JP6295573B2 - Decorative sheet and decorative resin molded product - Google Patents

Description

  The present invention relates to a decorative sheet with a small amount of residual solvent. 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. For example, an injection molding simultaneous transfer decorating method is known as a molding method of a decorative resin molded product having a complicated surface shape such as a three-dimensional curved surface. According to the injection transfer simultaneous transfer decoration method, a decorative sheet having a laminated structure such as a base layer / surface protective layer / colored layer / adhesive layer is brought into close contact with the inner surface of the mold and clamped, and then melted in the cavity. The injected resin is injected to the adhesive layer side, the decorative sheet and the injection resin are integrated through the adhesive layer, and then the decorative resin molded product is cooled and opened, and at the same time, the base material located on the surface By separating the layers, a decorated resin molded product to which the decorative sheet is transferred can be obtained.

  For example, Patent Document 1 is a decorative sheet used in an injection molding simultaneous transfer decorative method, and has a release layer and a surface protective layer in this order on one side of a base sheet, and the surface protective layer is, A resin composition comprising an ionizing radiation curable resin composition comprising a polyfunctional (meth) acrylate monomer having a molecular weight of 175 to 1000 and a thermoplastic resin having a weight average molecular weight converted to standard polystyrene of less than 10,000 to 100,000. A decorative sheet is disclosed in which the mass ratio of the polyfunctional (meth) acrylate monomer and the thermoplastic resin in the product is 10:90 to 75:25.

JP 2012-91498 A

  In recent years, along with the high design of such decorative sheets, not only single-color patterns and wood grain patterns, but also geometric patterns and patterns that combine high-gloss parts (gross) and low-gloss parts (matt) (so-called gloss) A layer (for example, a colored layer) to be laminated using ink, such as a mat, is also increasing. Since the solvent used to dilute the binder resin is used in the ink, when the layer formed using the ink in the decorative sheet increases, the amount of solvent laminated in the process of manufacturing the decorative sheet also increases. To do. For this reason, in a decorative sheet having a large proportion of layers laminated using ink, the solvent tends to remain in the decorative sheet, and the decorative sheet manufactured at the time of manufacturing the decorative sheet or using the decorative sheet is used. In decorative resin molded products, processing defects, odor generation, etc. may occur. As a result of the study by the present inventors, in particular, in the decorative sheet used in the injection molding simultaneous transfer decorative method, volatilization of the solvent from the decorative sheet is hindered by the adhesive layer, and the above-mentioned problems are remarkable. It became clear that it would occur.

  Moreover, the surface protective layer of such a decorative sheet is located in the outermost layer of the decorative resin molded product after the transfer. Therefore, as the surface protective layer, ionizing radiation curable resin that is cured by crosslinking with ionizing radiation such as ultraviolet rays and electron beams is used from the viewpoint of imparting scratch resistance, contamination resistance, etc. to the decorative resin molded product. May be formed. When a decorative sheet using an ionizing radiation curable resin is transferred to the surface protective layer to obtain a decorative resin molded product, the decorative resin molded product is transferred after the decorative sheet having an uncured surface protective layer is transferred. There are a method of curing the surface protective layer by irradiation with ionizing radiation (post-curing) and a method of transferring using a decorative sheet with the surface protective layer previously cured (pre-curing).

  A decorative sheet having an uncured surface protective layer retains appropriate flexibility at the time of transfer, and is therefore easily applied to three-dimensional molding. For this reason, a decorative sheet having an uncured surface protective layer has been widely adopted. However, when such a decorative sheet is used, it is necessary to irradiate ionizing radiation to the decorative resin molded product after molding, and there is a problem that the process becomes complicated.

On the other hand, it can be said that the decorative sheet having the surface protective layer cured in advance is suitable for mass production as compared with the post-curing because the irradiation process of ionizing radiation can be completed in the production process of the decorative sheet. However, when the present inventor examined, in the decorative sheet in which the ionizing radiation curable resin of the surface protective layer was previously cured, the gas barrier property of the surface protective layer was increased as compared with the case of being uncured. It has become clear that the evaporation of the solvent from the surface protective layer of the decorative sheet is unlikely to occur, and the increase in the residual solvent amount of the decorative sheet becomes more conspicuous in combination with the inhibition of the volatilization of the solvent by the adhesive layer described above. .
Under such circumstances, the main object of the present invention is to provide a decorative sheet with a small amount of residual solvent.

  The present inventor has intensively studied to solve the above problems. As a result, it has at least a base material layer, a surface protective layer, a colored layer, and an adhesive layer in this order, and the surface protective layer is formed of a cured product of an ionizing radiation curable resin composition, and is bonded. The layer is formed of a resin composition containing a resin and a filler. In the adhesive layer, the decorative sheet containing 1 part by mass or more of the filler with respect to 100 parts by mass of the resin is the adhesive layer and the cured ionizing radiation. It has been found that the amount of residual solvent is small in spite of having a surface protective layer formed of a curable resin composition. 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 surface protective layer, a colored layer, and an adhesive layer in this order,
The surface protective layer is formed of a cured product of an ionizing radiation curable resin composition,
The adhesive layer is formed of a resin composition containing a resin and a filler;
The said adhesive layer WHEREIN: The decorating sheet in which the said filler is contained 1 mass part 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 adhesive layer, the filler has an average particle size of 1 to 10 µm.
Item 3. Item 3. The decorative sheet according to item 1 or 2, wherein in the adhesive layer, the filler is a porous particle.
Item 4. Item 4. The decorative sheet according to any one of Items 1 to 3, wherein the adhesive layer has a thickness of 6 µm or less.
Item 5. In the adhesive layer, the resin is made of acrylic resin, vinyl chloride resin, vinyl acetate resin, vinyl chloride-vinyl acetate copolymer resin, styrene-acrylic copolymer resin, polyester resin, and polyamide resin. Item 5. The decorative sheet according to any one of Items 1 to 4, which is at least one selected from the group consisting of:
Item 6. Item 6. The decorative sheet according to any one of Items 1 to 5, wherein the colored layer has a thickness of 0.5 to 40 µm.
Item 7. The said ionizing radiation curable resin composition contains the polyfunctional (meth) acrylate monomer whose molecular weight is 175-1000, and the thermoplastic resin whose weight average molecular weight converted into standard polystyrene is 10,000-250,000. The decorative sheet according to any one of 1 to 6.
Item 8. Item 8. The decorative sheet according to Item 7, wherein the polyfunctional (meth) acrylate monomer has 3 to 8 functional groups.
Item 9. Item 9. The decorative sheet according to Item 7 or 8, wherein the thermoplastic resin is an acrylic resin having a (meth) acrylic acid ester monomer as a structural unit.
Item 10. At least a molded resin layer, an adhesive layer, a colored layer, and a surface protective layer are laminated in this order,
The surface protective layer is formed of a cured product of an ionizing radiation curable resin composition,
The adhesive layer is formed of a resin composition containing a resin and a filler;
The said resin layer WHEREIN: The decorative resin molded product in which the said filler is contained 1 mass part or more with respect to 100 mass parts of said resin.
Item 11. A process of clamping the decorative sheet according to any one of Items 1 to 9 in close contact with the inner surface of the mold, along the inner surface shape of the mold,
Injecting injection resin into the mold, and integrating the decorative sheet and the injection resin through the adhesive layer;
After cooling the injection resin, a step of taking out a decorative resin molded product from the mold,
A method for producing a decorated resin molded product.
Item 12. Item 12. The method for producing a decorated resin molded product according to Item 11, further comprising a step of removing the base material layer from the decorated resin molded product simultaneously with the step of taking out the decorated resin molded product from the mold.

