JP6690366B2 - Method for producing decorative sheet and decorative resin molded product - Google Patents

Description

  TECHNICAL FIELD The present invention relates to a decorative sheet having a concave-convex forming portion on the surface thereof and capable of imparting an excellent design property to a decorative resin molded product. Furthermore, the present invention relates to a method for producing a decorative resin molded product using the decorative sheet.

  2. Description of the Related Art Conventionally, a decorative resin molded product obtained by laminating a decorative sheet on the surface of a resin molded product has been used for vehicle interior / exterior parts, building material interior materials, home appliance housings, and the like. In the production of such a decorative resin molded product, a molding method or the like in which a decorative sheet having a design given in advance is integrated with a resin by injection molding is used. As a typical example of such a molding method, a decorative sheet is preliminarily molded into a three-dimensional shape by a vacuum molding die, the decorative sheet is inserted into an injection molding die, and a resin in a fluid state is injected into the die. Simultaneous injection molding that integrates the resin and the decorative sheet by using the insert molding method, or integrates the decorative sheet inserted into the mold during injection molding with the molten resin injected into the cavity. The decoration method can be mentioned.

  As a method of imparting unevenness, three-dimensionality, depth, etc. to the surface of such a decorative resin molded product, a pattern is printed on the back surface of the base sheet and the surface unevenness is obtained by embossing (embossing) processing. Attempts have been made to impart shape. However, if the surface is provided with an uneven shape by embossing, the uneven shape may be restored to a flat surface due to the effect of heat and stress at the time of injection molding or preliminary molding (vacuum molding) prior to the injection molding.

  As a decorative sheet having a concavo-convex shape formed by a method different from embossing, for example, Patent Document 1 discloses a decorative sheet having independent fine concavo-convex forming portions on its surface.

JP, 2009-234159, A

  However, in a decorative sheet having an independent fine unevenness forming portion on the surface as disclosed in Patent Document 1, for example, since the material of the unevenness forming portion and the layer located thereunder are usually different, There is a problem in that the difference in color and luster due to the difference in material makes it difficult to give a natural design feeling.

  Under such circumstances, the present invention provides a decorative sheet that can be used to produce a decorative resin molded product to easily and easily give a decorative resin molded product a design with a natural unevenness. Is the main purpose.

  The present inventor has diligently studied to solve the above problems. As a result, at least the surface layer, and comprises an unevenness forming portion formed on a part of the surface of the surface layer, the unevenness forming portion, on the surface of the surface layer, is exposed to the outside, and, By using a decorative sheet in which the unevenness forming portion is formed so that it can be removed from the surface of the surface layer in the production of the method for producing a decorative resin molded product, the decorative resin can easily and naturally give a decorative impression. We have found that it can be applied to molded products. The present invention has been completed by further studies based on these findings.

That is, the present invention provides the inventions of the following modes.
Item 1. At least, a surface layer, and comprises an unevenness forming portion formed on a part of the surface of the surface layer,
The unevenness forming portion is exposed to the outside on the surface of the surface layer,
The said uneven | corrugated formation part is a decorating sheet formed so that it can be removed from the surface of the said surface layer.
Item 2. Item 2. The decorative sheet according to Item 1, wherein the surface layer is formed of a cured product of a curable resin composition.
Item 3. Item 3. The decorative sheet according to Item 2, wherein the curable resin composition forming the surface layer contains a silicone component in an amount of 10% by mass or more.
Item 4. Item 4. The decorative sheet according to any one of Items 1 to 3, wherein the irregularity forming portion is formed of a cured product of an ionizing radiation curable resin composition.
Item 5. Item 5. The decorative sheet according to Item 4, wherein the ionizing radiation curable resin composition forming the irregularity forming portion contains a silicone component in an amount of 10% by mass or more.
Item 6. The decorative sheet according to any one of Items 1 to 5, wherein a plurality of the concavo-convex forming portions are formed, and at least some of the plurality of concavo-convex forming objects are formed independently of each other.
Item 7. The decorative sheet according to any one of Items 1 to 5, wherein a plurality of the concavo-convex forming portions are formed, and at least some of the plurality of concavo-convex forming objects are formed so as to be connected to each other.
Item 8. Item 8. The decorative sheet according to any one of Items 1 to 7, wherein the unevenness forming portion has a thickness of 1 μm to 200 μm.
Item 9. Item 9. The decorative sheet according to any one of Items 1 to 8, which includes at least a base material layer, the surface layer, and the unevenness forming portion in this order.
Item 10. Item 10. A step of vacuum forming the decorative sheet according to any one of Items 1 to 9 to obtain a formed sheet,
A resin in a fluid state is injected into the mold from the side opposite to the concavo-convex forming portion with respect to the molded sheet to solidify the resin, and the molded sheet is integrated with the outer surface of the resin molded article simultaneously with injection molding. The process of obtaining a resin molded product with a molding sheet,
From the surface of the resin molded article with the molding sheet, a step of removing the unevenness forming portion,
A method for producing a decorated resin molded product, comprising:

  By using the decorative sheet of the present invention in the production of a decorative resin molded product, it is possible to easily and easily give a design with a natural texture to the decorative resin molded product.

It is a schematic sectional drawing of an example of the decorative sheet of this invention. It is a schematic sectional drawing of an example of the decorative sheet of this invention. It is a schematic sectional drawing of an example of the decorative sheet of this invention. It is a schematic sectional drawing of an example of the decorative sheet of this invention. It is a schematic plan view of an example of the decorative sheet of this invention. It is a schematic plan view of an example of the decorative sheet of this invention. It is a schematic plan view of an example of the decorative sheet of this invention. It is a schematic sectional drawing of an example of the decorative resin molded product manufactured using the decorative sheet of the present invention. It is a schematic diagram for demonstrating the method of manufacturing a decorative resin molded product using the decorative sheet of this invention.

1. Decorative sheet The decorative sheet of the present invention comprises at least a surface layer and an unevenness forming portion formed on a part of the surface of the surface layer, and the unevenness forming portion is on the surface of the surface layer, And the unevenness forming portion is formed so as to be removable from the surface of the surface layer. In the decorative sheet of the present invention, by having such a configuration, in the production of a decorative resin molded product using the decorative sheet, the unevenness forming portion is pressed against the mold during injection molding. To be Then, the unevenness forming portion is buried in the surface layer side by heat and pressure applied at this time. Since the buried concave-convex forming portion is exposed to the outside even after the injection molding, it can be easily removed by using a chemical agent or an adhesive tape. The surface layer after the concavo-convex forming portion is removed has a concavo-convex shape due to the concavo-convex forming portion being buried. Since the concavo-convex shape is expressed by the surface layer, a decorative resin molded product using the decorative sheet of the present invention can be given a design with a natural feeling of concavity and convexity. 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 includes at least a surface layer and an unevenness forming portion formed on a part of the surface of the surface layer. For example, as shown in FIG. 1, the unevenness forming portion 2 is provided on a part 1 a of the surface of the surface layer 1. On the surface of the surface layer 1, a concavo-convex shape is formed by a portion 1 a provided with the concavo-convex forming portion 2 and a portion 1 b not provided with the concavo-convex forming portion 2.

