JP6015317B2 - Decorative sheet and decorative resin molded product - Google Patents

Description

  In the present invention, the support and the transfer layer can be peeled off at an appropriate peel strength, and even if the support is peeled and removed, it is possible to suppress the occurrence of peeling marks on the surface of the transfer layer and to have a low gloss feeling. The present invention relates to a decorative sheet having excellent design properties, and a decorative resin molded product using the decorative sheet.

  A decorative resin molded product in which a decorative sheet is laminated on the surface of a resin molded product is used for a vehicle interior part, a building material interior material, a home appliance housing, and the like. Conventionally, in the production of a decorative resin molded product, a molding method in which a decorative sheet to which design properties have been imparted in advance is integrated with a resin by injection molding has been used. As typical examples of such a method for producing a decorated resin molded product, an insert molding method and an injection molding simultaneous decoration method are known. In the insert molding method, a decorative sheet is molded into a three-dimensional shape in advance using a vacuum mold, the decorative sheet is inserted into an injection mold, and a resin in a flow state is injected into the mold to decorate the resin. This is a molding method that integrates the sheet. The injection molding simultaneous decoration method decorates the surface of the resin molded body by integrating the decorative sheet inserted into the mold during injection molding with the molten resin injected and injected into the cavity. Is a molding method.

  Some decorative resin molded products have a complicated surface shape such as a three-dimensional curved surface, and the decorative sheet is required to have three-dimensional formability that can sufficiently follow the shape of the decorative resin molded product. Yes. Also, in recent years, there is a tendency that a design with a rich luster and a high-class feeling has been desired, and in order to meet consumer preference, the decorative sheet should have an excellent design with a low gloss. Is also sought.

  Conventionally, as a decorative sheet, a laminated sheet in which a transfer layer is laminated on a support composed of a base film and a release layer so as to be in contact with the release layer is known. The decorative sheet is subjected to injection molding and integrally molded with the resin, and then the interface between the release layer and the transfer layer is removed to remove the support so that the design property of the transfer layer is exposed on the surface of the resin molded product. It is.

  So far, it is known that water-soluble polyester, polyvinyl alcohol, ethylene-vinyl alcohol copolymer, ionizing radiation curable resin, and the like can be used as the resin for forming the release layer of the decorative sheet (Patent Document 1). And 2). In addition, it is also known that the decorative sheet can have a low gloss feeling with a texture by forming irregularities on the transfer layer by using a release layer with irregularities on the surface ( Patent Document 2). As a method for forming irregularities on the surface of the release layer, a method is known in which the release layer is cured on a circular drum or sheet having irregularities and then transferred to a base film. However, such a method has a drawback in that the manufacturing process becomes complicated because a process for forming irregularities on the surface of the release layer is required separately. On the other hand, it is also known that irregularities can be formed on the surface of the release layer by adding a mat material to the resin forming the release layer. While this method has the advantage that irregularities can be formed on the surface of the mold layer by a simple method, the release layer and the transfer layer are firmly bonded, and the decorative sheet is supported after being integrally formed with the injection resin. There is a disadvantage that the body is difficult to peel off, and further, when the support is peeled off with a strong force, a local force is applied to the surface of the transfer layer, resulting in a peeling mark of the support and a loss of design. There is also a point.

  Against the backdrop of such conventional technology, in addition to being able to be manufactured by a simple method, the support and the transfer layer can be peeled off at an appropriate peel strength. New creation of a decorative sheet that can suppress the occurrence of peeling marks and can have excellent design properties with a low gloss feeling is desired.

JP-A-8-20199 JP-A-6-171037

  The object of the present invention is to be able to peel the support and the transfer layer with an appropriate peel strength, and even if the support is peeled and removed, it is possible to suppress the occurrence of peeling marks of the support on the surface of the transfer layer. It is providing the decorative sheet | seat provided with a certain outstanding design property, and the decorative resin molded product using the said decorative sheet | seat.

  The inventors of the present invention have made extensive studies to solve the above problems. As a result, a support having at least a base material layer and a release layer, and a transfer layer having at least a protective layer and a decoration layer are combined with the release layer. In the decorative sheet laminated in a state where the protective layer is in contact, the release layer is formed from a cured product of a resin composition containing synthetic resin particles and an ionizing radiation curable resin, and the protective layer is formed. By forming from a cured product of a resin composition containing an ionizing radiation curable resin, the support and the transfer layer can be peeled with an appropriate peel strength, and even if the support is peeled and removed, it is supported on the surface of the transfer layer. It was found that it was possible to suppress the occurrence of peeling marks on the body. Furthermore, in the decorative sheet according to the above aspect, by forming a release layer using a cured product of a resin composition containing synthetic resin particles and an ionizing radiation curable resin, unevenness due to the synthetic resin particles is formed on the surface of the release layer. It has also been found that it can be shaped and can be provided with a design that expresses a rich and low gloss feeling with a texture. The present invention has been completed by further studies based on this finding.

