JP7375417B2 - Decorative sheets and decorative resin molded products - Google Patents

Description

The present disclosure relates to a decorative sheet and a decorative resin molded product.

Conventionally, decorative resin molded products in which a decorative sheet is laminated on the surface of a resin molded product have been used for vehicle interior and exterior parts, building interior materials, home appliance casings, and the like. In the production of such decorative resin molded products, a molding method is used in which a decorative sheet, to which a design has been previously given, is integrated with resin by injection molding. A typical example of such a molding method is to previously mold a decorative sheet into a three-dimensional shape using a vacuum mold, insert the decorative sheet into an injection mold, and inject fluidized resin into the mold. Insert molding, which integrates the resin and decorative sheet, and simultaneous injection molding, which integrates the decorative sheet inserted into the mold during injection molding with the molten resin injected into the cavity. Decoration methods are mentioned. In addition to injection molding, decorative sheets are also used in decorating methods such as vacuum pressure bonding, in which the sheet is pasted onto a pre-formed body while being heated and pressurized.

Known methods for imparting a high quality texture to decorative resin molded products include a method of providing a resin layer containing a matting agent on a decorative sheet, and a method of providing an uneven shape on the surface of a decorative sheet. For example, Patent Document 1 describes a first resin layer containing a matting agent on a base layer, a second resin layer partially provided on the first resin layer, and a second resin layer on the second resin layer. A decorative sheet having a raised layer containing a resin and organic particles provided in this order is described. 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 the second resin layer is laminated with the area where the second resin layer is laminated. There is a difference in gloss between areas that are not coated, and a high level of design (glossy matte expression) is achieved. Furthermore, since the raised layer containing the resin and organic particles is laminated on the second resin layer, it is possible to provide an excellent tactile feel without impairing the gloss matte expression.

JP2017-65261A

The decorative sheet described in Patent Document 1 has a high design quality and exhibits an excellent tactile feel.

On the other hand, if a raised layer is partially provided on top of the layer that imparts a difference in gloss in order to provide texture by providing unevenness on the surface of the decorative sheet, it is also necessary to consider the effect of the raised layer on the gloss. , the selection of materials is restricted in order to approximate the gloss between the layer that gives the gloss difference and the top layer (there is a risk that the degree of freedom in material selection may be reduced), so it is important to have an excellent tactile feel and design of the decorative sheet. A new technology is required that balances the senses.

Under such circumstances, the main objective of the present disclosure is to provide a decorative sheet that has both excellent tactility and design. Furthermore, the present disclosure also aims to provide a decorated resin molded product using the decorative sheet.

The inventors of the present disclosure have conducted extensive studies to solve the above problems. As a result, a decorative sheet consisting of a laminate including at least a base material layer, a first resin layer, a partially provided ridge layer, and a partially provided second resin layer in this order, The first resin layer is provided on at least a portion of the base layer, the upper layer is partially provided on the first resin layer, and the second resin layer is provided on at least a portion of the upper layer. When the decorative sheet is viewed from the second resin layer side, a part of the surface of the first resin layer is exposed, and the first resin layer and the second resin layer are It has been found that decorative sheets having different glosses can have both excellent tactility and design. The present disclosure is an invention completed through further studies based on these findings.

That is, the present disclosure provides inventions of the following aspects.
Item 1. A decorative sheet consisting of a laminate including at least a base layer, a first resin layer, a partially provided ridge layer, and a partially provided second resin layer in this order,
The first resin layer is provided on at least a portion of the base layer,
The raised layer is partially provided on the first resin layer,
The second resin layer is provided on at least a portion of the upper layer,
When the decorative sheet is viewed from above from the second resin layer side, a part of the surface of the first resin layer is exposed,
A decorative sheet in which the first resin layer and the second resin layer have different glosses.
Item 2. Item 2. The decorative sheet according to Item 1, wherein the first resin layer is provided on the entire surface of the base layer.
Item 3. Item 3. The decorative sheet according to Item 1 or 2, wherein the raised layer contains a resin and organic particles.
Item 4. 4. The decorative sheet according to any one of Items 1 to 3, wherein the thickness of the raised layer is greater than the thickness of the second resin layer.
Item 5. 5. The decorative sheet according to any one of items 1 to 4, wherein the area of the raised layer is 100% or less of the area of the second resin layer.
Item 6. In any one of items 1 to 5, when the decorative sheet is viewed from the second resin layer side, 50% or more of the area of the raised layer is covered with the second resin layer. Decorative sheet as described.
Section 7. 7. The decorative sheet according to any one of items 1 to 6, wherein the first resin layer and the second resin layer are partially in contact with each other.
Section 8. 7. The decorative sheet according to any one of Items 1 to 6, wherein a part of the surface of the raised layer is exposed when the decorative sheet is viewed from the second resin layer side.
Item 9. Item 9. The decorative sheet according to any one of Items 1 to 8, which has a pattern layer between the base layer and the first resin layer.
Item 10. A decorative resin molded product consisting of a laminate comprising at least a molded resin layer, a base material layer, a first resin layer, a partially provided ridge layer, and a partially provided second resin layer in this order. hand,
The first resin layer is provided on at least a portion of the base layer,
The raised layer is partially provided on the first resin layer,
The second resin layer is provided on at least a portion of the upper layer,
When the decorative resin molded product is viewed in plan from the second resin layer side, a part of the surface of the first resin layer is exposed,
A decorated resin molded product, wherein the first resin layer and the second resin layer have different glosses.

According to the present disclosure, it is possible to provide a decorative sheet that has both excellent tactility and design. Furthermore, according to the present disclosure, it is also possible to provide a decorated resin molded product using the decorative sheet.

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

1. Decorative sheet The decorative sheet of the present disclosure is composed of a laminate including at least a base layer, a first resin layer, a partially provided ridge layer, and a partially provided second resin layer in this order. , the first resin layer is provided on at least a portion of the base layer, the upper layer is partially provided on the first resin layer, and the second resin layer is provided on at least a portion of the upper layer. When the decorative sheet is viewed from the second resin layer side, a part of the surface of the first resin layer is exposed, and the first resin layer and the second resin layer are It is characterized in that the layers have different luster. By having such a configuration, the decorative sheet of the present disclosure can have both excellent tactility and design. More specifically, an excellent tactile sensation is imparted by the uneven shape of the decorative sheet surface due to the partially provided raised layer, and furthermore, the second resin layer is formed on at least a portion of the raised layer. , and because the first resin layer and the second resin layer have different glosses, when the decorative sheet is viewed from above, the design based on the difference in gloss between the first resin layer and the second resin layer becomes a raised layer. Therefore, the desired design can be suitably exhibited.

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

Laminated structure of decorative sheet As shown in FIGS. 1 to 4, the decorative sheet 10 of the present disclosure has at least a base layer 1, a first resin layer 11, a raised layer 2, and a second resin layer 12. It has a laminated structure in which the layers are laminated in this order. The first resin layer 11 is provided on at least a portion of the base layer 1 . The first resin layer 11 is preferably provided on the entire surface of the base layer 1. Moreover, the surface of the first resin layer 11 is exposed when viewed in plan from the second resin layer 12 side of the decorative sheet 10. 1 to 4 illustrate an embodiment in which the first resin layer 11 is provided on the entire surface of one side of the decorative sheet 10, and the surface is exposed.

In the decorative sheet 10 of the present disclosure, the raised layer 2 is partially provided on the first protective layer 11 (that is, the area where the raised layer 2 is provided on the first resin layer 11). (There is a region where the raised layer 2 is not provided.) In the decorative sheet 10 of the present disclosure, the raised layer 2 is partially provided on the first resin layer 11, so that the region where the raised layer 2 is provided is a convex portion, and the raised layer 2 is provided in the convex portion. The areas that are not covered become recesses, and the surface has an uneven shape. It is preferable that the uneven shape is formed by providing a plurality of raised layers 2 that are independent from each other in plan view.

In the decorative sheet 10 of the present disclosure, the second resin layer 12 is provided on at least a portion of the raised layer 2. The second resin layer 12 is partially provided in the decorative sheet 10. The second resin layer 12 may be provided on at least a portion of the upper layer 2. For example, FIG. 1 shows a mode in which the second resin layer 12 covers the entire surface of the upper layer 2. It shows. Moreover, FIGS. 2 and 4 illustrate an embodiment in which the second resin layer 12 covers a part of the raised layer 2. Furthermore, as shown in FIG. 2, among the plurality of raised layers 2, there may be a raised layer 2 (the raised layer on the left side of FIG. 2) that is not covered with the second resin layer 12.

