JP6040835B2 - Decorative sheet and decorative resin molded product - Google Patents

Description

  The present invention relates to a decorative sheet having high formability, scratch resistance, and higher three-dimensional appearance. Furthermore, the present invention relates to a decorative resin molded product using the decorative sheet.

  Conventionally, a decorative resin molded product in which a decorative sheet is laminated on the surface of a resin molded product is used for an interior / exterior part of a vehicle, a building material interior material, a home appliance housing, and the like. In the production of such a decorated resin molded product, a molding method or the like is used in which a decorative sheet to which a design has been applied in advance is integrated with a resin by injection molding. As a typical example of a method for producing such a decorative resin molded product, for example, an insert molding method is known. In the insert molding method, a decorative sheet is molded into a three-dimensional shape in advance using a vacuum mold, the decorative sheet is inserted into an injection mold, and a resin in a flow state is injected into the injection mold. And a decorative sheet.

  Some decorative resin molded products have a complicated surface shape such as a three-dimensional curved surface. For this reason, the decorative sheet is required to have three-dimensional formability that can sufficiently follow the shape of the decorative resin molded product. Further, since the decorative sheet is used as a surface material of a decorative resin molded product, it is also required to have surface characteristics such as scratch resistance. Furthermore, with the recent trend toward high-class consumers, decorative resin molded products are required to express a high-quality design because the three-dimensional effect can be recognized when the appearance is visually observed.

  Up to now, there has been reported a technique for giving a decorative sheet an excellent design property with excellent formability and scratch resistance, a high three-dimensional effect, and the like. For example, Patent Document 1 discloses a decorative sheet having at least a surface protective layer on a base material and a transparent resin layer partially provided on the surface protective layer, and a partially provided transparent sheet. A method is disclosed in which a decorative sheet is given a three-dimensional effect due to a gloss difference or uneven shape between a resin layer and a surface protective layer. Further, for example, Patent Document 1 discloses a method of giving a real sense to a wood grain pattern by synchronizing the conduit part of the wood grain pattern of the picture layer and the portion from which the transparent resin layer is removed.

  However, in the conventional decorative sheet, the uneven shape formed in the transparent resin layer by the heat and pressure at the time of injection molding in the insert molding method or the like, or the preliminary molding (vacuum molding) preceding this, There exists a problem that the high three-dimensional impression expressed on the decorating sheet is impaired by becoming or becoming small.

JP 2009-113387 A

  The main object of the present invention is to provide a decorative sheet having high formability and scratch resistance, and having a high three-dimensional effect even when molded into a decorative resin molded product.

  The present inventor has intensively studied to solve the above problems. As a result, it has at least a base material layer, a first protective layer, and a second protective layer provided on a part of the first protective layer, and the first protective layer is When inorganic particles having a particle diameter of 5 μm or less and particles having a particle diameter of 8 μm or more are included, the resin has high moldability and scratch resistance, and also has a high three-dimensional effect when molded into a decorative resin molded product. It discovered that the decorating sheet | seat which has was obtained. The present invention has been completed by further studies based on these findings.

That is, this invention provides the invention of the aspect hung up below.
Item 1. At least a substrate layer, a first protective layer, and a second protective layer provided on a part of the first protective layer;
The decorative sheet, wherein the first protective layer includes inorganic particles having a particle diameter of 5 μm or less and particles having a particle diameter of 8 μm or more.
Item 2. Item 1. In the first protective layer, the content of the inorganic particles having a particle diameter of 5 μm or less is 1 to 70 parts by mass with respect to 100 parts by mass of the resin contained in the first protective layer. The decorative sheet as described.
Item 3. Claim | item 1 or 2 content whose particle | grains whose said particle diameter is 8 micrometers or more in said 1st protective layer are 1-200 mass parts with respect to 100 mass parts of resin contained in the said protective layer. Decorative sheet.
Item 4. In the first protective layer, the mass ratio of the content of the inorganic particles having a particle diameter of 5 μm or less and the particles having a particle diameter of 8 μm or more (inorganic particles having a particle diameter of 5 μm or less / particle diameter of 8 μm or more). Item 4. The decorative sheet according to any one of Items 1 to 3, wherein the particles are 10/1 to 1/4.
Item 5. Item 5. The decorative sheet according to any one of Items 1 to 4, wherein the inorganic particles having a particle diameter of 5 µm or less are silica particles.
Item 6. Item 6. The decorative sheet according to any one of Items 1 to 5, wherein the particles having a particle size of 8 µm or more are at least one of inorganic particles and resin particles.
Item 7. Item 7. The decorative sheet according to any one of Items 1 to 6, wherein the first protective layer has a thickness of 0.1 to 15 µm.
Item 8. Item 8. The decorative sheet according to any one of Items 1 to 7, wherein the thickness of the second protective layer is 0.1 to 15 µm.
Item 9. The decorative sheet according to any one of claims 1 to 8, wherein the second protective layer contains resin particles.
Item 10. Item 10. The decorative sheet according to any one of Items 1 to 9, further comprising a pattern layer.
Item 11. Item 11. The concave shape formed by the portion where the second protective layer is provided and the portion where the second protective layer is not provided on the first protective layer is synchronized with the pattern of the picture layer. Decorative sheet.
Item 12. At least an injection resin layer, a base material layer, a first protective layer, and a laminated body in which a second protective layer provided on a part of the first protective layer is laminated in this order. ,
The decorative resin molded product, wherein the first protective layer includes inorganic particles having a particle diameter of 5 μm or less and particles having a particle diameter of 8 μm or more.
Item 13. The vacuum forming process which shape | molds the decorating sheet in any one of claim | item 1 -11 in a solid shape beforehand with a vacuum forming die,
Trimming step of trimming an excess portion of the vacuum-decorated decorative sheet to obtain a molded sheet, and inserting the molded sheet into an injection mold, closing the injection mold, and injecting the resin in a fluid state into the injection mold An integration step of injecting the resin into the mold and integrating the resin and the molded sheet;
A method for producing a decorated resin molded product.

  According to the decorative sheet of the present invention, it has high moldability and scratch resistance, and even after being molded into a decorative resin molded product, a three-dimensional appearance can be recognized when the appearance is visually observed, and a high design It is possible to provide a decorative sheet that can impart the properties to the decorative resin molded product, and a decorative resin molded product using the decorative sheet.

It is a schematic sectional drawing of an example of the decorating sheet of this invention. It is a schematic sectional drawing of an example of the decorating sheet of this invention.

