JP2017177729A - Decorative sheet and manufacturing method of decorative resin molding - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a decorative sheet capable of easily imparting ornamental design with natural uneven feeling to a decorative resin molding.SOLUTION: A decorative sheet at least includes: a surface layer 1; and an unevenness formation part 2 disposed at part of a surface of the surface layer 1. The unevenness formation part 2 is exposed to an outside on the surface of the surface layer 1. The unevenness formation part 2 is formed removably from the surface of the surface layer 1.SELECTED DRAWING: Figure 9

Description

  The present invention relates to a decorative sheet having an unevenness forming portion on its surface, and relates to a decorative sheet capable of imparting excellent design properties to a decorative resin molded product. Furthermore, this invention relates to the manufacturing method of the decorating resin molded product using the said decorating 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 such a molding method, a decorative sheet is previously molded into a three-dimensional shape by a vacuum mold, the decorative sheet is inserted into an injection mold, and a resin in a fluid state is injected into the mold. The injection molding method that integrates the resin and the decorative sheet, and the injection molding that integrates the decorative sheet inserted into the mold during the injection molding with the molten resin injected into the cavity The decoration method is mentioned.

  As a method of imparting a feeling of 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 is uneven by embossing (embossing) on the surface side. Attempts have been made to impart shape. However, when an uneven shape is applied to the surface by embossing, the uneven shape may be restored to a flat surface by the action of heat and stress during injection molding or pre-formation (vacuum forming) prior to the injection molding.

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

JP 2009-234159 A

  However, for example, in a decorative sheet having an independent fine asperity forming part on the surface, as disclosed in Patent Document 1, for example, the material of the asperity forming part and the layer located thereunder is different, There is a problem that a difference in color and luster due to the difference in material occurs, making it difficult to achieve a natural design feeling.

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

  The present inventor has intensively studied to solve the above problems. As a result, at least a surface layer and a concavo-convex forming part formed on a part of the surface of the surface layer, the concavo-convex forming part is exposed to the outside on the surface of the surface layer, and By using the decorative sheet in which the concave-convex forming portion is formed so as to be removable from the surface of the surface layer in the production of a method for producing a decorative resin molded product, the design of a natural concave-convex feeling can be simply applied to the decorative resin. It has been found that it can be imparted to molded articles. 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 surface layer and an uneven portion formed on a part of the surface of the surface layer,
The unevenness forming part is exposed to the outside on the surface of the surface layer,
The said uneven | corrugated formation part is a decorating sheet | seat formed so that removal from the surface of the said surface layer is possible.
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 10% by mass or more of a silicone component.
Item 4. The said uneven | corrugated formation part is a decorating sheet in any one of claim | item 1 -3 currently formed with the hardened | cured material 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 unevenness-containing portion contains 10% by mass or more of a silicone component.
Item 6. Item 6. The decorative sheet according to any one of Items 1 to 5, wherein a plurality of the irregularities are formed, and at least some of the irregularities are formed independently of each other.
Item 7. Item 6. The decorative sheet according to any one of Items 1 to 5, wherein a plurality of the irregularities are formed, and at least some of the irregularities are connected to each other.
Item 8. Item 8. The decorative sheet according to any one of Items 1 to 7, wherein the unevenness forming part 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, comprising at least a base material layer, the surface layer, and the unevenness forming portion in this order.
Item 10. The process of obtaining the molded sheet by vacuum forming the decorative sheet according to any one of Items 1 to 9,
From the side opposite to the concavo-convex forming portion, the resin in a fluid state is injected into the mold and solidified, and the molded sheet is integrated with the outer surface of the resin molding simultaneously with the injection molding. Obtaining a resin molded product with a molded sheet,
From the surface of the resin-molded product with the molded sheet, removing the concavo-convex forming part,
A method for producing a decorated resin molded product.

  By using the decorative sheet of the present invention for the production of a decorative resin molded product, a design with a natural unevenness can be easily imparted to the decorative resin molded product.

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

1. The decorative sheet of the present invention comprises at least a surface layer and a concavo-convex forming part formed on a part of the surface of the surface layer, and the concavo-convex forming part is externally provided on the surface of the surface layer. And the concavo-convex forming portion is formed 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. It is done. And the uneven | corrugated formation part is embed | buried in the surface layer side with the heat and pressure which are added in this case. Since the buried irregularities are exposed to the outside even after injection molding, they can be easily removed using chemicals or adhesive tapes. On the surface layer after the unevenness forming portion is removed, an uneven shape is formed by embedding the unevenness forming portion. Since the uneven shape is expressed by a surface layer, a design with a natural uneven feeling can be imparted to the decorative resin molded product using the decorative sheet of the present invention. Hereinafter, the decorative sheet of the present invention will be described in detail.