  According to the decorative sheet of the present invention, a decorative sheet with a small amount of residual solvent can be provided. Since the decorative sheet of the present invention has a small amount of residual solvent, it is effective for processing defects, generation of odors, etc. during the production of the decorative sheet or in a decorative resin molded product manufactured using the decorative sheet. Can be suppressed. Moreover, according to this invention, the decorating resin molded product with little residual solvent amount using the said decorating sheet 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 resin molded product of this invention.

1. The decorative sheet of the present invention has at least a base material layer, a surface protective layer, a colored layer, and an adhesive layer in this order, and the surface protective layer is a cured ionizing radiation curable resin composition. The adhesive layer is formed of a resin composition including a resin and a filler, and the adhesive layer includes 1 part by mass or more of the filler with respect to 100 parts by mass of the resin. . The decorative sheet of the present invention includes a surface protective layer formed of an adhesive layer and a cured ionizing radiation curable resin composition by including 1 part by mass or more of a filler in 100 parts by mass of the resin in the adhesive layer. In spite of having, it can be set as a decorating sheet with little residual solvent amount. In the decorative sheet of the present invention, the details of the mechanism that exhibits such excellent effects are not necessarily clear, but can be considered as follows, for example. That is, as described above, the volatilization of the solvent contained in the ink used for the colored layer or the like is hindered by the adhesive layer or the cured surface protective layer, and this is the main reason that the amount of residual solvent in the decorative sheet increases. Although it becomes a factor, in the decorating sheet of this invention, the said adhesive layer contains 1 mass part or more of fillers. For this reason, in the surface portion of the adhesive layer, at least a part of the filler protrudes from the surface portion of the adhesive layer, the surface area of the adhesive layer is increased, and volatilization of the solvent from the adhesive layer having a large surface area is promoted. It is considered a thing. Furthermore, when the filler is porous, the solvent is likely to volatilize through the porosity, so that it is considered that the volatilization of the solvent from the adhesive layer is further promoted. Hereinafter, the decorative sheet of the present invention will be described in detail.

Laminated structure of decorative sheet The decorative sheet of the present invention has a laminated structure in which at least a base material layer 1, a surface protective layer 2, a colored layer 3, and an adhesive layer 4 are laminated in this order. In the decorative sheet of the present invention, the primer layer 5 is provided on the colored layer 3 side of the surface protective layer 2 for the purpose of improving the adhesion between the surface protective layer 2 and the adjacent layer (for example, the colored layer 3). May be provided. Moreover, in order to make it easy to peel the base material layer 1 after the decorative sheet of the present invention is transferred to the decorative resin molded product, a release layer 6 is provided between the base material layer 1 and the surface protective layer 2. It may be provided.

  As a laminated structure of the decorative sheet of the present invention, a laminated structure in which a base material layer / surface protective layer / colored layer / adhesive layer are laminated in this order; base material layer / release layer / surface protective layer / colored layer / adhesive layer Is laminated in this order; base material layer / surface protective layer / primer layer / colored layer / adhesive layer is laminated in this order; base material layer / release layer / surface protective layer / primer layer / colored Examples include a laminated structure in which layers / adhesive layers are laminated in this order. FIG. 1 shows a schematic cross-sectional view of an example of a decorative sheet in which a base material layer / surface protective layer / colored layer / adhesive layer are laminated in this order as an embodiment of the laminated structure of the decorative sheet of the present invention. FIG. 2 shows an example of a decorative sheet in which a base layer / release layer / surface protective layer / primer layer / colored layer / adhesive layer are laminated in this order as an embodiment of the laminated structure of the decorative sheet of the present invention. A schematic cross-sectional view 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 polyolefin resins such as polyethylene and polypropylene; vinyl resins such as polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, ethylene / vinyl acetate copolymer, and ethylene / vinyl alcohol copolymer. Resins; Polyester resins such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate; Acrylic resins such as poly (meth) methyl acrylate and poly (meth) ethyl acrylate; Styrene resins such as polystyrene, Acrylonitrile butadiene, Styrene copolymers, cellulose triacetate, cellophane, polycarbonate, polyurethane resins and other elastomer resins are used. Of these, polyester resins, particularly polyethylene terephthalate (hereinafter referred to as “PET”) are preferred from the viewpoint of good moldability and peelability. As a resin component which forms the base material layer 1, only 1 type may be used and 2 or more types may be mixed and used. Moreover, the base material layer 1 may be formed with the single layer sheet | seat of these resin, and may be formed with the multilayer sheet | seat by the same kind or different kind | species resin.

  The base material layer 1 is subjected to physical or chemical surface treatment such as an oxidation method or an unevenness method on one side or both sides as necessary for the purpose of improving the adhesion between adjacent layers. May be. 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.

  Even if the base material layer 1 performs the process of forming an easily bonding layer for the purpose of improving the adhesiveness with an adjacent layer, etc., it is given. In addition, when using a commercially available thing as the base material layer 1, this commercially available thing is what gave the surface treatment as mentioned above previously, the thing in which the easily bonding layer was provided, or the mold release layer 6 mentioned later. Those formed with can also be used.

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

  The thickness of the base material layer 1 is not particularly limited and is appropriately set according to the use of the decorative sheet, etc., but is usually about 10 to 150 μm, preferably about 10 to 125 μm, more preferably about 100 to 80 μm. It is done. When the thickness of the base material layer 1 is within the above range, the moldability and shape followability are enhanced, and handling is easy.

[Release layer 6]
The release layer 6 is provided as necessary in order to easily peel the base material layer 1 from the surface protective layer 2 of the decorative resin molded product after the decorative sheet is formed into the decorative resin molded product. Is a layer. That is, the release layer 6 is a layer that is peeled from the surface protective layer 2 together with the base material layer 1 after the decorative sheet is formed into a decorative resin molded product. Since the decorative sheet of the present invention has the release layer 6, the base material layer 1 and the release layer 6 can be reliably removed from the surface protective layer 2 after the decorative sheet of the present invention is formed into a decorative resin molded product. Can be peeled off. As shown in FIG. 2, the release layer 6 may be a solid release layer that covers the entire surface (a solid surface), or may be provided in part. Usually, a solid release layer is preferable in consideration of peelability.

  The release layer 6 includes a silicone resin, a fluorine resin, an acrylic resin (for example, an acrylic-melamine resin is included), a polyester resin, a polyolefin resin, a polystyrene resin, a polyurethane resin, and a cellulose resin. , Vinyl chloride-vinyl acetate copolymer resins, thermoplastic resins such as nitrified cotton, copolymers of monomers forming the thermoplastic resins, or those resins modified with (meth) acrylic acid or urethane It can be formed by using a single or a plurality of mixed resin compositions. Among these, acrylic resins, polyester resins, polyolefin resins, polystyrene resins, copolymers of monomers that form these resins, and those obtained by urethane modification thereof are more preferable. More specifically, acrylic-melamine Resin, acrylic-melamine resin-containing composition, polyester resin and ethylene / acrylic acid copolymer modified with urethane, acrylic resin / styrene / acrylic copolymer And a resin composition mixed with the above emulsion. Among these, it is particularly preferable that the release layer 6 is composed of an acrylic-melamine resin alone or a composition containing 50% by mass or more of the acrylic-melamine resin.

  Although it does not restrict | limit especially as thickness of the release layer 6, Usually, about 0.01-5 micrometers, Preferably it is about 0.05-3 micrometers.