That is, this invention provides the invention of the aspect hung up below.
Item 1. A support sheet having at least a base material layer and a release layer, and a transfer layer having at least a protective layer and a decoration layer are decorative sheets laminated in a state where the release layer and the protective layer are in contact with each other. ,
The release layer is formed from a cured product of a resin composition containing synthetic resin particles and an ionizing radiation curable resin, and the protective layer is formed from a cured product of a resin composition containing an ionizing radiation curable resin. A decorative sheet characterized by being made.
Item 2. Item 2. The decorative sheet according to Item 1, wherein the ionizing radiation curable resin used for forming the release layer is polycarbonate (meth) acrylate and / or acrylic silicone (meth) acrylate.
Item 3. Item 3. The decorative sheet according to item 1 or 2, wherein the ionizing radiation curable resin used for forming the protective layer is a polyfunctional (meth) acrylate monomer.
Item 4. Item 4. The decorative sheet according to any one of Items 1 to 3, wherein the synthetic resin particles are at least one selected from the group consisting of acrylic beads, silicone beads, and urethane beads.
Item 5. Item 5. The decorative sheet according to any one of Items 1 to 4, wherein the release layer contains 1 to 70 parts by mass of synthetic resin particles per 100 parts by mass of the ionizing radiation curable resin.
Item 6. Item 6. The decorative sheet according to any one of Items 1 to 5, wherein the synthetic resin particles have an average particle size of 0.5 to 25 µm.
Item 7. Item 7. The decorative sheet according to any one of Items 1 to 6, wherein the release layer has a thickness of 0.01 to 5 µm.
Item 8. Item 8. The decorative sheet according to any one of Items 1 to 7, wherein a primer layer is provided between the protective layer and the decorative layer.
Item 9. On the release layer of the support having at least a base material layer and a release layer, a protective layer, a decorative layer, and an injection resin layer are sequentially provided.
The release layer is formed from a cured product of a resin composition containing synthetic resin particles and an ionizing radiation curable resin, and the protective layer is formed from a cured product of a resin composition containing an ionizing radiation curable resin. A decorated resin molded product with a support, which is characterized in that
Item 10. Item 10. A decorative resin molded product obtained by removing the support from the decorated resin molded product with a support according to Item 9.

  The decorative sheet of the present invention has irregularities formed on the surface of the transfer layer (the surface of the protective layer) so as to follow the irregular shape of the release layer formed by the synthetic resin particles. Therefore, the decorative resin molded product can be provided with an excellent design with a high-class feeling. In addition, since the decorative sheet of the present invention can peel the support and the transfer layer with an appropriate peel strength, when the support is peeled off, a local force is applied to the surface of the transfer layer to cause a peeling mark. Can be suppressed. Furthermore, the decorative sheet of the present invention has excellent moldability and can follow complicated surface shapes such as a three-dimensional curved surface, which contributes to an improvement in the production efficiency of decorative resin molded products. Can do.

  In addition, according to the decorative sheet of the present invention, a uniform layer without unevenness of ink in the pattern layer in the transfer layer can be formed, so that the surface property of the transfer layer can be improved. Furthermore, according to the decorative sheet of the present invention, it is possible to adjust the low gloss feeling to be expressed according to the particle size and amount of the synthetic resin particles added to the release layer, so that the conventional technology using other mat materials is used. Compared to a wide range of gloss. Furthermore, since the decorative sheet of the present invention forms a protective layer using an ionizing radiation curable resin, surface properties such as scratch resistance are also good, and characteristics that are practically required as interior materials for automobiles and the like. Can be satisfied.

It is a schematic diagram of the cross-sectional structure of one form of the decorative sheet of the present invention. It is a schematic diagram of the cross-sectional structure of one form of the decorative resin molded product with a support of the present invention. It is a schematic diagram of the cross-sectional structure of one form of the decorative resin molded product of the present invention.