In the decorative sheet 10 of the present disclosure, a pattern layer 3 may be provided between the base layer 1 and the first resin layer 11, if necessary. Although not shown, the decorative sheet 10 may include a primer layer or the like between the top layer 2 and the first resin layer 11, and a primer layer or the like between the base layer 1 and the pattern layer 3. A concealing layer or the like may be provided, a back adhesive layer or the like may be provided on the back surface of the base material layer (the side opposite to the second resin layer 12 side), or other layers may be provided at any position. good.

The laminated structure of the decorative sheet of the present disclosure includes a laminated structure in which base layer 1 / first resin layer 11 / embossing layer 2 / second resin layer 12 are laminated in this order; base layer 1 / pattern layer 3 / third resin layer. Examples include a laminate structure in which 1 resin layer 11 / 2nd resin layer 1 / 2nd resin layer 12 are laminated in this order. FIGS. 1 and 2 show a decorative sheet in which a base layer 1 / first resin layer 11 / embossing layer 2 / second resin layer 12 are laminated in this order, as one embodiment of the laminated structure of the decorative sheet of the present disclosure. 1 shows an example schematic cross-sectional view; FIG. 3 and 4, as one embodiment of the laminated structure of the decorative sheet of the present disclosure, base material layer 1 / pattern layer 3 / first resin layer 11 / embossing layer 2 / second resin layer 12 / are laminated in this order. A schematic cross-sectional view of an example of a decorative sheet is shown.

Composition of each layer forming the decorative sheet [base layer 1]
The base material layer 1 is a resin sheet (resin film) that serves as a support in the decorative sheet of the present disclosure. The resin component used in the base layer 1 is not particularly limited and may be selected appropriately depending on moldability, compatibility with the molding resin, etc., but preferably a resin film made of a thermoplastic resin is used. . Specifically, the thermoplastic resins include acrylonitrile-butadiene-styrene resin (hereinafter sometimes referred to as "ABS resin") and acrylonitrile-styrene-acrylic acid ester resin (hereinafter referred to as "ASA resin"). ), acrylic resins, polyolefin resins such as polypropylene and polyethylene, polycarbonate resins, vinyl chloride resins, and polyethylene terephthalate (PET). Among these, ABS resin and acrylic resin are preferred from the viewpoint of moldability. Further, the base material layer 1 may be formed of a single layer sheet of these resins, or may be formed of a multilayer sheet of the same or different resins.

The bending modulus of the base layer 1 is not particularly limited. For example, when the decorative sheet of the present disclosure is integrated with a molded resin by an insert molding method, the bending elastic modulus of the base layer 1 in the decorative sheet of the present disclosure at 25° C. is 500 to 4,000 MPa, preferably Examples include 750 to 3,000 MPa. Here, the bending elastic modulus at 25° C. is a value measured in accordance with JIS K7171. When the flexural modulus at 25° C. is 500 MPa or more, the decorative sheet has sufficient rigidity, and even when subjected to insert molding, the surface properties and moldability are even better. In addition, if the bending elastic modulus at 25°C is 3,000 MPa or less, sufficient tension can be applied when manufacturing by roll-to-roll, making it difficult for sagging to occur, so it is possible to print overlapping images without shifting the pattern. This allows the so-called pattern registration to be improved.

The base material layer 1 may be subjected to physical or chemical surface treatment such as oxidation or roughening on one or both sides, as necessary, in order to improve adhesion with the layer provided thereon. It's okay. Examples of the oxidation method performed as the surface treatment of the base layer 1 include corona discharge treatment, chromium oxidation treatment, flame treatment, hot air treatment, ozone ultraviolet treatment, and the like. In addition, examples of the unevenening method performed as the surface treatment of the base layer 1 include a sandblasting method, a solvent treatment method, and the like. These surface treatments are appropriately selected depending on the type of resin component constituting the base layer 1, but from the viewpoint of effectiveness, operability, etc., corona discharge treatment is preferred.

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

Furthermore, the base material layer 1 may be colored using a coloring agent, or may not be colored. Moreover, the base material layer 1 may be opaque, colorless and transparent, colored and transparent, and translucent. The coloring agent used in the base material layer 1 is not particularly limited, but preferably includes a coloring agent that does not change color even at a temperature of 150° C. or higher, and specifically, existing dry colors, paste colors, masterbatch resins, etc. Examples include compositions.

The thickness of the base material layer 1 is appropriately set depending on the use of the decorative sheet, the molding method for integrating it with the molding resin, etc., and is usually about 25 to 1000 μm, and about 50 to 700 μm. More specifically, when the decorative sheet of the present disclosure is subjected to an insert molding method, the thickness of the base layer 1 is usually about 50 to 1000 μm, preferably about 100 to 700 μm, and more preferably 100 to 500 μm. The degree is mentioned. Further, when the decorative sheet of the present disclosure is subjected to a simultaneous injection molding decoration method, the thickness of the base layer 1 is usually about 25 to 200 μm, preferably about 50 to 200 μm, and more preferably about 70 to 200 μm. can be mentioned.

[First resin layer 11]
The first resin layer 11 is a layer having a gloss different from that of the second resin layer 12 described later, for the purpose of adjusting the gloss of the decorative sheet 10 and the like. In the decorative sheet 10 of the present disclosure, the first resin layer 11 is provided on at least a portion of the base layer 1 . The first resin layer 11 is preferably provided on the entire surface of the base layer 1. In this case, the first resin layer 11 is provided on the entire surface of one side of the decorative sheet 10 (that is, the entire surface is a solid layer). 1 to 4 illustrate an embodiment in which the first resin layer 11 is provided on the entire surface of one side of the decorative sheet 10. The first resin layer 11 may be in contact with the raised layer 2, or the first resin layer 11 and the raised layer 2 may be laminated via a primer layer or the like. Further, the first resin layer 11 may be in contact with a part of the second resin layer 12, which will be described later. That is, a part of the second resin layer 12 may be directly laminated on the first resin layer 11. The schematic diagrams of FIGS. 1 to 4 show an embodiment in which the first resin layer 11 and the second resin layer 12 are in contact with each other.

Further, the first resin layer 11 is exposed on the surface of the decorative sheet 10 on the second resin layer 12 side. As will be described later, the first resin layer 11 forms an exposed area and an unexposed area and creates a difference in gloss between the second resin layer 12 and the decorative sheet of the present disclosure. Design properties can be suitably imparted.

Examples of the resin constituting the first resin layer 11 include phenol resin, urea resin, diallyl phthalate, melamine resin, guanamine resin, unsaturated polyester resin, polyurethane resin, epoxy resin, aminoalkyd resin, and melamine-urea cocondensate. , 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, methacrylic ester, polycarbonate, cellulose triacetate, and other thermosetting resins.

Alternatively, the first resin layer 11 may be formed using an ionizing radiation-curable resin. As for the details of the ionizing radiation-curable resin, the same ones as shown in the column of [Top layer 2] described below are exemplified.

It is preferable that the first resin layer 11 contains a matting agent. There are no particular limitations on the matting agent, and a wide variety of known matting agents can be used. Examples of matting agents include inorganic particles such as silica, alumina, calcium carbonate, magnesium carbonate, aluminosilicate, and barium sulfate; resin (organic) particles such as acrylic beads, polyethylene, urethane resin, polycarbonate, and polyamide (nylon). Can be mentioned. The average particle size of the particles is preferably 0.5 to 20 μm, more preferably 0.5 to 10 μm. The amount of the matting agent added is preferably 2 to 40% by mass, more preferably 5 to 30% by mass based on the resin composition forming the first resin layer 11 (excluding the solvent). Note that the shape of the particles is polyhedral, spherical, scaly, etc. Among the above inorganic particles and organic particles, silica is preferred.

The thickness of the first resin layer 11 is preferably about 2 to 10 μm, more preferably about 0.1 to 20 μm, even more preferably about 0.3 to 10 μm, and still more preferably about 0.5 to 5 μm.

When the decorative sheet of the present disclosure is used for injection molding or vacuum forming, from the viewpoint of improving the scratch resistance of the decorative sheet and improving the three-dimensional formability, the ionizing radiation curability of the first resin layer 11 is As the resin, it is preferable to use polycarbonate (meth)acrylate, which will be described later.

In addition, when the decorative sheet of the present disclosure is used for injection molding or vacuum forming, the first resin layer 11 may be curable by ionizing radiation from the viewpoint of improving the scratch resistance of the decorative sheet and improving the three-dimensional formability. It is also preferable to use a mixture of resin and thermoplastic resin. Examples of thermoplastic resins include acrylic resins, urethane resins, olefin resins, and the like, with acrylic resins being particularly preferred. The mixing ratio of the ionizing radiation curable resin and the thermoplastic resin is preferably about 10:90 to 75:25 in mass ratio, more preferably about 25:75 to 50:50.