  From the viewpoint of imparting rigidity to the decorative sheet of the present invention and enhancing shape stability, a base material layer 3 may be provided as necessary, as shown in FIG. Further, as shown in FIG. 3, a decorative layer 4 may be provided as necessary for the purpose of imparting decorativeness to a decorative resin product manufactured using the decorative sheet of the present invention. Good. Further, if the decoration layer 4 is provided between the base material layer 3 and the surface layer 1 for the purpose of suppressing color change or variation of the base material layer 3, the base material layer 3 and the decoration layer 4 are provided. If necessary, a hiding layer may be provided between the gap and the like (not shown). Further, as shown in FIG. 4, if the decorative layer 4 is provided between the base material layer 3 and the surface layer 1 for the purpose of enhancing the formability of the decorative sheet and the adhesiveness of each layer, If necessary, a primer layer 5 or the like may be provided between the decorative layer 4 and the surface layer 1. Further, an adhesive layer or the like may be provided below the base material layer 3 (not shown). The decorative sheet of the present invention may be laminated with one or more other layers depending on the function imparted to the decorative sheet or the decorative resin molded product.

  As the laminated structure of the decorative sheet of the present invention, a laminated structure in which a surface layer / unevenness forming portion is laminated in this order; a substrate layer / surface layer / unevenness forming portion is laminated in this order; substrate layer / decoration Layer structure in which layer / surface layer / unevenness forming portion is laminated in this order; Base material layer / decoration layer / primer layer / surface layer / unevenness forming portion are laminated in this order; Adhesive layer / Base material layer / decoration Layered structure in which layer / primer layer / surface layer / irregularity forming part is laminated in this order; adhesive layer / base material layer / hiding layer / decoration layer / primer layer / surface layer / irregularity forming part are laminated in this order And so on. FIG. 1 shows a schematic cross-sectional view of an example of a decorative sheet in which a surface layer / unevenness forming portion is laminated in this order as one aspect of the laminated structure of the decorative sheet of the present invention. FIG. 2 shows a schematic cross-sectional view of an example of a decorative sheet in which a base material layer / surface layer / unevenness forming portion is laminated in this order as one aspect of the laminated structure of the decorative sheet of the present invention. FIG. 3 shows a schematic cross-sectional view of an example of a decorative sheet in which a base material layer / decorative layer / surface layer / unevenness forming portion is laminated in this order as one aspect of the laminated structure of the decorative sheet of the present invention. FIG. 4 is a schematic cross-sectional view of an example of a decorative sheet in which a base material layer / decorative layer / primer layer / surface layer / irregularity forming part is laminated in this order as one embodiment of the laminated structure of the decorative sheet of the present invention. Indicates.

Composition of each layer forming the decorative sheet [Base material layer 3]
The base material layer 3 is formed of a resin sheet (resin film) which functions as a support in the decorative sheet of the present invention. The resin component used in the base material layer 3 is not particularly limited and may be appropriately selected depending on the three-dimensional moldability, compatibility with the injection resin layer, and the like, but a thermoplastic resin is preferable. Specific examples of the thermoplastic resin include acrylonitrile-butadiene-styrene resin (hereinafter sometimes referred to as "ABS resin"); acrylonitrile-styrene-acrylic acid ester resin; acrylic resin; polypropylene-based polyolefin such as polyethylene. Resins; polycarbonate resins; vinyl chloride resins; polyethylene terephthalate (PET) resins and the like. Among these, ABS resin is preferable from the viewpoint of three-dimensional moldability. As the resin component forming the base material layer 3, only one kind may be used, or two or more kinds may be mixed and used. Further, the base material layer 3 may be formed of a single-layer sheet of these resins, or may be formed of a multi-layer sheet of the same or different resins.

  The base material layer 3 may be subjected to a physical or chemical surface treatment such as an oxidation method or a roughening method on one side or both sides, if necessary, in order to improve the adhesiveness with an adjacent layer. . Examples of the oxidation method performed as the surface treatment of the base material layer 3 include a corona discharge treatment, a plasma treatment, a chromium oxidation treatment, a flame treatment, a hot air treatment, an ozone ultraviolet treatment method, and the like. Further, examples of the roughening method performed as the surface treatment of the base material layer 3 include a sandblast method and a solvent treatment method. These surface treatments are appropriately selected according to the type of resin component constituting the base material layer 3, but from the viewpoint of effects and operability, the corona discharge treatment method is preferable.

  In addition, the base material layer 3 may be colored with a coloring agent or the like, coated for adjusting the color, or formed with a pattern for imparting designability.

  The thickness of the base material layer 3 is not particularly limited and may be appropriately set depending on the application of the decorative sheet, but is usually about 50 to 800 μm, preferably about 100 to 600 μm, and more preferably about 200 to 500 μm. To be When the thickness of the base material layer 3 is within the above range, it is possible to provide the decorative sheet with more excellent three-dimensional moldability and designability.

[Surface layer 1]
The surface layer 1 is a layer provided to give an uneven shape to the surface of the decorative resin molded product by removing the unevenness forming portion 2 to be described later after being buried in the surface layer 1. In the present invention, the resin forming the surface layer 1 is not particularly limited as long as the unevenness forming portion 2 is buried during the injection molding and then the unevenness forming portion 2 can be removed from the surface. , A thermosetting resin, an ionizing radiation curable resin, etc., but the scratch resistance of the surface of the decorative resin molded product is enhanced, and the surface layer 1 is not scratched, discolored, or glossy when the irregularity forming portion 2 is removed. A cured product of a curable resin composition such as a thermosetting resin or an ionizing radiation curable resin is preferable from the viewpoint of suppressing changes.

  The thermosetting resin composition forming the surface layer 1 is preferably urethane resin. As the urethane resin, a two-component curable polyurethane having a polyol (polyhydric alcohol) as a main component and an isocyanate as a crosslinking agent (curing agent) is preferable. By using the two-component curing type polyurethane for the surface layer 1, the chemical resistance and the solvent resistance are enhanced, and it is possible to suppress the erosion of the surface layer 1 when the removal of the unevenness forming portion 2 is promoted by the chemical or the solvent. . The polyol has two or more hydroxyl groups in the molecule, and for example, polyester polyol, polyethylene glycol, polypropylene glycol, acrylic polyol, polyether polyol, etc. are used. Examples of the isocyanate include polyisocyanates having two or more isocyanate groups in a molecule, aromatic isocyanates such as 4,4-diphenylmethane diisocyanate, or hexamethylene diisocyanate, isophorone diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated diphenylmethane diisocyanate. Aliphatic (or alicyclic) isocyanates such as It is also possible to mix urethane resin and butyral resin.

  Specific examples of the thermoplastic resin forming the surface layer 1 include acrylic resins such as polymethyl (meth) acrylate and polyethyl (meth) acrylate; polyolefin resins such as polypropylene and polyethylene; polycarbonate resins; vinyl chloride resins; Examples thereof include polyethylene terephthalate (PET); acrylonitrile-butadiene-styrene resin (ABS resin); acrylonitrile-styrene-acrylic acid ester resin; The thermoplastic resins may be used alone or in combination of two or more.