1. Decorative sheet The decorative sheet of the present invention has a support having at least a base material layer and a release layer, and a transfer layer having at least a protective layer and a decorative layer in a state where the release layer and the protective layer are in contact with each other. The release sheet is formed from a cured product of a resin composition containing synthetic resin particles and ionizing radiation curable resin, and the protective layer is ionizing radiation cured. It is formed from the hardened | cured material of the resin composition containing a conductive resin. Hereinafter, the decorative sheet of the present invention will be described in detail. Hereinafter, in the present specification, the support and the transfer layer can be peeled off at an appropriate peel strength, and the properties for suppressing the occurrence of peeling marks on the support on the surface of the transfer layer after peeling of the support are described below. It may be abbreviated as “peeling property”. In the present specification, unless otherwise specified, “(meth) acrylic acid” means “acrylic acid or methacrylic acid”, and other similar notations have the same meaning.

(1) Laminated structure of decorative sheet The decorative sheet of the present invention comprises a support having at least a base material layer and a release layer, and a transfer layer having at least a protective layer and a decorative layer. It has a stacked structure in which the layers are stacked so that the layers are in contact with each other. In the decorative sheet of the present invention, the support plays a role as a member of the transfer layer. That is, after integrally molding the decorative sheet of the present invention with the injection resin, by peeling off the support (base layer and release layer), the transfer layer is transferred to the surface of the resin molded product, The resin molded product is decorated.

  In the decorative sheet of the present invention, the transfer layer only needs to be provided with at least a protective layer and a decorative layer, and may include one or more other layers in addition to the protective layer and the decorative layer.

  For example, in the transfer layer, a primer layer may be provided between the protective layer and the decorative layer as necessary for the purpose of improving the adhesion between them.

  Furthermore, in the transfer layer, an adhesive layer is provided as necessary as a surface layer on the side opposite to the support for the purpose of improving the adhesion with the injection resin when performing integral molding with the injection resin. May be provided

  That is, as an example of the laminated structure in the decorative sheet of the present invention, there are a base layer / release layer / protective layer / primer layer / decoration layer / optional adhesive layer provided as necessary. A stacked structure in which layers are stacked in order is mentioned. FIG. 1 is a cross-sectional view of a decorative sheet in which a base layer / release layer / protective layer / primer layer / decoration layer / adhesive layer are sequentially laminated as a preferred embodiment of the laminated structure of the decorative sheet of the present invention. Indicates.

(2) Composition of each layer of the decorative sheet
[Support]
The decorative sheet of the present invention includes at least a base material layer and a release layer as a support. The support serves as a support member for the transfer layer. After the decorative sheet of the present invention and the injection resin are integrally formed, the interface between the release layer and the protective layer is peeled off and removed.
(Base material layer)
The material of the base material layer is not particularly limited as long as it can support the release layer and the transfer layer and has moldability, heat resistance, and the like, but a resin is preferably used.

  The type of resin used for the base material layer is not particularly limited, and may be appropriately selected in consideration of moldability, heat resistance, and the like. Specific examples of resins used for the base material layer include polyolefin resins such as polyethylene and polypropylene; polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, ethylene / vinyl acetate copolymer, and ethylene / vinyl alcohol copolymer. Vinyl resins such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate and other polyester resins; poly (meth) methyl acrylate, poly (meth) ethyl acrylate and other acrylic resins; polystyrene and other styrene resins, An acrylonitrile / butadiene / styrene copolymer, cellulose triacetate, cellophane, polycarbonate, polyurethane-based elastomer resin or the like is used. Among these resins, polyester resins are preferable, and polyethylene terephthalate is more preferable because of good moldability and release characteristics. It is preferable to use a film of these resins as the base material layer.

  The base material layer may be a single layer formed using a single resin, or may be a multiple layer formed using the same or different resins.

  The base material layer may be subjected to physical or chemical surface treatment such as oxidation treatment or roughening treatment on one or both sides as necessary for the purpose of improving the adhesion with the release layer described later. Good. Examples of the oxidation treatment include corona discharge treatment, chromium oxidation treatment, flame treatment, hot air treatment, ozone / ultraviolet treatment method, and the like. Moreover, as an uneven | corrugated process, a sandblasting method, a solvent processing method, etc. are mentioned, for example. Furthermore, in order to improve adhesiveness with the mold release layer mentioned later as a base material layer, you may use the thing in which the easily adhesive layer is formed in the single side | surface or both surfaces as needed.

  Although it does not restrict | limit especially as thickness of a base material layer, Although it considers moldability, the peelability of the support body after shaping | molding, etc., it sets suitably, Usually 10-150 micrometers, Preferably it is 10-125 micrometers, More preferably 10-80 micrometers is mentioned.