[Upper layer 2]
In the decorative sheet of the present disclosure, the raised layer 2 is formed on a portion of the first resin layer 11 . The embossed layer 2 in the present disclosure is preferably formed by embossed printing as a so-called embossed printing layer so as to impart a desired tactile sensation based on the uneven shape to the surface of the decorative sheet. In the present disclosure, the raised layer 2 has a convex shape in the cross-sectional schematic diagrams as shown in FIGS. 1 to 4, for example, a conical or cylindrical protrusion is formed on the surface of the decorative sheet. It includes not only forms in which the protrusions are formed in a straight line, but also forms in which protrusions extend linearly, such as a conduit pattern.

In the decorative sheet in which the second resin layer 12 is laminated on the decorative sheet of the present disclosure, the height of the raised layer 2 is preferably 5 μm or more, and more Preferably it is 10 μm or more, more preferably 15 μm or more, particularly preferably 20 μm or more. Further, the upper limit of the height of the raised layer 2 is preferably 50 μm or less, more preferably 40 μm or less. By setting the height of the raised layer 2 within the above range, the tactility and design of the decorative sheet can be improved more suitably. In this specification, the height of the raised layer 2 is a value calculated as the average value of 10 measured values obtained by observing the cross section of the decorative sheet using a scanning electron microscope (SEM).

Moreover, it is preferable that the thickness of the raised layer 2 is larger than the thickness of the second resin layer 12, which will be described later. Thereby, even if the second resin layer 12 is present in the decorative sheet 10, a high tactile sensation due to the height of the raised layer 2 can be ensured. The thickness of the raised layer 2 is preferably 1.5 times or more, more preferably 2 times or more, and even more preferably 4 times or more the thickness of the second resin layer 12. The thickness of the raised layer 2 is, for example, 20 times or less the thickness of the second resin layer 12. The thickness of the upper layer 2 and the thickness of the second resin layer 12 are compared by observing the cross section of the decorative sheet with a SEM in a range of length 1000 μm or more, and comparing the thickest part of the upper layer 2 and the thickness of the second resin layer 12. Compare the thickness of the thickest part.

The area of the raised layer 2 is preferably 100% or less of the area of the second resin layer 12, more preferably 90% or less, and even more preferably 80% or less. That is, by making the area of the second resin layer 12 sufficiently larger than the area of the raised layer 2, the proportion of the raised layer 2 that is not covered with the second resin layer 12 is reduced, and the influence of the raised layer 2 on gloss is reduced. can be effectively reduced, and high design quality can be achieved. In particular, even when the position where the raised layer 2 is formed and the position where the second resin layer 12 is formed are not in sync, the proportion of the raised layer 2 that is not covered with the second resin layer 12 becomes small, the effect of gloss caused by the raised layer 2 can be effectively reduced, and high design quality can be exhibited. Therefore, in the decorative sheet 10 of the present disclosure, it is also preferable that the position where the raised layer 2 is formed and the position where the second resin layer 12 is formed are out of phase. Note that the area of the raised layer 2 means the area on the first resin layer 11 side.

When the decorative sheet 10 is viewed in plan from the second resin layer 12 side, it is preferable that a part of the surface of the raised layer 2 is exposed.

In addition, in the decorative sheet 10, if the position where the raised layer 2 is formed and the position where the second resin layer 12 is formed can be accurately matched, the area of the raised layer 2 and the second resin layer For example, the first resin layer 11 is exposed at a position where the raised layer 2 is not provided, while the entire raised layer 2 is covered with the second resin layer 12 with the area of the raised layer 12 being substantially the same. I can do it. However, in manufacturing the decorative sheet 10, it is difficult to achieve such accurate matching. Therefore, as mentioned above, by making the area of the second resin layer 12 sufficiently larger than the area of the raised layer 2, it is important to reduce the proportion of the raised layer 2 that is not covered with the second resin layer 12. It can be said that it is large. The specific content of "synchronization" between the position where the raised layer 2 is formed and the position where the second resin layer 12 is formed will be described later.

From the same viewpoint, when the decorative sheet is viewed from the second resin layer 12 side, it is preferable that 50% or more of the area of the raised layer 2 is covered with the second resin layer 12. More preferably, 65% or more of the area of the raised layer 2 is covered with the second resin layer 12, and even more preferably 80% or more of the area of the raised layer 2 is covered with the second resin layer 12. Note that the upper limit of the area is, for example, 100%.

The resin forming the raised layer 2 is a curable resin such as a thermosetting resin, an ionizing radiation curable resin (for example, an electron beam curable resin), from the viewpoint of suppressing the deformation of the raised layer 2 and giving it a desired shape. is preferred. Ionizing radiation-curable resins are particularly preferred from the viewpoints of high surface hardness, productivity, and the like.

Examples of thermosetting resins include unsaturated polyester resins, polyurethane resins (including two-component curable polyurethanes), epoxy resins, aminoalkyd resins, phenolic resins, urea resins, diallyl phthalate resins, melamine resins, guanamine resins, and melamine. - Examples include urea cocondensation resins, silicone resins, and polysiloxane resins.

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

As a method for forming the upper layer 2 with a thermosetting resin, for example, a solution of a thermosetting resin is applied by a coating method such as a roll coating method, a gravure coating method, a gravure printing method, a silk screen printing method, etc., and then dried and cured. One example is how to do it.

Ionizing radiation-curable resins are resins that are crosslinked and cured by irradiation with ionizing radiation, and specifically include prepolymers, oligomers, and monomers that have polymerizable unsaturated bonds or epoxy groups in their molecules. Examples include a mixture of at least one of these. Here, ionizing radiation refers to electromagnetic waves or charged particle beams that have energy quanta that can polymerize or crosslink molecules, and ultraviolet rays (UV) or electron beams (EB) are usually used; It also includes electromagnetic waves such as rays and gamma rays, and charged particle beams such as alpha rays and ion beams. Among ionizing radiation curable resins, electron beam curable resins are suitable for forming the upper layer 2 because they can be made solvent-free, do not require a photopolymerization initiator, and have stable curing characteristics. used.

<Ionizing radiation curable resin>
As the monomer used as the ionizing radiation-curable resin, (meth)acrylate monomers having a radically polymerizable unsaturated group in the molecule are suitable, and polyfunctional (meth)acrylate monomers are particularly preferred. The polyfunctional (meth)acrylate monomer may be any (meth)acrylate monomer having two or more (bifunctional or more), preferably three or more (trifunctional or more) polymerizable unsaturated bonds in the molecule. Specifically, polyfunctional (meth)acrylates include ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, and 1,6-hexanediol di(meth)acrylate. ) 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 ) acrylate, ethylene oxide modified phosphoric di(meth)acrylate, allylated cyclohexyl di(meth)acrylate, isocyanurate di(meth)acrylate, trimethylolpropane tri(meth)acrylate, ethylene oxide modified trimethylolpropane tri(meth)acrylate, Dipentaerythritol tri(meth)acrylate, propionic acid modified dipentaerythritol tri(meth)acrylate, pentaerythritol tri(meth)acrylate, propylene oxide modified trimethylolpropane tri(meth)acrylate, tris(acryloxyethyl)isocyanurate, Examples include propionic acid-modified dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, ethylene oxide-modified dipentaerythritol hexa(meth)acrylate, and caprolactone-modified dipentaerythritol hexa(meth)acrylate. These monomers may be used alone or in combination of two or more.