(Ionizing radiation curable resin)
The ionizing radiation curable resin used for forming the surface layer 1 is a resin that is crosslinked and cured by irradiation with ionizing radiation, and specifically, has a polymerizable unsaturated bond or an epoxy group in its molecule. Examples thereof include a mixture of the prepolymer, oligomer, and / or monomer contained therein. Here, ionizing radiation means an electromagnetic wave or a charged particle beam having an energy quantum capable of polymerizing or cross-linking a molecule, and usually ultraviolet rays (UV) or electron beams (EB) are used. Electromagnetic waves such as rays and γ rays, and charged particle rays such as α rays and ion rays are also included. Among the ionizing radiation curable resins, the electron beam curable resin can be solvent-free, does not require a photopolymerization initiator, and can obtain stable curing characteristics, and thus is suitable for forming the surface layer 1. used.

  As the above-mentioned monomer used as the ionizing radiation-curable resin, a (meth) acrylate monomer having a radically polymerizable unsaturated group in the molecule is preferable, 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 (two or more functional), preferably three or more (three or more functional) in the molecule. As the polyfunctional (meth) acrylate, specifically, ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di ( (Meth) acrylate, neopentyl glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, hydroxypivalic acid neopentyl glycol di (meth) acrylate, dicyclopentanyl di (meth) acrylate, caprolactone-modified dicyclopentenyl di ( (Meth) acrylate, ethylene oxide-modified phosphoric acid di (meth) acrylate, allylated cyclohexyl di (meth) acrylate, isocyanurate di (meth) acrylate, 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 (Meth) acrylate, tris (acryloxyethyl) isocyanurate, propionic acid modified dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, ethylene oxide modified dipentaerythritol hexa (meth) acrylate, caprolactone modified dipentaerythritol Hexa (meth) acrylate and the like can be mentioned. These monomers may be used alone or in combination of two or more.

  Further, as the above-mentioned oligomer used as the ionizing radiation-curable resin, a (meth) acrylate oligomer having a radically polymerizable unsaturated group in the molecule is suitable, and among them, two or more polymerizable unsaturated bonds are included in the molecule. A polyfunctional (meth) acrylate oligomer having (bifunctional or more) is preferable. Examples of the polyfunctional (meth) acrylate oligomer include polycarbonate (meth) acrylate, acrylic silicone (meth) acrylate, urethane (meth) acrylate, epoxy (meth) acrylate, polyester (meth) acrylate, polyether (meth) acrylate. , Polybutadiene (meth) acrylate, silicone (meth) acrylate, oligomer having a cationically polymerizable functional group in the molecule (for example, novolac type epoxy resin, bisphenol type epoxy resin, aliphatic vinyl ether, aromatic vinyl ether, etc.) and the like. . 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, and for example, polycarbonate polyol (meth) It can be obtained by esterification with acrylic acid. The polycarbonate (meth) acrylate may be, for example, urethane (meth) acrylate having a polycarbonate skeleton. The urethane (meth) acrylate having a polycarbonate skeleton is 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 radically copolymerizing a silicone macromonomer with a (meth) acrylate monomer. The urethane (meth) acrylate can be obtained, for example, by esterifying a polyurethane oligomer obtained by reacting a polyether polyol or polyester polyol with a polyisocyanate with (meth) acrylic acid. Epoxy (meth) acrylate can be obtained by, for example, reacting (meth) acrylic acid with the oxirane ring of a bisphenol type epoxy resin or novolac type epoxy resin having a relatively low molecular weight to esterify. A carboxyl-modified epoxy (meth) acrylate obtained by partially modifying this epoxy (meth) acrylate with a dibasic carboxylic acid anhydride can also be used. Polyester (meth) acrylate is obtained by, for example, esterifying the hydroxyl groups of a polyester oligomer having hydroxyl groups at both ends obtained by condensation of a polyvalent carboxylic acid and a polyhydric alcohol with (meth) acrylic acid, or converting it to a polyvalent carboxylic acid. It can be obtained by esterifying the terminal hydroxyl group of the oligomer obtained by adding 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 a polybutadiene oligomer. The silicone (meth) acrylate can be obtained by adding (meth) (meth) acrylic acid to the terminal or side chain of silicone having a polysiloxane bond in the main chain. These oligomers may be used alone or in combination of two or more. In addition, in this specification, "(meth) acrylate" means "acrylate or methacrylate", and other similar ones have the same meaning.

  These ionizing radiation curable resins may be used alone or in combination of two or more.

  Among these ionizing radiation curable resins, polycarbonate (meth) acrylate is preferably used from the viewpoint of further improving moldability. Further, from the viewpoint of improving scratch resistance, chemical resistance, and other surface properties, it is more preferable to use urethane (meth) acrylate in addition to the above polycarbonate (meth) acrylate.

  Hereinafter, the polycarbonate (meth) acrylate and urethane (meth) acrylate that are preferably used as the ionizing radiation curable resin in the formation of the surface layer 1 will be described in detail.

<Polycarbonate (meth) acrylate>
Polycarbonate (meth) acrylate is not particularly limited as long as it has a carbonate bond in the polymer main chain and has (meth) acrylate in the terminal or side chain. In addition, the number of functional groups per molecule of the (meth) acrylate is preferably 2 to 6 from the viewpoint of improving crosslinking and curing. The polycarbonate (meth) acrylate is preferably a polyfunctional polycarbonate (meth) acrylate having two or more (meth) acrylates at the terminals or side chains. Polycarbonate (meth) acrylate may be used individually by 1 type, and may be used in combination of 2 or more type.

  Polycarbonate (meth) acrylate is obtained, for example, by converting a part or all of the hydroxyl groups of polycarbonate polyol into (meth) acrylate (acrylic acid ester or methacrylic acid ester). This esterification reaction can be performed by a usual 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 acid anhydride or a methacrylic acid anhydride in the presence of a catalyst, Alternatively, there may be mentioned 3) a method of condensing a polycarbonate polyol and acrylic acid or methacrylic acid in the presence of an acid catalyst. Further, the polycarbonate (meth) acrylate may be, for example, urethane (meth) acrylate having a polycarbonate skeleton. The urethane (meth) acrylate having a polycarbonate skeleton is obtained, for example, by reacting a polycarbonate polyol, a polyvalent isocyanate compound, and a hydroxy (meth) acrylate.

  The polycarbonate polyol is a polymer having a carbonate bond in the polymer main chain and having 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 is a method in which a polycondensation reaction is performed with a diol compound (A), a trihydric or higher polyhydric alcohol (B), and a compound (C) serving as a carbonyl component.

Diol compound used as a raw material of the polycarbonate polyol (A) 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, a cyclohexylene group, or a phenylene group.

  Specific examples of the diol compound include ethylene glycol, 1,2-propylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, polyethylene glycol, neopentyl glycol, 1,3-propanediol, 1,4-butanediol, 1 , 5-Pentanediol, 3-methyl-1,5pentanediol, 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 the trihydric or higher polyhydric alcohol (B) used as a raw material for the polycarbonate polyol include alcohols such as trimethylolpropane, trimethylolethane, pentaerythritol, ditrimethylolpropane, dipentaerythritol, glycerin and sorbitol. Is mentioned. Further, the trivalent or higher polyhydric alcohol 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), which serves as a carbonyl component used as a raw material for the polycarbonate polyol, is any compound selected from carbonic acid diesters, phosgene, and their equivalents. Specific examples of the compound include carbonic acid diesters such as dimethyl carbonate, diethyl carbonate, diisopropyl carbonate, diphenyl carbonate, ethylene carbonate and propylene carbonate; phosgene; halogenated formic acid such as methyl chloroformate, ethyl chloroformate and phenyl chloroformate. Esters and the like can be mentioned. These compounds may be used alone or in combination of two or more.