(Release layer)
The release layer is provided on the base material layer and exists in a state of being in contact with the protective layer. In the decorative sheet of the present invention, the release layer is formed from a cured product of a resin composition containing synthetic resin particles and an ionizing radiation curable resin. Thus, in the formation of the release layer, by selecting and blending the synthetic resin particles as an additive together with the ionizing radiation curable resin, the unevenness according to the shape of the synthetic resin particles can be shaped into the transfer layer, The unevenness for making the transfer layer have a rich low gloss feel is formed by the unevenness of the release layer. Furthermore, it is possible to provide excellent release characteristics by adopting a combination of synthetic resin particles and ionizing radiation curable resin as a release layer and laminating it in contact with a protective layer having a composition described later. Become.

<Synthetic resin particles>
The synthetic resin particles used for the release layer may be either a thermosetting resin or a thermoplastic resin. The type of synthetic resin particles is not particularly limited, and examples thereof include acrylic beads, urethane beads, nylon beads, silicone beads, silicone rubber beads, and polycarbonate beads. Among these synthetic resin particles, from the viewpoint of further improving the peeling characteristics and the low gloss feeling to be exposed, preferably acrylic beads, urethane beads, silicone beads, more preferably acrylic beads, particularly preferably cross-linked acrylic beads. Is mentioned. Further, since the dispersibility of the synthetic resin particles in the release layer is good, the decorative sheet of the present invention can be provided with a uniform surface property without color unevenness in the transfer layer, but the synthesis used for the release layer By selecting acrylic beads as the resin particles, the surface properties of the transfer layer can be further improved. These synthetic resin particles may be used individually by 1 type, and may be used in combination of 2 or more type.

Further, the specific gravity of the synthetic resin particles used in the present invention is not particularly limited, but for example, from the viewpoint of further improving the low gloss to be exposed while making the peel strength of the support moderate, for example, 0. 7-1.5 g / cm < ³ > is preferable, 0.8-1.3 g / cm < ³ > is more preferable, 0.85-1.2 g / cm < ³ > is mentioned. Also, by satisfying such specific gravity, the synthetic resin particles can be localized in the surface region in the ionizing radiation curable resin before curing, so the average particle diameter of the synthetic resin particles is Even if the thickness is equal to or less than the thickness of the mold layer, desired irregularities can be formed on the surface of the release layer.

  The average particle diameter of the synthetic resin particles is not particularly limited, but is usually 0.5 to 25 μm, preferably 0.5 to 5 μm, from the viewpoint of further improving moldability and low gloss. By satisfying such an average particle size, it is possible to further improve the peeling characteristics and the low gloss feeling to be expressed. Here, the average particle size of the synthetic resin particles is determined by using the Shimadzu laser diffraction particle size distribution analyzer SALD-2100-WJA1 and using compressed air to inject the powder to be measured from the nozzle and into the air. It is a value measured by a spray-type dry measurement method that is measured by dispersing.

  Further, the content of the synthetic resin particles in the release layer is appropriately set according to the low glossiness to be exposed on the decorative sheet, the moldability to be provided, etc., for example, ionizing radiation in the release layer 1-70 mass parts with respect to 100 mass parts of curable resin, Preferably it is 5-50 mass parts, More preferably, 5-30 mass parts is mentioned. By satisfying such a content, it is possible to combine both the moldability and the low gloss feeling to be expressed even better.

<Ionizing radiation curable resin>
The ionizing radiation curable resin used for forming the release layer refers to a resin that crosslinks and cures when irradiated with ionizing radiation. Here, the 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. In addition, electromagnetic waves such as X-rays and γ-rays, and charged particle beams such as α-rays and ion beams are also included. Among ionizing radiation curable resins, electron beam curable resins can be made solvent-free, do not require a photopolymerization initiator, and provide stable curing characteristics, which is suitable for forming a surface protective layer. used.

  Specific examples of the ionizing radiation curable resin include those obtained by appropriately mixing a prepolymer, an oligomer, and / or a monomer having a polymerizable unsaturated bond or an epoxy group in the molecule.