Furthermore, as the above-mentioned oligomer used as the ionizing radiation-curable resin, (meth)acrylate oligomers having radically polymerizable unsaturated groups in the molecule are suitable, and among them, two or more polymerizable unsaturated bonds in the molecule. A polyfunctional (meth)acrylate oligomer having (two or more functionalities) is preferred. Examples of polyfunctional (meth)acrylate oligomers include polycarbonate (meth)acrylate, acrylic silicone (meth)acrylate, urethane (meth)acrylate, epoxy (meth)acrylate, polyester (meth)acrylate, polyether (meth)acrylate, Examples include polybutadiene (meth)acrylate, silicone (meth)acrylate, and oligomers having a cationically polymerizable functional group in the molecule (for example, novolak-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 terminal or side chain. It can be obtained by esterification with acrylic acid. The polycarbonate (meth)acrylate may be, for example, urethane (meth)acrylate having a polycarbonate skeleton. Urethane (meth)acrylate having a polycarbonate skeleton can be obtained, for example, by reacting a polycarbonate polyol, a polyvalent isocyanate compound, and a hydroxy (meth)acrylate. Acrylic silicone (meth)acrylate can be obtained by radical copolymerization of a silicone macromonomer and a (meth)acrylate monomer. Urethane (meth)acrylate can be obtained, for example, by esterifying a polyurethane oligomer obtained by reacting a polyether polyol or polyester polyol with a polyisocyanate compound with (meth)acrylic acid. Epoxy (meth)acrylate can be obtained, for example, by reacting (meth)acrylic acid with the oxirane ring of a relatively low molecular weight bisphenol-type epoxy resin or novolak-type epoxy resin to esterify it. Furthermore, a carboxyl-modified epoxy (meth)acrylate obtained by partially modifying this epoxy (meth)acrylate with a dibasic carboxylic acid anhydride can also be used. Polyester (meth)acrylate can be produced by, for example, esterifying the hydroxyl groups of a polyester oligomer having hydroxyl groups at both ends obtained by condensation of polycarboxylic acid and polyhydric alcohol with (meth)acrylic acid, or by esterifying the hydroxyl groups of polyester oligomer with (meth)acrylic acid. It can be obtained by esterifying the terminal hydroxyl group of an oligomer obtained by adding alkylene oxide with (meth)acrylic acid. Polyether (meth)acrylate can be obtained by esterifying the hydroxyl group of polyether polyol with (meth)acrylic acid. Polybutadiene (meth)acrylate can be obtained by adding (meth)acrylic acid to the side chain of a polybutadiene oligomer. Silicone (meth)acrylate can be obtained by adding (meth)acrylic acid to the terminal or side chain of silicone having a polysiloxane bond in its main chain. Among these, polycarbonate (meth)acrylate, urethane (meth)acrylate, and the like are particularly preferred as the polyfunctional (meth)acrylate oligomer. These oligomers may be used alone or in combination of two or more.

When three-dimensional formability is required for the decorative sheet, such as when used in the production of decorated resin molded products, among the above-mentioned ionizing radiation curable resins, from the viewpoint of obtaining excellent three-dimensional formability, It is preferable to use polyfunctional polycarbonate (meth)acrylate. Moreover, from the viewpoint of achieving both three-dimensional formability and scratch resistance, it is more preferable to use a combination of polyfunctional polycarbonate (meth)acrylate and polyfunctional (meth)acrylate. In addition, when using a polyfunctional (meth)acrylate monomer as an ionizing radiation-curable resin, it is preferable to use it in combination with a thermoplastic resin such as an acrylic resin from the viewpoint of obtaining excellent three-dimensional moldability. From the viewpoint of achieving both properties and scratch resistance, it is more preferable that the mass ratio of the polyfunctional (meth)acrylate monomer and thermoplastic resin in the ionizing radiation-curable resin composition is 25:75 to 75:25. . Hereinafter, polyfunctional polycarbonate (meth)acrylate and polyfunctional (meth)acrylate will be explained in detail.

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

Polyfunctional polycarbonate (meth)acrylate is obtained, for example, by converting some or all of the hydroxyl groups of polycarbonate polyol into (meth)acrylate (acrylic ester or methacrylic ester). This esterification reaction can be performed by a normal esterification reaction. For example, 1) a method of condensing a polycarbonate polyol and an acrylic acid halide or a methacrylic acid halide in the presence of a base, 2) a method of condensing a polycarbonate polyol and an acrylic anhydride or a methacrylic anhydride in the presence of a catalyst, Or 3) a method of condensing polycarbonate polyol and acrylic acid or methacrylic acid in the presence of an acid catalyst.

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

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

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

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

The compound (C) serving as a carbonyl component used as a raw material for polycarbonate polyol is any compound selected from carbonic diester, phosgene, or equivalents thereof. Specifically, the compounds include carbonic acid diesters such as dimethyl carbonate, diethyl carbonate, diisopropyl carbonate, diphenyl carbonate, ethylene carbonate, and propylene carbonate; phosgene; halogenated formic acids such as methyl chloroformate, ethyl chloroformate, and phenyl chloroformate; Examples include esters. These compounds may be used alone or in combination of two or more.

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) and the polyhydric alcohol (B) may be set, for example, in the range of 50:50 to 99:1. In addition, the molar ratio of the compound (C) serving as a carbonyl component to the diol compound (A) and polyhydric alcohol (B) is, for example, 0.2 to 2 to hydroxyl groups of the diol compound and polyhydric alcohol. It may be set within an equivalent range.

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

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

The molecular weight of the polyfunctional polycarbonate (meth)acrylate is not particularly limited, but examples include weight average molecular weights of 5,000 or more, preferably 10,000 or more. The upper limit of the weight average molecular weight of the polyfunctional polycarbonate (meth)acrylate is not particularly limited, but from the viewpoint of controlling the viscosity so that it does not become too high, it is, for example, 100,000 or less, preferably 50,000 or less. The weight average molecular weight of the polyfunctional polycarbonate (meth)acrylate is preferably 10,000 to 50,000, more preferably 10,000 to 20,000.

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

The content of polyfunctional polycarbonate (meth)acrylate in the ionizing radiation-curable resin composition used to form the raised layer 2 is not particularly limited as long as it achieves the effects of the present disclosure, but it may be used during injection molding, etc. From the viewpoint of retaining the uneven shape formed by the raised layer 2 and more effectively suppressing the deterioration of the high texture that has been exposed on the decorative sheet, it is preferably 50% by mass or more even when subjected to heat and pressure. , more preferably 80% by mass or more, still more preferably 85% by mass or more.

<Multifunctional (meth)acrylate>
The polyfunctional (meth)acrylate is not particularly limited, but polyfunctional urethane (meth)acrylate is preferred. The polyfunctional urethane (meth)acrylate is not particularly limited as long as it has a urethane bond in the polymer main chain and two or more (meth)acrylates in the terminal or side chain. Such a polyfunctional urethane (meth)acrylate can be obtained, for example, by esterifying a polyurethane oligomer obtained by reacting a polyether polyol or a polyester polyol with a polyisocyanate with (meth)acrylic acid. Further, from the viewpoint of improving crosslinking and curing, the polyfunctional urethane (meth)acrylate preferably has 2 to 12 functional groups per molecule. Moreover, the polyfunctional (meth)acrylate may be one modified with silicone. One type of polyfunctional (meth)acrylate may be used alone, or two or more types may be used in combination.

The molecular weight of the polyfunctional (meth)acrylate is not particularly limited, but examples include weight average molecular weights 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 from the viewpoint of controlling the viscosity so that it does not become too high, it is, for example, 30,000 or less, preferably 10,000 or less.

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

The content of polyfunctional (meth)acrylate in the ionizing radiation-curable resin composition used to form the raised layer 2 is not particularly limited as long as it achieves the effects of the present disclosure, but it may be used during injection molding, etc. From the viewpoint of retaining the uneven shape formed by the raised layer 2 and more effectively suppressing the deterioration of the high texture that has been exposed on the decorative sheet, it is preferably 50% by mass or less even when subjected to heat and pressure. , more preferably 20% by mass or less, still more preferably 15% by mass or less.

In the ionizing radiation-curable resin composition used for forming the upper layer 2, when polyfunctional polycarbonate (meth)acrylate and polyfunctional (meth)acrylate are used together, their mass ratio (polyfunctional polycarbonate (meth)acrylate : As the polyfunctional (meth)acrylate, preferably about 50:50 to 99:1, more preferably about 80:20 to 99:1, still more preferably about 85:15 to 99:1.

The formation of the raised layer 2 is carried out, for example, by preparing the above-mentioned ionizing radiation-curable resin composition, applying it, and crosslinking and curing it. The ionizing radiation-curable resin composition may have a viscosity that allows an uncured resin layer to be formed on the layer adjacent to the raised layer 2 by the coating method described below. In the present disclosure, the prepared coating liquid is coated on the layer adjacent to the raised layer 2 to the above thickness using a known method such as gravure coating, bar coating, roll coating, reverse roll coating, comma coating, etc. It is preferably applied by gravure coating to form an uncured resin layer. The uncured resin layer thus formed is irradiated with ionizing radiation such as electron beams and ultraviolet rays to harden the uncured resin layer, thereby forming the raised layer 2. Here, when an electron beam is used as the ionizing radiation, the accelerating voltage thereof can be appropriately selected depending on the resin used and the thickness of the layer, but the accelerating voltage is usually about 70 to 300 kV.