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

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

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

  The molecular weight of the polycarbonate (meth) acrylate is not particularly limited, but examples thereof include a weight average molecular weight of 5,000 or more, preferably 10,000 or more. The upper limit of the weight average molecular weight of the polycarbonate (meth) acrylate is not particularly limited, but from the viewpoint of controlling so that the viscosity does not become too high, for example, 100,000 or less, preferably 50,000 or less. The weight average molecular weight of the polycarbonate (meth) acrylate is preferably 10,000 to 50,000, more preferably 10,000 to 20,000 from the viewpoint of further improving the effect of expressing a rich, low-gloss texture and the moldability. There are millions.

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

  When polycarbonate (meth) acrylate is used, the content of the polycarbonate (meth) acrylate in the ionizing radiation-curable resin composition used for forming the surface layer 1 is not particularly limited as long as the effect of the present invention is exhibited. However, from the viewpoint of further enhancing the moldability of the decorative sheet, it is preferably 50% by mass or more, more preferably 80% by mass or more, and further preferably 85% by mass or more.

<Urethane (meth) acrylate>
The urethane (meth) acrylate is not particularly limited as long as it has a urethane bond in the polymer main chain and a (meth) acrylate in the terminal or side chain. Such urethane (meth) acrylate can be obtained, for example, by esterifying a polyurethane oligomer obtained by the reaction of polyether polyol or polyester polyol and polyisocyanate with (meth) acrylic acid. In addition, the urethane (meth) acrylate preferably has 2 to 12 functional groups per molecule from the viewpoint of improving cross-linking and curing. The urethane (meth) acrylate is preferably a polyfunctional urethane (meth) acrylate having two or more (meth) acrylates at the terminal or side chain. The ionizing radiation curable resin composition used for forming the surface layer 1 may further contain urethane (meth) acrylate in addition to the above-mentioned polycarbonate (meth) acrylate. Urethane (meth) acrylate may be used individually by 1 type, and may be used in combination of 2 or more type.

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

  The weight average molecular weight of urethane (meth) acrylate in the present specification is a value measured by gel permeation chromatography using polystyrene as a standard substance.

  When a polycarbonate (meth) acrylate and a urethane (meth) acrylate are used in combination in the ionizing radiation curable resin composition used for forming the surface layer 1, the mass ratio of these (polycarbonate (meth) acrylate: urethane (meth)) is used. The acrylate) is preferably about 50:50 to 99: 1, more preferably about 80:20 to 99: 1, and further preferably about 85:15 to 99: 1.

  In the decorative sheet of the present invention, the silicone component is contained in the ionizing radiation curable resin composition forming the surface layer 1 from the viewpoint of suitably removing the unevenness forming portion 2 described below from the surface layer 1. It is preferable. The content of the silicone component is not particularly limited, but the resin composition can be easily decorated with a natural design by peeling and removing the unevenness forming portion 2 from the surface layer 1 using a tacky adhesive tape or the like. From the viewpoint of imparting to the above, it is preferably 10 mass% or more, more preferably about 10 to 20 mass%. The silicone component in the ionizing radiation-curable resin composition refers to a component having in its molecule a structure formed by alternately bonding silicon having an organic group and oxygen, specifically, a polysiloxane skeleton. Reactive silicone in which a reactive organic group such as amino group, vinyl group, epoxy group, carboxyl group, acryl group, methacryl group is introduced into the side chain or terminal of silicone oil as the main component, or side chain or terminal Examples include non-reactive silicones containing non-reactive organic groups such as alkyl groups, ether groups, higher fatty acids, and silicone-modified resins such as organic resins and ionizing radiation-curable resins whose side chains or terminals are modified with silicone. Can be mentioned.

  In addition to the above-mentioned ionizing radiation curable resin, various additives can be blended in the surface layer 1 depending on desired physical properties to be provided in the surface layer 1. Examples of the additives include weather resistance improvers such as ultraviolet absorbers and light stabilizers, abrasion resistance improvers, polymerization inhibitors, crosslinking agents, infrared absorbers, antistatic agents, adhesion improvers, leveling agents, Examples include thixotropic agents, coupling agents, plasticizers, defoamers, fillers, solvents, colorants and the like. These additives can be appropriately selected and used from commonly used additives. Further, as the ultraviolet absorber or the 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.

  The thickness of the surface layer 1 after curing is not particularly limited, but is preferably 1000 μm or less, more preferably about 1 to 50 μm, further preferably about 1 to 10 μm. When the thickness in such a range is satisfied, the decorative sheet is excellent in moldability and has sufficient physical properties as a surface layer such as scratch resistance. Further, since the ionizing radiation-curable resin composition forming the surface layer 1 can be uniformly irradiated with ionizing radiation, it can be uniformly cured, which is economically advantageous.

  The surface layer 1 is formed, for example, by preparing the above-mentioned ionizing radiation curable resin composition, applying it, and crosslinking-curing it. The ionizing radiation curable resin composition may have any viscosity as long as it can form an uncured resin layer on the layer adjacent to the surface layer 1 by a coating method described later. In the present invention, the prepared coating liquid, on the layer adjacent to the surface layer 1 so as to have the above-mentioned thickness, a known method such as gravure coating, bar coating, roll coating, reverse roll coating, or comma coating, Preferably, it is applied by gravure coating to form an uncured resin layer. The surface layer 1 is formed by irradiating the uncured resin layer thus formed with ionizing radiation such as electron beams and ultraviolet rays to cure the uncured resin layer. 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 usually the accelerating voltage is about 70 to 300 kV.

  In the electron beam irradiation, the higher the accelerating voltage is, the higher the transmission capability is. Therefore, when a resin that is easily deteriorated by the electron beam irradiation is used below the surface layer 1, the electron beam transmission depth and the surface layer 1 The accelerating voltage is selected so that the thicknesses of the two are substantially equal. Thereby, the irradiation of the extra electron beam to the layer located under the surface layer 1 can be suppressed, and the deterioration of each layer due to the excess electron beam can be minimized. The irradiation dose is preferably such that the crosslink 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, and for example, various electron beam accelerators such as Cockloft-Walton type, Van de Graft type, resonance transformer type, insulating core transformer type, linear type, dynamitron type, high frequency type, etc. Can be used. When ultraviolet rays are used as the ionizing radiation, light rays containing ultraviolet rays having a wavelength of 190 to 380 nm may be emitted. The ultraviolet source is not particularly limited, but examples thereof include a high pressure mercury lamp, a low pressure mercury lamp, a metal halide lamp, and a carbon arc lamp.