1. The decorative sheet of the present invention has at least a base material layer, a first protective layer, and a second protective layer provided on a part of the first protective layer, The first protective layer includes inorganic particles having a particle size of 5 μm or less and particles having a particle size of 8 μm or more. In the decorative sheet of the present invention, the first protective layer includes inorganic particles having a particle size of 5 μm or less and particles having a particle size of 8 μm or more, and thus is molded into a decorative resin molded product. When the appearance is visually observed, a three-dimensional effect can be recognized, and a decorative sheet that can impart high designability to the decorative resin molded product can be obtained. More specifically, the decorative sheet of the present invention contains the specific inorganic particles and particles as described above in the first protective layer, so that it can be pre-molded (vacuum molded) at the time of injection molding described below or prior to this. ) Even when heat and pressure are applied, the uneven shape formed by the second protective layer provided on a part of the first protective layer is maintained, and the high three-dimensional effect that is exposed on the decorative sheet Is effectively suppressed. Hereinafter, the decorative sheet of the present invention will be described in detail.

Laminated structure of decorative sheet The decorative sheet of the present invention has a laminated structure in which at least a base material layer 1, a first protective layer 2, and a second protective layer 3 are laminated. The second protective layer is provided on a part 2 a of the surface of the first protective layer 2. On the surface of the first protective layer 2, an uneven shape is formed by a portion 2 a provided with the second protective layer 3 and a portion 2 b provided with no second protective layer 3. .

  In the decorative sheet of the present invention, the pattern layer 4 may be provided as necessary for the purpose of imparting decorativeness to the resin molded product. Moreover, if the pattern layer 4 is provided between the base material layer 1 and the first protective layer 2 for the purpose of suppressing color change and variation of the base material layer 1, the base material layer 1 and the design layer 4 are provided. If necessary, a concealing layer 5 may be provided between them. Furthermore, if the pattern layer 4 is provided between the base material layer 1 and the first protective layer 2 for the purpose of improving the moldability of the decorative sheet, the pattern layer 4 and the first protective layer 2 are provided. If necessary, a transparent film layer 6 or the like may be provided between the two. Furthermore, an adhesive layer 7 or the like may be provided under the base material layer 1.

  As a laminated structure of the decorative sheet of the present invention, a laminated structure in which a base material layer / first protective layer / second protective layer are laminated in this order; base material layer / picture layer / first protective layer / second Layered structure in which the protective layers are laminated in this order; base material layer / hiding layer / picture layer / first protective layer / second protective layer laminated layer in this order; base material layer / hiding layer / picture Laminated structure in which layer / transparent film layer / first protective layer / second protective layer are laminated in this order; adhesive layer / base material layer / hiding layer / picture layer / first protective layer / second protective layer Are laminated in this order; a laminated structure in which an adhesive layer / base material layer / hiding layer / picture layer / transparent film layer / first protective layer / second protective layer are laminated in this order. FIG. 1 is a schematic cross-sectional view of an example of a decorative sheet in which a base material layer / first protective layer / second protective layer are laminated in this order as an aspect of the laminated structure of the decorative sheet of the present invention. Show. In FIG. 2, as an aspect of the laminated structure of the decorative sheet of the present invention, an adhesive layer / base material layer / hiding layer / picture layer / transparent film layer / first protective layer / second protective layer are laminated in this order. 1 shows a schematic cross-sectional view of an example of a decorated sheet.

Composition of each layer forming the decorative sheet [base material layer 1]
The base material layer 1 is formed of a resin sheet (resin film) that plays a role as a support in the decorative sheet of the present invention. The resin component used for the base material layer 1 is not particularly limited and may be appropriately selected depending on the three-dimensional moldability, compatibility with the injection resin layer, and the like, and preferably a thermoplastic resin. Specific examples of the thermoplastic resin include acrylonitrile-butadiene-styrene resin (hereinafter sometimes referred to as “ABS resin”); acrylonitrile-styrene-acrylic ester resin; acrylic resin; polyolefins such as polypropylene and polyethylene Resin; polycarbonate resin; vinyl chloride resin; polyethylene terephthalate (PET). Among these, ABS resin is preferable from the viewpoint of three-dimensional moldability. As a resin component which forms the base material layer 1, only 1 type may be used and 2 or more types may be mixed and used. Moreover, the base material layer 1 may be formed with the single layer sheet | seat of these resin, and may be formed with the multilayer sheet | seat by the same kind or different kind | species resin.

  The base material layer 1 is subjected to physical or chemical surface treatment such as an oxidation method or an unevenness method on one side or both sides as necessary in order to improve adhesion to the first protective layer 2 and the like described later. It may be given. Examples of the oxidation method performed as the surface treatment of the base material layer 1 include a corona discharge treatment, a plasma treatment, a chromium oxidation treatment, a flame treatment, a hot air treatment, and an ozone ultraviolet treatment method. Moreover, as the uneven | corrugated method performed as surface treatment of the base material layer 1, a sandblasting method, a solvent processing method, etc. are mentioned, for example. These surface treatments are appropriately selected according to the type of the resin component constituting the base material layer 1, and preferably a corona discharge treatment method from the viewpoints of effects and operability.

  In addition, the base material layer 1 may be colored with a colorant or the like, painted for adjusting the color, formation of a pattern for imparting design properties, or the like.

  The thickness of the base material layer 1 is not particularly limited and is appropriately set according to the use of the decorative sheet, etc., but is usually about 50 to 800 μm, preferably about 100 to 600 μm, more preferably about 200 to 500 μm. Can be mentioned. When the thickness of the base material layer 1 is within the above range, the decorative sheet can be provided with more excellent three-dimensional formability, designability, and the like.

[First protective layer 2]
The 1st protective layer 2 is a layer provided in order to improve the scratch resistance of a decorating sheet, a weather resistance, etc., and also to give a high three-dimensional effect to a decorating sheet with the 2nd protective layer 3 mentioned later. The first protective layer 2 includes inorganic particles having a particle size of 5 μm or less and particles having a particle size of 8 μm or more, and these inorganic particles and particles are dispersed in the resin. In the decorative sheet of the present invention, the first protective layer 2 is high in the decorative sheet together with the second protective layer 3 described later by including inorganic particles and particles having such a specific particle diameter. A three-dimensional appearance is exhibited, and a second second layer provided on a part of the first protective layer 2 is also provided by heat and pressure at the time of injection molding, which will be described later, or preliminary molding (vacuum molding) preceding this. The concavo-convex shape formed by the protective layer 3 is maintained, and deterioration of the high three-dimensional effect that has been exposed on the decorative sheet is effectively suppressed.

