made of the resin composition A-1 was in a semi-dried state, an ink made of resin composition A-2 "15% by mass of bifunctional urethane acrylate (weight average molecular weight 30,000) having a polycarbonate skeleton, 5% by mass of silica particles (average particle size 2 μm matting agent) as the first particles, 15% by mass of urethane particles (average particle size 20 μm, particle size 5 to 60 μm (90% of the particle sizes of all organic particles are in the range of particle size 5 to 60 μm)) as the second particles, and 65% by mass of dilution solvent" was partially coated by raised printing using a pattern plate with a plate depth of 90 μm, and dried for 30 seconds in a drying oven at 50 ° C. to form a raised portion. The pattern of the raised portion was a wood grain pattern, and was formed so that the area ratio to one side of the base layer was 25%.

[0146] Next, while the ink made of the resin composition A-2 was in a semi-dried state, the ink made of the resin composition A-1 was applied to the entire surface from above by gravure printing, and dried in a drying oven at 90°C for 3 minutes.

[0147] [Example 4] A decorative sheet was obtained in the same manner as in Example 1, except that the first resin layer was formed by the following three printing operations.

[0148] First, an ink consisting of 22.5% by mass of resin composition B-3 "an ionizing radiation curable resin consisting of pentaerythritol triacrylate:thermoplastic resin (homopolymer of methyl methacrylate) = 30:70 (mass ratio)", 7.5% by mass of silica particles (average particle size 2 μm, matting agent) as the first particles, and 70% by mass of a dilution solvent" was applied to the entire surface over the pattern layer by gravure printing, and then dried for 30 seconds in a drying oven at 50°C.

[0149] Next, while the ink made of the resin composition B-3 was in a semi-dried state, an ink made of the resin composition A-2 "15% by mass of a bifunctional urethane acrylate (weight average molecular weight 30,000) having a polycarbonate skeleton, 5% by mass of silica particles (average particle size 2 μm, matting agent) as the first particles, 15% by mass of urethane particles (average particle size 20 μm, particle size 5 to 60 μm (90% of the particle sizes of all organic particles are in the range of particle size 5 to 60 μm)) as the second particles, and 65% by mass of a dilution solvent" was partially coated by raised printing using a pattern plate with a plate depth of 90 μm, and dried for 30 seconds in a drying oven at 50 ° C. to form a raised portion. The pattern of the raised portion was a wood grain pattern, and was formed so that the area ratio to one side of the base layer was 25%.

[0150] Next, while the ink made of the resin composition A-2 was in a semi-dried state, the ink made of the resin composition B-3 was applied to the entire surface from above by gravure printing, and dried in a drying oven at 90°C for 3 minutes.

[0151] [Comparative Example 1] A black ABS sheet was prepared as the base layer, and a 1 μm thick full-colored layer (concealing layer) and a 4 μm thick wood grain pattern layer were coated in sequence by gravure printing using an ink containing a 5:5 mixture of acrylic resin and vinyl chloride-vinyl acetate copolymer with a coloring agent. The wood grain pattern was formed so that the winter wood grain parts were dark in color.

[0152] Next, an ink consisting of resin composition A-1 "22.5% by mass of bifunctional urethane acrylate having a polycarbonate skeleton (weight average molecular weight 30,000), 7.5% by mass of silica particles (average particle size 2 μm, matting agent) as the first particles, and 70% by mass of dilution solvent" was applied to the entire surface from above the design layer by gravure printing, and dried for 3 minutes in a drying oven at 90°C to form a first resin layer with a thickness of 5 μm. The gloss of the first resin layer was set to 1.0 (60° gloss).

[0153] Next, an ink consisting of 28% by mass of resin composition B-2 "ionizing radiation curable resin consisting of pentaerythritol triacrylate: thermoplastic resin (homopolymer of methyl methacrylate) = 30:70 (mass ratio)", 2% by mass of silica particles (average particle size 2 μm, matting agent) as the first particles, and 70% by mass of dilution solvent" was gravure printed in harmony with the wood grain pattern in a pattern excluding the grain part of the wood grain pattern of the design layer, and dried for 3 minutes in a drying oven at 90 °C to form a second resin layer with a thickness of 2 μm. The gloss of the second resin layer was set to 10.0 (60 ° gloss).