[Roughness forming part 2]
In the decorative sheet of the present invention, a plurality of unevenness forming portions 2 are formed on a part of the surface of the surface layer 1. The unevenness forming portion 2 is exposed to the outside on the surface of the surface layer 1. The unevenness forming portion 2 is formed so as to be removable from the surface of the surface layer 1. As described above, in the production of the decorative resin molded product using the decorative sheet of the present invention, the unevenness forming portion is pressed against the mold during injection molding. Then, the unevenness forming portion is buried in the surface layer side by heat and pressure applied at this time. Since the buried concave-convex portion is exposed to the outside even after injection molding, it can be easily removed by using a chemical such as an organic solvent or an adhesive tape. On the surface layer 1 after the concavo-convex forming portion is removed, a concavo-convex shape due to the concavo-convex forming portion being buried is formed. Therefore, by producing a decorative resin molded product using the decorative sheet of the present invention, it is possible to easily and easily give a design of natural unevenness to the surface of the decorative resin molded product.

  The resin forming the concavo-convex forming portion 2 is not particularly limited as long as the concavo-convex forming portion 2 is buried during injection molding and then the concavo-convex forming portion 2 can be removed from the surface, but a simple and natural design is possible. From the viewpoint of imparting to the decorative resin molded product, a thermoplastic resin, a thermosetting resin, a cured product of an ionizing radiation curable resin composition, and the like can be mentioned. Among these, a cured product of an ionizing radiation curable resin is preferable because it is easily removed from the surface of the surface layer 1, but the resin forming the surface layer 1 may be appropriately selected according to the application of the decorative sheet. it can. Examples of the thermoplastic resin, the thermosetting resin, and the ionizing radiation curable resin that form the unevenness forming portion 2 can be the same as those exemplified for the surface layer 1 described above.

  In the decorative sheet of the present invention, from the viewpoint of suitably removing the unevenness forming portion 2 described below from the surface layer 1, the ionizing radiation curable resin composition forming the unevenness forming portion 2 contains a silicone component. Is preferred. The content of the silicone component is not particularly limited, but the unevenness forming portion 2 is preferably peeled and removed from the surface layer 1 using a chemical such as an organic solvent to easily and naturally give a decorative design to a resin molded product. From the viewpoint of imparting to the above, it is preferably 10 mass% or more, more preferably about 10 to 20 mass%. The silicone component in the ionizing radiation-curable resin composition is as described in the surface layer 1 above.

One area of the unevenness forming portion 2 is not particularly limited, and is appropriately set according to a design to be given to the decorative resin molded product formed after the unevenness forming portion 2 is removed, for example, 50 mm ² Hereinafter, 10 mm ² or less, 5 mm ² or less, 2 mm ² or less and the like can be mentioned. The lower limit of the area is not particularly limited, but is preferably 0.01 mm ² or more from the viewpoint of being visually recognized as an uneven pattern after the uneven formation portion 2 is removed. The areas of the unevenness forming portion 2 may be the same or different from each other. In addition, in this specification, the area of the concave-convex forming portion 2 or the like means an area of the decorative sheet as viewed in the stacking direction, and more specifically, a value measured by a measuring method described later.

  The thickness (height) of the unevenness forming portion 2 is not particularly limited as long as the unevenness-shaped design is formed on the surface of the surface layer 1 after the unevenness forming portion 2 is buried in the surface layer 1 and removed. Although not provided, the thickness is preferably about 1 μm to 200 μm, preferably about 5 μm to 100 μm, and more preferably about 10 μm to 80 μm, from the viewpoint of easily giving a decorative resin molded product a design with a natural unevenness.

  The shape of the concavo-convex forming portion 2 is not particularly limited, and a shape such as a circle, an ellipse, a triangle, a quadrangle, a pentagon, a pentagon, a star, a line, a geometric pattern, and a letter is preferable. Further, the shapes of the unevenness forming portions 2 may be the same as or different from each other. The design represented by each concavo-convex forming portion 2 may be a regular pattern shape in which the concavo-convex forming portions 2 are regularly arranged, or an irregular pattern. An atypical pattern is preferable because it is excellent in touch, matte, gloss and design, and a regular pattern that is regularly arranged causes stress during decoration molding to concentrate on a specific portion. It is preferable because it is difficult to cause cracks in the uneven pattern on the surface to occur.

  A plurality of unevenness forming portions 2 may be formed. At least a part of the plurality of unevenness forming portions 2 may be formed independently of each other. For example, FIG. 5 is a schematic plan view of a decorative sheet in the case where all the unevenness forming portions 2 are independent. FIG. 6 is a schematic plan view of the decorative sheet in the case where some of the unevenness forming portions 2 are independent. At least some of the plurality of unevenness forming portions 2 may be formed so as to be connected to each other. For example, FIG. 6 is also a schematic plan view of the decorative sheet when some of the unevenness forming portions 2 are connected. FIG. 7 is a schematic plan view of the decorative sheet when all the concavo-convex forming parts 2 are connected, and the concavo-convex forming parts 2 are connected to form one concavo-convex forming part 2. In the portion where the concavo-convex forming portions 2 are connected to each other, the decorative sheet can be easily peeled from the surface of the surface layer 1 with an adhesive tape or the like after being subjected to injection molding. Further, even when the area of one concavo-convex forming portion 2 is large, it is possible to easily peel off from the surface of the surface layer 1 with the adhesive tape or the like. In addition, in this invention, "adhesive" means "adhesion or adhesion."

  The pattern formed by the concavo-convex forming unit 2 as a whole is not particularly limited, and examples thereof include geometric patterns such as circles, ellipses, polygons, line drawings, polka dots, stripes, and lattices, letters, woodgrain patterns, bamboo grain patterns, Preferable examples are a stone pattern, a tile pasting pattern, a brick laminated pattern, a cloth pattern, and a leather pattern, and these may be used alone or in combination of two or more depending on the purpose.

  The concavo-convex forming portion 2 is formed by, for example, printing the above ionizing radiation curable resin composition by silk screen printing, gravure overlay printing, rotary screen printing, or a molding plate cylinder method described in JP-A-2002-240078. Alternatively, it can be formed by coating a part of the surface of the surface layer 1 by a known method such as a coating method, forming an uncured resin layer, and then crosslinking and curing by irradiating with ionizing radiation.

  For example, when both the surface layer 1 and the unevenness forming portion 2 are formed of a cured product of an ionizing radiation curable resin composition, when forming the surface layer 1 and the unevenness forming portion 2, the ionizing radiation curing forming the surface layer 1 is performed. -Curing resin composition is uncured or semi-cured, the ionizing radiation-curable resin composition for forming the unevenness forming portion 2 is partially laminated on the ionizing radiation-curable resin composition, and then the surface layer 1 By irradiating the ionizing radiation under the condition that the ionizing radiation curable resin composition of both layers of the unevenness forming portion 2 can be cross-linked and cured, both layers can be formed by a single ionizing radiation irradiation step. Further, the ionizing radiation may be radiated twice at the time of forming the surface layer 1 and at the time of forming the unevenness forming portion 2. When the irradiation of the ionizing radiation is separately performed twice when the surface layer 1 and the unevenness forming portion 2 are formed, the type of the ionizing radiation used in each step may be the same or different. More specifically, a case where both the surface layer 1 and the unevenness forming portion 2 are cured by irradiation with an electron beam, a case where the surface layer 1 is cured by an electron beam, and the unevenness forming portion 2 is irradiated by ultraviolet rays are exemplified. It

[Decorative layer 4]
The decorative layer 4 is a layer that imparts decorative properties to the decorative resin molded product, and is provided between the base material layer 3 and the surface layer 1 as necessary. The decorative layer 4 may form a pattern, may be solid, or may be a combination thereof. The decorative layer 4 is formed by printing various patterns using ink and a printing machine, for example. The pattern formed by the decorative layer 4 is not particularly limited, and is, for example, a wood grain pattern, a marble pattern (for example, a travertine marble pattern), a stone pattern that imitates the surface of rock, or a cloth that imitates a texture or cloth-like pattern. Patterns, tile pasting patterns, brickwork patterns, and the like, and patterns such as parquet and patchwork that combine these are also included. These patterns are formed by multicolor printing using ordinary process colors of yellow, red, blue, and black, and also by multicolor printing using special colors prepared by preparing individual color plates that make up the pattern. It is formed.