  In the present invention, the inorganic particles having a particle diameter of 5 μm or less mainly function as a matting agent for the first protective layer 2. The inorganic particle having a particle size of 5 μm or less is not particularly limited as long as it is a particle formed of an inorganic compound, and examples thereof include silica particles, calcium carbonate particles, barium sulfate particles, alumina particles, and glass balloon particles. Of these, silica particles are preferable. One kind of inorganic particles having a particle diameter of 5 μm or less may be used alone, or two or more kinds may be used in combination.

  The particle diameter of the inorganic particles is preferably 4 μm or less, more preferably 3 μm or less, from the viewpoint of further enhancing the matte effect of the first protective layer 2 and further enhancing the three-dimensional effect expressed on the decorative sheet. Can be mentioned. From the same viewpoint, the lower limit of the particle size of the inorganic particles is usually about 0.1 μm.

  Although it does not restrict | limit especially as content of the inorganic particle whose particle diameter in the 1st protective layer 2 is 5 micrometers or less, From a viewpoint which raises the three-dimensional effect expressed on a decorating sheet, it is contained in the 1st protective layer 2. The amount is preferably about 1 to 70 parts by mass, more preferably about 10 to 60 parts by mass, and still more preferably about 20 to 50 parts by mass with respect to 100 parts by mass of the resin described later.

  In the present invention, particles having a particle diameter of 8 μm or more contained in the first protective layer 2 are mainly formed by a second protective layer 3 described later provided on a part of the first protective layer 2. When the uneven shape is made gentle or small due to heat and pressure at the time of injection molding or pre-molding (vacuum molding), the high three-dimensional appearance that is displayed on the decorative sheet deteriorates. Demonstrate the ability to suppress.

  In the present invention, when the first protective layer 2 contains particles having a particle diameter of 8 μm or more, the high three-dimensional appearance that is exposed on the decorative sheet deteriorates when the decorative resin molded product is molded. The details of the mechanism that can effectively suppress the above are not necessarily clear, but can be considered as follows, for example. That is, since the first protective layer 2 contains particles having a particle diameter of 8 μm or more (hereinafter sometimes referred to as “large particles”), the second protection of the surface of the first protective layer 2 is achieved. It is considered that such large particles protrude from the portion 2b where the layer 3 is not formed, and the protruding portion of the large particles exhibits the effect of supporting the second protective layer 3 from the side. Thereby, the uneven shape formed by the second protective layer 3 is strengthened, and it is suppressed that the uneven shape becomes gentle or small due to heat and pressure at the time of injection molding or preforming. it is conceivable that.

  The particle having a particle diameter of 8 μm or more is not particularly limited, and examples thereof include inorganic particles and resin particles. As an inorganic particle, the same thing as what was illustrated with the inorganic particle whose said particle diameter is 5 micrometers or less can be illustrated. Examples of the resin particles include urethane beads, acrylic beads, and polyethylene beads. Among these particles, from the viewpoint of improving the scratch resistance, resin particles are preferable, and urethane beads are more preferable. One type of particles having a particle size of 8 μm or more may be used alone, or two or more types of inorganic particles or resin particles may be used in combination.

  The particle diameter of the particles having a particle diameter of 8 μm or more is preferably 9 μm or more from the viewpoint of suppressing the deterioration of the high three-dimensional appearance that has been exposed on the decorative sheet when the decorative resin molded product is molded. More preferably, 10 micrometers or more are mentioned. Moreover, as an upper limit of the particle diameter of the said particle | grain, about 20 micrometers is normally mentioned.

  The content of the inorganic particles having a particle diameter of 8 μm or more in the first protective layer 2 is not particularly limited, but the high three-dimensional appearance that has been expressed on the decorative sheet deteriorates when the decorative resin molded product is molded. From the viewpoint of suppressing the loss, the amount is preferably about 1 to 200 parts by mass, more preferably about 3 to 100 parts by mass, and still more preferably, with respect to 100 parts by mass of the resin described later contained in the first protective layer 2. About 5-50 mass parts is mentioned.

  The mass ratio of the inorganic particles having a particle diameter of 5 μm or less and the particles having a particle diameter of 8 μm or more contained in the first protective layer 2 is not particularly limited. From the viewpoint of suppressing the deterioration of the feeling and giving the decorative sheet high scratch resistance, preferably about 10/1 to 1/4, more preferably about 9/1 to 1/2. .

  In the present invention, as the resin forming the first protective layer 2, the inorganic particles having a particle diameter of 5 μm or less and the particles having a particle diameter of 8 μm or more can be dispersed in the first protective layer 2. If it is a thing, it will not restrict | limit in particular, However, From viewpoints, such as the three-dimensional moldability of a decorating sheet, and scratch resistance, Preferably, a thermosetting resin, ionizing radiation curable resin, etc. are mentioned.

  The thermosetting resin is not particularly limited, and for example, epoxy resin, phenol resin, urea resin, unsaturated polyester resin, melamine resin, alkyd resin, polyimide resin, silicone resin, hydroxyl functional acrylic resin, carboxyl functional acrylic. Examples include resins, amide functional copolymers, and urethane resins.

  The mode of curing of these thermosetting resins is not particularly limited, and examples include the following modes. For example, in the case of an epoxy resin, reaction with an amine, an acid catalyst, a carboxylic acid, an acid anhydride, a hydroxyl group, dicyandiamide, or ketimine can be used. If it is a phenol resin, the reaction of a base catalyst and excess aldehyde etc. are mentioned. If it is a urea resin, a polycondensation reaction under alkaline or acidic conditions may be used. Examples of unsaturated polyester resins include co-condensation reaction of maleic anhydride and diol. If it is a melamine resin, the heat polycondensation reaction of methylol melamine etc. are mentioned. If it is an alkyd resin, the reaction by the air oxidation of the unsaturated groups introduced into the side chain etc. are mentioned. In the case of a polyimide resin, a reaction in the presence of an acid or a weak alkali catalyst, a reaction with an isocyanate compound (in the case of a two-component type), or the like can be given. In the case of a silicone resin, a condensation reaction in the presence of a silanol group acid catalyst may be used. If it is a hydroxyl functional acrylic resin, the reaction (in the case of 1 liquid type) with a hydroxyl resin and the amino resin which it has is mentioned. If it is a carboxyl functional acrylic resin, the reaction by carboxylic acid, such as acrylic acid or methacrylic acid, and an epoxy compound etc. are mentioned. If it is an amide functional copolymer, a reaction with a hydroxyl group or a self-condensation reaction may be mentioned. In the case of a urethane resin, a reaction between a hydroxyl group-containing polyester resin, a polyether resin, an acrylic resin or the like and an isocyanate compound or a modified product thereof may be used.