[0154] Next, an ink consisting of 15% by mass of resin composition B-1 "an ionizing radiation curable resin consisting of pentaerythritol triacrylate: thermoplastic resin (homopolymer of methyl methacrylate) = 30:70 (mass ratio)", 5% by mass of silica particles (average particle size 2 μm, matting agent) as first particles, 15% by mass of urethane particles (average particle size 20 μm, particle size 5 to 60 μm (90% of the particle sizes of all organic particles are in the range of particle size 5 to 60 μm)) as second particles, and 65% by mass of dilution solvent" was partially coated by raised printing using a pattern plate with a plate depth of 90 μm, and dried for 3 minutes in a drying oven at 90 ° C. to form a raised portion. The pattern of the raised portion was a wood grain pattern, and was formed so that the area ratio to one side of the base layer was 25%.

[0155] Finally, the surface was irradiated with an electron beam at an acceleration voltage of 165 kV and an exposure dose of 50 kGy (5 Mrad) to cure the ionizing radiation curable resin, thereby obtaining a decorative sheet.

[0156] [Comparative Example 2] A decorative sheet was obtained in the same manner as in Example 1, except that the first resin layer was formed by the following two printing operations.

[0157] First, an ink consisting of 15% by mass of resin composition B-1 "an ionizing radiation curable resin consisting of pentaerythritol triacrylate: thermoplastic resin (homopolymer of methyl methacrylate) = 30:70 (mass ratio)", 5% by mass of silica particles (average particle size 2 μm, matting agent) as first particles, 15% by mass of urethane particles (average particle size 20 μm, particle size 5 to 60 μm (90% of the particle sizes of all organic particles are in the range of particle size 5 to 60 μm)) as second particles, and 65% by mass of dilution solvent" was partially coated by raised printing using a pattern plate with a plate depth of 90 μm, and dried for 30 seconds in a drying oven at 50 ° C to form a raised portion. The pattern of the raised portion was a wood grain pattern, and was formed so that the area ratio to one side of the base layer was 25%.

[0158] Next, an ink consisting of resin composition A-1 "22.5% by mass of bifunctional urethane acrylate having a polycarbonate skeleton (weight average molecular weight 30,000), 7.5% by mass of silica particles (average particle size 2 μm, matting agent) as the first particles, and 70% by mass of dilution solvent" was applied from above to the entire surface by gravure printing, and dried for 3 minutes in a drying oven at 90° C. Thereafter, a decorative sheet was obtained in the same manner as in Example 1.

[0159] <Evaluation of the design of decorative sheets> From the viewpoint of deviation of the intended design of the decorative sheet and the viewpoint of the design feeling of the wood grain, the design was evaluated as follows. Each of the decorative sheets obtained above was visually observed from the surface on the second resin layer side (opposite the substrate layer), and the design was evaluated according to the following criteria. The results are shown in Table 1. A: The intended design has been realized, and the wood grain has a great sense of design. B: Due to the raised areas, the design is slightly different from the intended one, but the grain of the wood is still good. C: Due to the raised layer, there are some parts that are out of alignment with the intended design, but the wood grain design is normal and does not pose any problems for practical use. D: Due to the influence of the raised layer, the design is significantly different from the intended design, and the wood grain design is inferior.

[0160] <Evaluation of the texture of decorative sheets> The feel of each of the decorative sheets obtained above was evaluated as follows. The surface of each of the decorative sheets obtained above on the second resin layer side (the side opposite to the base layer) was touched with the fingers of a hand, and the feel was evaluated according to the following criteria. The results are shown in Table 1. A: There is a clear sense of unevenness B: Irregularities are felt C: The unevenness is not very noticeable, but it can be said to be a decorative sheet with a tactile feel. D: The unevenness is barely noticeable, and it cannot be said to be a decorative sheet with a tactile feel.

[0161] [Evaluation of interlayer adhesion] The interlayer adhesion of the decorative sheet was evaluated from two standpoints: initial interlayer adhesion and interlayer adhesion after a durability test.