Laminated structure of a decorative sheet The decorative sheet of the present invention includes at least a surface layer and a concavo-convex 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 where the concavo-convex forming portion 2 is provided and a portion 1 b where the concavo-convex forming portion 2 is not provided.

  From the viewpoint of imparting rigidity to the decorative sheet of the present invention to enhance shape stability, a base material layer 3 may be provided as necessary as shown in FIG. In addition, for the purpose of imparting decorativeness to a decorative resin product produced using the decorative sheet of the present invention, as shown in FIG. Good. Further, for the purpose of suppressing color change and variation of the base material layer 3, the base material layer 3 and the decorative layer 4 are provided when the decorative layer 4 is provided between the base material layer 3 and the surface layer 1. A concealing layer may be provided between the two and the like as necessary (not shown). Furthermore, 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 improving the moldability of the decorative sheet and the adhesion of each layer, etc. A primer layer 5 or the like may be provided between the decoration layer 4 and the surface layer 1 as necessary. Furthermore, you may provide an adhesive layer etc. under the base material layer 3 (illustration is abbreviate | omitted). One or more other layers may be laminated on the decorative sheet of the present invention depending on the function to be imparted to the decorative sheet or the decorative resin molded product.

  As a laminated structure of the decorative sheet of the present invention, a laminated structure in which surface layers / concave-convex forming portions are laminated in this order; a laminated structure in which base layer / surface layer / concave-formed forming portions are laminated in this order; base layer / decoration Laminated structure in which layer / surface layer / unevenness forming part is laminated in this order; Laminated structure in which base material layer / decoration layer / primer layer / surface layer / unevenness forming part are laminated in this order; adhesive layer / base material layer / decoration Laminated structure in which layer / primer layer / surface layer / unevenness forming part are laminated in this order; laminated structure in which adhesive layer / base layer / hiding layer / decoration layer / primer layer / surface layer / unevenness forming part are laminated in this order Etc. FIG. 1 shows a schematic cross-sectional view of an example of a decorative sheet in which surface layer / concave-convex forming portions are laminated in this order as an 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 / concave-convex forming portion are laminated in this order as an 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 layer / decoration layer / primer layer / surface layer / concave-convex forming portion are laminated in this order as an aspect 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) that plays a role as a support in the decorative sheet of the present invention. The resin component used for the base material layer 3 is not particularly limited, and may be appropriately selected according to 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) resin. Among these, ABS resin is preferable from the viewpoint of three-dimensional moldability. As a resin component which forms the base material layer 3, only 1 type may be used and 2 or more types may be mixed and used. Moreover, the base material layer 3 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 3 may be subjected to physical or chemical surface treatment such as an oxidation method or an unevenness method on one surface or both surfaces as necessary in order to improve the adhesion with the 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, and an ozone ultraviolet treatment method. Moreover, as the uneven | corrugated method performed as surface treatment of the base material layer 3, 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 3, and from the viewpoints of effects and operability, a corona discharge treatment method is preferable.

  In addition, the base material layer 3 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 3 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. It is done. When the thickness of the base material layer 3 is within the above range, the decorative sheet can be provided with more excellent three-dimensional formability, designability, and the like.

[Surface layer 1]
The surface layer 1 is a layer provided in order to give uneven | corrugated shape to the surface of a decorative resin molded product by removing after the uneven | corrugated formation part 2 mentioned later is buried in the surface layer 1, and is removed. In the present invention, the resin for forming the surface layer 1 is not particularly limited as long as the unevenness forming portion 2 is buried at the time of injection molding and thereafter the unevenness forming portion 2 can be removed from the surface. , Thermosetting resins, ionizing radiation curable resins, etc., while enhancing the scratch resistance of the surface of the decorative resin molded product, the surface layer 1 may be scratched, discolored, or glossy when removing the concavo-convex forming portion 2. From the viewpoint of suppressing the change, a cured product of a curable resin composition such as a thermosetting resin or an ionizing radiation curable resin is preferable.

  As a thermosetting resin composition which forms the surface layer 1, Preferably a urethane resin is mentioned. 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 making the surface layer 1 into a two-component curable polyurethane, chemical resistance and solvent resistance are enhanced, and the surface layer 1 can be prevented from being eroded when the removal of the concavo-convex portion 2 is promoted by the chemical or solvent. . As the polyol, one having two or more hydroxyl groups in the molecule, for example, polyester polyol, polyethylene glycol, polypropylene glycol, acrylic polyol, polyether polyol and the like are used. Examples of the isocyanate include polyvalent isocyanate having two or more isocyanate groups in the molecule, aromatic isocyanate such as 4,4-diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated diphenylmethane diisocyanate. Aliphatic (or alicyclic) isocyanates such as are used. 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; And polyethylene terephthalate (PET); acrylonitrile-butadiene-styrene resin (ABS resin); acrylonitrile-styrene-acrylic ester resin; A thermoplastic resin may be used individually by 1 type, and may be used in combination of 2 or more types.