  The resin for forming the first protective layer 2 is more preferably an ionizing radiation curable resin from the viewpoint of curability, and an electron beam curable resin is particularly preferable from the viewpoint that it is not necessary to use a solvent or the like. . Hereinafter, the ionizing radiation curable resin forming the first protective layer 2 will be described in detail.

(Ionizing radiation curable resin)
The ionizing radiation curable resin used for forming the first protective layer 2 is a resin that crosslinks and cures when irradiated with ionizing radiation. Specifically, a polymerizable unsaturated bond or What mixed suitably at least 1 sort (s) among the prepolymer, an oligomer, a monomer, etc. which have an epoxy group is mentioned. Here, ionizing radiation means an electromagnetic wave or charged particle beam having an energy quantum capable of polymerizing or cross-linking molecules, and usually ultraviolet (UV) or electron beam (EB) is used. It also includes electromagnetic waves such as rays and γ rays, and charged particle rays such as α rays and ion rays. Among the ionizing radiation curable resins, the electron beam curable resin can be made solvent-free, does not require a photopolymerization initiator, and provides stable curing characteristics. Therefore, the first protective layer 2 is formed. Are preferably used.

  As the monomer used as the ionizing radiation curable resin, a (meth) acrylate monomer having a radically polymerizable unsaturated group in the molecule is suitable, and a polyfunctional (meth) acrylate monomer is particularly preferable. The polyfunctional (meth) acrylate monomer may be a (meth) acrylate monomer having two or more polymerizable unsaturated bonds (bifunctional or more), preferably three or more (trifunctional or more) in the molecule. Specific examples of the polyfunctional (meth) acrylate include ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, and 1,6-hexanediol di ( (Meth) acrylate, neopentyl glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, hydroxypivalate neopentyl glycol di (meth) acrylate, dicyclopentanyl di (meth) acrylate, caprolactone modified dicyclopentenyl di ( (Meth) acrylate, ethylene oxide-modified phosphoric acid di (meth) acrylate, allylated cyclohexyl di (meth) acrylate, isocyanurate di (meth) acrylate, trimethylolpropane tri (meth) acrylate , Ethylene oxide modified trimethylolpropane tri (meth) acrylate, dipentaerythritol tri (meth) acrylate, propionic acid modified dipentaerythritol tri (meth) acrylate, pentaerythritol tri (meth) acrylate, propylene oxide modified trimethylolpropane tri ( (Meth) acrylate, tris (acryloxyethyl) isocyanurate, propionic acid modified dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, ethylene oxide modified dipentaerythritol hexa (meth) acrylate, caprolactone modified dipentaerythritol Examples include hexa (meth) acrylate. These monomers may be used individually by 1 type, and may be used in combination of 2 or more type.

  The oligomer used as the ionizing radiation curable resin is preferably a (meth) acrylate oligomer having a radical polymerizable unsaturated group in the molecule, and more than two polymerizable unsaturated bonds in the molecule. A polyfunctional (meth) acrylate oligomer having (bifunctional or higher) is preferred. Examples of the polyfunctional (meth) acrylate oligomer include polycarbonate (meth) acrylate, acrylic silicone (meth) acrylate, urethane (meth) acrylate, epoxy (meth) acrylate, polyester (meth) acrylate, and polyether (meth) acrylate. , Polybutadiene (meth) acrylate, silicone (meth) acrylate, oligomer having a cationic polymerizable functional group in the molecule (for example, novolac type epoxy resin, bisphenol type epoxy resin, aliphatic vinyl ether, aromatic vinyl ether, etc.) . Here, the polycarbonate (meth) acrylate can be obtained, for example, by esterifying a polycarbonate polyol with (meth) acrylic acid. The acrylic silicone (meth) acrylate can be obtained by radical copolymerizing a silicone macromonomer with a (meth) acrylate monomer. Urethane (meth) acrylate can be obtained, for example, by esterifying a polyurethane oligomer obtained by reaction of polyether polyol or polyester polyol and polyisocyanate with (meth) acrylic acid. Epoxy (meth) acrylate can be obtained, for example, by reacting (meth) acrylic acid with an oxirane ring of a relatively low molecular weight bisphenol type epoxy resin or novolak type epoxy resin and esterifying it. Also, a carboxyl-modified epoxy (meth) acrylate obtained by partially modifying this epoxy (meth) acrylate with a dibasic carboxylic acid anhydride can be used. Polyester (meth) acrylate is obtained by esterifying the hydroxyl group of a polyester oligomer having hydroxyl groups at both ends obtained by condensation of a polyvalent carboxylic acid and a polyhydric alcohol with (meth) acrylic acid, for example, or It can be obtained by esterifying the terminal hydroxyl group of an oligomer obtained by adding an alkylene oxide with (meth) acrylic acid. The polyether (meth) acrylate can be obtained by esterifying the hydroxyl group of the polyether polyol with (meth) acrylic acid. Polybutadiene (meth) acrylate can be obtained by adding (meth) acrylic acid to the side chain of the 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 the main chain. These oligomers may be used individually by 1 type, and may be used in combination of 2 or more type.

  These curable resins may be used alone or in a combination of two or more. Among these curable resins, polycarbonate (meth) acrylate and acrylic silicone (meth) acrylate are preferably used from the viewpoint of further improving the three-dimensional formability and scratch resistance of the decorative sheet.

(Other additive ingredients)
In the resin forming the first protective layer 2, in addition to the inorganic particles having a particle diameter of 5 μm or less and the particles having a particle diameter of 8 μm or more, depending on the desired physical properties to be provided in the first protective layer 2 Various additives can be blended. Examples of the additive include a weather resistance improver such as an ultraviolet absorber and a light stabilizer, an abrasion resistance improver, a polymerization inhibitor, a crosslinking agent, an infrared absorber, an antistatic agent, an adhesion improver, a leveling agent, Examples include a thixotropic agent, a coupling agent, a plasticizer, an antifoaming agent, a filler, a solvent, and a colorant. These additives can be appropriately selected from those commonly used. In addition, 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 be used.

(Thickness of the first protective layer 2)
Although there is no restriction | limiting in particular about the thickness after hardening of the 1st protective layer 2, For example, about 0.1-15 micrometers, Preferably it is about 0.5-10 micrometers, More preferably, about 1-5 micrometers is mentioned. When the thickness in such a range is satisfied, sufficient physical properties as a surface protective layer such as scratch resistance can be obtained. Further, if the first protective layer 2 is formed of an ionizing radiation curable resin, the ionizing radiation curable resin composition can be uniformly irradiated with ionizing radiation, and thus is uniformly cured. Can be made economically advantageous.