[0162] <Initial interlayer adhesion> On the surface of each decorative sheet, 11 vertical and 11 horizontal cuts were made with a cutter, each 5 mm long and spaced 2 mm apart, forming a total of 100 grid-like cuts, 10 vertical and 10 horizontal. Cellophane tape (registered trademark) (No. 405-1P) manufactured by Nichiban Co., Ltd. was pressed onto the cuts, and then rapidly peeled off in a 90-degree direction to evaluate the interlayer adhesion. The results are shown in Table 1. A: No peeling is observed B: Partial peeling is observed, but not to the extent that it causes any practical problems. C: Peeling is observed to a degree that is problematic for practical use.

[0163] <Interlayer adhesion after durability test> Each decorative sheet was subjected to durability tests under the following conditions: leaving it at 100°C for 500 hours (heat resistance test), leaving it at a temperature of 50°C and humidity of 95% for 500 hours (humid heat resistance test), testing with an Atlas xenon weather meter (program: SAE J1885) until the integrated illuminance reached 100MJ (weather resistance test 1), and testing with an ultraviolet carbon arc lamp fade meter conforming to JIS B 7751 (black panel temperature 63°C) for 500 hours (weather resistance test 2). After that, the interlayer adhesion was evaluated using the same method as the initial adhesion described above. A: No peeling was observed after any durability test. B: Partial peeling was observed after any of the durability tests, but it was not a problem for practical use. C: Peeling that is problematic for practical use is observed after any of the durability tests.

[0164] [Table 1] [Explanation of symbols]

[0165] 1...First resin layer 1a...first particle 1b…Second particle 11...More part 12...Between the raised parts 2...Second resin layer 3...Base material layer 4…Pattern layer 5...Molded resin layer 10…Decorative sheet 20...Decorated resin molded products

Claims

1. The insulating film includes at least a base layer and a first resin layer formed on an entire surface of one side of the base layer, the first resin layer includes first particles and second particles that are different in type from the first particles and are relatively larger than the first particles; the first particles are dispersed throughout the first resin layer, the first resin layer includes a plurality of raised portions protruding from a surface opposite to the base layer side, the second particles are not in contact with a layer of the first resin layer located on the base layer side, A decorative sheet, wherein no interface exists inside the first resin layer.

2. The decorative sheet according to claim 1 , wherein the second particles are unevenly distributed in the raised portion of the first resin layer.

3. 3. The decorative sheet according to claim 1, wherein the average height of the raised portion is 5 μm or more.

4. The raised portion forms an uneven shape on the surface of the decorative sheet, The decorative sheet according to any one of claims 1 to 3, wherein the proportion of the area of ​​the portion on the surface of the decorative sheet where the uneven shape is formed is 1% or more and 50% or less, with the area of ​​the surface of the decorative sheet being 100%.

5. The decorative sheet according to any one of claims 1 to 4, wherein the first resin layer comprises a cured product of an ionizing radiation curable resin.

6. The decorative sheet according to any one of claims 1 to 5, further comprising a second resin layer having a different luster from that of the first resin layer, on the opposite side of the first resin layer from the base layer side.

7. The decorative sheet according to any one of claims 1 to 6, wherein the first resin layer has a thickness of 2 µm or more and 80 µm or less.

8. The decorative sheet according to any one of claims 1 to 7, wherein the first particles are inorganic particles.

9. The decorative sheet according to any one of claims 1 to 8, wherein the second particles are organic particles.

10. The decorative sheet according to any one of claims 1 to 9, wherein the second particles have an average particle size of 10 µm or more.

11. The decorative sheet according to any one of claims 1 to 10, further comprising a pattern layer between the base layer and the first resin layer.

12. At least a molded resin layer, a base layer, and a first resin layer formed on the entire surface of one side of the base layer, the first resin layer includes first particles and second particles that are different in type from the first particles and are relatively larger than the first particles; the first particles are dispersed throughout the first resin layer, the first resin layer includes a plurality of raised portions protruding from a surface opposite to the base layer side, the second particles are not in contact with a layer of the first resin layer located on the base layer side, A decorated resin molded product, wherein no interface exists inside the first resin layer.

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