(Ionizing radiation curable resin)
The ionizing radiation curable resin used for the formation of the surface layer 1 is a resin that crosslinks and cures when irradiated with ionizing radiation. Specifically, a polymerizable unsaturated bond or an epoxy group is present in the molecule. What mixed the prepolymer, oligomer, and / or monomer which it has suitably 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 an initiator for photopolymerization, and provides stable curing characteristics. Therefore, it is suitable for forming the surface layer 1. 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 is not particularly limited as long as it has a carbonate bond in the polymer main chain and a (meth) acrylate group in the terminal or side chain. It can be obtained by esterification with acrylic acid. The polycarbonate (meth) acrylate may be, for example, urethane (meth) acrylate having a polycarbonate skeleton. The urethane (meth) acrylate having a polycarbonate skeleton can be obtained, for example, by reacting a polycarbonate polyol, a polyvalent isocyanate compound, and hydroxy (meth) acrylate. 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) (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. In the present 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. 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, in the formation of the surface layer 1, the polycarbonate (meth) acrylate and the urethane (meth) acrylate that are suitably used as the ionizing radiation curable resin will be described in detail.

<Polycarbonate (meth) acrylate>
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 in the terminal or side chain. The (meth) acrylate is preferably 2 to 6 functional groups per molecule 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 types.

  The polycarbonate (meth) acrylate is obtained, for example, by converting a part or all of the hydroxyl groups of the polycarbonate polyol into (meth) acrylate (acrylic acid ester or methacrylic acid ester). This esterification reaction can be performed by a normal esterification reaction. For example, 1) a method of condensing polycarbonate polyol and acrylic acid halide or methacrylic acid halide in the presence of a base, 2) a method of condensing polycarbonate polyol and acrylic acid anhydride or methacrylic acid anhydride in the presence of a catalyst, Or 3) a method of condensing polycarbonate polyol and acrylic acid or methacrylic acid in the presence of an acid catalyst. The polycarbonate (meth) acrylate may be, for example, urethane (meth) acrylate having a polycarbonate skeleton. The urethane (meth) acrylate having a polycarbonate skeleton can be obtained, for example, by reacting a polycarbonate polyol, a polyvalent isocyanate compound, and 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 in the terminal or side chain. A typical method for producing the polycarbonate polyol includes a method by a polycondensation reaction from a diol compound (A), a trihydric or higher polyhydric alcohol (B), and a compound (C) to be a carbonyl component.

The diol compound (A) used as a raw material for the polycarbonate polyol is represented by the general formula HO—R ¹ —OH. Here, R < ¹ > is a C2-C20 bivalent hydrocarbon group, Comprising: The group may contain the ether bond. 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, , 5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,3-bis (2-hydroxyethoxy) benzene, 1,4-bis (2 -Hydroxyethoxy) benzene, neopentyl glycol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol and the like. These diols may be used alone or in combination of two or more.

  Examples of the trihydric or higher polyhydric alcohol (B) used as a raw material for polycarbonate polyol include alcohols such as trimethylolpropane, trimethylolethane, pentaerythritol, ditrimethylolpropane, dipentaerythritol, glycerin and sorbitol. Is mentioned. The trihydric or higher polyhydric alcohol may be an alcohol having a hydroxyl group in which 1 to 5 equivalents of ethylene oxide, propylene oxide, or other alkylene oxide is added to the hydroxyl group of the polyhydric alcohol. Good. These polyhydric alcohols may be used individually by 1 type, and may be used in combination of 2 or more type.

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

  The polycarbonate polyol is synthesized by subjecting the diol compound (A), a trihydric or higher polyhydric alcohol (B), and a compound (C) to be a carbonyl component to a polycondensation reaction under general conditions. What is necessary is just to set the preparation molar ratio of a diol compound (A) and a polyhydric alcohol (B) in the range of 50: 50-99: 1, for example. Further, the charged molar ratio of the compound (C) serving as the 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. What is necessary is just to set to the range of an equivalent.

  The number of equivalents of hydroxyl groups (eq./mol) present in the polycarbonate polyol after the polycondensation reaction at the above-mentioned charge ratio is, for example, 3 or more on average in one molecule, preferably 3 to 50, more preferably 3-20 are mentioned. When such an equivalent number is satisfied, a necessary amount of (meth) acrylate groups are formed by an esterification reaction described later, and moderate flexibility is imparted to the polycarbonate (meth) acrylate resin. 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 in, for example, JP-A No. 64-1726. The polycarbonate polyol can also be produced by an ester exchange 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. For example, the weight average molecular weight is 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 is, for example, 100,000 or less, preferably 50,000 or less, from the viewpoint of controlling the viscosity not to be too high. The weight average molecular weight of the polycarbonate (meth) acrylate is preferably 10,000 to 50,000, and more preferably 10,000 to 2, from the viewpoint of further improving the expression effect and rich formability of a rich low gloss feeling with a texture. Million.

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

  When the 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 particularly limited as long as the effects of the present invention are achieved. However, from the viewpoint of further improving the moldability of the decorative sheet, it is preferably 50% by mass or more, more preferably 80% by mass or more, and still more preferably 85% by mass or more.

<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 reaction of polyether polyol or polyester polyol and polyisocyanate with (meth) acrylic acid. The urethane (meth) acrylate preferably has 2 to 12 functional groups per molecule from the viewpoint of improving crosslinking 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. In addition to the above polycarbonate (meth) acrylate, the ionizing radiation curable resin composition used for forming the surface layer 1 may further contain urethane (meth) acrylate. Urethane (meth) acrylate may be used individually by 1 type, and may be used in combination of 2 or more types.

  Although there is no restriction | limiting in particular about the molecular weight of urethane (meth) acrylate, For example, a weight average molecular weight is 5000 or more, Preferably 10,000 or more is mentioned. The upper limit of the weight average molecular weight of the urethane (meth) acrylate is not particularly limited, but is, for example, 100,000 or less, preferably 50,000 or less, from the viewpoint of controlling the viscosity not to be too high.

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

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

  In the decorative sheet of the present invention, a 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 later from the surface layer 1. It is preferable. Although there is no restriction | limiting in particular as content of a silicone component, The uneven | corrugated formation part 2 is peeled off suitably from the surface layer 1 using an adhesive tape etc., and a natural design is simply decorated resin molded product. From the viewpoint of imparting to, 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 a structure in the molecule formed by alternately bonding silicon having organic groups and oxygen, specifically, a polysiloxane skeleton. Reactive silicone in which a reactive organic group such as amino group, vinyl group, epoxy group, carboxyl group, acrylic group, methacryl group is introduced into the side chain or terminal of the silicone oil as the main component, or in the side chain or terminal Non-reactive silicones introduced with non-reactive organic groups such as alkyl groups, ether groups, higher fatty acids, silicone-modified resins with modified side chains or terminals such as organic resins, ionizing radiation curable resins, etc. Can be mentioned.

  In addition to the ionizing radiation curable resin, various additives can be blended in the surface layer 1 according to desired physical properties to be provided in the surface layer 1. 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.

  Although there is no restriction | limiting in particular about the thickness after hardening of the surface layer 1, Preferably it is 1000 micrometers or less, More preferably, it is about 1-50 micrometers, More preferably, about 1-10 micrometers is mentioned. When the thickness within such a range is satisfied, the decorative sheet is excellent in moldability and sufficient physical properties as a surface layer such as scratch resistance can be obtained. Further, since the ionizing radiation curable resin composition forming the surface layer 1 can be uniformly irradiated with ionizing radiation, it can be cured uniformly, which is economically advantageous.

  Formation of the surface layer 1 is performed by, for example, preparing the above ionizing radiation curable resin composition, applying it, and crosslinking and curing it. 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 surface layer 1 with the below-mentioned application system. In the present invention, on the layer adjacent to the surface layer 1 so that the prepared coating liquid has the above thickness, known methods such as gravure coating, bar coating, roll coating, reverse roll coating, comma coating, Preferably, it is applied by gravure coating to form an uncured resin layer. The surface layer 1 is formed by irradiating the thus formed uncured resin layer with ionizing radiation such as an electron beam and ultraviolet rays to cure the uncured resin layer. 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 increases. Therefore, when a resin that is easily deteriorated by electron beam irradiation is used under the surface layer 1, the electron beam transmission depth and the surface layer 1 are increased. The acceleration voltage is selected so that the thicknesses of the two are substantially equal. Thereby, irradiation of the extra electron beam to the layer located under the surface layer 1 can be suppressed, and deterioration of each layer due to the excess electron beam can be minimized. 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.

[Unevenness forming part 2]
The uneven | corrugated formation part 2 is formed in multiple numbers in a part of surface of the surface layer 1 in the decorating sheet of this invention. Further, the unevenness forming portion 2 is exposed to the outside on the surface of the surface layer 1. And the uneven | corrugated formation part 2 is formed so that removal from the surface of the surface layer 1 is possible. As described above, in the production of a decorative resin molded product using the decorative sheet of the present invention, the unevenness forming portion is pressed against the mold during injection molding. And the uneven | corrugated formation part is embed | buried in the surface layer side with the heat and pressure which are added in this case. Since the buried irregularities are exposed to the outside even after injection molding, they can be easily removed using chemicals such as organic solvents or adhesive tapes. On the surface layer 1 after the unevenness forming portion is removed, an uneven shape is formed by embedding the unevenness forming portion. Therefore, by producing a decorated resin molded product using the decorative sheet of the present invention, a design with a natural unevenness can be easily applied to the surface of the decorated resin molded product.

  The resin for forming the concavo-convex forming part 2 is not particularly limited as long as the concavo-convex forming part 2 is buried at the time of injection molding, and thereafter the concavo-convex forming part 2 can be removed from the surface. From the viewpoint of imparting to the decorative resin molded article, thermoplastic resins, thermosetting resins, cured products of ionizing radiation curable resin compositions, and the like can be given. Among these, since it is easy to remove from the surface of the surface layer 1, a cured product of an ionizing radiation curable resin is preferable. However, the resin forming the surface layer 1 can be appropriately selected according to the use 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 are the same as those exemplified in the surface layer 1 described above.

  In the decorative sheet of the present invention, a silicone component is contained in the ionizing radiation curable resin composition for forming the unevenness forming part 2 from the viewpoint of suitably removing the unevenness forming part 2 described later from the surface layer 1. Preferably it is. The content of the silicone component is not particularly limited, but a chemical design such as an organic solvent is suitably used to peel off and remove the unevenness forming part 2 from the surface layer 1 so that a natural design can be easily and simply decorated resin molded product. From the viewpoint of imparting to, preferably 10 mass% or more, more preferably about 10 to 20 mass%. The silicone component in the ionizing radiation curable resin composition is that described in the surface layer 1 described above.

As one area of the unevenness forming unit 2 is not particularly limited, but is appropriately set in accordance with the design to be applied to the decorated resin molded article uneven formation portion 2 is formed after being removed, for example, 50 mm ² Hereinafter, 10 mm ² or less, 5 mm ² or less, 2 mm ² or less, etc. may 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 visually recognizing a concavo-convex pattern after the concavo-convex forming portion 2 is removed. The area of the unevenness forming part 2 may be the same or different. In addition, in this specification, the area of uneven | corrugated formation part 2 etc. means an area when it sees from the lamination direction of a decorating sheet, More specifically, it means the value measured by the measuring method mentioned later.

  Further, the thickness (height) of the concavo-convex forming portion 2 is not particularly limited as long as the concavo-convex shaped design is formed on the surface of the surface layer 1 after the concavo-convex forming portion 2 is buried in the surface layer 1 and removed. However, it 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 imparting a natural uneven design to the decorated resin molded product.

  The shape of the concavo-convex forming portion 2 is not particularly limited, and preferred examples include a circular shape, an elliptical shape, a triangular shape, a quadrangular shape, a 5 to 10-sided shape, a star shape, a linear shape, a geometric pattern, and a character shape. Moreover, the shape of each uneven | corrugated formation part 2 may mutually be the same, and may differ. The design expressed by each concavo-convex forming portion 2 may be a regular pattern shape in which the respective concavo-convex forming portions 2 are regularly arranged, or may be an irregular pattern. An irregular pattern is preferable because it has excellent tactile sensation, matte feeling, glossiness, and design, and if it has a regular pattern shape that is regularly arranged, stress during decorative molding concentrates on a specific part. This is preferable in that it is difficult to cause cracks on the surface uneven pattern.

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

  The pattern formed by the unevenness forming part 2 as a whole is not particularly limited, and for example, a geometric pattern such as a circle, an ellipse, a polygon, a line drawing, a polka dot, a stripe, a lattice, a character, a grain pattern, a bamboo pattern, A stone pattern, a tiled pattern, a brick laminate pattern, a cloth pattern, a leather pattern, etc. are preferably mentioned, and these may be used alone or in combination of two or more.

  The concavo-convex forming part 2 is, for example, printing the above ionizing radiation curable resin composition by silk screen printing, gravure overlay printing, rotary screen printing, or a printing 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 irradiation with ionizing radiation.

  For example, when both the surface layer 1 and the concavo-convex forming portion 2 are formed of a cured product of an ionizing radiation curable resin composition, the ionizing radiation curing that forms the surface layer 1 is performed when the surface layer 1 and the concavo-convex forming portion 2 are formed. The ionizing radiation curable resin composition for forming the concavo-convex forming part 2 is partially laminated on the ionizing radiation curable resin composition in the uncured or semi-cured state, and then the surface layer 1 And by irradiating ionizing radiation on the conditions which can bridge-harden the ionizing radiation curable resin composition of both layers of the uneven | corrugated formation part 2, both layers can be formed by one ionizing radiation irradiation process. Further, the ionizing radiation may be irradiated twice at the time of forming the surface layer 1 and at the time of forming the unevenness forming portion 2. When the ionizing radiation is irradiated twice at the time of forming the surface layer 1 and the concavo-convex forming portion 2, the type of ionizing radiation used in each step may be the same or different. More specifically, there are exemplified cases where both the surface layer 1 and the concavo-convex forming portion 2 are cured by irradiation with an electron beam, and when the surface layer 1 is cured by irradiating an electron beam and the concavo-convex forming portion 2 is irradiated with ultraviolet rays. The

[Decoration layer 4]
The decorative layer 4 is a layer that gives decorativeness 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 a combination thereof. The decoration layer 4 is formed, for example, by printing various patterns using ink and a printing machine. The pattern formed by the decorative layer 4 is not particularly limited, and for example, a wood pattern, a marble pattern (for example, a travertine marble pattern) or the like, a stone pattern that simulates the surface of a rock, or a cloth that simulates a cloth or 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 ink used for the decorative layer 4, an ink 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 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.

  Although the thickness in particular of the decoration layer 4 is not restrict | limited, For example, about 1-30 micrometers, Preferably about 1-20 micrometers is mentioned.

  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 alloys 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, a sputtering method, and an ion plating method using the above-described metal. Moreover, in order to improve adhesiveness with an adjacent layer, you may provide the primer layer using well-known resin in the surface and back surface of a metal thin film layer.

[Hidden layer]
For the purpose of suppressing the color change and variation of the base material layer 3, the concealing layer is provided between the base material layer 3 and the surface layer 1 and between the base material layer 3 and the decorative layer 4. It is a layer provided as needed, such as between (not shown).

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

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

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

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

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

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

  From the viewpoints of adhesion to the surface layer after crosslinking, difficulty in interaction after laminating the surface layer 1, physical properties, and moldability, acrylic polyol or polyester polyol as polyol and hexamethylene diisocyanate as crosslinking material, 4 , 4-diphenylmethane diisocyanate is preferable, and acrylic polyol and hexamethylene diisocyanate are particularly preferably used in combination.

  (Meth) acrylic resins include (meth) acrylic acid ester homopolymers, copolymers of two or more different (meth) acrylic acid ester monomers, or (meth) acrylic acid esters and other monomers. Polymers, specifically, poly (meth) methyl acrylate, poly (meth) ethyl acrylate, poly (meth) acrylate propyl, poly (meth) acrylate butyl, methyl (meth) acrylate- (Meth) butyl acrylate copolymer, (meth) ethyl acrylate- (meth) butyl acrylate copolymer, ethylene- (meth) methyl acrylate copolymer, styrene- (meth) methyl acrylate copolymer A (meth) acrylic resin made of a homopolymer or a copolymer containing a (meth) acrylic acid ester such as the above is preferably used.

  As the (meth) acryl-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. The acrylic-urethane (polyester urethane) block copolymer resin adjusts the acrylic / urethane ratio (mass ratio) in the range of preferably 9/1 to 1/9, more preferably 8/2 to 2/8, if desired. It is preferable.

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

Although it does not restrict | limit especially as thickness of the primer layer 5, Preferably 0.1 micrometer or more is mentioned. When it is 0.1 μm or more, the surface layer 1 has an effect of preventing cracking, breaking, whitening, and the like. On the other hand, if the thickness of the primer layer 5 is 10 μm or less, it is preferable that the three-dimensional formability does not fluctuate since the drying and curing of the coating film is stable when the primer layer 5 is applied.
[Adhesive layer]
The adhesive layer is a layer provided on the back surface of the base material layer 3 as necessary for the purpose of improving the adhesion and adhesion between the decorative sheet and the molding resin (not shown). The resin forming the adhesive layer is not particularly limited as long as it can improve the adhesion and adhesion between the decorative sheet and the molding resin, and for example, a thermoplastic resin or a thermosetting resin is used. It is done. 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.

  Although the adhesive layer is not necessarily a necessary layer, when it is assumed that the decorative sheet of the present invention is applied to a decorative method by sticking onto a resin molded body prepared in advance, such as a vacuum pressure bonding method described later. Are preferably provided. In the case of using in the vacuum pressure bonding method, it is preferable to use an ordinary resin as a resin that exhibits adhesiveness by pressurization or heating among the various resins described above to form the adhesive layer.

By using the decorative sheet of the present invention for the production of a decorative resin molded product, a design with a natural unevenness can be easily imparted to the decorative resin molded product. For this reason, for example, interior materials or exterior materials for vehicles such as automobiles; fittings such as window frames and door frames; interior materials for buildings such as walls, floors, and ceilings; housings for home appliances such as television receivers and air conditioners. Body: It can be suitably used as a decorative sheet used for applications such as containers.

