JP6221571B2 - Decorative sheet and decorative resin molded product - Google Patents

Description

  The present invention relates to a decorative sheet capable of recognizing a high three-dimensional effect in addition to high moldability and scratch 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.

  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 exhibit designs that can recognize a three-dimensional effect.

  Until now, the technique which provides the designability which can recognize a three-dimensional effect visually by providing an unevenness | corrugation and matte on the surface of a decorating sheet has been reported. For example, Patent Document 1 discloses a decorative sheet having at least a surface protective layer on a base material and a transparent resin layer partially provided on the surface protective layer, and a partially provided transparent sheet. A method for giving a three-dimensional appearance to the appearance of a decorative sheet by a gloss difference or uneven shape between a resin layer and a surface protective layer is disclosed. However, in the decorative sheet, the height difference of the unevenness formed on the surface was very small and almost smooth, and when the touch was actually touched, an excellent stereoscopic effect could not be felt.

  In addition, in the case of a decorative sheet used for the insert molding method and the simultaneous injection molding method, the surface unevenness tends to be attenuated by receiving heat and pressure in the resin injection and the vacuum forming process preceding it. It is done. The same problem may occur when applied to a decoration method such as a vacuum pressure bonding method that is stuck on a molded body with heating or pressurization. Therefore, even after processing into a decorated resin molded product, the development of a decorative sheet that provides an excellent three-dimensional effect when touched by hand has not been sufficiently performed.

JP 2009-113387 A

  In recent years, there has been a demand for the development of designs that can recognize even better three-dimensional effects, and the development of decorative sheets that have a surface that can be felt not only in appearance but also in three-dimensional appearance when actually touched by hand is required. It has been. The main object of the present invention is to provide a decorative sheet and a decorative resin molded article that have excellent moldability and scratch resistance, and also have an excellent tactile sensation that allows a three-dimensional effect to be sensed even when actually touched by hand. And

  The present inventor has intensively studied to solve the above problems. As a result, at least the base material layer, the first surface layer, and the second surface layer provided on a part of the first surface layer in this order, the second surface layer, The decorative sheet is formed of a resin composition containing a resin and synthetic resin particles, and in the second surface layer, the decorative resin sheet containing 50 parts by mass or more of synthetic resin particles with respect to 100 parts by mass of the resin has moldability and It has been found that it has excellent scratch resistance and also has an excellent tactile sensation that allows a three-dimensional effect to be sensed even when actually touched with a hand. 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 base material layer, a first surface layer, and a second surface layer provided on a part of the first surface layer in this order,
The second surface layer is formed of a resin composition containing a resin and synthetic resin particles;
The said 2nd surface layer WHEREIN: The decorative sheet in which the said synthetic resin particle is contained 50 mass parts or more with respect to 100 mass parts of said resin.
Item 2. Item 2. The decorative sheet according to Item 1, wherein in the resin composition forming the second surface layer, the resin contains an ionizing radiation curable resin.
Item 3. Item 3. The decorative sheet according to Item 2, wherein in the resin composition forming the second surface layer, the resin contains polycarbonate (meth) acrylate.
Item 4. Item 4. The decorative sheet according to Item 3, wherein in the resin composition forming the second surface layer, the resin further contains a polyfunctional (meth) acrylate.
Item 5. Item 5. The decorative sheet according to Item 4, wherein a mass ratio of the polycarbonate (meth) acrylate and the polyfunctional (meth) acrylate is 98: 2 to 60:40.
Item 6. Item 6. The decorative sheet according to any one of Items 1 to 5, wherein the first surface layer is formed of a resin composition containing an ionizing radiation curable resin.
Item 7. Item 7. The decorative sheet according to any one of Items 1 to 6, wherein the synthetic resin particles have a particle size of 2 to 15 µm.
Item 8. Item 8. The decorative sheet according to any one of Items 1 to 7, wherein the second surface layer has a thickness of 0.1 to 15 µm.
Item 9. 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, The decorative sheet according to any one of 8.
Item 10. Item 10. The decorative sheet according to any one of Items 1 to 9, further comprising a pattern layer between the base material layer and the first surface layer.
Item 11. At least a molded resin layer, a first surface layer, and a second surface layer provided on a part of the first surface layer is a laminated body laminated in this order,
The second surface layer is formed of a resin composition containing a resin and synthetic resin particles;
In the second surface layer, a decorative resin molded product in which the synthetic resin particles are contained in an amount of 50 parts by mass or more with respect to 100 parts by mass of the resin.