  In the first protective layer 2, the particle diameter of the particles having a particle diameter of 8 μm or more may be larger or smaller than the thickness of the first protective layer 2, but is formed by the second protective layer 3. From the viewpoint of further strengthening the uneven shape, it is preferable that the particle diameter of the particles having a particle diameter of 8 μm or more is larger than the thickness of the first protective layer 2. Moreover, the particle diameter of the inorganic particles having a particle diameter of 5 μm or less may be larger or smaller than the thickness of the first protective layer 2. When the particle diameter of these particles is larger than the thickness of the first protective layer 2, these particles protrude from the first protective layer 2 to the second protective layer 3 side. The thickness of the first protective layer 2 refers to the thickness of the resin portion on the surface. For example, the particle diameter of inorganic particles having a particle diameter of 5 μm or less, or particles having a particle diameter of 8 μm or more is When the thickness is greater than the thickness of the protective layer 2, the thickness of the first protective layer 2 refers to the thickness of the portion where these particles do not protrude.

(Method for forming first protective layer 2)
The first protective layer 2 is formed by applying a resin composition containing inorganic particles having a particle diameter of 5 μm or less, particles having a particle diameter of 8 μm or more, and the above resin on the base material layer 1. Can do. As the raw material for inorganic particles having a particle size of 5 μm or less, for example, the above-described inorganic particles having an average particle size of 5 μm or less, preferably an average particle size of 4 μm or less, more preferably an average particle size of 3 μm or less can be used. . In addition, as a lower limit of the average particle diameter of the said inorganic particle used as a raw material, Preferably it is 0.1 micrometer. In addition, as a raw material for particles having a particle diameter of 8 μm or more, for example, the above-described particles having an average particle diameter of 8 μm or more, preferably an average particle diameter of 9 μm or more, more preferably an average particle diameter of 10 μm or more is used. it can. In addition, as an upper limit of the average particle diameter of the said particle | grain used as a raw material, Preferably it is 20 micrometers. In the present invention, the average particle size of the above inorganic particles and the above particles is determined using the Shimadzu laser diffraction particle size distribution measuring device SALD-2100, and the powder to be measured from the nozzle using compressed air. It means a spray-type dry measurement method in which measurement is performed by spraying and dispersing in the air.

  For example, when the 1st protective layer 2 is formed with said thermosetting resin, the thermosetting resin before hardening is apply | coated on the base material layer 1, and thermosetting resin is applied in the above-mentioned aspect. The protective layer 2 can be formed by curing.

  Moreover, when the 1st protective layer 2 is formed with said ionizing radiation curable resin, formation of the 1st protective layer 2 is an ionizing radiation curable resin composition containing ionizing radiation curable resin, for example. It is carried out by preparing, applying this, and curing by crosslinking. In addition, the viscosity of ionizing radiation curable resin composition should just be a viscosity which can form a non-hardened resin layer on the layer adjacent to the 1st protective layer 2 with the coating method mentioned later. In the present invention, the prepared coating solution is known on the layer adjacent to the first protective layer 2 so as to have the thickness, such as gravure coating, bar coating, roll coating, reverse roll coating, comma coating, etc. This method 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 cure the uncured resin layer, thereby forming the first protective layer 2. Here, when an electron beam is used as the ionizing radiation, the acceleration voltage can be appropriately selected according to the resin to be used and the thickness of the layer, but usually includes an acceleration voltage of about 70 to 300 kV.

  In the electron beam irradiation, the transmission capability increases as the acceleration voltage is higher. Therefore, when a resin that is easily deteriorated by electron beam irradiation is used under the first protective layer 2, the transmission depth of the electron beam The acceleration voltage is selected so that the thicknesses of the first protective layer 2 are substantially equal. Thereby, the irradiation of the extra electron beam to the layer located under the 1st protective layer 2 can be suppressed, and degradation of each layer by an excess electron beam can be suppressed to the minimum. The irradiation dose is preferably such that the crosslinking density of the protective layer 2 is saturated, 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). Further, the electron beam source is not particularly limited. For example, various electron beam accelerators such as a cockroft Walton type, a bandegraft type, a resonant transformer type, an insulated core transformer type, a linear type, a dynamitron type, and a high frequency type are used. Can be used. When ultraviolet rays are used as the ionizing radiation, light rays including ultraviolet rays having a wavelength of 190 to 380 nm may be emitted. The ultraviolet ray source is not particularly limited, and examples thereof include a high pressure mercury lamp, a low pressure mercury lamp, a metal halide lamp, and a carbon arc lamp.

[Second protective layer 3]
The second protective layer 3 is provided on a part of the first protective layer 2 in the decorative sheet of the present invention, and the uneven shape formed thereby gives the decorative sheet a high three-dimensional effect. Has been granted. Further, the second protective layer 3 imparts a high three-dimensional effect to the decorative sheet due to the difference in gloss with the first protective layer 2. For example, as described later, the second protective layer is in a high glossy state (gross), the first protective layer 2 is in a low glossy state (matte), and a gloss difference is developed between the two layers. A high stereoscopic effect can be imparted. Moreover, the effect of further enhancing the authenticity and the high-class feeling can be expected by making the concavo-convex shape perceived when the surface of the decorative resin molded product is touched by hand.

  Moreover, the shape formed by the recessed part shape formed by the part 2a in which the 2nd protective layer 3 on the surface of the 1st protective layer 2 was provided, and the part 2b in which it is not provided, and the pattern layer 4 mentioned later By synchronizing with, it is possible to give the decorative sheet a high three-dimensional feeling and a genuine design feeling. For example, when the pattern formed on the pattern layer 4 is a wood grain pattern, the wood grain pattern can have a real feeling by synchronizing the conduit portion expressed by the pattern with the concave and convex portions of the above-described uneven shape. . Furthermore, in the second protective layer 3, the first protective layer 2 contains particles having a particle diameter of 8 μm or more, so that the three-dimensional effect and the authenticity appearing on the decorative sheet are likely to be real. It is effectively suppressed that the design feeling deteriorates during the molding of the decorative resin molded product.

  Although it does not restrict | limit especially as resin which comprises the 2nd protective layer 3, Preferably the thermosetting resin similar to said resin which comprises the 1st protective layer 2, and an ionizing radiation curable resin are mentioned.

  From the viewpoint of imparting high gloss to the second protective layer 3 and imparting a high three-dimensional effect to the decorative sheet due to the gloss difference with the first protective layer 2, the second protective layer 3 includes resin particles. It is preferable. Examples of the resin particles include the same resin particles as those exemplified in the first protective layer 2.