2. Production method of decorated resin molded product In the present invention, a decorated resin molded product can be suitably produced using the above-described decorated sheet of the present invention. Specifically, the decorative resin molded product is obtained by removing the concavo-convex forming portion 2 from the surface of the resin molded product with a molded sheet obtained by integrating the injection resin 6 (molded resin) with the decorative sheet of the present invention. It is obtained. That is, as shown in FIG. 8, the decorative resin molded product includes at least a molded resin layer 6 formed by resin injection and a surface layer 1. If necessary, the base material layer 3 described above is provided. And a laminated structure in which a decorative layer 4, a primer layer 5, a concealing layer, an adhesive layer and the like are laminated.

  The method for removing the unevenness forming portion 2 from the surface of the surface layer 1 of the resin molded product with a molded sheet is not particularly limited. A method of peeling off from the surface of the surface layer 2, a method of applying a chemical of an organic solvent (for example, ethanol) on the surface of a resin molded product with a molded sheet, and reducing the adhesion of the concavo-convex forming portion 2 to remove it. Is mentioned.

  In the decorative resin molded product produced using the decorative sheet of the present invention, the depth of the concave portion having the concave and convex shape that appears by removing the concave and convex portion 2 is not particularly limited. From the viewpoint of performance, it 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 various injection molding methods such as insert molding, simultaneous injection molding, blow molding, and gas injection molding using the decorative sheet of the present invention. The Among these injection molding methods, an insert molding method and an injection molding simultaneous decorating method are preferable.

  For example, as shown in the schematic diagram of FIG. 9, the decorative sheet of the present invention is inserted into the injection mold 10 (FIG. 9A). Next, the resin in a fluid state is injected into the mold from the side opposite to the unevenness forming portion 2 of the decorative sheet and solidified to integrate the decorative sheet and the injection resin (FIG. 9B). . 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 the 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 manufactured using the decorative sheet of the present invention. In the product, due to heat and pressure when the unevenness forming part 2 is buried in the surface layer 1, one surface of the surface layer 1 as shown in FIG. Not only on the side surface) but also on the other side surface of the surface layer 1 (lamination surface with the layer such as the base material layer 3) or when the decorative sheet and the molded resin layer 6 are laminated. An uneven shape may also be formed on the surface.

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 forming the decorative sheet of the present invention From the opposite side of the molded sheet, a resin in a fluid state is injected into a mold, solidified, and injected. A step of obtaining the resin molded product with the molded sheet by integrating the molded sheet with the outer surface of the resin molded product simultaneously with the molding. A step of removing the unevenness forming portion from the surface of the resin molded product with the molded sheet.
Further specific various manufacturing methods will be described in detail below.

  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, and a resin in a fluid state is injected into the mold from the side opposite to the concavo-convex forming portion 2 and solidified. A decorative resin molded product is manufactured by integrating the decorative sheet on the outer surface of the resin 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 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-formed decorative sheet to obtain the molded sheet,
Insert the molded sheet into the injection mold, clamp the injection mold, and inject the fluidized resin into the mold from the side opposite to the concavo-convex forming part 2, solidify it, and mold the resin simultaneously with the injection molding Integrating the molded sheet with the outer surface of the resin to obtain a resin molded product with a molded sheet, and
A step of removing the uneven portion from the surface of a resin molded product with a 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 3 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, and the resin in a fluid state is injected and filled into the mold from the side opposite to the concavo-convex portion 2, solidified, and simultaneously with the injection molding, on the outer surface of the resin molding A decorative resin molded product is manufactured by integrating the decorative sheet of the present invention and removing the unevenness forming part 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 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 product with a molded sheet, and integrating and integrating the resin molded body and the decorative sheet to obtain a resin molded product with a molded sheet,
A step of removing the movable mold away from the fixed mold and taking out the resin molded product with the molded sheet, and a step of removing the irregularities from the surface of the resin molded product with the molded sheet.

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, etc. 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 molded resin layer may be formed by selecting a resin according to the application. The molding resin that forms 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, 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.

  Since the decorative resin molded product of the present invention has a design with a natural unevenness, for example, interior materials or exterior materials of vehicles such as automobiles; fittings such as window frames and door frames; architectures such as walls, floors, and ceilings It can be used as an interior material of a product; a housing of a home appliance such as a television receiver or an air conditioner; a container or 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 1-2 and Comparative Example 1>
(Preparation of a decorative sheet before forming the irregularities)
A decorative layer (thickness 5 μm) was formed by gravure printing on an ABS resin film (thickness: 400 μm) as a base material using an ink containing 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 mass of acrylic polyol resin (weight average molecular weight 8000), 10.1 parts by mass of polyurethane resin (weight average molecular weight 6000), and 7 parts by mass of hexamethylene diisocyanate. Next, the ionizing radiation curable resin A or the ionizing radiation curable resin B shown in Table 1 was applied by bar coating so that the cured thickness of the resin composition was 10 μm, and an uncured electron beam curable resin was applied. A surface layer was formed. 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 layer / decoration layer / primer layer / surface The decorative sheet before forming the uneven | corrugated formation part by which the layer was laminated | stacked in this order was obtained. Next, a 2 mm diameter dot (area of about 3 mm ² ) is printed on the surface layer by screen printing using the ultraviolet curable resin a or the ultraviolet curable resin b shown in Table 1 so that the coating thickness is 30 μm. A plurality of uncured uneven 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 layer / decoration layer / primer layer A decorative sheet was obtained in which / surface layer / unevenness forming part was laminated in this order.

<Example 3 and Comparative Example 2>
In the same manner as in Example 1, a decorative layer was provided on the ABS resin film. Next, a surface layer (thickness 4 μm) was provided on the decorative layer by gravure printing using the curable resin I described in Table 1. Next, using the ultraviolet curable resin a or the ultraviolet curable resin b, a concavo-convex forming part was produced in the same manner as in Example 2, and the base material layer / decoration layer / surface layer / concave forming part were 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 (preliminary forming) is performed using a vacuum forming die having a portion with a draw ratio of 100 to 300% to obtain a formed sheet. It was. Next, the obtained molded sheet is inserted into an injection mold, the injection mold is clamped, the ABS resin in a fluid state is injected into the mold from the ABS resin film side, and is cooled and solidified as it is. A resin molded product with a molded sheet was obtained. The temperature of the injection resin at the time of injection molding was 260 ° C.
Next, the uneven | corrugated formation part was removed by the method of Table 1 from the surface of each resin molded product with a molding sheet, and the decorative resin molded product was obtained.

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

(Evaluation of design properties)
The design property of the obtained decorative resin molded product was evaluated. In the decorative resin molded products of Examples 1 to 3, the region where the concavo-convex forming portion was provided becomes a concave portion, thereby having a concavo-convex shape on the surface, and a design having a concavo-convex feeling both visually and tactilely. Was formed (good design). On the other hand, in Comparative Examples 1 and 2, the unevenness forming portion was not removed and remained on the surface of the decorative resin molded product, and the target design was not obtained (poor design).

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% by mass
Bifunctional polycarbonate acrylate (weight average molecular weight: 20,000) 29% by 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% by mass

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

(UV curable resin a)
20% by mass of urethane acrylate oligomer (weight average molecular weight about 2000)
60% by mass of bifunctional acrylate monomer
5% by weight of photosensitive compound
5% by mass of photopolymerization initiator
10% by mass of filler and pigment

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

DESCRIPTION OF SYMBOLS 1 ... Surface layer 2 ... Unevenness formation part 3 ... Base material layer 4 ... Decoration layer 5 ... Primer layer 6 ... Molding resin layer

Claims (10)

At least a surface layer and an uneven portion formed on a part of the surface of the surface layer,
The unevenness forming part is exposed to the outside on the surface of the surface layer,
The said uneven | corrugated formation part is a decorating sheet | seat formed so that removal from the surface of the said surface layer is possible.   The said surface layer is a decorating sheet of Claim 1 currently formed with the hardened | cured material of curable resin composition.   The decorative sheet according to claim 2, wherein the curable resin composition forming the surface layer contains 10% by mass or more of a silicone component.   The said uneven | corrugated formation part is a decorating sheet in any one of Claims 1-3 currently formed with the hardened | cured material 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 10% by mass or more of a silicone component.   The decorative sheet according to any one of claims 1 to 5, wherein a plurality of the concave and convex portions are formed, and at least some of the plurality of concave and convex portions are formed independently of each other.   The decorative sheet according to any one of claims 1 to 5, wherein a plurality of the concave and convex portions are formed, and at least some of the plurality of concave and convex portions are connected to each other.   The decorative sheet according to any one of claims 1 to 7, wherein the unevenness forming portion has a thickness of 1 µm to 200 µm.   The decorating sheet in any one of Claims 1-8 provided with a base material layer, the said surface layer, and the said uneven | corrugated formation part at least in this order. A step of vacuum forming the decorative sheet according to claim 1 to obtain a molded sheet;
From the side opposite to the concavo-convex forming portion, the resin in a fluid state is injected into the mold and solidified, and the molded sheet is integrated with the outer surface of the resin molding simultaneously with the injection molding. Obtaining a resin molded product with a molded sheet,
From the surface of the resin-molded product with the molded sheet, removing the concavo-convex forming part,
A method for producing a decorated resin molded product.