  According to the decorative sheet of the present invention, the decorative sheet has excellent formability and scratch resistance, and has an excellent tactile sensation that allows a three-dimensional effect to be sensed even when actually touched with the hand, and the decorative sheet is used. The decorated decorative resin molded product can be provided.

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. Decorative sheet The decorative sheet of the present invention has at least a base material layer, a first surface layer, and a second surface layer provided on a part of the first surface layer in this order. The second surface layer is formed of a resin composition containing a resin and synthetic resin particles. In the second surface layer, the synthetic resin particles are contained in an amount of 50 parts by mass or more with respect to 100 parts by mass of the resin. It is characterized by that. In the decorative sheet of the present invention, in the second surface layer provided on a part of the first surface layer, the synthetic resin particles are included in an amount of 50 parts by mass or more with respect to 100 parts by mass of the resin. Thus, it is possible to obtain a decorative sheet having excellent formability and scratch resistance, and having an excellent tactile sensation in which not only the appearance but also a three-dimensional effect can be sensed when actually touched with a hand. More specifically, the second surface layer provided on a part of the first surface layer contains a large amount of synthetic resin particles of 50 parts by mass or more with respect to 100 parts by mass of the resin. Since the gloss of the second surface layer that is partially formed is greatly reduced, it is possible to impart a three-dimensional effect to the appearance of the decorative sheet by the difference in gloss between the first surface layer and the second surface layer. it can. Furthermore, the surface of the second surface layer containing such a large amount of resin particles is more slippery than the first layer. Thereby, on the first surface layer, a large difference in slipperiness is provided between the portion where the second surface layer is formed and the portion where the second surface layer is not formed, and the decorative sheet When the surface of the surface is actually touched with a hand, the formation part of the second surface layer that is slippery is perceived as protruding from the non-formation part of the second surface layer that is difficult to slip, and a large three-dimensional feeling is felt It becomes possible. Furthermore, in the decorative sheet of the present invention, the three-dimensional feeling when touched with a hand is maintained even after being processed as a decorative resin molded product. 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 at least a base material layer 1, a first surface layer, and a second surface layer provided on a part of the first surface layer. It has a laminated structure laminated in this order. In the decorative sheet of the present invention, a primer layer 4 may be provided under the first surface layer 2 for the purpose of making it difficult for fine cracks and whitening to occur in the stretched portion of the first surface layer 2. . Moreover, you may provide the pattern layer 5 as needed for the purpose of providing a decorative property to a resin molded product. If the pattern layer 5 is provided between the base layer 1 and the first surface layer 2 for the purpose of suppressing the color change and variation of the base layer 1, the base layer 1 and the pattern layer 5 You may provide the concealing layer 6 between them as needed. Furthermore, if the pattern layer 5 is provided between the base material layer 1 and the first surface layer 2 for the purpose of enhancing the moldability of the decorative sheet, the pattern layer 5 and the first surface layer 2 are provided. If necessary, a transparent film layer 7 or the like may be provided. Furthermore, an adhesive layer 8 or the like may be provided under the base material layer 1.

  As a laminated structure of the decorative sheet of the present invention, a laminated structure in which a base material layer / first surface layer / second surface layer are laminated in this order; base material layer / primer layer / first surface layer / second Layered structure in which surface layers are laminated in this order; substrate layer / picture layer / first surface layer / second surface layer are laminated in this order; substrate layer / picture layer / primer layer / number Laminated structure in which 1 surface layer / second surface layer is laminated in this order; Laminated structure in which base layer / hiding layer / picture layer / first surface layer / second surface layer are laminated in this order; Laminated structure in which material layer / hiding layer / picture layer / primer layer / first surface layer / second surface layer are laminated in this order; base material layer / hiding layer / picture layer / transparent film layer / first surface Layer / laminated structure in which the second surface layer is laminated in this order; adhesive layer / base material layer / hiding layer / pattern layer / primer layer / first surface layer / Laminated structure in which two surface layers are laminated in this order; adhesive layer / base material layer / hiding layer / pattern layer / transparent film layer / primer layer / first surface layer / second surface layer are laminated in this order Examples include a laminated structure. FIG. 1 is a schematic cross-sectional view of an example of a decorative sheet in which a base material layer / first surface layer / second surface layer are laminated in this order as an aspect of the laminated structure of the decorative sheet of the present invention. Show. FIG. 2 shows an example of a decorative sheet in which a base layer / picture layer / primer layer / first surface layer / second surface layer are stacked in this order as an embodiment of the laminated structure of the decorative sheet of the present invention. The schematic sectional drawing of is shown. In FIG. 3, as an aspect of the laminated structure of the decorative sheet of the present invention, an adhesive layer / base material layer / hiding layer / pattern layer / transparent film layer / primer layer / first surface layer / second surface layer The schematic sectional drawing of an example of the decorative sheet laminated | stacked in this order is shown.

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.

[First surface layer 2]
The 1st surface layer 2 is a layer provided in order to improve the abrasion resistance etc. of a decorating sheet, and also to give a high three-dimensional effect to a decorating sheet with the 2nd surface layer 3 mentioned later. The first surface layer 2 is formed of a resin composition containing a resin. Specifically, the 1st surface layer 2 is comprised by the hardened | cured material of the said resin composition. The resin contained in the resin composition forming the first surface layer 2 is not particularly limited. For example, the ionizing radiation curable resin, the thermosetting resin, and the thermoplastic exemplified in the second surface layer 3 described later. Resin etc. are mentioned. The 1st surface layer 2 is ionizing radiation containing the below-mentioned polyfunctional polycarbonate (meth) acrylate similarly to the 2nd surface layer 3 from viewpoints, such as the three-dimensional moldability of a decorating sheet, and abrasion resistance. It is preferable that it is formed of a curable resin composition. Moreover, in the 1st surface layer 2, you may use together the below-mentioned (meth) acrylate similarly to the 2nd surface layer 3. FIG.

  As will be described later, in the present invention, the difference in slipperiness between the first surface layer 2 and the second surface layer 3 is increased, and the surface of the decorative sheet of the present invention is actually touched by hand. From the viewpoint of imparting excellent tactile sensation in which a three-dimensional feeling can be felt, it is preferable that the first surface layer 2 is substantially free of particles such as synthetic resin particles and inorganic particles that improve the slipperiness of the surface. . When the 1st surface layer 2 contains these particle | grains, it is preferable to set it as 40 mass parts or less with respect to 100 mass parts of resin. In addition, when mix | blending particles, such as a synthetic resin particle and an inorganic particle, with the 1st surface layer 2, a part of these particle | grains may protrude from the surface of the 1st surface layer 2, or 1st surface. These particles may be buried in the layer 2.

  In addition to the resin, various additives can be blended in the first surface layer 2 in accordance with desired physical properties to be provided in the first surface layer 2. As this additive, the thing similar to what was illustrated by the 2nd surface layer 3 mentioned later can be illustrated.

  Although there is no restriction | limiting in particular about the thickness after hardening of the 1st surface 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 in such a range is satisfied, sufficient physical properties as a surface protective layer such as scratch resistance can be obtained. In addition, since the ionizing radiation curable resin composition forming the first surface layer 2 can be uniformly irradiated with ionizing radiation, it can be uniformly cured, which is economically advantageous. Become. In addition, when the 1st surface layer 2 contains the above inorganic particles, synthetic resin particles, etc., the thickness of the 1st surface layer 2 means the thickness of the part which these particles do not protrude from the surface.

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

[Second surface layer 3]
The second surface layer 3 is provided on a part of the first surface layer 2 in the decorative sheet of the present invention. The second surface layer 3 is formed of a resin composition containing a resin and synthetic resin particles. Specifically, the 2nd surface layer 3 is comprised by the hardened | cured material of the said resin composition. In the second surface layer 3, the synthetic resin particles are contained in an amount of 50 parts by mass or more with respect to 100 parts by mass of the resin, so that the moldability and the scratch resistance are excellent. An excellent tactile sensation that gives a three-dimensional feel even when touched is imparted to the decorative sheet. That is, in the second surface layer 3 provided on a part of the first surface layer 2, the synthetic resin particles are contained in a large amount of 50 parts by mass or more with respect to 100 parts by mass of the ionizing radiation curable resin. As a result, the gloss of the partially formed second surface layer 3 is greatly reduced, so that the appearance of the decorative sheet is three-dimensional due to the difference in gloss between the first surface layer 2 and the second surface layer 3. A feeling can be imparted. Furthermore, the surface of the second surface layer 3 containing such a large amount of resin particles is more slippery than the first layer 2. Thereby, on the 1st surface layer 2, a big difference is provided in slipperiness between the part in which the 2nd surface layer 3 is formed, and the part in which the 2nd surface layer 3 is not formed, When the surface of the decorative sheet is actually touched with a hand, a large three-dimensional effect can be felt.

  The resin contained in the resin composition forming the second surface layer 3 is not particularly limited, and examples thereof include an ionizing radiation curable resin, a thermosetting resin, and a thermoplastic resin. The thermosetting resin is not particularly limited, and for example, epoxy resin, phenol resin, urea resin, unsaturated polyester resin, melamine resin, alkyd resin, polyimide resin, silicone resin, hydroxyl functional acrylic resin, carboxyl functional acrylic. Examples include resins, amide functional copolymers, and urethane resins. The thermoplastic resin is not particularly limited, and is an acrylic resin such as polymethyl (meth) acrylate and polyethyl (meth) acrylate; a polyolefin resin such as polypropylene and polyethylene; a polycarbonate resin; a vinyl chloride resin; and a polyethylene terephthalate ( PET); acrylonitrile-butadiene-styrene resin (ABS resin); acrylonitrile-styrene-acrylate resin;

  The second surface layer 3 is preferably formed of a resin composition containing an ionizing radiation curable resin from the viewpoints of the three-dimensional formability and scratch resistance of the decorative sheet. Hereinafter, the ionizing radiation curable resin preferably used as the resin contained in the resin composition forming the second surface layer 3 will be described in detail.

(Ionizing radiation curable resin)
An ionizing radiation curable resin is a resin that crosslinks and cures when irradiated with ionizing radiation. Specifically, a prepolymer, oligomer, and / or having a polymerizable unsaturated bond or an epoxy group in the molecule. What mixed the monomer 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 a photopolymerization initiator, and provides stable curing characteristics. Therefore, formation of the second surface layer 3 is possible. Are preferably used.

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

  The oligomer used as the ionizing radiation curable resin is preferably a (meth) acrylate oligomer having a radical polymerizable unsaturated group in the molecule, and more than two polymerizable unsaturated bonds in the molecule. A polyfunctional (meth) acrylate oligomer having (bifunctional or higher) is preferred. Examples of the polyfunctional (meth) acrylate oligomer include polycarbonate (meth) acrylate, acrylic silicone (meth) acrylate, urethane (meth) acrylate, epoxy (meth) acrylate, polyester (meth) acrylate, and polyether (meth) acrylate. , Polybutadiene (meth) acrylate, silicone (meth) acrylate, oligomer having a cationic polymerizable functional group in the molecule (for example, novolac type epoxy resin, bisphenol type epoxy resin, aliphatic vinyl ether, aromatic vinyl ether, etc.) . Here, the polycarbonate (meth) acrylate can be obtained, for example, by esterifying a polycarbonate polyol with (meth) acrylic acid. The acrylic silicone (meth) acrylate can be obtained by radical copolymerizing a silicone macromonomer with a (meth) acrylate monomer. Urethane (meth) acrylate can be obtained, for example, by esterifying a polyurethane oligomer obtained by reaction of polyether polyol or polyester polyol and polyisocyanate with (meth) acrylic acid. Epoxy (meth) acrylate can be obtained, for example, by reacting (meth) acrylic acid with an oxirane ring of a relatively low molecular weight bisphenol type epoxy resin or novolak type epoxy resin and esterifying it. Also, a carboxyl-modified epoxy (meth) acrylate obtained by partially modifying this epoxy (meth) acrylate with a dibasic carboxylic acid anhydride can be used. Polyester (meth) acrylate is obtained by esterifying the hydroxyl group of a polyester oligomer having hydroxyl groups at both ends obtained by condensation of a polyvalent carboxylic acid and a polyhydric alcohol with (meth) acrylic acid, for example, or It can be obtained by esterifying the terminal hydroxyl group of an oligomer obtained by adding an alkylene oxide with (meth) acrylic acid. The polyether (meth) acrylate can be obtained by esterifying the hydroxyl group of the polyether polyol with (meth) acrylic acid. Polybutadiene (meth) acrylate can be obtained by adding (meth) acrylic acid to the side chain of the polybutadiene oligomer. Silicone (meth) acrylate can be obtained by adding (meth) (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 for forming the second surface layer 3, 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. 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 second surface layer 3 will be described.

<Polycarbonate (meth) acrylate>
In the second surface layer 3 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. If it is, it will not be restrict | limited in particular. 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.

  In the second surface layer 3, the synthetic resin particles 9 are dispersed in the second surface layer 3. In the 2nd surface layer 3, the synthetic resin particle 9 is contained 50 mass parts or more with respect to 100 mass parts of resin. As content of the synthetic resin particle 9 in the 2nd surface layer 3, Preferably 65 mass parts or more is mentioned. In addition, the upper limit of the content of the synthetic resin particles 9 in the second surface layer 3 is not particularly limited as long as the effects of the present invention are achieved, but the second surface layer 3 is formed by a printing method described later. In consideration of formation, the amount is preferably 200 parts by mass or less, more preferably 150 parts by mass or less, and still more preferably 100 parts by mass or less with respect to 100 parts by mass of the resin.

  The synthetic resin particle 9 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 9, 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 9 may be used alone or in combination of two or more. The particle diameter of the synthetic resin particle 9 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, a part of the synthetic resin particles 9 may protrude from the surface of the second surface layer 3, or the synthetic resin particles 9 are embedded in the second surface layer 3. You may do it.

  In addition to the resin, various additives can be blended in the second surface layer 3 according to desired physical properties to be provided in the second surface layer 3. 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.

  The thickness of the second surface layer 3 after curing is not particularly limited, but is preferably about 0.1 to 15 μm, more preferably about 0.5 to 10 μm, and still more preferably about 1 to 5 μm. When the thickness in such a range is satisfied, sufficient physical properties as a surface protective layer such as scratch resistance can be obtained. Moreover, since it is possible to uniformly irradiate the resin composition forming the second surface layer 3 with ionizing radiation, the resin composition can be cured uniformly, which is economically advantageous. In addition, the thickness of the 2nd surface layer 3 means the thickness of the part which the synthetic resin particle 9 does not protrude.

  For example, the second surface layer 3 is formed by preparing a resin composition containing the resin and the synthetic resin particles 9, applying the resin composition, and curing it by heating or irradiation with ionizing radiation as necessary. Done. In addition, the viscosity of a resin composition should just be a viscosity which can form an uncured resin layer on the 1st surface layer 2 with the below-mentioned application | coating system. In the present invention, a known printing method such as gravure printing, offset printing, silk screen printing, and ink jet printing is preferably applied to a part of the first surface layer 2 so that the prepared coating liquid has the thickness described above. Is applied by gravure printing to form an uncured resin layer. The uncured resin layer thus formed is cured to form the second surface layer 3. Curing can be performed by irradiation with ionizing radiation such as electron beam or ultraviolet rays when using an ionizing radiation curable resin as a resin, heating when using a thermosetting resin, or drying when using a thermoplastic resin. It can be performed by cooling or the like. 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 electron beam irradiation, since the transmission capability increases as the acceleration voltage is higher, when using a resin that is easily deteriorated by electron beam irradiation under the first surface layer 2 and the second surface layer 3 The accelerating voltage is selected so that the penetration depth of the electron beam and the thicknesses of the first surface layer 2 and the second surface layer 3 are substantially equal. Thereby, irradiation of the extra electron beam to the layer located under the first surface layer 2 and the second surface layer 3 can be suppressed, and deterioration of each layer due to the excess electron beam is minimized. Can do. The irradiation dose is preferably such that the crosslinking density of the first surface layer 2 and the second surface layer 3 is saturated, usually 5 to 300 kGy (0.5 to 30 Mrad), preferably 10 to 50 kGy (1 to 5 Mrad). ) Is selected. 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.

  When both the first surface layer 2 and the second surface layer 3 are formed of an ionizing radiation curable resin composition, the ionizing radiation curable resin composition forming the first surface layer 2 is uncured or semi-cured. In the cured state, the ionizing radiation curable resin composition for forming the second surface layer 3 is partially laminated on the ionizing radiation curable resin composition, and then the first surface layer 2 and the second surface layer 2 are laminated. By irradiating the ionizing radiation curable resin composition of both layers of the surface layer 3 under conditions that can be crosslinked and cured, both layers can be formed by a single ionizing radiation irradiation step. Further, the ionizing radiation may be irradiated twice at the time of forming the first surface layer 2 and at the time of forming the second surface layer 3.

  If the 2nd surface layer 3 is formed on a part of 1st surface layer 2, it will not specifically limit about the position and range, but from a viewpoint of obtaining a high design feeling, for example, It is preferably formed so as to express patterns represented by wood grain patterns, lattice patterns, fabric patterns, stone patterns, tiled patterns, brickwork patterns, hairline patterns, and the like. There is no particular limitation on the ratio of the area of the portion where the second surface layer 3 is formed to the area of the portion where the second surface layer 3 is not formed on the first surface layer 2, and the area of any portion may be large. The area of both may be the same.

  Furthermore, when providing the pattern layer 5 mentioned later, you may form so that the pattern formed by the 2nd surface layer 3 and the pattern formed by the pattern layer 5 may synchronize. According to such a configuration, it is possible to give a higher three-dimensional effect to the decorative sheet due to the synergistic effect of vision and touch.

[Primer layer 4]
The decorative sheet of the present invention is provided between the base material layer 1 and the first surface layer 2 as desired for the purpose of making fine cracks and whitening difficult to occur in the stretched portion of the first surface layer 2. When the pattern layer 5 is provided, the primer layer 4 may be provided between the pattern layer 5 and the first surface layer 2. The primer layer 4 preferably has a thickness of 0.1 μm or more. When the thickness is 0.1 μm or more, the first surface layer 2 has an effect of preventing cracking, breakage, whitening, and the like. On the other hand, if the thickness of the primer layer 4 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 4 is preferably 1 to 10 μm.

  In addition, the primer layer 4 has a breaking elongation at 120 ° C. measured under the following measurement conditions of preferably 150% or more, 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 first surface 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 formed by curing (heating at 50 ° C. for 72 hours) the primer composition constituting the primer layer 4 was formed. 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.

  Primer compositions constituting the primer layer 4 include 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 first surface layer 2 after crosslinking, difficulty of interaction after laminating the first surface layer 2, physical properties, and moldability, crosslinking with acrylic polyol or polyester polyol as a polyol It is preferable to combine hexamethylene diisocyanate and 4,4-diphenylmethane diisocyanate as materials, and it is particularly preferable to use a combination of acrylic polyol and hexamethylene diisocyanate.

  (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 4 preferably contains 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 4, it is possible to remarkably improve the matte surface effect and scratch resistance. Moreover, when the unevenness | corrugation is formed in the surface of the primer layer 4 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 4 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 9.

  The primer layer 4 is 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.

[Picture layer 5]
The pattern layer 5 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 5 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 5, a binder appropriately mixed with 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 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 5 is not restrict | limited, For example, about 1-30 micrometers, Preferably about 1-20 micrometers is mentioned.

[Hidden layer 6]
The hiding layer 6 is provided with the base material layer 1 if the pattern layer 5 is provided between the base material layer 1 and the first surface layer 2 for the purpose of suppressing the color change and variation of the base material layer 1. It is a layer provided as needed between the pattern layer 5 and the like.

  Since the concealing layer 6 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 6 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 6 is appropriately selected from those used for the pattern layer 5 described above.

  The concealing layer 6 is normally set to a thickness of about 1 to 20 μm and is desirably formed as a so-called solid printing layer.

[Transparent film layer 7]
The transparent film layer 7 serves as a support for enhancing the scratch resistance and weather resistance of the decorative sheet of the present invention and also for improving the moldability. If necessary, the transparent film layer 7 such as the base material layer 1 and the pattern layer 5 is used. Provided on top. The transparent film layer 7 is formed of a resin film. By providing the transparent film layer 7, the moldability is improved, and cracks are hardly generated in the first surface layer 2 and the second surface layer 3 when the decorative sheet is three-dimensionally formed. The resin film forming the transparent film layer 7 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 5 when provided on the pattern layer 5. 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 7 is not specifically limited, Usually, about 10-200 micrometers, Preferably it is about 15-150 micrometers. The method for forming the transparent film layer 7 is not particularly limited. For example, the above-described resin film is laminated on the surface of an adjacent layer such as the base material layer 1 or the picture layer 5 by heat lamination, dry lamination, or the like. Is mentioned.

[Adhesive layer 8]
The adhesive layer 8 is a layer provided on the back surface of the base material layer 1 as necessary for the purpose of improving the adhesiveness and adhesion between the decorative sheet and the molding resin. The resin for forming the adhesive layer 8 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 8 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 8 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, in the decorative resin molded product of the present invention, at least the molded resin layer, the first surface layer, and the second surface layer provided on a part of the first surface layer are laminated in this order. The second surface layer is formed of a resin composition containing a resin and synthetic resin particles, and in the second surface layer, the synthetic resin particles are based on 100 parts by mass of the resin. 50 parts by mass or more is included. 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 primer layer 4, the pattern layer 5, the concealing layer 6, the transparent film layer 7, and the adhesive layer 8. 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. 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 1-5 and Comparative Examples 1-4>
(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. Next, a primer layer (thickness 2 μm) was formed on the pattern layer by gravure printing using a primer composition described later. Next, the resin described in Table 1 was applied on the primer layer by gravure printing so that the thickness after curing was 2 μm (becomes a first surface layer). Next, the resin composition containing the resin and filler described in Table 1 was applied by gravure printing so as to form a lattice pattern having a width of 2 mm, a thickness of 2 μm, and an interval of 2 mm (becomes a second surface layer). Next, an electron beam is irradiated from the second surface layer side (acceleration voltage: 165 kV, irradiation dose: 50 kGy (5 Mrad)), and the ionizing radiation curable resin is cured to form the first surface layer and the second surface layer. Formed. As described above, a decorative sheet having a configuration as shown in Table 1 and obtained by laminating a base layer / picture layer / primer layer / first surface layer / second surface layer in this order was obtained. .

(Production of decorative resin molded products)
Each of the decorative sheets of Examples 1 to 5 and Comparative Examples 1 to 4 is heated at a heater hot platen temperature of 170 ° C., and molded so as to conform to the shape of the injection mold (maximum draw ratio: 100%). Then, the second surface layer side was brought into close contact with the inner surface of the mold. On the other hand, ABS resin was used as the injection resin, which was melted at 230 ° C. and then injected into the cavity. When the mold temperature reached 30 ° C., the decorated resin molded product was taken out of the mold to obtain a decorated resin molded product.

(Formability evaluation test)
The decorative sheets of Examples 1 to 5 and Comparative Examples 1 to 4 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 and whitening were observed in the three-dimensional molded part and the maximum stretched part (300%) of the surface 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 layer, there was no practical problem. ×: Cracking or whitening of the coating film was observed in the surface layer The

(Abrasion resistance evaluation test)
In accordance with JIS L0849 (Abrasion testing machine type II (Gakushin type)) for the surface of the above-mentioned decorative resin molded product obtained from the decorative sheets of Examples 1 to 5 and Comparative Examples 1 to 4 A scratch resistance evaluation test was conducted. The apparatus used for the test was a “Gakushin Abrasion Tester” manufactured by Tester Sangyo Co., Ltd., and evaluated using a test piece after 100 reciprocations with a 500 g load using Kanakin No. 3 as a white cotton cloth for friction. The evaluation criteria are as follows. The results are shown in Table 1.
○: No scratch on the surface Δ: Scratch or gloss change on the surface occurred in a portion of 1/4 or more and 1/2 or less ×: Scratch or gloss change on the surface occurred in a portion exceeding 1/2