  Although it does not restrict | limit especially as a particle diameter of the resin particle contained in the 2nd protective layer 3, A high gloss is given to the 2nd protective layer 3, By the gloss difference with the 1st protective layer 2, it becomes a decoration sheet | seat. From the viewpoint of imparting a high three-dimensional effect, and from the viewpoint of imparting an uneven shape that can actually be perceived by hand to the surface of the decorative resin molded product, for example, about 0.1 to 10 μm, preferably about 0.5 to 8 μm More preferably, about 1-5 micrometers is mentioned.

  As content of the resin particle contained in the 2nd protective layer 3, it does not restrict | limit in particular, Preferably it is about 0-80 mass parts with respect to 100 mass parts of said resin contained in the 2nd protective layer 3, More preferably, about 1-60 mass parts, More preferably, about 10-40 mass parts is mentioned.

  Although the thickness of the 2nd protective layer 3 is not restrict | limited in particular, Even after shaping | molding, the uneven | corrugated shape formed by the 2nd protective layer 3 is hold | maintained, and the high three-dimensional effect which was exposed to the decorating sheet | seat is high. From the viewpoint of effectively suppressing deterioration, it is preferably about 0.1 to 15 μm, more preferably about 0.5 to 10 μm, and still more preferably about 1 to 5 μm.

  The second protective layer 3 can be formed by the same method as the first protective layer 2 described above.

[Picture layer 4]
The pattern layer 4 is a layer that gives decorativeness to the resin molded product, and is formed by printing various patterns using ink and a printing machine. The pattern formed by the pattern layer 4 is not particularly limited. For example, a grain pattern simulating the surface of a rock such as a grain pattern, a marble pattern (for example, a travertine marble pattern), a cloth simulating a texture or a cloth pattern Patterns, tiled patterns, brickwork patterns, etc., and patterns such as marquetry and patchwork that combine these are also included. These patterns can be formed by multicolor printing with normal yellow, red, blue and black process colors, or by multicolor printing with special colors prepared by preparing individual color plates constituting the pattern. It is formed.

  As the pattern ink used for the pattern layer 4, a binder appropriately mixed with a colorant such as a pigment or dye, an extender pigment, a solvent, a stabilizer, a plasticizer, a catalyst, or a curing agent is used. The binder is not particularly limited, and examples thereof include polyurethane resins, vinyl chloride-vinyl acetate copolymer resins, vinyl chloride-vinyl acetate-acrylic copolymer resins, chlorinated polypropylene resins, acrylic resins, Examples thereof include polyester resins, polyamide resins, butyral resins, polystyrene resins, nitrocellulose resins, and cellulose acetate resins. These resins may be used alone or in combination of two or more.

  The colorant is not particularly limited. For example, carbon black (black), iron black, titanium white, antimony white, chrome yellow, titanium yellow, petal, cadmium red, ultramarine, cobalt blue, and other inorganic pigments, quinacridone red Organic pigments or dyes such as isoindolinone yellow and phthalocyanine blue, metallic pigments composed of scaly foils such as aluminum and brass, pearl luster composed of scaly foils such as titanium dioxide-coated mica and basic lead carbonate (pearl) ) Pigments.

[Hidden layer 5]
If the hiding layer 5 is provided with a pattern layer 4 between the base layer 1 and the protective layer 2 for the purpose of suppressing the color change and variation of the base layer 1, the base layer 1 and the pattern layer 4 are provided. It is a layer provided as needed, for example.

  Since the concealing layer 5 is provided in order to prevent the base material layer 1 from adversely affecting the color tone and design of the decorative sheet, it is generally formed as an opaque layer.

  The masking layer 5 is formed using an ink composition in which a binder, a colorant such as a pigment or a dye, an extender pigment, a solvent, a stabilizer, a plasticizer, a catalyst, or a curing agent is appropriately mixed. The ink composition for forming the masking layer 5 is appropriately selected from those used for the pattern layer 4 described above.

  The concealing layer 5 is usually set to a thickness of about 1 to 20 μm and is desirably formed as a so-called solid printing layer.

[Transparent film layer 6]
The transparent film layer 6 serves as a support for improving the scratch resistance and weather resistance of the decorative sheet of the present invention, and also enhances moldability, and as necessary, such as the base material layer 1 and the pattern layer 4 Provided on top. The transparent film layer 6 is formed of a resin film. By providing the transparent film layer 6, the moldability is improved, and cracks are hardly generated in the first protective layer 2 and the second protective layer 3 when the decorative sheet is three-dimensionally molded. The resin film forming the transparent film layer 6 is not particularly limited as long as it can enhance the moldability of the decorative sheet and does not conceal the design by the pattern layer 4 when provided on the pattern layer 4. For example, a film of a polyester resin such as polyethylene terephthalate (PET) or polyethylene naphthalate (PEN), or an acrylic resin can be used. Although the thickness of the transparent film layer 6 is not specifically limited, Usually, it is about 15-200 micrometers, Preferably it is about 30-150 micrometers. The method for forming the transparent film layer 6 is not particularly limited. For example, a method of laminating the above resin film on the surface of an adjacent layer such as the base material layer 1 or the picture layer 4 by heat lamination, dry lamination, or the like. Is mentioned.

[Adhesive layer 7]
The adhesive layer 7 is a layer provided on the back surface of the base material layer 1 as necessary for the purpose of improving the adhesion between the decorative sheet and the injection resin. The resin forming the adhesive layer 7 is not particularly limited as long as it can improve the adhesion between the decorative sheet and the injection resin, and for example, a thermoplastic resin or a thermosetting resin is used. Examples of the thermoplastic resin include acrylic resin, acrylic-modified polyolefin resin, chlorinated polyolefin resin, vinyl chloride-vinyl acetate copolymer, thermoplastic urethane resin, thermoplastic polyester resin, polyamide resin, and rubber-based resin. . A thermoplastic resin may be used individually by 1 type, and may be used in combination of 2 or more types. Examples of the thermosetting resin include a urethane resin and an epoxy resin. A thermosetting resin may be used individually by 1 type, and may be used in combination of 2 or more types.

2. Decorative resin molded product The decorative resin molded product of the present invention is formed by integrating an injection resin with the decorative sheet of the present invention. That is, the decorative resin molded product of the present invention includes at least an injection resin layer, a base material layer, a first protective layer, and a second protection provided on a part of the first protective layer. The first protective layer includes inorganic particles having a particle size of 5 μm or less and particles having a particle size of 8 μm or more. In the decorative resin molded product of the present invention, if necessary, at least one layer such as the above-described pattern layer 4, concealing layer 5, transparent film layer 6, and adhesive layer 7 may be further provided on the decorative sheet. .

  The decorative resin molded product of the present invention is produced by using the decorative sheet of the present invention, for example, by various injection molding methods such as insert molding, simultaneous injection molding, blow molding, and gas injection molding. The Among these injection molding methods, an insert molding method and an injection molding simultaneous decorating method are preferable.

  In the insert molding method, first, in the vacuum forming step, the decorative sheet of the present invention is vacuum formed (off-line pre-molding) into a molded product surface shape in advance by a vacuum forming die, and then an excess portion is trimmed as necessary. A molded sheet is obtained. This molded sheet is inserted into an injection mold, the injection mold is clamped, the resin in a fluid state is injected into the mold and solidified, and the decorative sheet is integrated on the outer surface of the resin molding simultaneously with the injection molding. By decorating, a decorative resin molded product is manufactured.

More specifically, the decorative resin molded product of the present invention is manufactured by an insert molding method including the following steps.
A vacuum forming step of forming the decorative sheet of the present invention into a three-dimensional shape in advance by a vacuum forming die,
Trimming process to trim the excess part of the vacuum-decorated decorative sheet to obtain the molded sheet, and insert the molded sheet into the injection mold, close the injection mold, and inject the fluid resin into the injection mold Integration process to integrate the resin and the molded sheet.

  In the vacuum forming step in the insert molding method, the decorative sheet may be heated and molded. 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, and the like. For example, when an ABS resin film is used as the base material layer If it is, it can be normally about 120-200 degreeC. In the integration step, the temperature of the resin in a fluid state is not particularly limited, but can usually be about 180 to 320 ° C.

  In addition, in the simultaneous injection molding decoration method, the decorative sheet of the present invention is placed in a female mold that also serves as a vacuum forming mold provided with a suction hole for injection molding, and preliminary molding (in-line preliminary molding) is performed with this female mold. After performing, the injection mold is clamped, the resin in a fluid state is injected into the mold, solidified, and the decorative sheet of the present invention is integrated on the outer surface of the resin molding simultaneously with the injection molding Thus, a decorative resin molded product is manufactured.

More specifically, the decorative resin molded product of the present invention is manufactured by the simultaneous injection molding method including the following steps.
After the decorative sheet of the present invention is installed so that the surface of the base material layer of the decorative sheet faces the molding surface of the movable mold having a molding surface of a predetermined shape, the decorative sheet is heated, A pre-molding step of pre-molding the decorative sheet by softening and vacuum-sucking from the movable mold side and bringing the softened decorative sheet into close contact with the molding surface of the movable mold,
After the movable mold and the fixed mold having the decorative sheet adhered along the molding surface are clamped, the fluidized resin is injected into the cavity formed by both molds, and is solidified by filling. Forming a resin molded body, integrating the resin molded body and the decorative sheet, and integrating the decorative sheet, separating the movable mold from the fixed mold and resin molding Extraction process to remove the body.

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

  In the decorative resin molded product of the present invention, the injection resin layer may be formed by selecting a resin according to the application. The injection resin for forming the injection resin layer 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. These thermoplastic resins may be used individually by 1 type, and may be used in combination of 2 or more type.

  Moreover, as a thermosetting resin, a urethane resin, an epoxy resin, etc. are mentioned, for example. These thermosetting resins may be used individually by 1 type, and may be used in combination of 2 or more type.

  The decorative resin molded product of the present invention has high moldability and scratch resistance, and also has a high three-dimensional effect when molded into a decorative resin molded product. For example, an interior material for a vehicle such as an automobile. Or exterior materials; fittings such as window frames and door frames; interior materials of buildings such as walls, floors, and ceilings; housings of home appliances such as television receivers and air conditioners; containers and the like.

  Hereinafter, the present invention will be described in detail with reference to Examples and Comparative Examples. However, the present invention is not limited to the examples.

<Examples 1-9 and Comparative Examples 1-7>
(Preparation of decorative sheet)
On a colored ABS resin film having a thickness of 400 μm as a base material layer, a pattern layer (thickness 5 μm) using an acrylic resin as a binder was formed by gravure printing. The pattern of the pattern layer was a wood grain pattern. Next, a first protective layer (thickness 3 μm) was formed by gravure printing using the resin composition having the composition shown in Table 1 on the pattern layer. Next, using the resin composition having the composition shown in Table 1 on the first protective layer, the position corresponding to the conduit portion of the wood grain pattern of the pattern layer is synchronized with the wood grain pattern. The second protective layer thus formed was formed in a pattern. As described above, a decorative sheet having a configuration as shown in Table 1 and having a base layer / picture layer / first protective layer / second protective layer laminated in this order was obtained.

(Design property evaluation of decorative sheet)
Confirming the three-dimensional effect of visually observing the appearance of the decorative sheets obtained in Examples 1 to 9 and Comparative Examples 1 to 7, and the unevenness perceived when the surface of the decorative sheet was touched by hand. The design properties of the decorative sheet were evaluated according to the following evaluation criteria. The results are shown in Table 1.
◎: The three-dimensional effect of the design expressed by the first protective layer and the second protective layer can be firmly recognized, and the unevenness can be perceived by hand. ○: With the first protective layer and the second protective layer Δ: Recognizes the three-dimensional effect of the design to be expressed Δ: Recognizes the three-dimensional effect of the design expressed by the first protective layer and the second protective layer ×: The design expressed by the first protective layer and the second protective layer □: Cannot recognize the three-dimensional effect of the design expressed by the first protective layer and the second protective layer

(Design evaluation after injection molding)
Each of the decorative sheets of Examples 1 to 9 and Comparative Examples 1 to 7 was used, and each decorative sheet was heated at a hot platen temperature of 170 ° C. and molded so as to conform to the shape in the mold of the injection molding. The protective layer side was adhered to the inner surface of the mold. The mold used was a 80 mm square size, 10 mm rising and 2R tray shape with a high deep drawing degree. On the other hand, an ABS resin [manufactured by Nippon A & L Co., Ltd., trade name “Clarastic MTH-2”] was used as an injection resin, which was melted at 230 ° C. and then injected into the cavity. When the mold temperature reached 30 ° C., the decorated resin molded product was taken out of the mold to obtain a decorated resin molded product. Check the appearance of the decorative resin molded product visually, and the unevenness perceived when the surface of the decorative resin molded product is touched by hand. Were evaluated according to the following evaluation criteria. The results are shown in Table 1.
◎: The three-dimensional effect of the design expressed by the first protective layer and the second protective layer can be firmly recognized, and the unevenness can be perceived by hand. ○: With the first protective layer and the second protective layer Δ: Recognizes the three-dimensional effect of the design to be expressed Δ: Recognizes the three-dimensional effect of the design expressed by the first protective layer and the second protective layer ×: The design expressed by the first protective layer and the second protective layer □: Cannot recognize the three-dimensional effect of the design expressed by the first protective layer and the second protective layer

(Formability evaluation test)
The decorative sheets of Examples 1 to 9 and Comparative Examples 1 to 7 were each heated to 160 ° C. with an infrared heater and softened. Next, using a vacuum forming mold, vacuum forming was performed under the condition that the maximum draw ratio was 150%, and a decorative sheet was formed so as to have an internal shape of the vacuum forming mold. Next, the decorative sheet was cooled and then released from the vacuum forming mold. About each mold-released decorative sheet, the moldability was evaluated according to the following evaluation criteria. The results are shown in Table 1.
○: No cracking or whitening was observed on the surface of the detached decorative sheet, and the internal shape of the vacuum forming mold was satisfactorily followed. Δ: Three-dimensional molded part of the detached decorative sheet, maximum stretch Part of the coating was finely cracked or whitened, but there was no problem in practical use. X: Cracked or whitened on the surface of the decorative sheet that was released, following the internal shape of the vacuum mold XX not completed: Remarkable cracks and whitening were observed on the surface of the decorative sheet released from the mold, and the internal shape of the vacuum forming mold could not be followed.

(Scratch resistance evaluation test)
The surface on the transparent resin layer side of the decorative sheets of Examples 1 to 9 and Comparative Examples 1 to 7 was scratched 5 times with a nail, the surface state was visually observed, and evaluated according to the following criteria. The results are shown in Table 1.
○: No scratch on the surface Δ: Fine scratch was observed on the surface, but there was no shaving or whitening ×: Scratches were observed on the surface, and glossiness of the scratched portion was observed XX: The surface was markedly scratched and the surface was shaved

As each component shown in Table 1, the following were used.
(Transparent resin layer)
Urethane beads: average particle size 3.5μm
In Examples, the average particle size of various particles is a value obtained by measurement by the above method.
Resin A: Acrylic polyol (weight average molecular weight 15000-20000)
Resin B: Bifunctional polycarbonate acrylate (protective layer)
Silica α: average particle size 4 μm
Silica β: average particle size 1.3 μm
Silica γ: average particle size 10 μm
Urethane beads A: average particle size 3.5 μm
Urethane beads B: average particle size 10 μm
Urethane beads C: average particle size 14 μm
Acrylic 1: acrylic polyol (weight average molecular weight 15000-20000)
Acrylic 2: acrylic polyol (weight average molecular weight 30000)
Urethane: Polyurethane

  As shown in Table 1, in the decorative sheets of Examples 1 to 9 including inorganic particles having a particle diameter of 5 μm or less and particles having a particle diameter of 8 μm or more, the design of the decorative sheet and the decorative resin molded product From the viewpoints of property, moldability, and scratch resistance, it has been found that it is good or practically satisfactory. On the other hand, the decorative sheets of Comparative Examples 1 to 7 that do not include any one of inorganic particles having a particle diameter of 5 μm or less and particles having a particle diameter of 8 μm or more are decorative sheets, design properties of decorative resin molded products, and molding It was inferior in the point of property or scratch resistance. For example, the decorative sheet of Comparative Example 1 that contains inorganic particles having a particle diameter of 5 μm or less and no particles having a particle diameter of 8 μm or more is a decorative resin molded product, although the decorative sheet has excellent design properties. The designability of the case, the formability of the decorative sheet, and the evaluation of scratch resistance were poor. Further, in Comparative Example 2 in which the amount of inorganic particles having a particle size of 5 μm or less was increased, the designability of the decorative resin molded product remained low although the moldability of the decorative sheet was improved. Further, for example, in Comparative Example 4 that does not include inorganic particles, the design properties of the decorative sheet and the design properties of the decorative resin molded product were low.

DESCRIPTION OF SYMBOLS 1 ... Base material layer 2 ... 1st protective layer 3 ... 2nd protective layer 4 ... Pattern layer 5 ... Concealing layer 6 ... Transparent film layer 7 ... Adhesive layer

Claims (13)

At least a substrate layer, a first protective layer, and a second protective layer provided on a part of the first protective layer;
The decorative sheet, wherein the first protective layer includes inorganic particles having a particle diameter of 5 μm or less and particles having a particle diameter of 8 μm or more.   2. In the first protective layer, the content of the inorganic particles having a particle diameter of 5 μm or less is 1 to 70 parts by mass with respect to 100 parts by mass of the resin contained in the first protective layer. The decorative sheet described in 1.   In the first protective layer, the content of the particles having a particle diameter of 8 µm or more is 1 to 200 parts by mass with respect to 100 parts by mass of the resin contained in the first protective layer. 2. The decorative sheet according to 2.   In the first protective layer, the mass ratio of the content of the inorganic particles having a particle diameter of 5 μm or less and the particles having a particle diameter of 8 μm or more (inorganic particles having a particle diameter of 5 μm or less / particle diameter of 8 μm or more). The decorative sheet according to any one of claims 1 to 3, wherein the particles are 10/1 to 1/4.   The decorative sheet according to any one of claims 1 to 4, wherein the inorganic particles having a particle diameter of 5 µm or less are silica particles.   The decorative sheet according to any one of claims 1 to 5, wherein the particles having a particle diameter of 8 µm or more are at least one of inorganic particles and resin particles.   The decorative sheet according to any one of claims 1 to 6, wherein a thickness of the first protective layer is 0.1 to 15 µm.   The decorative sheet according to any one of claims 1 to 7, wherein the thickness of the second protective layer is 0.1 to 15 µm.   The decorative sheet according to any one of claims 1 to 8, wherein the second protective layer contains resin particles.   The decorative sheet according to any one of claims 1 to 9, further comprising a pattern layer.   The concave shape formed by the portion where the second protective layer is provided and the portion where the second protective layer is not provided on the first protective layer is synchronized with the pattern of the picture layer. The decorative sheet as described. At least an injection resin layer, a base material layer, a first protective layer, and a laminated body in which a second protective layer provided on a part of the first protective layer is laminated in this order. ,
The decorative resin molded product, wherein the first protective layer includes inorganic particles having a particle diameter of 5 μm or less and particles having a particle diameter of 8 μm or more. A vacuum forming step in which the decorative sheet according to any one of claims 1 to 11 is previously formed into a three-dimensional shape by a vacuum forming die,
Trimming step of trimming an excess portion of the vacuum-decorated decorative sheet to obtain a molded sheet, and inserting the molded sheet into an injection mold, closing the injection mold, and injecting the resin in a fluid state into the injection mold An integration step of injecting the resin into the mold and integrating the resin and the molded sheet;
A method for producing a decorated resin molded product.