In addition, in electron beam irradiation, the higher the accelerating voltage, the higher the penetration ability, so when using a resin that is easily deteriorated by electron beam irradiation under the raised layer 2, the penetration depth of the electron beam and the raised layer 2 The accelerating voltage is selected so that the thicknesses of the two are substantially equal. Thereby, it is possible to suppress the irradiation of excess electron beams to the layers located under the raised layer 2, and it is possible to minimize the deterioration of each layer due to the excess electron beams. The irradiation dose is preferably an amount that saturates the crosslinking density of the raised layer 2, and is usually selected in the range of 5 to 300 kGy (0.5 to 30 Mrad), preferably 10 to 50 kGy (1 to 5 Mrad). Furthermore, there are no particular restrictions on the electron beam source, and various electron beam accelerators such as Cockroft-Walton type, Vandegraft type, resonant transformer type, insulated core transformer type, linear type, dynamitron type, and high frequency type can be used. Can be used. When using ultraviolet rays as the ionizing radiation, it is sufficient to emit light rays containing ultraviolet rays with a wavelength of 190 to 380 nm. Examples of the ultraviolet light source include, but are not limited to, high-pressure mercury lamps, low-pressure mercury lamps, metal halide lamps, carbon arc lamps, and the like.

It is preferable that the raised layer 2 contains particles. When the raised layer 2 contains particles, it becomes easy to form the raised layer 2 thickly, and an excellent tactile feel and design can be ensured. The particles contained in the raised layer 2 are not particularly limited and may be either organic particles or inorganic particles, but organic particles are particularly preferred from the viewpoint of achieving both excellent tactility and design. Moreover, the organic particles can also suppress whitening of the raised layer 2 during molding of the decorative sheet. In addition, since the combination of organic particles tends to increase the gloss of the upper layer, in conventional decorative sheets, the influence of the upper layer on the gloss tends to be large. On the other hand, in the decorative sheet 10 of the present disclosure, even when the raised layer 2 contains organic particles, the second resin layer 12 is provided on at least a portion of the raised layer 2. It is possible to reduce the influence of gloss caused by the upper layer, and it is possible to exhibit high design quality.

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 whitening of the raised layer 2, imparting an excellent tactile feel, and increasing the scratch resistance of the decorative sheet. In particular, from the viewpoint of suppressing whitening of the raised layer 2, it is preferable to use acrylic beads or urethane beads, and from the viewpoint of improving scratch resistance, it is preferable to use urethane beads. Further, from the viewpoint of imparting an excellent tactile sensation and increasing the scratch resistance of the raised layer 2, it is preferable to use crosslinked resin beads. Specific examples of the crosslinked resin beads include crosslinked acrylic beads, crosslinked urethane beads, and the like.

The organic particles contained in the raised layer 2 preferably have an average particle diameter of 3 to 60 μm. The average particle diameter of the organic particles is more preferably 10 to 35 μm. If the average particle diameter of the organic particles is less than 3 μm, there is a possibility that excellent tactile sensation may not be obtained. Furthermore, if the average particle diameter of the organic particles exceeds 60 μm, production stability may decrease and it may become difficult to form the raised layer 2 in a desired shape with good reproducibility. By uniformly distributing the organic particles in the raised layer 2, the height of the raised layer 2 approximates the average particle diameter of the organic particles. When the raised layer 2 is formed by raised printing, the average particle diameter of the organic particles is preferably 1/2 or less of the plate depth from the viewpoint of ink transfer stability. In the present disclosure, the average particle diameter was randomly selected by observing a cross section in the thickness direction of the layer with a scanning electron microscope (SEM) under the conditions of an accelerating voltage of 3.0 kV and a magnification of 50,000 times. It means the average value (arithmetic mean diameter) of particle diameters measured for non-agglomerated particles of 100 particles.

In the decorative sheet of the present disclosure, the organic particles are preferably contained in a proportion of 50% by mass or less in the solid content of the resin composition forming the raised layer 2, and preferably contained in a proportion of 40% by mass or less. More preferred. When the content of the organic particles is 50% by mass or less, the organic particles are uniformly distributed in the coating film (top layer 2), so that the feel is stable. If the content of the organic particles exceeds 50% by mass, the organic particles may aggregate and the height of the upper layer may become unstable, and the transparency of the upper layer 2 may be impaired, resulting in a decrease in design. be. The content of the organic particles is preferably 2% by mass, more preferably 10% by mass or more. If the content of the organic particles is less than 2% by mass, not only will the tactile sensation be insufficient, but the thixotropic property of the resin composition forming the raised layer will also be insufficient, making it difficult to form the raised layer 2 by thick printing. It may become difficult.

The inorganic particles are not particularly limited as long as they are particles formed from inorganic compounds, and examples thereof include silica particles, calcium carbonate particles, barium sulfate particles, alumina particles, and glass balloon particles. Among these, silica particles are preferable. Examples include particles. One type of inorganic particles may be used alone, or two or more types may be used in combination. The particle size of the inorganic particles is, for example, about 0.5 to 20 μm, preferably about 1 to 10 μm.

When the raised layer 2 contains inorganic particles, the content of the inorganic particles is not particularly limited, but is preferably about 1 to 60 parts by mass, more preferably 1 to 100 parts by mass of the resin contained in the raised layer 2. ~40 parts by mass may be mentioned. One type of inorganic particles may be used alone, or two or more types may be used in combination.

Various additives can be blended into the raised layer 2 depending on the desired physical properties that the raised layer 2 is provided with. These additives include, for example, weather resistance improvers such as ultraviolet absorbers and light stabilizers, wear resistance improvers, polymerization inhibitors, crosslinking agents, infrared absorbers, antistatic agents, adhesion improvers, leveling agents, Examples include thixotropic agents, coupling agents, plasticizers, antifoaming agents, fillers, solvents, colorants, and the like. These additives can be appropriately selected from commonly used additives. Further, as the ultraviolet absorber or light stabilizer, a reactive ultraviolet absorber or light stabilizer having a polymerizable group such as a (meth)acryloyl group in the molecule can also be used.

In the decorative sheet 10 of the present disclosure, the ratio of the area where the raised layer 2 is provided is preferably 5 to 80%, and 7 to 50%, with the area of one side of the base layer 1 being 100%. % is more preferable. By providing the raised layer 2 within the above range, a decorative sheet with a more excellent tactile feel can be obtained. Here, if the area of the upper surface and the lower surface of the raised layer 2 is different, such as when the cross section of the raised layer 2 is trapezoidal or conical, the area where the raised layer 2 is provided is is the area of the surface on the base material layer 1 side.

As described above, when the decorative sheet of the present disclosure is used for injection molding or vacuum forming, from the viewpoint of suppressing deformation of the raised layer 2 and giving it a desired shape while improving three-dimensional formability, the raised layer 2 is As the ionizing radiation-curable resin constituting 2, it is preferable to use polycarbonate (meth)acrylate.

In addition, when the decorative sheet of the present disclosure is used for injection molding or vacuum forming, from the viewpoint of improving the scratch resistance of the decorative sheet and improving three-dimensional formability, the upper layer 2 is made of an ionizing radiation-curable resin. It is also preferable to use a mixture with a thermoplastic resin. The type of thermoplastic resin and the preferable mixing ratio of the ionizing radiation-curable resin and the thermoplastic resin can be the same as those described for the first resin layer 11.

[Second resin layer 12]
The decorative sheet 10 of the present disclosure partially has the second resin layer 12 for the purpose of gloss adjustment and the like. The second resin layer 12 is provided on at least a portion of the raised layer 2 and has a gloss different from that of the first resin layer 11. The second resin layer 12 may be provided on at least a portion of the raised layer 2 . That is, the second resin layer 12 may be provided on the entire surface of the raised layer 2, or may be provided on a part of the raised layer 2. As described above, for example, FIG. 1 shows a mode in which the second resin layer 12 covers the entire surface of the raised layer 2. Moreover, FIGS. 2 and 4 illustrate an embodiment in which the second resin layer 12 covers a part of the raised layer 2. Furthermore, as shown in FIG. 2, among the plurality of raised layers 2, there may be a raised layer 2 (the raised layer on the left side of FIG. 2) that is not covered with the second resin layer 12.

There is a difference in gloss between a portion where the second resin layer 12 is not provided and where the first resin layer 11 is provided and a portion where the second resin layer 12 is provided. Accordingly, a high design quality can be imparted to the decorative sheet 10 of the present disclosure. In the decorative sheet 10 of the present disclosure, the first resin layer 11 forms an exposed region and an unexposed region, and creates a difference in gloss between the first resin layer 11 and the second resin layer 12. High design quality can be imparted to the decorative sheet. From the viewpoint of obtaining better design, it is preferable that the second resin layer 12 has a higher gloss than the first resin layer 11. That is, the first resin layer 11 has a relatively low gloss by containing a matting agent, the second resin layer 12 has a relatively high gloss, and there is a layer between the first resin layer 11 and the second resin layer 12. It is preferable to provide a difference in gloss.