  Examples of the oligomer used as the ionizing radiation curable resin include a urethane (meth) acrylate oligomer, an epoxy (meth) acrylate oligomer, a polyester (meth) acrylate oligomer, a polyether (meth) acrylate oligomer, and a polybutadiene (meth) acrylate. An oligomer etc. are mentioned. Here, the urethane (meth) acrylate oligomer can be obtained, for example, by esterifying a polyurethane oligomer obtained by a reaction of polyether polyol or polyester polyol and polyisocyanate with (meth) acrylic acid. The epoxy (meth) acrylate oligomer 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. A carboxyl-modified epoxy (meth) acrylate oligomer obtained by partially modifying this epoxy (meth) acrylate oligomer with a dibasic carboxylic acid anhydride can also be used. Polyester (meth) acrylate oligomer 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, for example, with (meth) acrylic acid, or a polyvalent carboxylic acid. It can be obtained by esterifying the terminal hydroxyl group of an oligomer obtained by adding alkylene oxide to (meth) acrylic acid. The polyether (meth) acrylate oligomer can be obtained by esterifying the hydroxyl group of the polyether polyol with (meth) acrylic acid. The polybutadiene (meth) acrylate oligomer can be obtained by adding (meth) acrylate acid to the side chain of the polybutadiene oligomer. These oligomers may be used individually by 1 type, and may be used in combination of 2 or more type.

  As the monomer used as the ionizing radiation curable resin, a (meth) acrylate monomer having a radically polymerizable unsaturated group in the molecule is preferable, and a polyfunctional (meth) acrylate monomer is particularly preferable. The polyfunctional (meth) acrylate monomer may be a (meth) acrylate monomer having two or more polymerizable unsaturated bonds 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.

  Among these ionizing radiation curable resins, from the viewpoint of release characteristics and moldability, an oligomer having a polymerizable unsaturated bond or an epoxy group in the molecule, more preferably polycarbonate (meth) acrylate and / or acrylic silicone ( And (meth) acrylate. Hereinafter, polycarbonate (meth) acrylate and acrylic silicone (meth) acrylate that are preferably used as the ionizing radiation curable resin for forming the release layer will be described in detail.

The polycarbonate (meth) acrylate used as the polycarbonate (meth) acrylate ionizing radiation curable resin is particularly limited as long as it has a carbonate bond in the polymer main chain and a (meth) acrylate in the terminal or side chain. Not. Moreover, the said (meth) acrylate is 2 or more normally as a number of the functional groups per molecule from a viewpoint of making bridge | crosslinking and hardening favorable, Preferably 2-6 are mentioned.

  The polycarbonate (meth) acrylate is obtained, for example, by converting 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 divalent hydrocarbon group having 2 to 20 carbon atoms, and the group may contain an ether bond. For example, a linear or branched alkylene group, a cyclohexylene group, or a phenylene group.

  Specific examples of the diol compound include ethylene glycol, 1,2-propylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, polyethylene glycol, neopentyl glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-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 500 or more, preferably 1,000 or more, and more preferably 2,000 or more. The upper limit of the weight average molecular weight of the polycarbonate (meth) acrylate is not particularly limited, but may be, for example, 100,000 or less, preferably 50,000 or less from the viewpoint of controlling the viscosity not to be too high. From the viewpoint of further improving the moldability, the weight average molecular weight of the polycarbonate (meth) acrylate is preferably more than 2,000 and not more than 50,000, and more preferably 5,000 to 20,000.

  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.

The acrylic silicone (meth) acrylate used as the acrylic silicone (meth) acrylate ionizing radiation curable resin is not particularly limited, and a part of the structure of the acrylic resin becomes a siloxane bond (Si-O) in one molecule. What is necessary is just to be substituted and to have two or more (meth) acryloyloxy groups (acryloyloxy group or methacryloyloxy group) at the side chain and / or main chain terminal of the acrylic resin as a functional group. . As a suitable 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, for example. Moreover, the said acrylic silicone (meth) acrylate is 2 or more normally as a number of the functional groups per molecule from a viewpoint of making bridge | crosslinking and hardening favorable, Preferably 3-8 pieces are mentioned.

  The acrylic silicone (meth) acrylate 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 used as a raw material for the acrylic silicone (meth) acrylate include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl ( Examples include meth) acrylate and glycidyl (meth) acrylate. These (meth) acrylate monomers may be used individually by 1 type, and may be used in combination of 2 types.

  The silicone macromonomer used as a raw material for the acrylic silicone (meth) acrylate is, for example, living anion polymerization of hexaalkylcyclotrisiloxane using n-butyllithium or lithium silanolate as a polymerization initiator, and further radical polymerizable unsaturated. It is synthesized by capping with a group-containing silane. As the silicone macromonomer, a compound represented by the 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. N represents the number of repeating units-[Si (R ³ ) ₂ ]-, and the number is not particularly limited, but the number average molecular weight of the silicone macromonomer is 1,000 to 30,000, preferably 1 It is desirable that the range of 20,000 to 20,000 is satisfied.