  As the ink used for the decoration layer 4, a mixture of a binder with a colorant such as a pigment or a dye, an extender pigment, a solvent, a stabilizer, a plasticizer, a catalyst, a curing agent, etc. is used. The binder is not particularly limited and includes, for example, polyurethane resin, vinyl chloride-vinyl acetate copolymer resin, vinyl chloride-vinyl acetate-acrylic copolymer resin, chlorinated polypropylene resin, acrylic resin, 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, and examples thereof include inorganic pigments such as carbon black (black ink), iron black, titanium white, antimony white, yellow lead, titanium yellow, rouge, cadmium red, ultramarine blue, cobalt blue, and quinacridone red. , Isoindolinone yellow, phthalocyanine blue and other organic pigments or dyes, aluminum, brass and other scale-like foil piece metal pigments, titanium dioxide coated mica, and basic lead carbonate and other scale-like foil piece pearlescent luster (pearl ) Examples include pigments.

  The thickness of the decorative layer 4 is not particularly limited, but is, for example, about 1 to 30 μm, preferably about 1 to 20 μm.

  The decoration layer 4 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 an alloy containing at least one of these. The method for forming the metal thin film layer is not particularly limited, and examples thereof include a vapor deposition method such as a vacuum vapor deposition method using the above metal, a sputtering method, an ion plating method, and the like. Further, in order to improve the adhesiveness with the adjacent layer, a primer layer using a known resin may be provided on the front surface or the back surface of the metal thin film layer.

[Hiding layer]
The concealing layer is provided between the base material layer 3 and the surface layer 1 between the base material layer 3 and the surface layer 1 in the case of providing the base material layer 3 and the decoration layer 4 for the purpose of suppressing the color change and the variation of the base material layer 3. It is a layer provided as needed between the layers (not shown).

  Since the concealing layer is provided in order to prevent the base material layer 3 from adversely affecting the color tone and the pattern of the decorative sheet, it is generally formed as an opaque layer.

  The hiding layer is formed by using an ink composition in which a binder is appropriately mixed with a colorant such as a pigment and a dye, an extender pigment, a solvent, a stabilizer, a plasticizer, a catalyst, and a curing agent. The ink composition for forming the concealing layer is appropriately selected and used from those used for the decorative layer 4 described above.

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

[Primer layer 5]
In the decorative sheet of the present invention, a decorative layer 4 is optionally provided between the base material layer 3 and the surface layer 1 for the purpose of making it difficult to cause fine cracks or whitening in the stretched portion of the surface layer 1. In some cases, the primer layer 5 may be provided between the decoration layer 4 and the surface layer 1.

  As the primer composition constituting the primer layer 5, urethane resin, (meth) acrylic resin, (meth) acrylic-urethane copolymer resin, vinyl chloride-vinyl acetate copolymer, polyester resin, butyral resin, chlorinated polypropylene Those using chlorinated polyethylene or the like as a binder resin are preferably used, and these resins may be used alone or in combination of two or more. Among these, urethane resin, (meth) acrylic resin, and (meth) acrylic-urethane copolymer resin are preferable.

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

  From the aspects of adhesion with the surface layer after cross-linking, difficulty of interaction after laminating the surface layer 1, physical properties, and moldability, acrylic polyol or polyester polyol as the polyol and hexamethylene diisocyanate as the cross-linking agent, 4 , 4-diphenylmethane diisocyanate is preferably used in combination, and it is particularly preferable to use an acrylic polyol and hexamethylene diisocyanate in combination.

  The (meth) acrylic resin may be a homopolymer of (meth) acrylic acid ester, a copolymer of two or more different (meth) acrylic acid ester monomers, or a copolymer of (meth) acrylic acid ester and another monomer. Examples thereof include polymers such as 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- (meth) acrylic acid methyl copolymer, styrene- (meth) acrylic acid methyl copolymer A (meth) acrylic resin composed of a homopolymer or a copolymer containing a (meth) acrylic acid ester such as

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

  The primer layer 5 uses a primer composition and is gravure coat, gravure reverse coat, gravure offset coat, spinner coat, roll coat, reverse roll coat, kiss coat, wheeler coat, dip coat, solid coat by silk screen, wire bar coat, It is formed by a usual coating method such as a flow coating, a comma coating, a pouring coating, a brush coating, a spray coating or a transfer coating method. Here, the transfer coating method is a method in which a coating film for a primer layer or an adhesive layer is formed on a thin sheet (film base material), and then the target layer surface in the decorative sheet is coated.

The thickness of the primer layer 5 is not particularly limited, but preferably 0.1 μm or more. When it is 0.1 μm or more, it has an effect of preventing the surface layer 1 from cracking, breaking, whitening and the like. On the other hand, when the thickness of the primer layer 5 is 10 μm or less, the three-dimensional moldability does not change because the dried and cured coating film is stable when the primer layer 5 is applied, which is preferable.
[Adhesive layer]
The adhesive layer is a layer (not shown) provided on the back surface of the base material layer 3 as needed for the purpose of improving the adhesiveness or adhesion between the decorative sheet and the molding resin. The resin forming the adhesive layer is not particularly limited as long as it can improve the adhesiveness and adhesion between the decorative sheet and the molding resin, and for example, a thermoplastic resin or a thermosetting resin is used. To be Examples of the thermoplastic resin include acrylic resin, acryl-modified polyolefin resin, chlorinated polyolefin resin, vinyl chloride-vinyl acetate copolymer, thermoplastic urethane resin, thermoplastic polyester resin, polyamide resin, and rubber resin. . The thermoplastic resins may be used alone or in combination of two or more. Further, examples of the thermosetting resin include urethane resin and epoxy resin. The thermosetting resin may be used alone or in combination of two or more.

  Although the adhesive layer is not always a necessary layer, when it is assumed that the decorative sheet of the present invention is applied to a decorative method by sticking on a resin molded body prepared in advance, such as a vacuum pressure bonding method described below. , Are preferably provided. When used in the vacuum pressure bonding method, it is preferable to form the adhesive layer by using, among the above-mentioned various resins, a resin that is commonly used as a resin that exhibits adhesiveness when pressed or heated.

By using the decorative sheet of the present invention in the production of a decorative resin molded product, it is possible to easily and easily give a design with a natural texture to the decorative resin molded product. Therefore, for example, interior materials or exterior materials of vehicles such as automobiles; fittings such as window frames and door frames; interior materials of buildings such as walls, floors, and ceilings; housings for home electric appliances such as television sets and air conditioners. Body: It can be suitably used as a decorative sheet used for applications such as containers.