Furthermore, in the decorative sheet 10 of the present disclosure, the position where the raised layer 2 is formed and the position where the second resin layer 12 is formed may or may not be in sync. good. Synchronization here means that the position where the raised layer 2 is formed and the position where the second resin layer 12 is formed are located at mutually related positions in a plan view. . Specifically, in plan view, (a) when the second resin layer 12 exists at the same position as the raised layer 2, (b) when the second resin layer 12 exists at a different position from the raised layer 2. , (c) a case where the second resin layer 12 is present at a position apart from the raised layer 2 with a certain distance and direction maintained, and the like. More specifically, as shown in FIG. 1, the position where the raised layer 2 is formed becomes a convex portion on the surface of the decorative sheet 10, and the second resin layer 12 is formed on the raised layer 2, Since the first resin layer 11 is exposed at the position of the recess between the raised layers 2, the difference in gloss between the first resin layer 11 (low gloss) and the second resin layer 12 (high gloss) makes it difficult to see. The three-dimensional effect can be further enhanced by the combination of design and tactile sensation. Although not shown, the second resin layer 12 may be partially formed in the recess between the raised layers 2 at the positions where the raised layers 2 are formed. In this case as well, the first resin layer 11 has an exposed portion at the position of the recess between the raised layers 2.

When the decorative sheet is viewed from the second resin layer 12 side, it is preferable that 50% or more of the area of the first resin layer 11 is covered with the second resin layer 12. More preferably, 65% or more of the area is covered with the second resin layer 12, and even more preferably 80% or more of the area of the first resin layer 11 is covered with the second resin layer 12. Note that the upper limit of the area is, for example, 99%.

The second resin layer 12 is preferably a transparent resin layer. Note that transparent includes all of colorless transparent, colored transparent, translucent, etc.

Examples of the resin constituting the second resin layer 12 include phenol resin, urea resin, diallyl phthalate, melamine resin, guanamine resin, unsaturated polyester resin, polyurethane resin, epoxy resin, aminoalkyd resin, and melamine-urea cocondensate. , 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 ester, methacrylic ester, polycarbonate, cellulose triacetate, and the like. Further, the above-mentioned ionizing radiation curable resin may also be used. These resins can be used alone or in combination of two or more.

Note that the second resin layer 12 may contain a matting agent for gloss adjustment. When the second resin layer 12 contains a matting agent, the content of the matting agent in the second resin layer 12 is preferably smaller than the content of the matting agent in the first resin layer 11 . By making the content of the matting agent in the second resin layer 12 lower than the content of the matting agent in the first resin layer 11, the gloss of the second resin layer 12 is made higher than that of the first resin layer 11, It becomes easy to obtain excellent design quality.

Examples of the matting agent used in the second resin layer 12 include the same ones listed for the first resin layer 11. The amount of the matting agent added is preferably 0.5 to 20% by mass, more preferably 1 to 15% by mass based on the resin composition forming the second resin layer 12 (excluding the solvent). Note that the content of the matting agent in the second resin layer 12 is lower than the content of the matting agent in the first resin layer 11 per unit mass of the solid content of the resin composition forming the second resin layer 12. This means that the mass of the matting agent contained in the first resin layer 11 is smaller than the mass of the matting agent contained per unit mass of the solid content of the resin composition forming the first resin layer 11.

When the decorative sheet 10 of the present disclosure includes a pattern layer 3 to be described later, it is preferable that the second resin layer 12 is provided in synchronization with the pattern of the pattern layer 3. By configuring the pattern of the picture layer 3 and the pattern of the second resin layer 12 to be in sync with each other, it is possible to obtain a decorative sheet with a more excellent design. In the present disclosure, synchronization between the pattern of the pattern layer 3 and the second resin layer 12 refers to, for example, the position of the pattern of the pattern layer 3 and the synchronization of the second resin layer 12 when observing the decorative sheet in plan. 12 corresponds to the position where the second resin layer 12 is formed (so-called positive), and the position of the pattern of the picture layer 3 corresponds to the position where the second resin layer 12 is not formed (the so-called positive). , negative). 3 and 4 illustrate a negative mode as an example of synchronization between the pattern of the picture layer 3 and the second resin layer 12. In FIG. 3, the pattern of the picture layer 3, the second resin layer 12, and the raised layer 2 are in sync. Further, in FIG. 4, the pattern of the picture layer 3 and the second resin layer 12 are in sync, and the pattern of the picture layer 3 and the top layer 2 are out of sync, and in the decorative sheet of the present disclosure, this Such an embodiment is also suitable.

In the decorative sheet 10 of the present disclosure, the pattern layer 3 has a wood grain pattern, and a second resin layer 12 having a higher gloss than the first resin layer 11 is provided on a portion other than the winter grain pattern and/or the conduit pattern of the wood grain. is preferably provided. As a result, the luster of the winter grain pattern and/or conduit pattern portion of the wood grain becomes low, so that an excellent design similar to that of natural wood can be obtained. In order to form the second resin layer as described above, a plate with the same winter grain pattern and/or conduit pattern as the pattern layer 3 is inverted (that is, a negative state) is used, and a known printing method is used. It is preferable to print using Preferred printing methods include gravure printing, screen printing, and the like.

Note that the second resin layer 12 may be colored, but it is particularly preferable that no coloring agent is added thereto.

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

Note that when the decorative sheet 10 of the present disclosure is used for injection molding or vacuum forming, the second resin layer 12 is configured from the viewpoint of improving the scratch resistance of the decorative sheet 10 and improving the three-dimensional formability. As the ionizing radiation curable resin, it is preferable to use polycarbonate (meth)acrylate. The same polycarbonate (meth)acrylate as exemplified in the section of [Top layer 2] can be used.

Further, when the decorative sheet 10 of the present disclosure is used for injection molding or vacuum forming, the second resin layer 12 may be exposed to ionizing radiation from the viewpoint of improving the scratch resistance of the decorative sheet 10 and improving the three-dimensional formability. It is also preferable to use a mixture of a curable resin and a thermoplastic resin. The type of thermoplastic resin and the preferable mixing ratio of the ionizing radiation-curable resin and the thermoplastic resin can be the same as those described in the section [First resin layer 11].

[Picture layer 3]
The pattern layer 3 is a layer provided as necessary between the base material layer 1 and the first resin layer 11 for the purpose of imparting decorativeness to the decorative sheet. The first resin layer 11 and the pattern layer 3 may be in contact with each other, or may be laminated with another layer interposed therebetween.

The pattern layer 3 can be, for example, a layer in which a desired pattern is formed using an ink composition. The ink composition used to form the pattern layer 3 is a mixture of a binder, a pigment, a colorant such as a dye, an extender, a solvent, a stabilizer, a plasticizer, a catalyst, a hardening agent, etc. as appropriate. .

The binder used in the ink composition is not particularly limited, but includes, for example, polyurethane resin, vinyl chloride/vinyl acetate copolymer resin, vinyl chloride/vinyl acetate/acrylic copolymer resin, chlorinated polypropylene resin, and acrylic resin. , polyester resin, polyamide resin, butyral resin, polystyrene resin, nitrocellulose resin, cellulose acetate resin, and the like. These binders may be used alone or in combination of two or more.

Colorants used in the ink composition are not particularly limited, but include, for example, carbon black, iron black, titanium white, antimony white, yellow lead, titanium yellow, Bengara, cadmium red, ultramarine blue, and cobalt blue. Inorganic pigments such as quinacridone red, isoindolinone yellow, phthalocyanine blue, etc.; Metal pigments made of flaky foil pieces of aluminum, brass, etc.; Scale-like foils such as titanium dioxide-coated mica, basic lead carbonate, etc. Examples include pearlescent (pearl) pigments consisting of flakes.

The pattern formed by the pattern layer 3 is not particularly limited, but may include, for example, a stone pattern imitating a rock surface such as a wood grain pattern, a marble pattern (for example, a travertine marble pattern), a cloth pattern or a cloth-like pattern. Examples include fabric patterns, tiling patterns, brickwork patterns, etc., and patterns such as parquet and patchwork that combine these may be used, or monochromatic solid colors (so-called solid surfaces) may be used. These patterns are formed by multicolor printing using the usual process colors of yellow, red, blue, and black, but they can also be formed by multicolor printing using spot colors, which is performed by preparing plates for the individual colors that make up the pattern. can be formed.

The thickness of the pattern layer 3 is not particularly limited, but may be, for example, 1 to 30 μm, preferably 1 to 20 μm.

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

[Primer layer]
The primer layer is provided under the raised layer 2 as necessary for the purpose of improving the adhesion of the raised layer 2.

From the viewpoint of improving the adhesion between the raised layer 2 and the layer located below it, it is preferable that a primer layer is provided directly under the raised layer 2. The primer layer is provided, for example, between the raised layer 2 and the first resin layer 11.