(Tactile evaluation test)
The surfaces of the decorative resin molded products obtained from the decorative sheets of Examples 1 to 5 and Comparative Examples 1 to 4 were touched with fingers of the hand, and the tactile sensation was evaluated according to the following criteria. The results are shown in Table 1.
○: A feeling of unevenness was felt Δ: Slightly unevenness was felt ×: Unevenness was not felt

As each component shown in Table 1, the following were used.
(Ionizing radiation curable resin)
EB-1: bifunctional polycarbonate acrylate (weight average molecular weight 10,000) / 6-functional urethane acrylate oligomer (weight average molecular weight 6,000) mixed resin (mass ratio 80/20)
(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 5 in which the synthetic resin particles are used in an amount of 50 parts by mass or more with respect to 100 parts by mass of the resin in the second surface layer, the moldability and the decorative resin are used. When the molded article was made, the scratch resistance was good or practically unproblematic, and when the surface of the decorated resin molded article was actually touched with a hand, a large three-dimensional feeling was felt, and the tactile sensation was excellent. On the other hand, the decorative resin molded product of Comparative Example 1 using 65 parts by mass of silica particles in the second surface layer was inferior in scratch resistance and touch. Further, in the decorative resin molded product of Comparative Example 2 in which the synthetic resin particles were not used in the second surface layer, the three-dimensional effect was not felt when the surface of the decorative resin molded product was actually touched by hand. Was inferior. In the second surface layer, the decorative sheet of Comparative Example 3 using 30 parts by mass of silica particles is inferior in moldability and scratch resistance when used as a decorative resin molded product. As for the tactile sensation when actually touching the surface of the hand, the surface was slightly uneven. Moreover, in the 2nd surface layer, in the decorating sheet of the comparative example 4 which used 40 mass parts of synthetic resin particles with respect to 100 mass parts of resin, a moldability and abrasion resistance when it is set as a decorative resin molded product However, as for the tactile sensation when the surface of the decorative resin molded product was actually touched with the hand, the unevenness was slightly felt.

DESCRIPTION OF SYMBOLS 1 ... Base material layer 2 ... 1st surface layer 3 ... 2nd surface layer 4 ... Primer layer 5 ... Pattern layer 6 ... Concealing layer 7 ... Transparent film layer 8 ... Adhesive layer 9 ... Synthetic resin particle

Claims (10)

At least a base material layer, a first surface layer, and a second surface layer provided on a part of the first surface layer in this order,
The second surface layer is formed of a resin composition containing a resin and synthetic resin particles;
In the second surface layer, the synthetic resin particles are included in an amount of 50 parts by mass or more based on 100 parts by mass of the resin .
Particle diameter of the synthetic resin particles, Ru 2~8μm der, decorative sheet for three-dimensional molding. 3. The decorative sheet for three-dimensional molding according to claim 1, wherein in the resin composition forming the second surface layer, the resin contains an ionizing radiation curable resin. The resin composition which forms a said 2nd surface layer WHEREIN: The decorating sheet for three-dimensional shaping | molding of Claim 2 in which the said resin contains a polycarbonate (meth) acrylate. The decorative composition for three-dimensional molding according to claim 3, wherein in the resin composition forming the second surface layer, the resin further contains a polyfunctional (meth) acrylate. The decorative sheet for three-dimensional molding according to claim 4, 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 5, wherein the first surface layer is formed of a resin composition containing an ionizing radiation curable resin. The decorative sheet for three-dimensional molding according to any one of claims 1 to 6 , wherein the thickness of the second surface layer is 0.1 to 15 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 7 to 7 . The decorative sheet for three-dimensional molding according to any one of claims 1 to 8 , further comprising a pattern layer between the base material layer and the first surface layer. At least a molded resin layer, a first surface layer, and a second surface layer provided on a part of the first surface layer is a laminated body laminated in this order,
The second surface layer is formed of a resin composition containing a resin and synthetic resin particles;
In the second surface layer, the synthetic resin particles are included in an amount of 50 parts by mass or more based on 100 parts by mass of the resin .
Particle diameter of the synthetic resin particles, Ru 2~8μm der, decorated resin molded article.