2. Method for Manufacturing Decorative Resin Molded Product In the present invention, a decorative resin molded product can be suitably manufactured using the decorative sheet of the present invention described above. Specifically, the decorative resin molded product is obtained by removing the unevenness forming portion 2 from the surface of the resin molded product with a molded sheet obtained by integrating the injection resin 6 (molding resin) with the decorative sheet of the present invention. Is what you get. That is, as shown in FIG. 8, the decorative resin molded product includes at least a molding resin layer 6 formed by injection of a resin and a surface layer 1, and, if necessary, the above-mentioned base material layer 3 The decorative layer 4, the primer layer 5, the hiding layer, the adhesive layer and the like are laminated.

  The method of removing the unevenness forming portion 2 from the surface of the surface layer 1 of the resin molded product with a molding sheet is not particularly limited, and for example, a tacky adhesive tape or the like is attached to the unevenness forming portion 2 to form the unevenness forming portion 2 A method of peeling the resin from the surface of the surface layer 2 or a method of applying a chemical such as an organic solvent (eg ethanol) to the surface of the resin molded product with a molding sheet to reduce the adhesiveness of the unevenness forming portion 2 and remove it. Is mentioned.

  In the decorative resin molded product manufactured using the decorative sheet of the present invention, the depth of the concave and convex portions formed by removing the concave-convex forming portion 2 is not particularly limited, but a design with a natural uneven feeling is provided. From the viewpoint of performance, the thickness is preferably about 1 μm to 200 μm, preferably about 5 μm to 100 μm, and more preferably about 10 μm to 100 μm.

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

  For example, as shown in the schematic view of FIG. 9, the decorative sheet of the present invention is inserted into the injection mold 10 (FIG. 9 (a)). Next, a resin in a fluid state is injected into the mold from the side opposite to the concavo-convex forming portion 2 of the decorative sheet and solidified to integrate the decorative sheet and the injected resin (Fig. 9 (b)). . Next, the obtained resin molded product with a molded sheet is taken out from the injection resin mold (FIG. 9C), and the unevenness forming portion 2 is removed from the surface of the resin molded product with a molded sheet (FIG. 9D). Through the above steps, a decorative resin molded product can be manufactured using the decorative sheet of the present invention. Although not shown, the decorative resin molded product manufactured using the decorative sheet of the present invention In the product, one surface of the surface layer 1 as shown in FIG. 9D (the unevenness forming portion 2 was laminated due to heat and pressure when the unevenness forming portion 2 was buried in the surface layer 1). Side surface) as well as the other surface of the surface layer 1 (a laminated surface with a layer such as the base material layer 3), or a case where the decorative sheet and the molding resin layer 6 are laminated. There may be a case where unevenness is formed on the surface as well.

For example, the decorative resin molded product of the present invention can be manufactured by a method including the following steps.
Step of obtaining a molded sheet by vacuum-molding the decorative sheet of the present invention With respect to the molded sheet, a resin in a fluid state is injected into a mold from a side opposite to the concave-convex forming portion, solidified, and injected. A step of integrating the molded sheet with the outer surface of the resin molded article at the same time as molding to obtain a resin molded article with a molded sheet A step of removing the unevenness forming portion from the surface of the resin molded article with a molded sheet.
Further, various specific manufacturing methods will be described in detail below.

  In the insert molding method, first, in a vacuum forming step, the decorative sheet of the present invention is vacuum formed (offline preforming) into a surface shape of a formed product in advance by a vacuum forming die, and then an extra portion is trimmed as necessary. Obtain a formed sheet. This molding sheet is inserted into an injection molding die, the injection molding die is clamped, and a resin in a fluid state is injected into the mold from the side opposite to the concavo-convex forming portion 2 to solidify the resin molding product at the same time as the injection molding. The decorative resin molded product is manufactured by integrating the decorative sheet on the outer surface of the product and removing the unevenness forming portion 2 from the surface of the obtained resin molded product with a molded sheet.

More specifically, the decorated 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 obtain a formed sheet by trimming the excess part of the vacuum formed decorative sheet.
A molding sheet is inserted into an injection molding die, the injection molding die is clamped, and a resin in a fluid state is injected into the mold from the side opposite to the concavo-convex forming portion 2 to be solidified. A step of integrating the molded sheet with the outer surface of the resin to obtain a resin molded article with a molded sheet, and
The process of removing the irregularity forming part from the surface of the resin molded product with the molding sheet.

  In the vacuum forming step in the insert forming 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 forming 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 3. If so, the temperature can be usually set to about 120 to 200 ° C. Further, in the integration step, the temperature of the resin in a fluid state is not particularly limited, but can be usually about 180 to 320 ° C.

  In the injection molding simultaneous decoration method, the decorative sheet of the present invention is arranged in a female mold that is also used as a vacuum forming mold having a suction hole for injection molding, and preforming (in-line preforming) is performed with this female mold. After that, the injection molding die is clamped, and a resin in a fluid state is injected and filled into the mold from the side opposite to the concavo-convex forming portion 2 and solidified, and the resin is molded on the outer surface of the resin molding simultaneously with the injection molding. The decorative resin molded product is manufactured by integrating the decorative sheet of the present invention and removing the unevenness forming portion 2 from the surface of the obtained resin molded product with a molded sheet.

More specifically, the decorative resin molded product of the present invention is manufactured by an injection-molding simultaneous decoration method including the following steps.
The decorative sheet of the present invention, with respect to the molding surface of the movable mold having a molding surface of a predetermined shape, after the surface of the base material layer of the decorative sheet is installed so as to face, heating the decorative sheet, Along with softening, vacuum suction from the movable mold side, by adhering the softened decorative sheet along the molding surface of the movable mold, a preforming step of preforming the decorative sheet,
After clamping the movable mold and the fixed mold having the decorative sheet adhered along the molding surface, the resin in the fluid state is injected and filled into the cavity formed by both molds to solidify. An integrated step of forming a resin molded product with a molding sheet by laminating and integrating the resin molded body and the decorative sheet to obtain a resin molded product with a molding sheet,
A step of separating the movable mold from the fixed mold and taking out the resin molded product with the molding sheet, and a process of removing the unevenness forming portion from the surface of the resin molded product with the molding sheet.

In the preforming step of the injection molding simultaneous decorating method, the heating temperature of the decorating sheet is not particularly limited, and may be appropriately selected depending on the type of resin constituting the decorating sheet, the thickness of the decorating sheet, and the like. When 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. In addition, in the injection molding process, the temperature of the resin in a fluid state is not particularly limited, but can be usually about 180 to 320 ° C.

  In the decorated resin molded product of the present invention, the molded resin layer may be formed by selecting a resin according to the application. The molding resin forming the molding 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, vinyl chloride resins and the like. These thermoplastic resins may be used alone or in combination of two or more.

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

  Since the decorative resin molded product of the present invention has a design of natural unevenness, for example, interior materials or exterior materials of vehicles such as automobiles; fittings such as window frames and door frames; constructions such as walls, floors and ceilings. It can be used as an interior material for things; a housing for home electric appliances such as a television receiver and an air conditioner; and a container.