Primer compositions constituting the primer layer include urethane resin, (meth)acrylic resin, (meth)acrylic-urethane copolymer resin, vinyl chloride-vinyl acetate copolymer, polyester resin, butyral resin, chlorinated polypropylene, A binder resin such as chlorinated polyethylene is preferably used, and these resins may be used alone or in combination of two or more. Among these, urethane resins, (meth)acrylic resins, and (meth)acrylic-urethane copolymer resins are preferred.

As the urethane resin, polyurethane containing polyol (polyhydric alcohol) as a main ingredient and isocyanate as a crosslinking agent (curing agent) can be used. The polyol has two or more hydroxyl groups in its molecule, such as polyester polyol, polyethylene glycol, polypropylene glycol, acrylic polyol, polyether polyol, and the like. The isocyanate includes polyvalent isocyanates having two or more isocyanate groups in the molecule, aromatic isocyanates such as 4,4-diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, hydrogenated tolylene diisocyanate, and hydrogenated diphenylmethane diisocyanate. Aliphatic (or alicyclic) isocyanates such as are used. Further, it is also possible to configure the composition by mixing urethane resin and butyral resin.

From the viewpoint of adhesion with the upper layer 2, difficulty of interaction after laminating the upper layer 2, physical properties, and moldability, acrylic polyol or polyester polyol is used as the polyol, and hexamethylene diisocyanate, 4,4 as the crosslinking agent. -diphenylmethane diisocyanate, and particularly preferably acrylic polyol and hexamethylene diisocyanate.

(Meth)acrylic resins include homopolymers of (meth)acrylic esters, copolymers of two or more different (meth)acrylic ester monomers, or copolymers of (meth)acrylic esters and other monomers. Examples include polymers, specifically methyl poly(meth)acrylate, ethyl poly(meth)acrylate, propyl poly(meth)acrylate, butyl poly(meth)acrylate, and methyl(meth)acrylate. Butyl (meth)acrylate copolymer, ethyl (meth)acrylate-butyl (meth)acrylate copolymer, ethylene-methyl (meth)acrylate copolymer, styrene-methyl (meth)acrylate copolymer A (meth)acrylic resin consisting of a single or copolymer containing a (meth)acrylic acid ester such as the following is suitably used.

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

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

The primer layer is coated with a primer composition using a gravure coat, a gravure reverse coat, a gravure offset coat, a spinner coat, a roll coat, a reverse roll coat, a kiss coat, a wheeler coat, a dip coat, a solid coat by silk screen, a wire bar coat, and a flow coat. It is formed by a normal coating method such as coating, comma coating, continuous coating, brush coating, spray coating, or transfer coating method. 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 base material), and then coated on the surface of the target layer in the decorative sheet.

[Hidden layer]
The concealing layer is used between the base layer 1 and the first resin layer 11, or between the base layer 1 and the pattern layer if the pattern layer 3 is provided, for the purpose of suppressing color changes and variations in the base layer 1. This layer is provided between the layers 3 and 3 as necessary.

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

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

The thickness of the hiding layer is usually set to about 1 to 20 μm, and it is desirable to form it as a so-called solid printing layer.

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

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

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

Examples of the thermoplastic resin used for forming the back adhesive layer include acrylic resin, acrylic modified polyolefin resin, chlorinated polyolefin resin, vinyl chloride/vinyl acetate copolymer, thermoplastic urethane resin, thermoplastic polyester resin, and polyamide. Examples include resins, rubber resins, and the like. These thermoplastic resins may be used alone or in combination of two or more.

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

2. Method for manufacturing a decorative sheet The decorative sheet 10 of the present disclosure described above includes at least the base layer 1, the first resin layer 11, the upper layer 2, and the second resin layer 12 on one side of the base layer 1. can be manufactured by a method including a step of laminating each layer so as to obtain a laminate in which the layers are laminated in this order. The components used to form each layer, the thickness, the specific conditions of the method for forming each layer, etc. are as described in the section of the composition of each layer. Further, as described above, the decorative sheet 10 may be laminated with a pattern layer 3, a primer layer, a concealing layer, a back adhesive layer, etc., if necessary.

3. Decorative Resin Molded Product The decorative 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 decorative resin molded product 20 of the present disclosure includes at least the molded resin layer 4, the base material layer 1, the first resin layer 11, and the partially provided raised layer. 2, and a partially provided second resin layer 12 in this order, the first resin layer 11 is provided on at least a part of the base material layer 1, and the raised layer 2 is , the second resin layer 12 is provided on at least a portion of the upper layer 2, and the second resin layer 12 is provided on at least a portion of the upper layer 2, and the first resin layer 11 and the second resin layer It is characterized by having a gloss different from that of No. 12. One surface of the decorative resin molded product 20 of the present disclosure has an uneven shape. In the decorative resin molded product 20 of the present disclosure, at least one layer such as the above-described pattern layer 3, primer layer, concealing layer, back adhesive layer, etc. may be further provided as necessary.

The decorated resin molded product of the present disclosure can be produced by various injection molding methods such as insert molding, simultaneous injection molding decoration, blow molding, and gas injection molding, using the decorative sheet of the present disclosure. Ru. In the present disclosure, by subjecting the decorative sheet of the present disclosure to various injection molding methods to produce a decorative resin molded product, the decorative sheet and the molded resin layer can exhibit excellent adhesion. Among these injection molding methods, insert molding method and injection molding simultaneous decoration method are preferably mentioned.

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

More specifically, the decorated resin molded product of the present disclosure is manufactured by an insert molding method including the following steps.
A vacuum forming step of forming the decorative sheet of the present disclosure into a three-dimensional shape using a vacuum forming mold,
A trimming process to obtain a molded sheet by trimming the excess portion of the vacuum-formed decorative sheet, and inserting the molded sheet into an injection mold, closing the injection mold, and injecting fluidized resin into the injection mold. An integration process that integrates the resin and molded sheet.

In the vacuum forming step in the insert molding method, the decorative sheet may be heated and formed.
The heating temperature at this time is not particularly limited and may be appropriately selected depending on the type of resin constituting the decorative sheet, the thickness of the decorative sheet, etc. For example, when using an ABS resin film as the base layer 1 If so, the temperature can usually be set at about 120 to 200°C. Further, in the integration step, the temperature of the fluidized resin is not particularly limited, but can usually be about 180 to 320°C.

In addition, in the injection molding simultaneous decoration method, the decorative sheet of the present disclosure is placed in a female mold that also serves as a vacuum molding mold provided with suction holes for injection molding, and preforming (in-line preforming) is performed in this female mold. After that, the injection molding mold is clamped, and the fluidized resin is injected and filled into the mold, solidified, and the decorative sheet of the present disclosure is integrated on the outer surface of the resin molded product at the same time as the injection molding. In this way, a decorated resin molded product is manufactured.

More specifically, the decorated resin molded product of the present disclosure is manufactured by an injection molding and simultaneous decoration method including the following steps.
After installing the decorative sheet of the present disclosure so that the base layer 1 side of the decorative sheet faces the molding surface of a movable mold having a molding surface of a predetermined shape, the decorative sheet is heated and softened. a preforming step of preforming the decorative sheet by applying vacuum suction from the movable mold side and bringing the softened decorative sheet into close contact along the molding surface of the movable mold;
After clamping a movable mold and a fixed mold that have a decorative sheet closely attached along the molding surface, a fluid resin is injected into the cavity formed by both molds, and is then filled and solidified. An integration process in which a resin molded body is formed by laminating and integrating the resin molded body and the decorative sheet, and a resin molding in which the movable mold is separated from the fixed mold and all layers of the decorative sheet are laminated. Extraction process to remove the body.

In the preforming step of the injection molding simultaneous 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. If a polyester resin film or an acrylic resin film is used as the base layer 1, the temperature can usually be about 70 to 130°C. Further, in the injection molding process, the temperature of the fluidized resin is not particularly limited, but can usually be about 180 to 320°C.

In addition, the decorative resin molded product of the present disclosure can be produced using a decorating method such as a vacuum pressure bonding method, in which the decorative sheet of the present disclosure is pasted onto a three-dimensional resin molded body (molded resin layer 4) prepared in advance. It can also be produced by In the vacuum crimping method, first, the decorative sheet and resin molded article of the present disclosure are placed in a vacuum crimping machine consisting of a first vacuum chamber located on the upper side and a second vacuum chamber located on the lower side. The two vacuum chambers are placed in a vacuum pressure bonding machine so that the resin molded body is on the second vacuum chamber side and the base layer 1 side of the decorative sheet is facing the resin molded body side. do. The resin molded body is installed on a lifting platform provided on the second vacuum chamber side and capable of moving up and down. Next, while pressurizing the first vacuum chamber, the molded body is pressed against the decorative sheet using a lifting table, and the resin molded body is stretched while stretching the decorative sheet using the pressure difference between the two vacuum chambers. to be attached to the surface. Finally, the two vacuum chambers are opened to atmospheric pressure and, if necessary, the excess portion of the decorative sheet is trimmed to obtain the decorated resin molded product of the present disclosure.

In the vacuum pressure bonding method, it is preferable to include a step of heating the decorative sheet in order to soften the decorative sheet and improve moldability before the step of pressing the molded body against the decorative sheet. The vacuum pressure bonding method including this step is sometimes particularly called a vacuum heat pressure bonding method. The heating temperature in this step may be appropriately selected depending on the type of resin constituting the decorative sheet, the thickness of the decorative sheet, etc., but even when a polyester resin film or acrylic resin film is used as the base layer 1, For example, the temperature can usually be about 60 to 200°C.

In the decorated resin molded product of the present disclosure, the molded resin layer 4 may be formed by selecting a resin depending on the application. The molding resin forming the molded resin layer 4 may be a thermoplastic resin or a thermosetting resin.

Examples of the thermoplastic resin include polyolefin resins such as polyethylene and polypropylene, ABS resins, styrene resins, polycarbonate resins, acrylic resins, and vinyl chloride resins, which have particularly excellent adhesion to the base layer 1. Therefore, ABS resin is preferred among these resins. These thermoplastic resins may be used alone or in combination of two or more.

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

The decorative resin molded product of the present disclosure can be used, for example, as an interior or exterior material for vehicles such as automobiles; fittings such as window frames and door frames; interior materials for buildings such as walls, floors, and ceilings; television receivers, and air conditioners. It can be used as a housing for home appliances such as machines; containers, etc.

Hereinafter, the present disclosure will be explained in detail by showing Examples and Comparative Examples. However, the present disclosure is not limited to the examples.

(Preparation of decorative sheet)
[Example 1]
A black ABS original fabric was prepared as a base material layer, and a 1 μm thick full-surface colored layer (hidden layer) and a 4 μm thick colored layer were printed by gravure printing using an ink containing a copolymer resin of vinyl chloride and vinyl acetate with a coloring agent. Layers of wood grain patterns were applied sequentially. In addition, the wood grain pattern was formed so that the winter wood grain part was a dark color.

Next, an ink containing 70% by mass of an ionizing radiation-curable resin made of polyfunctional urethane (meth)acrylate having a polycarbonate skeleton and 30% by mass of silica particles (average particle size 2 μm) as a matting agent was used to form a base material layer. A first resin layer having a thickness of 5 μm was formed by gravure printing (full-surface solid printing) on the entire surface. Note that the first resin layer was set to have a gloss of 1.0 (60° gloss).

Next, an ink containing 60% by mass of an ionizing radiation curable resin made of a polyfunctional urethane (meth)acrylate having a polycarbonate skeleton and 30% by mass of urethane beads (average particle diameter 20 μm, particle diameter 10 to 70 μm) as organic particles was prepared. The coating was carried out by build-up printing using a pattern plate with a depth of 90 μm to partially form a build-up layer on the first resin layer. The raised pattern was a wood grain pattern, and was formed so that the area ratio to one side of the base material layer was 25%.

Next, an ink containing 6% by mass of silica particles (average particle size 2 μm) as a matting agent and 94% by mass of an ionizing radiation-curable resin made of polyfunctional urethane (meth)acrylate having a polycarbonate skeleton was used to form a pattern layer. A second resin layer having a thickness of 2 μm was formed by gravure printing using a pattern excluding the winter-grained portion of the wood grain pattern so as to be in sync with the wood grain pattern. Note that the second resin layer was set to have a gloss of 10.0 (60° gloss).

Finally, an electron beam was irradiated from the second resin layer side to cure the ionizing radiation-curable resins of the first resin layer, the upper layer, and the second resin layer, thereby obtaining a decorative sheet. The area of the raised layer is 80% of the area of the second resin layer. Furthermore, when the decorative sheet of Example 1 is viewed in plan from the second resin layer side, 80% of the area of the raised layer is covered with the second resin layer. Moreover, 80% of the area of the first resin layer is covered with the second resin layer. The area of the raised layer is a value measured using a microscope when the decorative sheet of Example 1 is viewed in plan from the second resin layer side.

[Example 2]
The area of the raised layer is 100% of the area of the second resin layer, 50% of the area of the raised layer is covered with the second resin layer, and 50% of the area of the first resin layer is covered with the second resin layer. A decorative sheet was obtained in the same manner as in Example 1, except that the first resin layer, the upper layer, and the second resin layer were formed so as to be coated. The area of the raised layer is a value measured by viewing the decorative sheet of Example 2 from the second resin layer side using a microscope.

[Comparative example 1]
A decorative sheet was obtained in the same manner as in Example 1 except that the second resin layer was not provided.

[Comparative example 2]
A decorative sheet was obtained in the same manner as in Example 1 except that the stacking order of the upper layer and the second resin layer was changed.

[Comparative example 3]
A decorative sheet was obtained in the same manner as in Example 1, except that the raised layer was not provided.

<Evaluation of design of decorative sheet>
Each of the decorative sheets obtained above was visually observed from the surface opposite to the base layer side, and the design was evaluated according to the following criteria. The results are shown in Table 1.
A: The intended design of the decorative sheet has been realized.B: Due to the influence of the gloss of the upper layer, the design is slightly different from the intended design of the decorative sheet.C: Due to the influence of the gloss of the upper layer, the decorative sheet has been realized. It deviates greatly from the intended design.

<Evaluation of tactility of decorative sheet>
For each of the decorative sheets obtained above, the surface opposite to the base layer side was touched with the fingers of the hand, and the tactile sensation was evaluated according to the following criteria. The results are shown in Table 1.
A: Unevenness is clearly felt B: Unevenness is felt C: Unevenness is not felt very much

The decorative sheets of Examples 1 and 2 are composed of a laminate including at least a base layer, a first resin layer, a partially provided ridge layer, and a partially provided second resin layer in this order. , the first resin layer is provided on at least a portion of the base layer, the raised layer is partially provided on the first resin layer, and the second resin layer is provided on at least a portion of the base layer; is provided on at least a portion of the upper layer, and when the decorative sheet is viewed from above from the second resin layer side, a portion of the surface of the first resin layer is exposed; The first resin layer and the second resin layer have different glosses. The decorative sheets of Examples 1 and 2 were decorative sheets that had both excellent tactility and design.

1... Base material layer 2... Top layer 11... First resin layer 12... Second resin layer 3... Pattern layer 4... Molded resin layer 10... Decorative sheet 20... Decorative resin molded product

Claims (9)

A decorative sheet consisting of a laminate including at least a base layer, a first resin layer, a partially provided ridge layer, and a partially provided second resin layer in this order,
The first resin layer is provided on at least a portion of the base layer,
The raised layer is partially provided on the first resin layer,
The second resin layer is provided on at least a portion of the upper layer,
When the decorative sheet is viewed from above from the second resin layer side, a part of the surface of the first resin layer is exposed,
the first resin layer and the second resin layer have different glosses,
In the decorative sheet , the thickness of the raised layer is greater than the thickness of the second resin layer . The decorative sheet according to claim 1, wherein the first resin layer is provided on the entire surface of the base layer. The decorative sheet according to claim 1 or 2, wherein the raised layer contains resin and organic particles. The decorative sheet according to any one of claims 1 to 3 , wherein the area of the raised layer is 100% or less of the area of the second resin layer. 5. Any one of claims 1 to 4 , wherein when the decorative sheet is viewed in plan from the second resin layer side, 50% or more of the area of the raised layer is covered with the second resin layer. Decorative sheet described in. The decorative sheet according to any one of claims 1 to 5 , wherein the first resin layer and the second resin layer are partially in contact with each other. The decorative sheet according to any one of claims 1 to 5 , wherein a part of the surface of the raised layer is exposed when the decorative sheet is viewed from the second resin layer side. The decorative sheet according to any one of claims 1 to 7 , further comprising a pattern layer between the base layer and the first resin layer. A decorative resin molded product consisting of a laminate comprising at least a molded resin layer, a base material layer, a first resin layer, a partially provided ridge layer, and a partially provided second resin layer in this order. hand,
The first resin layer is provided on at least a portion of the base layer,
The raised layer is partially provided on the first resin layer,
The second resin layer is provided on at least a portion of the upper layer,
When the decorative resin molded product is viewed in plan from the second resin layer side, a part of the surface of the first resin layer is exposed,
the first resin layer and the second resin layer have different glosses,
The decorative resin molded product , wherein the thickness of the raised layer is greater than the thickness of the second resin layer .