[Surface protective layer 2]
The surface protective layer 2 is a layer that imparts surface characteristics such as scratch resistance and contamination resistance to a decorated resin molded article using the decorative sheet of the present invention, and is a cured product of an ionizing radiation curable resin composition. Is formed. The ionizing radiation curable resin suitably used for forming the surface protective layer 2 is a resin that is cross-linked and cured by irradiation with ionizing radiation. 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. Therefore, they are suitable for forming the surface protective layer 2. Used for.

  The surface protective layer 2 may be a completely cured or semi-cured product of the ionizing radiation curable resin composition. It becomes good. Moreover, since it is a completely hardened | cured material, since the irradiation process of ionizing radiation can be completed in the production process of a decorating sheet, it becomes possible to manufacture a decorating resin molded product simply. In the decorative sheet of the present invention, the surface protective layer 2 is formed of a cured product of an ionizing radiation curable resin composition having a high gas barrier property. As described later, in the adhesive layer 4, the filler is 100 parts by mass of the resin. The amount of residual solvent is effectively reduced by containing 1 mass part or more with respect to this.

  The ionizing radiation curable resin composition used for forming the surface protective layer 2 is preferably a polyfunctional (meth) acrylate monomer having a molecular weight of 175 to 1000 and a weight average molecular weight converted to standard polystyrene of 10,000 to 1,000. What contains 250,000 thermoplastic resins is mentioned. Hereinafter, the preferable aspect of the ionizing radiation curable resin composition used for formation of the surface protective layer 2 of this invention is explained in full detail. In the present specification, “(meth) acrylate” means “acrylate or methacrylate”, and other similar ones have the same meaning.

<Multifunctional (meth) acrylate monomer>
The polyfunctional (meth) acrylate monomer having a molecular weight of 175 to 1000 refers to a (meth) acrylate monomer having a functional group number of 2 or more and a molecular weight of 175 to 1000. The number of functional groups of the polyfunctional (meth) acrylate monomer is preferably 3 or more, more preferably 3 to 8 from the viewpoint of imparting excellent stain resistance and moldability to the decorative resin molded product. 3 to 6 are more preferable. The molecular weight of the polyfunctional (meth) acrylate monomer is preferably 200 to 800, more preferably 250 to 600, and more preferably 250 to 400 from the viewpoint of imparting excellent stain resistance and moldability to the decorative resin molded product. Is more preferable.

  Specific examples of such polyfunctional (meth) acrylate monomers include ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, and 1,6-hexane. Diol 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 dicyclo Pentenyl 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 di Pentaerythritol hexa (meth) acrylate and the like are preferred. Of these, pentaerythritol tri (meth) acrylate is more preferable. In this invention, said polyfunctional (meth) acrylate monomer may be used individually by 1 type, and may be used in combination of 2 or more type.

<Thermoplastic resin>
The thermoplastic resin preferably has a weight average molecular weight of 10,000 to 250,000 converted to standard polystyrene. Here, the weight average molecular weight is a value measured by gel permeation chromatography (GPC), and is a value measured under conditions using polystyrene as a standard sample.

  Thermoplastic resins include acrylic resin, polyvinyl acetal (butyral resin) such as polyvinyl butyral, polyester resin such as polyethylene terephthalate and polybutylene terephthalate, polyolefin such as vinyl chloride resin, urethane resin, polyethylene and polypropylene, polystyrene, α-methyl Examples include styrene resins such as styrene, acetal resins such as polyamide, polycarbonate, and polyoxymethylene, fluorine resins such as ethylene-tetrafluoroethylene copolymer, polyimide, polylactic acid, polyvinyl acetal resin, and liquid crystalline polyester resin. These may be used alone or in combination of two or more. When combining 2 or more types, the copolymer of the monomer which comprises these resin may be sufficient, and each resin may be mixed and used.

  Among the above thermoplastic resins, an acrylic resin is preferable, and an acrylic resin having at least a (meth) acrylic acid ester monomer as a structural unit is more preferable. More specifically, a homopolymer of (meth) acrylate monomer, a copolymer of two or more different (meth) acrylate monomers, or a copolymer of (meth) acrylate monomers and other monomers. Polymers are preferred.

  Here, examples of the (meth) acrylate monomer include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, cyclohexyl (meth) acrylate, and normal butyl (meth) acrylate. , Isobutyl (meth) acrylate, secondary butyl (meth) acrylate, tertiary butyl (meth) acrylate, isobonyl (meth) acrylate, 2-methyl-2-adamantyl (meth) acrylate, 2-ethyl-2- Adamantyl (meth) acrylate and the like are preferable, and methyl (meth) acrylate is more preferable among these.

  Examples of the copolymer of two or more different (meth) acrylic acid ester monomers include a copolymer of two or more (meth) acrylic acid esters selected from those exemplified above, and these copolymers May be a random copolymer or a block copolymer.

  The other monomer that forms a copolymer with the (meth) acrylic acid ester monomer is not particularly limited as long as it is copolymerizable with the (meth) acrylic acid ester, but in the present invention, (meth) acrylic acid, Styrene, maleic anhydride, fumaric acid, divinylbenzene, vinylbiphenyl, vinylnaphthalene, diphenylethylene, vinyl acetate, vinyl chloride, vinyl fluoride, vinyl alcohol, acrylonitrile, acrylamide, butadiene, isoprene, isobutene, 1-butene, Alicyclic olefin monomers such as 2-butene, N-vinyl-2-pyrrolidone, dicyclopentadiene, ethylidene norbornene, norbornene, vinylcaprolactam, citraconic anhydride, maleimides such as N-phenylmaleimide, vinyl ethers, etc. It is preferably exemplified, in particular styrene and (anhydrous) maleic acid is preferable as a copolymerization component. That is, a binary copolymer of (meth) acrylic acid ester and styrene or (anhydrous) maleic acid, or a terpolymer of (meth) acrylic acid ester, styrene and (anhydrous) maleic acid is preferable. In addition, the copolymer of (meth) acrylic acid ester and another monomer may be a random copolymer or a block copolymer.

The polydispersity (weight average molecular weight Mw / number average molecular weight Mn) of the acrylic resin is 1.1 to 3.
A range of 0 is preferred. When the polydispersity is within this range, surface characteristics such as wear resistance and scratch resistance are obtained in addition to excellent moldability and stain resistance. From the same viewpoint, the polydispersity is more preferably in the range of 1.5 to 2.5.

<Mass ratio of polyfunctional (meth) acrylate monomer and thermoplastic resin>
The mass ratio of the polyfunctional (meth) acrylate monomer in the ionizing radiation curable resin composition used in the present invention and the thermoplastic resin having a weight average molecular weight converted to standard polystyrene of less than 10,000 to 100,000 is 10 : It is preferable that it exists in the range of 90-75: 25. If this mass ratio is less than 10:90, that is, if the content of the polyfunctional (meth) acrylate monomer in the resin composition is less than 10, excellent surface properties may not be obtained, and printability may be reduced. On the other hand, if this mass ratio is greater than 75:25, that is, if the content of the polyfunctional (meth) acrylate monomer in the resin composition is greater than 75, excellent moldability may not be obtained, In addition, the adhesion between the molded transfer layer and the resin molded product may be lowered. In addition, the mass ratio of the polyfunctional (meth) acrylate monomer in the ionizing radiation curable resin composition used in the present invention and the thermoplastic resin having a weight average molecular weight converted to standard polystyrene of 100,000 to 250,000 is as follows: It is preferably in the range of 25:75 to 75:25. If this mass ratio is less than 25:75, that is, if the content of the polyfunctional (meth) acrylate monomer in the resin composition is less than 25, excellent surface characteristics may not be obtained, and printability may deteriorate. On the other hand, if this mass ratio is greater than 75:25, that is, if the content of the polyfunctional (meth) acrylate monomer in the resin composition is greater than 75, excellent moldability may not be obtained, In addition, the adhesion between the molded transfer layer and the resin molded product may be lowered. Whether using a thermoplastic resin having a weight average molecular weight converted to standard polystyrene of less than 10,000 to 100,000 or a thermoplastic resin having a weight average molecular weight of 100,000 to 250,000, the decorative resin molded product From the viewpoint of imparting excellent surface characteristics, the mass ratio is preferably 30:70 to 70:30, and more preferably 35:65 to 65:35.

<Other additives>
The ionizing radiation curable resin composition used in the present invention can contain components other than the polyfunctional (meth) acrylate monomer and the thermoplastic resin as long as the effects of the present invention are not impaired. For example, the ionizing radiation curable resin composition used in the present invention includes urethane (meth) acrylate oligomers, epoxy (meth) acrylate oligomers, polyester (meth) acrylate oligomers, polyether (meth) acrylate oligomers, and the like. Multifunctional (meth) acrylate oligomer, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, cyclohexyl (meth) acrylate Monofunctional (meth) acrylates such as 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, and isobornyl (meth) acrylate It can be.

  Other additives include a weather resistance improver, an abrasion resistance improver, a polymerization inhibitor, a crosslinking agent, an infrared absorber, an antistatic agent, an adhesion improver, a leveling agent, a thixotropic agent, a coupling agent, Also included are various additives commonly used in resin compositions such as plasticizers, antifoaming agents, fillers, solvents, and colorants.

  Although it does not restrict | limit especially as thickness of the surface protective layer 2, Usually, about 1-50 micrometers, Preferably it is about 3-20 micrometers. When the thickness of the surface protective layer 2 is within the above range, it is possible to impart excellent moldability as well as excellent surface characteristics to the decorative resin molded product.

  The surface protective layer 2 has various functions by adding various additives, for example, a so-called hard coat function, anti-fogging coat function, anti-fouling coating function, anti-glare coating function having high hardness and scratch resistance, An antireflection coating function, an ultraviolet shielding coating function, an infrared shielding coating function, and the like can also be imparted. In addition, the surface protective layer 2 can be subjected to corona discharge treatment or plasma treatment as necessary for the purpose of improving adhesion with a primer layer 5 described later provided as necessary.

[Primer layer 5]
The decorative sheet of the present invention may have a primer layer 5 between the surface protective layer 2 and a layer adjacent to the surface protective layer 2 (for example, the colored layer 3) as necessary. By providing the primer layer 5, the adhesion between the surface protective layer 2 and the layer adjacent thereto can be further improved. The primer layer 5 is preferably a transparent or translucent layer. For the formation of the primer layer 5, a polyurethane resin, a polyester resin, an acrylic resin, a vinyl acetate resin, a vinyl chloride-vinyl acetate copolymer resin One kind of a resin such as cellulose resin, chlorinated polyethylene, chlorinated polypropylene, or a mixture of two or more kinds is used, and it is particularly preferable to use a polyurethane two-component curable resin.

Examples of polyurethane two-component curable resins include vinyl chloride-vinyl acetate copolymer systems,
A polymer polyol such as polyester series, urethane series, acrylic series, polyether series, polycarbonate series, or the like, or a mixture thereof with a curing agent added just before use is used. As the polymer polyol, an acrylic polymer polyol or a polyester polymer polyol is preferable, and an acrylic polymer polyol is more preferable. As the acrylic polymer polyol, (meth) acrylic acid alkyl ester such as ethyl (meth) acrylate is copolymerized with hydroxy acrylate such as 2-hydroxyethyl acrylate, 2-hydroxy-3-phenoxypropyl acrylate, and the like. The thing which introduce | transduced the hydroxyl group is mentioned preferably. Examples of the polyester polymer polyol include poly (ethylene adipate), poly (butylene adipate), poly (neopentyl adipate), poly (hexamethylene adipate), poly (butylene azelate), and poly (butylene sebacate). Polycaprolactone is used.

  Moreover, in this invention, it is also preferable to use the mixture of said acrylic polymer polyol and urethane resin. In this case, the compounding ratio (mass ratio) of the acrylic polymer polyol and the urethane resin is preferably 40:60 to 95: 5, and more preferably 60:40 to 90:10. When the blending ratio is within the above range, excellent adhesion can be obtained.

  As the curing agent, polyisocyanate is preferable, for example, aromatic isocyanate such as 2,4-tolylene diisocyanate, xylylene diisocyanate, naphthalene diisocyanate, 4,4′-diphenylmethane diisocyanate; 1,6-hexamethylene diisocyanate, 2 , 2,4-trimethylhexamethylene diisocyanate, isophorone diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated diphenylmethane diisocyanate, or the like, or adducts of the above-mentioned various isocyanates. Alternatively, a multimer such as an adduct of tolylene diisocyanate, a tolylene diisocyanate trimer, or the like can also be used.

  Further, in the present invention, the glass transition temperature Tg of the polymer polyol (when uncured) used as the polyurethane two-component curable resin is preferably 65 ° C. or higher, and the upper limit of the glass transition temperature Tg is not particularly limited. Although it is not usually, it is about 110 degreeC and preferable Tg is the range of 70-100 degreeC. When the glass transition temperature Tg is within the above range, excellent adhesion can be obtained, and the transferability of the colored layer 3 and the like is also improved.

  The primer layer 5 can be obtained by applying and drying a coating solution obtained by dissolving the resin in a solvent by a known method. Although it does not restrict | limit especially as the thickness of the primer layer 5, Usually, about 0.5-20 micrometers, Preferably it can be set to 1-5 micrometers.

[Colored layer 3]
The colored layer 3 in the present invention is usually composed of at least one of a picture layer and a concealing layer. The pattern layer is a layer provided to express a pattern such as a pattern or characters. Although the pattern of the pattern layer is arbitrary, for example, a pattern composed of wood grain, stone grain, cloth grain, sand grain, geometric pattern, character, and the like can be mentioned. Further, the concealing layer is usually a solid surface layer, and is a layer provided to conceal coloring such as an injection resin described later. In addition to the case where the masking layer is provided inside the picture layer to enhance the picture of the picture layer, a decorative layer may be formed alone. Further, the decorative layer may be a transparent transfer foil or a colored transfer foil.

  The colored layer 3 is a gravure printing, offset printing, silk screen printing, transfer printing from a transfer sheet, sublimation transfer printing, ink jet printing, etc., on the surface protective layer 2 or the primer layer 5 provided as necessary. By forming it by a known printing method, for example, it is formed between the surface protective layer 2 and the adhesive layer 4 as shown in FIG. 1 or FIG.

  As the binder resin of the printing ink used for forming the colored layer 3, polyester resins, polyurethane resins, acrylic resins, vinyl acetate resins, vinyl chloride-vinyl acetate copolymer resins, cellulose resins, and the like are preferable. The main component is preferably an acrylic resin alone or a mixture of an acrylic resin and a vinyl chloride-vinyl acetate copolymer resin. Among these, when an acrylic resin, a vinyl chloride-vinyl acetate copolymer resin or another acrylic resin is mixed, the printability and moldability are improved, which is preferable. Here, the acrylic resin includes polymethyl (meth) acrylate, polyethyl (meth) acrylate, polybutyl (meth) acrylate, methyl (meth) acrylate-butyl (meth) acrylate copolymer, methyl (meth) acrylate-styrene copolymer. Examples thereof include acrylic resins such as polymers and modified acrylic resins by fluorine, and these can be used as one kind or a mixture of two or more kinds. In addition, (meth) acrylic acid alkyl esters such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, and 2-hydroxyethyl ( An acrylic polyol obtained by copolymerizing a (meth) acrylic acid ester having a hydroxyl group in a molecule such as (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, etc. It can also be used. As the vinyl chloride-vinyl acetate copolymer resin, those having a vinyl acetate content of about 5 to 20% by mass and an average degree of polymerization of about 350 to 900 are usually used. If necessary, the vinyl chloride-vinyl acetate copolymer resin may be further copolymerized with a carboxylic acid such as maleic acid or fumaric acid. The mixing ratio of the acrylic resin and the vinyl chloride-vinyl acetate copolymer resin is about acrylic resin / vinyl chloride-vinyl acetate copolymer resin = 1/9 to 9/1 (mass ratio). In addition, as a subcomponent resin, if necessary, other resins, for example, resins such as thermoplastic polyester resins, thermoplastic urethane resins, chlorinated polyethylene, chlorinated polypropylene, and other chlorinated polyolefin resins. May be mixed.

  The coloring agent used for the coloring layer 3 is a metallic pigment made of a scale-like foil powder of a metal such as aluminum, chromium, nickel, tin, titanium, iron phosphide, copper, gold, silver, brass, an alloy, or a metal compound. Pearl luster made from foil powder such as mica-like iron oxide, titanium dioxide coated mica, titanium dioxide coated bismuth oxychloride, bismuth oxychloride, titanium dioxide coated talc, fish scale foil, colored titanium dioxide coated mica, basic lead carbonate ) Pigments, fluorescent pigments such as strontium aluminate, calcium aluminate, barium aluminate, zinc sulfide, calcium sulfide, white inorganic pigments such as titanium dioxide, zinc white, antimony trioxide, zinc white, petal, vermilion, ultramarine, Inorganic pigments such as cobalt blue, titanium yellow, yellow lead, carbon black, isoindolinone yellow, Hansa Yellow A, quinacridone red, permanent red 4R, phthalocyanine blue, can be used as a mixture Indanthrene Blue RS, (including dyes) organic pigments such as aniline black one or more.

  Although such a colored layer 3 is a layer provided in order to provide the designability to the decorating sheet of this invention, you may form a metal thin film layer etc. further in order to improve the designability. The metal thin film layer can be formed by using a metal such as aluminum, chromium, gold, silver, or copper by a method such as vacuum deposition or sputtering. The metal thin film layer may be provided on the entire surface or may be partially provided in a pattern.

  The printing ink is provided in a form in which the above components are usually dissolved or dispersed in a solvent. That is, the printing ink used for forming the colored layer 3 further contains a solvent. Any solvent can be used as long as it dissolves or disperses the binder resin, and an organic solvent and / or water can be used. Examples of the organic solvent include hydrocarbons such as toluene and xylene, ketones such as acetone and methyl ethyl ketone, esters such as ethyl acetate, cellosolve acetate, and butyl cellosolve acetate, and alcohols. As described above, in the decorative sheet of the present invention, the filler is contained in the adhesive layer 4 described later even when a colored layer formed using an ink containing a solvent is laminated in the process of manufacturing the decorative sheet. By containing 1 part by mass or more with respect to 100 parts by mass of the resin, the amount of residual solvent is effectively reduced. Among these solvents, methyl ethyl ketone, ethyl acetate and the like are preferable from the viewpoint of further reducing the residual solvent amount of the decorative sheet of the present invention.

  In the printing ink used for forming the colored layer 3, the content of the solvent is not particularly limited as long as the binder resin or the like can be dissolved or dispersed in the solvent, but for example 100 to 100 parts by mass of the binder resin. About 1000 parts by mass, preferably about 300 to 600 parts by mass can be mentioned.

  In addition to the above components such as resin binder and solvent, the printing ink used for forming the colored layer 3 includes an anti-settling agent, a curing catalyst, an ultraviolet absorber, an antioxidant, a leveling agent, a thickener, an antifoaming agent, A lubricant and the like can be appropriately added.

  Although it does not restrict | limit especially as thickness of the colored layer 3, Preferably it is about 0.5-40 micrometers from a viewpoint of the designability, More preferably, about 1-10 micrometers is mentioned.

[Adhesive layer 4]
The adhesive layer 4 is a layer formed in order to adhere the decorative sheet of the present invention and an injection resin described later to obtain a decorative resin molded product.

  Examples of the adhesive layer 4 include those composed of a heat-sensitive adhesive, a pressure adhesive, and the like. In the present invention, the adhesive layer 4 exhibits adhesion to a decorative resin molded product by heating and pressurizing as necessary. It is preferable that it is a heat seal layer.

  The adhesive layer 4 is formed of a resin composition containing a resin and a filler 4a. Furthermore, in this invention, 1 mass part or more of fillers are contained in the resin composition which forms the contact bonding layer 4 with respect to 100 mass parts of resin. As described above, in the decorative sheet of the present invention, the filler 4a is added to the resin 100 in the adhesive layer 4 even when a colored layer formed using a solvent-containing ink is laminated in the process of manufacturing the decorative sheet. By containing 1 part by mass or more with respect to part by mass, the amount of residual solvent is effectively reduced.

  Examples of the resin contained in the resin composition forming the adhesive layer 4 include an acrylic resin, a vinyl chloride resin, a vinyl acetate resin, a vinyl chloride-vinyl acetate copolymer resin, a styrene-acryl copolymer resin, Examples thereof include polyester resins and polyamide resins. These resins may be used alone or in combination of two or more.

  Although it does not restrict | limit especially as a shape of the filler 4a, From a viewpoint of reducing the residual solvent amount of a decorating sheet more effectively, Preferably it is a porous particle.

  The average particle size of the filler 4a is not particularly limited, but preferably about 1 to 10 μm, more preferably about 2 to 7 μm, and still more preferably about 2 to 5 μm. In the present invention, the average particle size of the filler is dispersed in the air by using the Shimadzu laser diffraction particle size distribution analyzer SALD-2100, injecting the powder to be measured from the nozzle using compressed air. It is a value measured by an injection-type dry measurement method.

  From the viewpoint of more effectively reducing the residual solvent amount of the decorative sheet, the oil absorption amount of the filler 4a is preferably 100 mL / 100 g or more, more preferably 200 to 400 mL / 100 g. In addition, the oil absorption amount of a filler is a value measured by the method based on JISK5101-13-1: 2004.

  The filler 4a may be either an inorganic filler or an organic filler, but an inorganic filler is more preferable. The inorganic filler is not particularly limited as long as it is an inorganic particle formed of an inorganic compound, and examples thereof include silica particles, calcium carbonate particles, barium sulfate particles, alumina particles, glass balloon particles, and the like. Includes silica particles, particularly preferably colloidal silica. Moreover, as an organic filler, the synthetic resin particle formed with the synthetic resin is mentioned, for example. The synthetic resin particles are not particularly limited, and examples thereof include urethane beads, nylon beads, acrylic beads, silicone beads, styrene beads, melamine beads, urethane acrylic beads, polyester beads, and polyethylene beads. A filler may be used individually by 1 type and may be used in combination of 2 or more types.

  As content of the filler 4a, in the resin composition which forms the contact bonding layer 4, although 1 mass part or more of fillers should just be contained with respect to 100 mass parts of resin, Preferably it is about 1-50 mass parts. Preferably about 3-30 mass parts, More preferably, about 5-20 mass parts is mentioned.

  The adhesive layer 4 is a gravure printing method, a screen printing method, a reverse coating method using a gravure plate, or the like in which the above resin, filler 4a, etc. are mixed with a solvent and made into a form that can be applied as a solution or emulsion It can be formed by coating and drying by the means described above.

  The solvent used in the resin composition for forming the adhesive layer 4 is not particularly limited as long as it can be applied as a solution or emulsion by mixing the above resin, filler 4a, and the like with a solvent. Examples include methyl ethyl ketone and ethyl acetate. These solvents may be used alone or in combination of two or more. The amount of the solvent is not particularly limited, but as the amount of the filler 4a in the resin composition increases, the viscosity of the resin composition increases and it becomes difficult to apply, so the content of the solvent tends to increase. As content of a solvent, Preferably it is about 500-3000 mass parts with respect to 100 mass parts in the resin composition which forms the contact bonding layer 4, More preferably, about 1000-2500 mass parts is mentioned. .

  The adhesive layer 4 includes organic UV absorbers such as benzophenone compounds, benzotriazole compounds, oxalic acid anilide compounds, cyanoacrylate compounds, salicylate compounds, zinc, titanium, cerium, tin, iron, and the like. An additive of fine particles having an inorganic ultraviolet absorbing ability such as an oxide can be contained. Further, as additives, fillers, antistatic agents, antioxidants, fluorescent brighteners and the like can be appropriately contained as necessary.

  The thickness of the adhesive layer 4 is preferably 6 μm or less, more preferably 3 μm or less, and still more preferably 1-1, from the viewpoint that the decorative sheet can be efficiently transferred to the decorative resin molded product with good adhesion. .5 μm or less. In addition, from the viewpoint of ensuring the adhesion between the adhesive layer 4 and the molded resin layer 7, the thickness of the adhesive layer 4 is preferably 0.1 μm or more.

[Method for producing decorative sheet]
The decorative sheet of the present invention can be produced, for example, by the following steps [1] to [4].
[1] A step of laminating an ionizing radiation curable resin composition layer on the base material layer 1,
[2] A step of irradiating the ionizing radiation curable resin composition layer with ionizing radiation to cure or semi-cure the ionizing radiation curable resin composition layer to form the surface protective layer 2;
[3] A step of laminating the colored layer 3 on the surface protective layer 2, and [4] a step of laminating the adhesive layer 4 on the colored layer 3.

In addition to the steps [1] to [4] described above, the following steps may further be included as desired.
[1-1] Step [1] In the step [1], the release layer 6 is laminated on the base material layer 1 and the ionizing radiation curable resin composition layer is laminated on the release layer 6 [2-1] step [ Between step 2] and step [3], the surface of the surface protective layer 2 is subjected to corona discharge treatment or plasma treatment [3-1] In step [3], the primer layer 5 is laminated on the surface protective layer 2 And laminating the colored layer 3 on the primer layer 5

  The release layer 6, the surface protective layer 2, the primer layer 5, the coloring layer 3, and the adhesive layer 4 that are laminated on the base material layer 1 are laminated by a known printing or coating means such as gravure printing or roll coating. Used. When the colored layer 3 is a combination of a picture layer and a concealing layer as described above, for example, one layer may be stacked and then dried, and then the next layer may be stacked.

  In the step of forming the surface protective layer 2 in the present invention, the ionizing radiation curable resin composition layer laminated on the release layer 6 may be semi-cured or completely cured. If it is, the surface performance will be good, and by setting the resin composition to the predetermined one described later, even if it is a cured product, the moldability will be good, so it is preferable to completely cure. When the ionizing radiation curable resin composition layer is cured, the resin composition layer can be cured by irradiation with ionizing radiation such as an electron beam or ultraviolet rays. Here, when an electron beam is used as the ionizing radiation, the accelerating voltage can be appropriately selected according to the resin used and the thickness of the layer, but the ionizing radiation curable resin composition layer is usually used at an accelerating voltage of about 70 to 300 kV. It is preferable to cure.

  In addition, in electron beam irradiation, the transmission capability increases as the acceleration voltage increases. Therefore, when a base material that deteriorates due to an electron beam is used as the base material layer 1, the transmission depth of the electron beam and the surface protective layer 2 are increased. By selecting an accelerating voltage so that the thicknesses of the substrates are substantially equal, it is possible to suppress the irradiation of the excess electron beam to the substrate layer 1 and to minimize the deterioration of the substrate due to the excess electron beam. You can stay. The irradiation dose is preferably such that the crosslinking density of the resin composition layer is saturated, and is usually selected in the range of 5 to 300 kGy (0.5 to 30 Mrad), preferably 10 to 70 kGy (1 to 7 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. Can be used.

  When ultraviolet rays are used as the ionizing radiation, those containing ultraviolet rays having a wavelength of 190 to 380 nm are emitted. There is no restriction | limiting in particular as an ultraviolet-ray source, For example, a high pressure mercury lamp, a low pressure mercury lamp, a metal halide lamp, a carbon arc lamp, etc. are used.

[Use of decorative sheet]
Since the amount of residual solvent is reduced in the decorative sheet of the present invention, in the process of manufacturing the decorative sheet or in a decorative resin molded product manufactured using the decorative sheet, processing defects and generation of odors Etc. can be effectively suppressed. For this reason, the decorative sheet of the present invention is preferably used for decorating members used in a wide range of fields such as household appliances, automobile interior parts, personal computer fields, especially personal computer housings. Can do.

[Method of manufacturing decorative resin molded product]
The decorating sheet of the present invention is suitably used for injection molding simultaneous transfer decorating. And the decorating resin molded product of this invention can be manufactured by injection molding simultaneous transfer decorating using the decorating sheet of this invention, for example. More specifically, the decorative resin molded product of the present invention can be produced by, for example, the following steps (1) to (3).
(1) A process of clamping the decorative sheet of the present invention so as to be in close contact with the inner surface of the mold, along the inner surface shape of the mold,
(2) A step of injecting the injection resin into the mold and integrating the decorative sheet and the injection resin through the adhesive layer;
(3) A step of taking out the decorative molded product from the mold after cooling the injection resin.

  In the above step (1), as a method of bringing the decorative sheet along the inner surface shape of the mold so as to be in close contact with the inner surface of the mold, (i) heating the decorative sheet with a hot plate and evacuating it. And (ii) a method of evacuating at room temperature. In the case of the above method (i), the heating temperature is preferably in the range of near the glass transition temperature of the base material layer 1 and less than the melting temperature (or melting point). Usually, it is more preferable to carry out at a temperature near the glass transition temperature. In addition, said glass transition temperature vicinity refers to the range of about glass transition temperature +/- 5 degreeC, and when using a suitable polyester sheet as the base material layer 1, it is about 70-130 degreeC generally.

  According to the knowledge of the present inventor, particularly when the method (ii) is adopted, there is a tendency that a problem of residual solvent tends to occur after processing into a decorated resin molded product. In the method (i), the solvent remaining in the decorative sheet before decorative molding can be volatilized by the heating step, whereas in the method (ii), the decorative sheet before molding is formed. This is considered to be based on the difference that the solvent inside remains in the decorative resin molded product almost as it is. That is, particularly when the method (ii) is employed, the effect of the decorative sheet of the present invention that can reduce the amount of residual solvent before molding is more suitably exhibited.

  In the step (2), an injection resin, which will be described later, is melted and injected into the cavity, and the decorative sheet and the injection resin are integrated via the adhesive layer 4. When the injection resin is a thermoplastic resin, it is made into a fluid state by heating and melting, and when the injection resin is a thermosetting resin, the uncured liquid composition is injected in a fluid state at room temperature or appropriately heated. Cool and solidify. As a result, the decorative sheet is attached integrally with the formed resin molded body, and becomes a decorative resin molded product. The heating temperature of the injection resin depends on the injection resin, but is generally about 180 to 320 ° C.

  Next, after cooling and taking out from the mold (step (3)), the molded resin layer 7, the adhesive layer 4, the colored layer 3, the surface protective layer 2, and the base material layer 1 in which the injection resin is molded and cured are sequentially formed. The decorative resin molded product with the base material layer 1 of the present invention is obtained. Further, (4) by peeling the base material layer 1 in the step of peeling the base material layer 1 from the decorative resin molded product, the molding resin layer 7, the adhesive layer 4, and the colored layer as shown in FIG. 3 and the decorative resin molded product of the present invention having the surface protective layer 2 in this order are obtained. In addition, when it has the release layer 6 under the base material layer 1, the base material layer 1 is peeled with the release layer 6. FIG.

  Moreover, the said process (4) may be performed simultaneously with the said process (3). That is, by removing the molded decorative resin molded product from the mold and simultaneously peeling the base material layer 1, as shown in FIG. 3, the molded resin layer 7, the adhesive layer 4, the colored layer 3, and You may obtain the decorative resin molding of this invention which has the surface protective layer 2 in order. According to this method, the process of peeling the base material layer 1 is simplified, and the decorative resin molded product is separated in units such as cutting the decorative sheet every time one decorative resin molded product is manufactured. Since it is not necessary, it is possible to manufacture the decorative sheet after use as it is, so-called roll-to-roll manufacturing, and a decorative resin molded product can be manufactured efficiently.

  Moreover, the decorative resin molded product of the present invention is decorated by transfer using a 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. It can also be produced by a method.

  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 is placed in a vacuum pressure bonding machine so that the resin molded body is on the second vacuum chamber side and the adhesive layer 4 side of the decorative sheet faces the resin molded body side, and the two vacuum chambers are in a vacuum state. . 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 atmospheric pressure, and the base material layer 1 is peeled off, whereby the decorated resin molded product of the present invention can be obtained.

  In the vacuum pressure bonding method, (i) a method of heating the decorative sheet in order to soften the decorative sheet and improve moldability before the step of pressing the resin molded body against the decorative sheet; and (ii) ) A method of pressing the molded body against the decorative sheet at room temperature is conceivable, but for the same reason as in the case of the above-described simultaneous injection molding of the injection molding, the method according to the present invention is particularly employed when the method (ii) is adopted. The effect is remarkable.

[Molded resin layer 7]
The resin used for the molded resin layer 7 of the decorative resin molded product of the present invention is not particularly limited, and various resins such as a thermoplastic resin or a thermosetting resin (including a two-component curable resin) are used. Can do. Examples of such thermoplastic resin materials include vinyl polymers such as polyvinyl chloride and polyvinylidene chloride; polystyrene, acrylonitrile-styrene copolymers, ABS resins (acrylonitrile-butadiene-styrene copolymer resins), and the like. Styrene resins; acrylic resins such as polymethyl (meth) acrylate, polyethyl (meth) acrylate, polyacrylonitrile; polyolefin resins such as polyethylene, polypropylene, polybutene, polyethylene terephthalate, ethylene glycol-terephthalic acid-isophthalic acid copolymer, Examples thereof include polyester resins such as polybutylene terephthalate; polycarbonate resins. Examples of the thermosetting resin include a two-component reaction curable polyurethane resin and an epoxy resin. These resins may be used alone or in combination of two or more.

  These resins include various additives as required, such as antioxidants, heat stabilizers, ultraviolet absorbers, light stabilizers, flame retardants, plasticizers, silica, alumina, calcium carbonate, aluminum hydroxide, etc. Inorganic powders, wood powders, fillers such as glass fibers, lubricants, mold release agents, antistatic agents, colorants and the like can be added. As the colorant, a known colorant similar to that which can be used for the substrate layer described above can be used. There is no restriction | limiting in particular about the thickness of the injection resin layer 7 which comprises a decorative resin molded product, Although it selects according to the use of the said decorative resin molded product, it is 1-5 mm normally, Preferably it is 2-3 mm.

[Decorative resin molded product]
In this invention, the decorating resin molded product before the base material layer 1 peels can be manufactured, for example using the decorating sheet of this invention as mentioned above, for example, said process (1)-( It is obtained by going through 3). The structure has at least a molded resin layer 7, an adhesive layer 4, a colored layer 3, a surface protective layer 2, and a base material layer 1 in this order, and the surface protective layer 2 cures the ionizing radiation curable resin composition. The adhesive layer 4 is formed of a resin composition including a resin and a filler, and the adhesive layer 4 includes 1 part by mass or more of the filler with respect to 100 parts by mass of the resin. It is what. That is, in the decorative resin molded product, the base material layer 1 is formed on the surface protective layer 2. Here, since the base material layer 1 has a function as a protective sheet (masking film), it may be peeled off, stored as it is without being peeled off, and peeled off immediately before use. Moreover, when the base material layer 1 is used as a protective sheet, there is an advantage that it can be used as a layer for protecting the surface protective layer from the generation of scratches caused by rubbing or the like that occurs during transportation.

  Moreover, the decorating resin molded product of this invention after the base material layer 1 was peeled can be manufactured, for example using the decorating sheet of this invention as mentioned above, for example, said process (1)- It is obtained by going through (4). For example, as shown in FIG. 3, the configuration includes at least a molding resin layer 7, an adhesive layer 4, a colored layer 3, and a surface protective layer 2, and the surface protective layer 2 is an ionizing radiation curable resin. It is formed with the hardened | cured material of the composition, the contact bonding layer 4 is formed with the resin composition containing resin and a filler, and the filler contains 1 mass part or more with respect to 100 mass parts of resin in the contact bonding layer 4. It is characterized by that. That is, in the decorative resin molded product, the surface protective layer 2 is located on the outermost surface.

  Since the decorative resin molded product of the present invention is manufactured using the decorative sheet of the present invention, the amount of residual solvent is reduced, and the generation of odors is effectively suppressed. Moreover, since the ionizing radiation curable resin composition which forms the surface protection layer of the decorating sheet of this invention is hardened | cured previously, the decorating resin molded product of this invention can be manufactured with sufficient productivity. The decorative resin molded product of the present invention can be suitably used in a wide range of fields such as household appliances and automobile interior parts, and in the field of personal computers, especially personal computer casings, taking advantage of these excellent characteristics. be able to.

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

<Examples 1-2 and Comparative Example 1>
(Preparation of decorative sheet)
An acrylic-melamine resin was coated on a biaxially stretched PET sheet (thickness: 75 μm) to form a release layer (thickness: 0.1 μm). Next, 40 parts by mass of a polyfunctional (meth) acrylate monomer (pentaerythritol triacrylate, molecular weight: 298), a thermoplastic resin having a weight average molecular weight Mw of 150,000 (acrylic resin (copolymer of methyl methacrylate and methacrylic acid, glass transition) (Tg: 95 ° C.) 60 parts by mass, 1.1 parts by mass of an ultraviolet absorber, 0.6 parts by mass of a light stabilizer, and 0.2 parts by mass of a leveling agent. It was applied onto the mold layer with a bar coater, and irradiated with an electron beam having an acceleration voltage of 165 kV and an irradiation dose of 50 kGy (5 Mrad) to be cured by crosslinking to form a surface protective layer (thickness: 6 μm). After the corona discharge treatment is applied to the surface of the layer, a polyurethane two-component curable resin (acrylic polymer polyol and The composition containing N diisocyanate so that the NCO equivalent and the OH equivalent are the same amount, a solution having a glass transition temperature Tg (when the polyol is uncured): 100 ° C. is applied by gravure printing, and the primer layer ( Next, a black printing ink (acrylic resin: 50% by mass) using an acrylic resin and a vinyl chloride-vinyl acetate copolymer resin as a binder resin on the primer layer. A gravure printing was applied to a vinyl chloride-vinyl acetate copolymer resin (50% by mass) at a coating amount of 2 g / m ² to form a solid color layer on the entire surface, and an acrylic resin (softening temperature: 125 ° C.), silica particles (average particle size of about 2 to 3 μm, oil absorption 250 mL / 100 g) and dilution solvent methyl ethyl ketone: ethyl acetate = 1: 1 The adhesive composition was formed by performing gravure printing on the resin composition containing the coating composition at a coating amount of 1.5 g / m ² , and then remaining in the decorative sheets obtained in Examples 1-2 and Comparative Example 1. The amount of solvent was measured as follows.

<Measurement of residual amount of solvent in decorative sheet immediately after production>
In the manufacturing process of the decorative sheet, every time the primer layer, the colored layer, and the adhesive layer were printed, hot air from a dryer was applied for 10 seconds from a location 20 cm away. Next, the decorative sheet immediately after production was sealed in a gas chromatography bottle. After 1 hour, gas chromatography measurement was performed on the gas in the bottle, and the amount of solvent released from the decorative sheet was measured. The results are shown in Table 1.

<Measurement of remaining amount of solvent in decorative sheet after one week from production>
In the manufacturing process of the decorative sheet, every time the primer layer, the colored layer, and the adhesive layer were printed, hot air from a dryer was applied for 10 seconds from a location 20 cm away. Next, the decorative sheet immediately after production was left at room temperature for one week. Next, after the decorative sheet left for one week was heated at 100 ° C. for 20 seconds, the decorative sheet was packed in a gas chromatography bottle and sealed. After 1 hour, gas chromatography measurement was performed on the gas in the bottle, and the amount of solvent released from the decorative sheet was measured. The results are shown in Table 1.

  As shown in Table 1, in the decorative sheets of Examples 1 and 2 in which silica particles were blended in the adhesive layer, as compared with the decorative sheet of Comparative Example 1 in which silica particles were not blended, immediately after production. The residual amount of solvent was small, and the residual amount of solvent after one week from the production was considerably reduced.

<Evaluation of initial adhesion>
The decorative sheets obtained in Examples 1 and 2 and Comparative Example 1 were vacuum-formed so as to conform to the in-mold shape of the injection molding, and adhered to the inner surface of the mold. The mold used was a shape of 160 × 100 mm, a plate shape of 3 mm aperture and 5R corners. On the other hand, PC + ABS resin (“XCY620 (trade name)”, manufactured by CYCOLOY) was used as the injection resin, which was melted at 265 ° C. and then injected into the cavity. At the same time as taking out from the mold at a temperature of 60 ° C., the base material layer was peeled off to obtain a decorated resin molded product in which a surface protective layer, a primer layer, a colored layer, an adhesive layer, and a molded resin layer were laminated in order.
Next, from the surface protective layer side of the obtained decorative resin molded product, 6 crosscuts are formed at 1 mm intervals using a cutter, and 1 inch cellophane tape (manufactured by Nichiban Co.) is pressure-bonded from above, The initial adhesiveness of the decorated resin molded product was evaluated by repeating the procedure of abrupt peeling five times at the same location. As a result, in any of the decorative resin molded products using the decorative sheets obtained in Examples 1 and 2 and Comparative Example 1, no peeling was observed and the initial adhesion was good.

<Measurement of gross value (60 °)>
Using a gloss made by BYK Gardner, the gloss value (60 °) of the surface of the decorative resin molded product using the decorative sheet obtained in Examples 1-2 and Comparative Example 1 was measured. As a result, the gloss value (60 °) of the decorative resin molded product of Example 1 was 80.8, the gloss value (60 °) of the decorative resin molded product of Example 2 was 81.3, and Comparative Example 1 The gloss value (60 °) of the decorative resin molded product was 80.9, which was almost the same value. From this, in the decorative sheets of Examples 1 and 2, it is possible to reduce the residual solvent without impairing the design feeling by reducing the gloss of the decorative resin molded product by including a filler in the adhesive layer. It can be said that it was made.

DESCRIPTION OF SYMBOLS 1 ... Base material layer 2 ... Surface protective layer 3 ... Colored layer 4 ... Adhesive layer 4a ... Filler 5 ... Primer layer 6 ... Release layer 7 ... Molding resin layer

Claims (11)

At least a base material layer, a surface protective layer, a colored layer, and an adhesive layer in this order,
The surface protective layer is formed of a cured product of an ionizing radiation curable resin composition,
The adhesive layer is formed of a resin composition containing a resin and a filler;
The filler is porous particles;
The filler has an oil absorption of 200 to 400 mL / 100 g,
The said adhesive layer WHEREIN: The decorating sheet in which the said filler is contained 1 mass part or more with respect to 100 mass parts of said resin.   The decorative sheet according to claim 1, wherein in the adhesive layer, the filler has an average particle diameter of 1 to 10 μm. The decorative sheet according to claim 1 or 2 , wherein the adhesive layer has a thickness of 6 µm or less. In the adhesive layer, the resin is made of acrylic resin, vinyl chloride resin, vinyl acetate resin, vinyl chloride-vinyl acetate copolymer resin, styrene-acrylic copolymer resin, polyester resin, and polyamide resin. The decorative sheet according to any one of claims 1 to 3 , which is at least one selected from the group consisting of: The decorative sheet according to any one of claims 1 to 4 , wherein the colored layer has a thickness of 0.5 to 40 µm. The ionizing radiation curable resin composition contains a polyfunctional (meth) acrylate monomer having a molecular weight of 175 to 1000, and a thermoplastic resin having a weight average molecular weight of 10,000 to 250,000 converted to standard polystyrene. Item 6. The decorative sheet according to any one of items 1 to 5 . The decorative sheet according to claim 6 , wherein the polyfunctional (meth) acrylate monomer has 3 to 8 functional groups. The decorative sheet according to claim 6 or 7 , wherein the thermoplastic resin is an acrylic resin having a (meth) acrylic acid ester monomer as a structural unit. At least a molded resin layer, an adhesive layer, a colored layer, and a surface protective layer are laminated in this order,
The surface protective layer is formed of a cured product of an ionizing radiation curable resin composition,
The adhesive layer is formed of a resin composition containing a resin and a filler;
The filler is porous particles;
The filler has an oil absorption of 200 to 400 mL / 100 g,
The said resin layer WHEREIN: The decorative resin molded product in which the said filler is contained 1 mass part or more with respect to 100 mass parts of said resin. A step of clamping the decorative sheet according to any one of claims 1 to 8 along the inner surface shape of the mold so as to adhere to the inner surface of the mold, and
Injecting injection resin into the mold, and integrating the decorative sheet and the injection resin through the adhesive layer;
After cooling the injection resin, a step of taking out a decorative resin molded product from the mold,
A method for producing a decorated resin molded product. The method for producing a decorated resin molded product according to claim 10 , further comprising a step of peeling the base material layer from the decorated resin molded product simultaneously with the step of taking out the decorated resin molded product from the mold.