  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 and 2 and Comparative Example 1>
(Preparation of a decorative sheet before forming the unevenness forming portion)
A decorative layer (thickness 5 μm) was formed by gravure printing on an ABS resin film (thickness: 400 μm) as a substrate, using an ink containing a vinyl chloride-vinyl acetate-acrylic copolymer resin. Next, a primer layer (thickness: 3 μm) was provided on the decorative layer by gravure printing using the primer composition. The primer composition is a composition containing 89.9 parts by weight of an acrylic polyol resin (weight average molecular weight 8000), 10.1 parts by weight of a polyurethane resin (weight average molecular weight 6000), and 7 parts by weight of hexamethylene diisocyanate. Next, the ionizing radiation-curable resin A or the ionizing radiation-curable resin B in Table 1 is applied by bar coating so that the cured resin composition has a thickness of 10 μm. Was formed on the surface layer. Next, the uncured surface layer is irradiated with an electron beam having an acceleration voltage of 165 kV and an irradiation dose of 50 kGy (5 Mrad) to cure the electron beam curable resin, and the base material layer / decorative layer / primer layer / surface A decorative sheet in which the layers were laminated in this order and before forming the unevenness forming portion was obtained. Next, dots having a diameter of 2 mm (area about 3 mm ² ) were printed on the surface layer by using the ultraviolet curable resin a or the ultraviolet curable resin b shown in Table 1 by screen printing so that the coating thickness was 30 μm. A plurality of uncured unevenness forming portions were prepared. Next, the uncured unevenness forming portion is irradiated with ultraviolet rays having an integrated light amount of 600 mJ / cm ² to cure the ultraviolet curable resin a or the ultraviolet curable resin b, and the base material layer / decorative layer / primer layer A decorative sheet was obtained by laminating the / surface layer / unevenness forming portion in this order.

<Example 3 and Comparative Example 2>
A decorative layer was provided on the ABS resin film in the same manner as in Example 1. Next, a surface layer (thickness 4 μm) was provided on the decorative layer by gravure printing using the curable resin I shown in Table 1. Next, using the ultraviolet curable resin a or the ultraviolet curable resin b, a concavo-convex forming portion was prepared in the same manner as in Example 2, and the base material layer / decorative layer / surface layer / concavo-convex forming portion was laminated in this order. , A decorative sheet was obtained.

(Manufacture of decorative resin molded products using decorative sheets)
Each of the decorative sheets obtained above is heated to 180 ° C., and vacuum forming (preforming) is performed using a vacuum forming die having a portion having a draw ratio of 100 to 300% to obtain a formed sheet. It was Next, by inserting the obtained molded sheet into an injection molding die, clamping the injection molding die, injecting the ABS resin in a fluid state into the mold from the ABS resin film side, and cooling and solidifying as it is, A resin molded product with a molded sheet was obtained. The temperature of the injection resin during injection molding was 260 ° C.
Next, the irregularity forming portion was removed from the surface of each resin molded product with a molding sheet by the method described in Table 1 to obtain a decorative resin molded product.

(Evaluation of releasability of unevenness forming part)
The releasability of the concavo-convex forming portion from the surface of each resin molded product with a molding sheet during the production of the decorated resin molded product was evaluated by whether or not the concavo-convex forming portion could be separated. The results are shown in Table 1.

(Evaluation of design)
The design of the obtained decorative resin molded product was evaluated. In the decorative resin molded products of Examples 1 to 3, the regions having the concave-convex forming portion became concave portions, so that the surface has a concave-convex shape and a design having a visual and tactile sense of unevenness. Was formed (good design). On the other hand, in Comparative Examples 1 and 2, the concavo-convex portion was not removed and remained on the surface of the decorative resin molded product, and the intended design could not be obtained (design failure).

The composition of the resin in Table 1 is as follows.
(Ionizing radiation curable resin A)
Bifunctional polycarbonate acrylate (weight average molecular weight: 10,000) 58 mass%
Bifunctional polycarbonate acrylate (weight average molecular weight: 20,000) 29 mass%
Bifunctional silicone modified urethane acrylate (weight average molecular weight: 1,000) 3% by mass
Silicone oil 10% by mass

(Ionizing radiation curable resin B)
Bifunctional polycarbonate acrylate (weight average molecular weight: 10,000) 67% by mass
Bifunctional polycarbonate acrylate (weight average molecular weight: 20,000) 33 mass%

(Curable resin I)
Acrylic polyol 90 mass%
Isocyanate 10% by mass

(UV curable resin a)
Urethane acrylate oligomer (weight average molecular weight about 2000) 20% by mass
Bifunctional acrylate monomer 60% by mass
Photosensitive compound 5% by mass
Photopolymerization initiator 5% by mass
Filler and pigment 10% by mass

(UV curable resin b)
Urethane acrylate oligomer (weight average molecular weight about 2000) 18% by mass
55% by weight of bifunctional acrylate monomer
Photosensitive compound 4% by mass
Photopolymerization initiator 4% by mass
Filler and pigment 9% by mass
Silicone oil 10% by mass

DESCRIPTION OF SYMBOLS 1 ... Surface layer 2 ... Concavo-convex formation part 3 ... Base material layer 4 ... Decorative layer 5 ... Primer layer 6 ... Molding resin layer

Claims (10)

At least, a surface layer, and comprises an unevenness forming portion formed on a part of the surface of the surface layer,
The surface layer is formed of resin,
The unevenness forming portion is exposed to the outside on the surface of the surface layer,
The said uneven | corrugated formation part is a decorating sheet formed so that it can be removed from the surface of the said surface layer.   The decorative sheet according to claim 1, wherein the surface layer is formed of a cured product of a curable resin composition.   The decorative sheet according to claim 2, wherein the curable resin composition forming the surface layer contains a silicone component in an amount of 10% by mass or more.   The decorative sheet according to any one of claims 1 to 3, wherein the unevenness forming portion is formed of a cured product of an ionizing radiation curable resin composition.   The decorative sheet according to claim 4, wherein the ionizing radiation curable resin composition forming the unevenness forming portion contains a silicone component in an amount of 10% by mass or more.   The decorative sheet according to any one of claims 1 to 5, wherein a plurality of the concavo-convex forming portions are formed, and at least some of the plurality of concavo-convex forming objects are formed independently of each other.   The decorative sheet according to any one of claims 1 to 5, wherein a plurality of the concavo-convex forming portions are formed, and at least some of the plurality of concavo-convex forming objects are formed so as to be connected to each other.   The decorative sheet according to claim 1, wherein the unevenness forming portion has a thickness of 1 μm to 200 μm.   The decorative sheet according to any one of claims 1 to 8, which comprises at least a base material layer, the surface layer, and the unevenness forming portion in this order. Vacuum-molding the decorative sheet according to any one of claims 1 to 9 to obtain a molded sheet;
A resin in a fluid state is injected into the mold from the side opposite to the concavo-convex forming portion with respect to the molded sheet to solidify the resin, and the molded sheet is integrated with the outer surface of the resin molded article simultaneously with injection molding. The process of obtaining a resin molded product with a molding sheet,
From the surface of the resin molded article with the molding sheet, a step of removing the unevenness forming portion,
A method for producing a decorated resin molded product, comprising: