JP6255846B2 - Decorative sheet and decorative resin molded product - Google Patents

Description

  The present invention relates to a decorative sheet having excellent moldability, scratch resistance, and fingerprint resistance. Furthermore, the present invention relates to a decorative resin molded product using the decorative sheet.

  Conventionally, a decorative resin molded product in which a decorative sheet is laminated on the surface of a resin molded product is used for an interior / exterior part of a vehicle, a building material interior material, a home appliance housing, and the like. In the production of such a decorated resin molded product, a molding method or the like is used in which a decorative sheet to which a design has been applied in advance is integrated with a resin by injection molding. As a typical example of such a molding method, a decorative sheet is formed in a three-dimensional shape in advance 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. In addition to a molding method by injection molding, a decorative sheet is also used in a decoration method in which a pre-molded molded body is attached with heating or pressurization, such as a vacuum pressure bonding method.

  Some decorative resin molded products have a complicated surface shape such as a three-dimensional curved surface. For this reason, the decorative sheet is required to have three-dimensional formability that can sufficiently follow the shape of the decorative resin molded product. Further, since the decorative sheet is used as a surface material of a decorative resin molded product, it is also required to have surface characteristics such as scratch resistance. Furthermore, with the recent trend toward high-class consumers, decorative resin molded products are required to have fingerprint resistance that makes the fingerprints attached when the surface of the decorative resin molded product is touched by hand inconspicuous. .

  So far, techniques for imparting fingerprint resistance to decorative sheets have been reported. For example, in Patent Document 1, a mat layer forming ink containing a matting agent using two kinds of particles having a difference of 1.5 μm or more in average particle diameter among particles having an average particle diameter of 2 to 20 μm, and A decorative article having a matte surface using the ink is disclosed.

JP 2012-41390 A

  However, as a result of examination by the inventors, for example, a decorative sheet using a matting agent as in Patent Document 1 may be insufficient in terms of formability, scratch resistance, and fingerprint resistance. It became clear. Under such circumstances, the main object of the present invention is to provide a decorative sheet having excellent moldability, scratch resistance, and fingerprint resistance.

  The present inventor has intensively studied to solve the above problems. As a result, it has at least a base material layer and a surface protective layer, and the surface protective layer is formed of a resin composition containing an ionizing radiation curable resin and synthetic resin particles. It has been found that a decorative sheet containing 65 parts by mass or more of particles with respect to 100 parts by mass of ionizing radiation curable resin is excellent in moldability, scratch resistance, fingerprint resistance, and tactile sensation. 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. Having at least a base material layer and a surface protective layer,
The surface protective layer is formed of a resin composition containing an ionizing radiation curable resin and synthetic resin particles,
In the surface protective layer, a decorative sheet in which the synthetic resin particles are contained in an amount of 65 parts by mass or more with respect to 100 parts by mass of the ionizing radiation curable resin.
Item 2. Item 2. The decorative sheet according to Item 1, wherein the ionizing radiation curable resin contains polycarbonate (meth) acrylate.
Item 3. Item 3. The decorative sheet according to Item 2, wherein the ionizing radiation curable resin further comprises a polyfunctional (meth) acrylate.
Item 4. Item 4. The decorative sheet according to Item 3, wherein a mass ratio of the polycarbonate (meth) acrylate and the polyfunctional (meth) acrylate is 98: 2 to 60:40.
Item 5. Item 5. The decorative sheet according to any one of Items 1 to 4, wherein the synthetic resin particles have a particle size of 2 to 15 µm.
Item 6. Item 6. The decorative sheet according to any one of Items 1 to 5, wherein the surface protective layer has a thickness of 1 to 30 µm.
Item 7. The synthetic resin particles are at least one selected from the group consisting of urethane beads, nylon beads, acrylic beads, silicone beads, styrene beads, melamine beads, urethane acrylic beads, polyester beads, and polyethylene beads. 6. The decorative sheet according to any one of 6.
Item 8. Item 9. The decorative sheet according to any one of Items 1 to 7, further comprising a pattern layer between the base material layer and the surface protective layer.
Item 9. At least a molded resin layer, a base material layer, and a surface protective layer are laminated in this order,
The surface protective layer is formed of a resin composition containing an ionizing radiation curable resin and synthetic resin particles,
In the surface protective layer, a decorative resin molded product in which the synthetic resin particles are contained in an amount of 65 parts by mass or more with respect to 100 parts by mass of the ionizing radiation curable resin.

  According to the decorative sheet of the present invention, it is possible to provide a decorative sheet excellent in moldability, scratch resistance, fingerprint resistance, and touch, and a decorative resin molded product using the decorative sheet.

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

1. The decorative sheet of the present invention has at least a base material layer and a surface protective layer, and the surface protective layer is formed of a resin composition containing an ionizing radiation curable resin and synthetic resin particles. In the surface protective layer, the synthetic resin particles are contained in an amount of 65 parts by mass or more with respect to 100 parts by mass of the ionizing radiation curable resin. In the decorative sheet of the present invention, in the surface protective layer, the synthetic resin particles are contained in an amount of 65 parts by mass or more with respect to 100 parts by mass of the ionizing radiation curable resin, so that the moldability, scratch resistance, and fingerprint resistance are increased. And it can be set as the decorating sheet excellent in touch. Although it has been conventionally known that synthetic resin particles are added to the surface protective layer for the purpose of obtaining a low-gloss (matte) design, in the present invention, the surface protective layer contains 100 mass of ionizing radiation curable resin. 65 parts by mass or more with respect to the part, which is considered excessive to form the mat surface, and contains a large amount of synthetic resin particles that is not normally assumed, thereby providing moldability, scratch resistance, and fingerprint resistance. It can be set as the decorating sheet which is excellent in. Furthermore, in such a decorative sheet, the touch feeling when touched by hand is as smooth as it was not seen in conventional products, and it is very slippery and gives the consumer a unique and soft impression. There is also an unexpected effect. Hereinafter, the decorative sheet of the present invention will be described in detail.

Laminated structure of decorative sheet The decorative sheet of the present invention has a laminated structure in which at least a base material layer 1 and a surface protective layer 2 are laminated. In the decorative sheet of the present invention, the primer layer 3 may be provided under the surface protective layer 2 for the purpose of making it difficult for fine cracks and whitening to occur in the stretched portion of the surface protective layer 2. Moreover, you may provide the pattern layer 4 as needed for the purpose of providing a decorative property to a resin molded product. For the purpose of suppressing the color change and variation of the base material layer 1, between the base material layer 1 and the surface protective layer 2, or between the base material layer 1 and the design layer 4 if a pattern layer 4 is provided. Moreover, you may provide the concealment layer 5 as needed. Furthermore, between the base material layer 1 and the surface protective layer 2 for the purpose of improving the moldability of the decorative sheet, or between the pattern layer 4 and the surface protective layer 2 if a pattern layer 4 is provided. Moreover, you may provide the transparent film layer 6 etc. as needed. Furthermore, an adhesive layer 7 or the like may be provided under the base material layer 1.

  As a laminated structure of the decorative sheet of the present invention, a laminated structure in which a base material layer / surface protective layer are laminated in this order; a laminated structure in which a base material layer / primer layer / surface protective layer are laminated in this order; Laminate structure in which picture layer / surface protective layer is laminated in this order; Laminate structure in which base material layer / picture layer / primer layer / surface protective layer are laminated in this order; base material layer / hiding layer / picture layer / surface protective layer Laminated structure in which the layers are laminated in this order; Laminated structure in which the base layer / masking layer / picture layer / primer layer / surface protective layer are laminated in this order; Base layer / masking layer / picture layer / transparent film layer / surface protection Laminated structure in which layers are laminated in this order; Laminated structure in which adhesive layer / base material layer / hiding layer / picture layer / primer layer / surface protective layer are laminated in this order; adhesive layer / base material layer / hiding layer / picture layer / Transparent film layer / primer layer / surface protective layer are laminated in this order Etc. The laminated structure. In FIG. 1, the schematic sectional drawing of an example of the decorating sheet | seat in which the base material layer / surface protective layer was laminated | stacked in this order is shown as one aspect | mode of the laminated structure of the decorating sheet of this invention. In FIG. 2, the schematic sectional drawing of an example of the decorating sheet | seat in which the base material layer / picture layer / primer layer / surface protective layer was laminated | stacked in this order as one aspect | mode of the laminated structure of the decorating sheet of this invention is shown. In FIG. 3, as an aspect of the laminated structure of the decorative sheet of the present invention, a decorative sheet in which an adhesive layer / base material layer / hiding layer / picture layer / transparent film layer / primer layer / surface protective layer are laminated in this order. FIG. 2 shows a schematic cross-sectional view of an example.

Composition of each layer forming the decorative sheet [base material layer 1]
The base material layer 1 is formed of a resin sheet (resin film) that plays a role as a support in the decorative sheet of the present invention. The resin component used for the base material layer 1 is not particularly limited, and may be appropriately selected according to the three-dimensional moldability, compatibility with the molded 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 1, only 1 type may be used and 2 or more types may be mixed and used. Moreover, the base material layer 1 may be formed with the single layer sheet | seat of these resin, and may be formed with the multilayer sheet | seat by the same kind or different kind | species resin.

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

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

  The thickness of the base material layer 1 is not particularly limited and is appropriately set depending on 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 1 is within the above range, the decorative sheet can be provided with more excellent three-dimensional formability, designability, and the like.

[Surface protective layer 2]
The surface protective layer 2 is a layer provided on the outermost layer of the decorative sheet in order to improve the scratch resistance and fingerprint resistance of the decorative sheet, and includes a resin composition containing an ionizing radiation curable resin and synthetic resin particles 8 It is formed by. Specifically, the surface protective layer 2 is composed of a cured product of the resin composition. In the decorative sheet of the present invention, in the surface protective layer 2, the synthetic resin particles 8 are contained in an amount of 65 parts by mass or more with respect to 100 parts by mass of the ionizing radiation curable resin. It can be set as the decorating sheet excellent in fingerprint property and touch.

(Ionizing radiation curable resin)
The ionizing radiation curable resin used for forming the surface protective layer 2 is a resin that crosslinks and cures when irradiated with ionizing radiation. Specifically, a polymerizable unsaturated bond or an epoxy group in the molecule. A prepolymer, an oligomer, and / or a monomer appropriately mixed with each other. 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 ionizing radiation curable resins, electron beam curable resins can be made solvent-free, do not require a photopolymerization initiator, and provide stable curing characteristics, which is suitable for forming a surface protective layer. used.

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

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

  When polycarbonate (meth) acrylate is used to form the surface protective layer 2, it may be used alone as an ionizing radiation curable resin, or a combination of polycarbonate (meth) acrylate and another ionizing radiation curable resin may be used. May be. When polycarbonate (meth) acrylate and other ionizing radiation curable resin are used in combination, the combination mode is not particularly limited, but the expression effect and formability of rich low gloss with a texture are further improved. From the viewpoint, a combination of polycarbonate (meth) acrylate and polyfunctional (meth) acrylate is preferable.

  As the polyfunctional (meth) acrylate used in combination with the polycarbonate (meth) acrylate, either the polyfunctional (meth) acrylate monomer or the oligomer described above or both of them may be used, but preferably polyfunctional (meth). An acrylate oligomer is mentioned. In particular, a polyfunctional urethane (meth) acrylate oligomer is preferable, a trifunctional or higher functional urethane (meth) acrylate oligomer is particularly preferable, and a 3- to 8-functional urethane (meth) acrylate oligomer is particularly preferable.

  Further, the molecular weight of the polyfunctional (meth) acrylate oligomer used in combination with the polycarbonate (meth) acrylate is not particularly limited. For example, the weight average molecular weight is about 1,000 to 20,000, preferably about 1,000 to 10,000. Can be mentioned. The weight average molecular weight is a value measured with polystyrene as a standard substance by gel permeation chromatography.

  Moreover, when combining a polycarbonate (meth) acrylate and polyfunctional (meth) acrylate, as these ratios, the mass ratio of polycarbonate (meth) acrylate: polyfunctional (meth) acrylate is, for example, 98: 2-60. : 40, preferably 95: 5 to 65:35.

  Hereinafter, polycarbonate methacrylate and acrylic silicone (meth) acrylate that are suitably used as the ionizing radiation curable resin in the formation of the surface protective layer 2 will be described.

<Polycarbonate (meth) acrylate>
In the surface protective layer 2 of the present invention, the polycarbonate (meth) acrylate contained in the resin composition has a carbonate bond in the polymer main chain and one or more (meth) acrylates in the terminal or side chain. There is no particular limitation. The (meth) acrylate is preferably 2 to 6 functional groups per molecule from the viewpoint of improving crosslinking and curing. 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 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.

<Acrylic silicone (meth) acrylate>
The acrylic silicone (meth) acrylate used in the present invention is not particularly limited, and a part of the acrylic resin structure is substituted with a siloxane bond (Si—O) in one molecule, and the acrylic resin is a functional group. Any of those having 2 or more, preferably 3 to 8, (meth) acryloyloxy groups (acryloyloxy group or methacryloyloxy group) at the side chain and / or main chain terminal of the above. As an example of this acrylic silicone (meth) acrylate, the structure of the acrylic resin which has a siloxane bond in a side chain as disclosed by Unexamined-Japanese-Patent No. 2007-070544 is mentioned preferably, for example.

The acrylic silicone (meth) acrylate used in the present invention can be synthesized, for example, by radical copolymerizing a silicone macromonomer with a (meth) acrylate monomer in the presence of a radical polymerization initiator.
Examples of the (meth) acrylate monomer include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, glycidyl (meth) acrylate, and the like. These (meth) acrylate monomers are used alone or in combination of two.

  The silicone macromonomer is synthesized, for example, by living anionic polymerization of hexaalkylcyclotrisiloxane using n-butyllithium or lithium silanolate as a polymerization initiator and capping with a radically polymerizable unsaturated group-containing silane. As a silicone macromonomer, following formula (1);

Is preferably used. Here, in the formula (1), R ¹ represents an alkyl group having 1 to 4 carbon atoms, a methyl group or an n- butyl group are preferable. R ² represents a monovalent organic group, —CH═CH ₂ , —C ₆ H ₄ —CH═CH ₂ , — (CH ₂ ) ₃ O (CO) CH═CH ₂ or — (CH ₂ ) _3. O (CO) C (CH ₃ ) ═CH ₂ is preferred. R ^{3 s} may be the same or different and each represents a hydrocarbon group having 1 to 6 carbon atoms, preferably an alkyl group having 1 to 4 carbon atoms or a phenyl group, and more preferably a methyl group. The numerical value of n is not particularly limited, and for example, the number average molecular weight of the silicone macromonomer is preferably 1,000 to 30,000, and more preferably 1,000 to 20,000.

  The acrylic silicone (meth) acrylate obtained using the above-mentioned raw materials has structural units represented by the following formulas (2), (3) and (4), for example.

In formulas (2), (3) and (4), R ¹ and R ³ have the same meanings as in formula (1), R ⁴ represents a hydrogen atom or a methyl group, and R ⁵ represents the (meth) acrylate. An alkyl group or glycidyl group in the monomer, or an alkyl group which may have a functional group such as an alkyl group or glycidyl group in the (meth) acrylate monomer, and R ⁶ is an organic compound having a (meth) acryloyloxy group. Indicates a group.
The above-mentioned acrylic silicone (meth) acrylates are used alone or in combination of two.

  The acrylic silicone (meth) acrylate has a weight average molecular weight in terms of standard polystyrene as measured by GPC analysis of preferably 1,000 or more, and more preferably 2,000 or more. The upper limit of the weight average molecular weight of the acrylic silicone (meth) acrylate is not particularly limited, but is preferably 150,000 or less and more preferably 100,000 or less from the viewpoint of controlling the viscosity not to be too high. From the viewpoint of improving the three-dimensional formability, chemical resistance and scratch resistance, it is particularly preferably 2,000 to 100,000.

Moreover, it is preferable that the average molecular weight between crosslinking points of acrylic silicone (meth) acrylate is 100-2,500. If the average molecular weight between crosslinking points is 100 or more, it is preferable from the viewpoint of three-dimensional formability, and if it is 2,500 or less, it is preferable from the viewpoint of chemical resistance and scratch resistance. From the same viewpoint, the average molecular weight between crosslinking points of the acrylic silicone (meth) acrylate is more preferably 100 to 1,500, still more preferably 100 to 1,000.
In the ionizing radiation curable resin composition, polycarbonate (meth) acrylate and acrylic silicone (meth) acrylate may be used alone or in combination of two or more.

  The details of the mechanism by which the decorative sheet of the present invention is excellent in formability, scratch resistance, fingerprint resistance, and tactile sensation are not clear, but can be considered as follows, for example. In the surface protective layer 2 of the decorative sheet of the present invention, 65 parts by mass or more of the synthetic resin particles 8 are included with respect to 100 parts by mass of the ionizing radiation curable resin. That is, in the decorative sheet of the present invention, the surface of the surface protective layer 2 is considered to be excessive for forming the mat surface, and the surface protective layer 2 contains a large amount of synthetic resin particles 8 that is not normally assumed. Is substantially filled with the synthetic resin particles 8. Furthermore, this is considered that the decorative sheet is excellent in formability, scratch resistance, fingerprint resistance, and tactile sensation. Such a decorative sheet of the present invention is excellent in touch when touched by hand. That is, when the surface of the decorative sheet is touched by hand, it has a tactile feel that is easy to slip. In the surface protective layer 2, the content of the synthetic resin particles 8 is not particularly limited as long as the effect of the present invention is achieved, but ionization is considered in consideration of forming the surface protective layer 2 by a printing method described later. Preferably it is 200 mass parts or less with respect to 100 mass parts of radiation curable resin, More preferably, it is 150 mass parts or less, More preferably, 100 mass parts or less is mentioned.

  The synthetic resin particle 8 is not particularly limited as long as it is a particle formed of a synthetic resin. For example, urethane beads, nylon beads, acrylic beads, silicone beads, styrene beads, melamine beads, urethane acrylic beads, polyester beads, Examples thereof include polyethylene beads. Among these synthetic resin particles 8, urethane beads, nylon beads, and acrylic beads are preferably used from the viewpoint of further improving the scratch resistance of the decorative sheet. The synthetic resin particles 8 may be used alone or in combination of two or more. The particle diameter of the synthetic resin particle 8 is preferably about 2 to 15 μm, more preferably about 5 to 12 μm. The particle diameter of the synthetic resin particles in the present invention is determined by using a Shimadzu laser diffraction particle size distribution measuring device SALD-2100-WJA1, using the compressed air to inject the powder to be measured from the nozzle, It is based on a spray-type dry measurement method that is measured by dispersing in a liquid crystal.

  In the decorative sheet of the present invention, part of the synthetic resin particles 8 may protrude from the surface of the surface protective layer 2, or the synthetic resin particles 8 may be embedded in the surface protective layer 2.

  In the surface protective layer 2, various additives can be blended in addition to the ionizing radiation curable resin and the synthetic resin particles 8 according to desired physical properties to be provided in the surface protective layer 2. 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 protective layer 2, For example, about 0.1-30 micrometers, Preferably it is about 5-20 micrometers, More preferably, about 7-15 micrometers is mentioned. When the thickness within such a range is satisfied, sufficient physical properties as a surface protective layer such as scratch resistance can be obtained. Further, since the ionizing radiation curable resin composition forming the surface protective layer 2 can be uniformly irradiated with ionizing radiation, it can be uniformly cured, which is economically advantageous. The thickness of the surface protective layer 2 refers to the thickness of the portion where the synthetic resin particles 8 do not protrude from the surface.

  The surface protective layer 2 is formed, for example, by preparing the above resin composition, applying it, and crosslinking and curing it. In addition, the viscosity of a resin composition should just be a viscosity which can form an uncured resin layer on the layer adjacent to the surface protective layer 2 with the application | coating system mentioned later. In the present invention, the prepared coating solution is formed on the layer adjacent to the surface protective layer 2 so as to have the above thickness, such as gravure coat, gravure reverse coat, bar coat, roll coat, reverse roll coat, comma coat, etc. Is applied by a known method, preferably gravure coating, to form an uncured resin layer. The uncured resin layer thus formed is irradiated with ionizing radiation such as electron beams and ultraviolet rays to cure the uncured resin layer to form the surface protective layer 2. Here, when an electron beam is used as the ionizing radiation, the acceleration voltage can be appropriately selected according to the resin to be used and the thickness of the layer, but usually includes an acceleration voltage of about 70 to 300 kV.

  In addition, 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 protective layer 2, the electron beam transmission depth and the surface protection are used. The acceleration voltage is selected so that the thicknesses of the layers 2 are substantially equal. Thereby, irradiation of the extra electron beam to the layer located under the surface protective layer 2 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.

[Primer layer 3]
The decorative sheet of the present invention is optionally provided between the base layer 1 and the surface protective layer 2 between the base layer 1 and the surface protective layer 2 for the purpose of making fine cracks and whitening difficult to occur in the stretched portion of the surface protective layer 2. In the case of providing the primer layer 3, the primer layer 3 may be provided between the pattern layer 4 and the surface protective layer. The primer layer 3 preferably has a thickness of 0.1 μm or more. When it is 0.1 μm or more, the surface protective layer has an effect of preventing cracking, breaking, whitening, and the like. On the other hand, if the thickness of the primer layer 3 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 is applied. From this viewpoint, the thickness of the primer layer 3 is preferably 1 to 10 μm.

  In addition, the primer layer 3 preferably has a breaking elongation at 120 ° C. of 150% or more measured under the following measurement conditions, and more preferably 200% or more. When the elongation at break is 150% or more, fine cracks and whitening hardly occur in the stretched portion of the surface protective layer 2 during vacuum forming.

(Measurement conditions for measuring elongation at break)
In accordance with JIS K7127: 1999, a sample having a width of 25 mm × length (distance between chucks) of 50 mm × thickness of 40 ± 10 μm was formed by curing (heating at 50 ° C. for 72 hours) the primer composition constituting the primer layer 3. After leaving the oven at 120 ° C. and leaving it for 120 seconds, the elongation at break is measured at a tensile rate of 50 mm / min.

  The primer composition constituting the primer layer 3 includes 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 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 standpoints of adhesion to the surface protective layer after crosslinking, difficulty of interaction after laminating the surface protective layer 2, 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.

<Inorganic particles, synthetic resin particles>
The primer layer 3 preferably includes inorganic particles and / or synthetic resin particles from the viewpoint of improving design properties. By including inorganic particles and / or synthetic resin particles in the primer layer 3, it is possible to remarkably improve the surface matting effect and scratch resistance. Moreover, when unevenness | corrugation is formed in the surface of the primer layer 3 with an inorganic particle and / or a synthetic resin particle, the adhesiveness with the other layer which touches can also be improved further.

  Preferred examples of the inorganic particles include silica, alumina, calcium carbonate, magnesium carbonate, calcium sulfate, barium sulfate, kaolin, and hydrophobic treated products thereof. These inorganic particles may be used individually by 1 type, and may be used in combination of 2 or more type. As the synthetic resin particles, acrylic beads, urethane beads, nylon beads, silicone beads, silicone rubber beads, polycarbonate beads, polyolefin wax (polypropylene wax, polyethylene wax, a mixture thereof, etc.) are preferably exemplified. These synthetic resin particles may be used individually by 1 type, and may be used in combination of 2 or more type.

  The primer layer 3 may contain any one of inorganic particles and synthetic resin particles, or a combination thereof. The average particle size of the inorganic particles and the synthetic resin particles is preferably from 0.1 to 5 μm, more preferably from 1 to 5 μm, and even more preferably from 2 to 5 μm, from the viewpoint of improving design properties. In addition, the measuring method of the particle diameter of an inorganic particle and a synthetic resin particle is the value measured by the measuring method similar to the synthetic resin particle 8.

  Primer layer 3 is a gravure coat, gravure reverse coat, gravure offset coat, spinner coat, roll coat, reverse roll coat, kiss coat, wheeler coat, dip coat, solid screen by silk screen, 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.

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

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

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

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

[Hidden layer 5]
The concealing layer 5 is provided with the base layer 1 and the pattern layer if the pattern layer 4 is provided between the base layer 1 and the surface protective layer 2 for the purpose of suppressing the color change and variation of the base layer 1. 4 is a layer provided as necessary, for example.

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

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

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

[Transparent film layer 6]
The transparent film layer 6 serves as a support for improving the scratch resistance and weather resistance of the decorative sheet of the present invention, and also enhances moldability, and as necessary, such as the base material layer 1 and the pattern layer 4 Provided on top. The transparent film layer 6 is formed of a resin film. By providing the transparent film layer 6, moldability is improved, and cracks are hardly generated in the surface protective layer 2 and the second protective layer 3 when the decorative sheet is three-dimensionally molded. The resin film forming the transparent film layer 6 is not particularly limited as long as it can enhance the moldability of the decorative sheet and does not conceal the design by the pattern layer 4 when provided on the pattern layer 4. For example, a film of a polyester resin such as polyethylene terephthalate (PET) or polyethylene naphthalate (PEN), or an acrylic resin can be used. Although the thickness of the transparent film layer 6 is not specifically limited, Usually, about 10-200 micrometers, Preferably it is about 15-150 micrometers. The method for forming the transparent film layer 6 is not particularly limited. For example, a method of laminating the above resin film on the surface of an adjacent layer such as the base material layer 1 or the picture layer 4 by heat lamination, dry lamination, or the like. Is mentioned.

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

  Although the adhesive layer 7 is not necessarily a necessary layer, it is assumed that the decorative sheet of the present invention is applied to a decoration method by sticking on a resin molded body prepared in advance, such as a vacuum pressure bonding method described later. Is preferably provided. When used in the vacuum pressure bonding method, it is preferable to form the adhesive layer 8 using a conventional resin that exhibits adhesiveness by pressurization or heating among the various resins described above.

  Although the thickness in particular of the contact bonding layer 7 is not restrict | limited, For example, about 0.1-30 micrometers, Preferably it is about 0.5-20 micrometers, More preferably, about 1-8 micrometers is mentioned.

2. Decorated resin molded product The decorated resin molded product of the present invention is formed by integrating a molded resin with the decorated sheet of the present invention. That is, the decorative resin molded product of the present invention comprises a laminate in which at least a molded resin layer, a base material layer, and a surface protective layer are laminated in this order, and the surface protective layer comprises an ionizing radiation curable resin and It is formed of a resin composition containing synthetic resin particles, and the surface protective layer contains 65 mass parts or more of synthetic resin particles with respect to 100 mass parts of ionizing radiation curable resin. In the decorative resin molded product of the present invention, if necessary, the decorative sheet is further provided with at least one layer such as the above-described primer layer 3, pattern layer 4, concealing layer 5, transparent film layer 6, adhesive layer 7, and the like. It may be.

  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. In addition, the decorative resin molded product of the present invention can be obtained by a decorative method of sticking the decorative sheet of the present invention on a three-dimensional resin molded body (molded resin layer) prepared in advance, such as a vacuum pressure bonding method. Can also be made.

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

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

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

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

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

  In the preforming step of the simultaneous injection molding method, the heating temperature of the decorative sheet is not particularly limited, and may be appropriately selected depending on the type of resin constituting the decorative sheet, the thickness of the decorative sheet, 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 vacuum bonding method, first, the decorative sheet and the resin molded body of the first pressure chamber located on the upper side and the second vacuum chamber located on the lower side in the vacuum pressure bonding machine, the decorative sheet is the first. The vacuum chamber side is placed in a vacuum press so that the resin molded body is on the second vacuum chamber side, and the base material layer 1 side of the decorative sheet faces the resin molded body side, and the two vacuum chambers are in a vacuum state. To do. The resin molding is installed on a lifting platform that is provided on the second vacuum chamber side and can be moved up and down. Next, while pressurizing the first vacuum chamber, the molded body is pressed against the decorative sheet using an elevator, and the resin molded body is stretched while stretching the decorative sheet using the pressure difference between the two vacuum chambers. Adhere to the surface. Finally, the two vacuum chambers are opened to the atmospheric pressure, and the decorative resin molded product of the present invention can be obtained by trimming the excess portion of the decorative sheet as necessary.

  In the vacuum pressure bonding method, it is preferable to include a step of heating the decorative sheet in order to soften the decorative sheet and improve the formability before the step of pressing the molded body against the decorative sheet. The vacuum pressure bonding method provided with the said process may be especially called a vacuum thermocompression bonding method. Although the heating temperature in the said process should just be suitably selected with the kind of resin which comprises a decorating sheet, the thickness of a decorating sheet, etc., if it is a case where a polyester resin film or an acrylic resin film is used as a base material layer Usually, it can be about 60-200 degreeC.

  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.

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

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

<Examples 1-6 and Comparative Examples 1-3>
(Preparation of decorative sheet)
A pattern layer (thickness 10 μm) was formed by gravure printing on an ABS resin film (thickness 400 μm) as a base material layer using an ink containing vinyl chloride-vinyl acetate-acrylic copolymer resin. The pattern of the pattern layer was a wood grain pattern. Next, a primer layer (thickness 2 μm) was formed on the pattern layer by gravure printing using a primer composition described later. Next, an ionizing radiation curable resin, which will be described later, was applied on the primer layer by gravure reverse coating so that the thickness after curing was 8 μm. Next, the coated ionizing radiation curable resin is irradiated with an electron beam (acceleration voltage 165 kV, irradiation dose 50 kGy (5 Mrad)) to cure the ionizing radiation curable resin to form a surface protective layer. A decorative sheet having a configuration as shown in Table 1 and having a base layer / picture layer / primer layer / surface protective layer laminated in this order was obtained.

(Formability evaluation test)
The decorative sheets of Examples 1 to 6 and Comparative Examples 1 to 3 were each heated to 160 ° C. with an infrared heater and softened. Next, using a vacuum forming mold, vacuum forming was performed under the condition that the maximum draw ratio was 300%, and a decorative sheet was formed so as to have an internal shape of the vacuum forming mold. Next, the decorative sheet was cooled and then released from the vacuum forming mold. About each mold-released decorative sheet, the moldability was evaluated according to the following evaluation criteria. The results are shown in Table 1.
◯: No coating film cracking or whitening was observed in the three-dimensional molded part and the maximum stretched part (300%) of the surface protective layer.
Δ: Although cracking or whitening of the coating film was observed in a part of the three-dimensional molded portion and the maximum stretched portion (300%) of the surface protective layer, there was no practical problem. Seen

(Scratch resistance evaluation test)
The surfaces of the decorative sheets of Examples 1 to 6 and Comparative Examples 1 to 3 were reciprocated 10 times with a weight of 1.5 kgf using # 0000 steel wool, and the state of the surface of the decorative sheet was visually observed. The evaluation was performed according to the criteria. The results are shown in Table 1.
○: Fine scratches were observed on the surface, but there was no cracking or whitening of the coating film. Δ: Slight scratches were observed on the surface, but there were no practical problems. ×: Significant scratches were observed on the surface.

(Fingerprint resistance evaluation test)
A finger was pressed against the surfaces of the decorative sheets of Examples 1 to 6 and Comparative Examples 1 to 3 for several seconds, and the attached fingerprint was visually observed and evaluated according to the following criteria. The results are shown in Table 1.
○: Almost no trace of fingerprints left △: A few traces of fingerprints left ×: Some traces of fingerprints left

(Tactile evaluation test)
The surface of the decorative sheets of Examples 1 to 6 and Comparative Examples 1 to 3 was touched with a finger, and the tactile sensation was evaluated according to the following criteria. The results are shown in Table 1.
○: Smooth and slippery △: Smooth and slippery ×: Rough and slippery

As each component shown in Table 1, the following were used.
(Ionizing radiation curable resin)
EB1: Mixed resin (mass ratio 80/20) of bifunctional polycarbonate acrylate (weight average molecular weight 10,000) / 6 functional urethane acrylate oligomer (weight average molecular weight 6,000)
(Primer composition)
Mixture of acrylic polyol and hexamethylene diisocyanate. Hexamethylene diisocyanate was blended so as to have the same NCO equivalent as the OH equivalent of the acrylic polyol.

As shown in Table 1, in the decorative sheet of Examples 1 to 6 in which 65 parts by mass or more of synthetic resin particles are used with respect to 100 parts by mass of the resin in the surface protective layer, the moldability, scratch resistance, and fingerprint resistance Both the property and the tactile sensation evaluation were satisfactory, and there was no practical problem. On the other hand, in the decorative sheet of Comparative Example 1 in which no synthetic resin particles were used in the surface protective layer, fingerprint resistance and tactile sensation were extremely poor. Moreover, in the surface protective layer, in the decorative sheet of Comparative Example 2 using 30 parts by mass of silica particles, the moldability and scratch resistance were inferior. Furthermore, in the decorative sheet of Comparative Example 3 using 40 parts by mass of synthetic resin particles in the surface protective layer, the fingerprint resistance was inferior.

DESCRIPTION OF SYMBOLS 1 ... Base material layer 2 ... Surface protective layer 3 ... Primer layer 4 ... Picture layer 5 ... Concealing layer 6 ... Transparent film layer 7 ... Adhesive layer 8 ... Synthetic resin particle

Claims (9)

At least a base layer, a decorative sheet for three-dimensional molding to have a surface protecting layer,
The surface protective layer covers the entire surface of one side of the decorative sheet,
The surface protective layer is formed of a resin composition containing an ionizing radiation curable resin and synthetic resin particles,
In the surface protective layer, the decorative sheet for three-dimensional molding , wherein the synthetic resin particles are contained in an amount of 65 parts by mass or more with respect to 100 parts by mass of the ionizing radiation curable resin. The decorative sheet for three-dimensional molding according to claim 1, wherein the ionizing radiation curable resin contains polycarbonate (meth) acrylate. The decorative sheet for three-dimensional molding according to claim 2, wherein the ionizing radiation curable resin further contains a polyfunctional (meth) acrylate. The decorative sheet for three-dimensional molding according to claim 3, wherein a mass ratio of the polycarbonate (meth) acrylate and the polyfunctional (meth) acrylate is 98: 2 to 60:40. The decorative sheet for three-dimensional molding according to any one of claims 1 to 4, wherein a particle diameter of the synthetic resin particles is 2 to 15 µm. The decorative sheet for three-dimensional molding according to any one of claims 1 to 5, wherein the surface protective layer has a thickness of 1 to 30 µm. The synthetic resin particle is at least one selected from the group consisting of urethane beads, nylon beads, acrylic beads, silicone beads, styrene beads, melamine beads, urethane acrylic beads, polyester beads, and polyethylene beads. The decorative sheet for three-dimensional molding according to any one of -6. The decorative sheet for three-dimensional molding according to any one of claims 1 to 7, further comprising a pattern layer between the base material layer and the surface protective layer. At least a molding resin layer, a substrate layer, a surface protective layer is a decorated resin molded article ing a laminate are laminated in this order,
The surface protective layer covers the entire surface of one side of the decorative resin molded product,
The surface protective layer is formed of a resin composition containing an ionizing radiation curable resin and synthetic resin particles,
In the surface protective layer, a decorative resin molded product in which the synthetic resin particles are contained in an amount of 65 parts by mass or more with respect to 100 parts by mass of the ionizing radiation curable resin.