  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. Represents a group, and n has the same meaning as in formula (1).

  The said acrylic silicone (meth) acrylate may be used individually by 1 type, and may be used in combination of 2 or more type.

  Although there is no restriction | limiting in particular about the molecular weight of the said acrylic silicone (meth) acrylate, For example, the weight average molecular weight of standard polystyrene conversion by GPC analysis is 1,000 or more, Preferably 2,000 or more is mentioned. The upper limit of the weight average molecular weight of the acrylic silicone (meth) acrylate is not particularly limited, but may be, for example, 150,000 or less, preferably 100,000 or less from the viewpoint of controlling the viscosity not to be too high. From the viewpoint of further improving the moldability, the weight average molecular weight in terms of standard polystyrene by GPC analysis of the acrylic silicone (meth) acrylate is preferably 2,000 to 100,000.

  Further, the average molecular weight between the crosslinking points of the acrylic silicone (meth) acrylate is not particularly limited, and examples thereof include 100 to 2,500, preferably 100 to 1,500, and more preferably 100 to 1,000. .

<Other additives>
Moreover, various additives can be mix | blended with the resin composition used for formation of a mold release layer according to the desired physical property with which a mold release layer is equipped. 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.

<Thickness of release layer>
Although there is no restriction | limiting in particular about the thickness after hardening of a mold release layer, For example, 0.01-5 micrometers, Preferably it is 0.01-4 micrometers, More preferably, 0.01-3.5 micrometers is mentioned. By satisfying the thickness in such a range, the unevenness due to the synthetic resin particles can be shaped more effectively, and furthermore, it has excellent moldability with high followability for complex three-dimensional shapes. Can be made.

<Formation of release layer>
The release layer is formed by preparing a resin composition containing synthetic resin particles and an ionizing radiation curable resin, applying the resin composition on the base material layer, and curing by crosslinking. In addition, the viscosity of the said resin composition should just be a viscosity which can form a non-hardened resin layer on the surface of a base material with the below-mentioned application system.

  The method for applying the resin composition on the base material layer is not particularly limited, and examples include gravure coating, bar coating, roll coating, reverse roll coating, comma coating, and preferably gravure coating. It is done.

  In this way, the resin composition (uncured resin layer) applied on the base material layer is irradiated with ionizing radiation such as electron beam or ultraviolet ray to cure the resin composition to form a release layer. . Here, when an electron beam is used as the ionizing radiation, the acceleration voltage can be appropriately selected according to the resin to be used and the thickness of the layer, but usually includes an acceleration voltage of about 70 to 300 kV.

  In addition, in electron beam irradiation, the transmission capability increases as the acceleration voltage increases. Therefore, when using a base material that deteriorates due to the electron beam as the base material layer, the transmission depth of the electron beam and the thickness of the resin layer are substantially equal. By selecting the accelerating voltage so as to be equal to each other, it is possible to suppress the irradiation of the electron beam to the base material layer, and to minimize the deterioration of the base material due to the excess electron beam.

  The irradiation dose is preferably such that the crosslink density of the resin layer is saturated, and is usually selected in the range of 5 to 300 kGy (0.5 to 30 Mrad), preferably 10 to 50 kGy (1 to 5 Mrad).

  Furthermore, there is no restriction | limiting in particular as an electron beam source, For example, various electron beam accelerators, such as a cock loft Walton type, a van de Graft type, a resonance transformer type, an insulated core transformer type, or a linear type, a dynamitron type, a high frequency type 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.

[Transfer layer]
The transfer layer is a layer that is provided on the support and plays a role of imparting design properties. When the support is peeled and removed after the decorative sheet of the present invention and the injection resin are integrally formed, the transfer layer forms a surface layer of the decorative resin molded product, and the decorative resin molded product has a low gloss design Is granted.

  The transfer layer only needs to have at least a protective layer and a decorative layer. If necessary, a primer layer may be provided between the protective layer and the decorative layer, and further on the decorative layer (with the support). May be provided with an adhesive layer.

  In the decorative sheet of the present invention, the transfer layer is formed with irregularities on the protective layer side so as to follow the irregularities of the release layer, and thus has a texture separate from the design by the decorative layer. A low gloss feeling is expressed.

(Protective layer)
The protective layer is a layer provided between the release layer and the decorative layer so as to be in contact with the release layer.

  In the decorative sheet of the present invention, the protective layer is formed from a cured product of a resin composition containing an ionizing radiation curable resin. Thus, by forming the protective layer with a cured product of an ionizing radiation curable resin, it is possible to provide excellent release characteristics due to the interaction with the release layer. In addition, by forming a protective layer with a cured product of ionizing radiation curable resin, unevenness is formed in the protective layer in a form that follows the unevenness of the release layer, and a rich low gloss feeling is exhibited in the transfer layer. In addition, surface properties such as improvement of scratch resistance of the decorative sheet can be enhanced.

  The type of ionizing radiation curable resin used for forming the protective layer is not particularly limited, and specific examples include the same ionizing radiation curable resin used for forming the release layer. . The ionizing radiation curable resin used for forming the protective layer preferably has a molecular weight of 175 to 1000, more preferably 200 to 800, from the viewpoint of further improving the peeling characteristics and the low gloss feeling to be exposed. And a polyfunctional (meth) acrylate monomer having two or more functional groups, more preferably pentaerythritol tri (meth) acrylate.

  Moreover, a protective layer can also be formed with the hardened | cured material of the resin composition containing an ionizing radiation curable resin and the said thermoplastic resin. Such a resin composition is suitable when a molded product is obtained using the simultaneous injection molding method. In the formation of the protective layer, the type of the thermoplastic resin used in combination with the ionizing radiation curable resin is not particularly limited. For example, acrylic resin; polyvinyl acetal (butyral resin) such as polyvinyl butyral; polyethylene terephthalate, polybutylene terephthalate Polyester resin such as polyvinyl chloride resin; Urethane resin; Polyolefin such as polyethylene and polypropylene; Styrenic resin such as polystyrene and α-methylstyrene; Polyamide; Polycarbonate; Acetal resin such as polyoxymethylene; Fluorine resin such as polymer; polyimide; polylactic acid; polyvinyl acetal resin; liquid crystalline polyester resin. These thermoplastic resins may be used individually by 1 type, and may be used in combination of 2 or more type.

  Among these thermoplastic resins, an acrylic resin is preferably used from the viewpoint of further improving the peeling characteristics and moldability. In particular, an acrylic resin having at least a (meth) acrylic acid ester monomer as a structural unit is preferably used.

  Specifically, as the acrylic resin, a homopolymer of (meth) acrylate monomer, a copolymer of two or more different (meth) acrylate monomers, (meth) acrylate monomers and other Examples thereof include a copolymer with a monomer.

  Examples of the (meth) acrylate monomer include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, cyclohexyl (meth) acrylate, normal butyl (meth) acrylate, ( (Meth) acrylic acid isobutyl, (meth) acrylic acid secondary butyl, (meth) acrylic acid tertiary butyl, (meth) acrylic acid isobonyl, 2-methyl-2-adamantyl (meth) acrylate, 2-ethyl-2-adamantyl ( And (meth) acrylate. Of these, methyl (meth) acrylate is preferable.

  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. The copolymer may be either a random copolymer or a block copolymer.

  Moreover, in the copolymer of the said (meth) acrylic acid ester monomer and another monomer, as another monomer, if it can be copolymerized with (meth) acrylic acid ester, it will not specifically limit, For example, ( (Meth) acrylic acid, styrene, maleic acid, maleic anhydride, fumaric acid, divinylbenzene, vinylbiphenyl, vinylnaphthalene, diphenylethylene, vinyl acetate, vinyl chloride, vinyl fluoride, vinyl alcohol, acrylonitrile, acrylamide, butadiene, isoprene, Examples include isobutene, 1-butene, 2-butene, N-vinyl-2-pyrrolidone, dicyclopentadiene, ethylidene norbornene, norbornene, vinylcaprolactam, citraconic anhydride, N-phenylmaleimide and the like. Among these monomers, styrene, maleic acid, and maleic anhydride are preferable. That is, a copolymer of (meth) acrylic acid ester and at least one monomer selected from the group consisting of styrene, maleic acid, and maleic anhydride is preferably used. In addition, the copolymer of (meth) acrylic acid ester and another monomer may be a random copolymer or a block copolymer.

  In the formation of the protective layer, the weight average molecular weight of the thermoplastic resin used in combination with the ionizing radiation curable resin is not particularly limited, but is, for example, 10,000 to 250,000, preferably 100,000 to 200,000, more preferably 100,000 to 17 Million. 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.

  The combination mode of the ionizing radiation curable resin and the thermoplastic resin used for forming the protective layer is not particularly limited, but is preferably multifunctional (meta) from the viewpoint of further improving the peeling characteristics and moldability. An acrylic resin having a structural unit of an acrylate monomer and an acrylic resin, more preferably pentaerythritol tri (meth) acrylate and a (meth) acrylic acid ester monomer may be mentioned.

  In addition, when the ionizing radiation curable resin and the thermoplastic resin are used in combination in the formation of the protective layer, the mixing ratio is not particularly limited, but for example, the mass ratio of the ionizing radiation curable resin and the thermoplastic resin is 5:95 to 75:25, preferably 10:90 to 70:30.

<Other additive components>
Various additives can be blended in the protective layer according to desired physical properties to be provided in the protective layer. 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.

<Thickness of protective layer>
Although it does not restrict | limit especially about the thickness of a protective layer, For example, 1-1000 micrometers, Preferably it is 1-50 micrometers, More preferably, 1-30 micrometers is mentioned. When the thickness in this range is satisfied, the unevenness to express a rich low-gloss feel can be effectively applied to the protective layer by following the uneven shape of the release layer while further improving the peeling characteristics. Can be formed. Here, the thickness of the protective layer means the thickness of the protective layer after curing.

<Formation of protective layer>
The protective layer is formed by gravure coating, bar coating, roll coating, reverse roll coating using a resin composition in which an ionizing radiation curable resin, a thermoplastic resin as necessary, and various additives are mixed as necessary. It is performed by coating the release layer by a method such as comma coating, and irradiating the resin composition with ionizing radiation and curing it. The irradiation conditions of ionizing radiation are the same as in the case of forming the release layer.

  By adding various additives to the protective layer thus formed, a hard coat function, an antifogging coat function, an antifouling coating function, an antiglare coating function, an antireflection coating function, an ultraviolet shielding coating function, an infrared shielding function You may perform the process which provides functions, such as a coat function.

(Primer layer)
The primer layer is a layer that is provided between the protective layer and the decorative layer as necessary for the purpose of improving the adhesion between the protective layer and the decorative layer.

  Although it does not restrict | limit especially as resin which forms a primer layer, It is preferable to use the binder resin which has a property which does not produce interaction with the ionizing radiation curable resin used by a protective layer or a decoration layer. Specific examples of such binder resins include urethane resins, (meth) acrylic resins, (meth) acrylic / urethane copolymer resins, vinyl chloride / vinyl acetate copolymers, polyester resins, butyral resins, and chlorinated products. Examples include polypropylene and chlorinated polyethylene. These binder resins may be used individually by 1 type, and may be used in combination of 2 or more type. Among these binder resins, a urethane resin, a (meth) acrylic resin, and a (meth) acrylic / urethane copolymer resin are preferable. Moreover, you may perform formation of a primer layer using a crosslinking agent.

  As the urethane resin, a two-component reaction curable polyurethane having a polyol (polyhydric alcohol) as a main component and an isocyanate as a crosslinking agent (curing agent) can be used. The polyol may be any compound having two or more hydroxyl groups in the molecule, and specific examples include polyester polyol, polyethylene glycol, polypropylene glycol, acrylic polyol, polyether polyol and the like. Specific 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, Examples include aliphatic (or alicyclic) isocyanates such as hydrogenated diphenylmethane diisocyanate.

  Among the two-component reaction curable polyurethanes, from the viewpoints of improving the adhesion between the protective layer and the decorative layer, reducing the interaction between the protective layer and the resin of the decorative layer, improving the physical properties, improving the moldability, etc. In addition, a combination of acrylic polyol or polyester polyol as a polyol and hexamethylene diisocyanate or 4,4-diphenylmethane diisocyanate as a cross-linking agent; and a combination of acrylic polyol and hexamethylene diisocyanate is more preferable.

  Although it does not restrict | limit especially as said (meth) acrylic resin, For example, the homopolymer of (meth) acrylic acid ester, the copolymer of 2 or more types of different (meth) acrylic acid ester monomers, or (meth) acrylic acid Examples include copolymers of esters and other monomers. More specifically, as a (meth) acrylic resin, poly (meth) acrylate methyl, poly (meth) ethyl acrylate, poly (meth) acrylate propyl, poly (meth) acrylate butyl, (meth) acrylic acid Methyl / (meth) butyl acrylate copolymer, (meth) ethyl acrylate / (meth) butyl acrylate copolymer, ethylene / (meth) methyl acrylate copolymer, styrene / methyl (meth) acrylate copolymer Examples include (meth) acrylic acid esters such as polymers. These (meth) acrylic resins may be used alone or in combination of two or more.

  Although it does not restrict | limit especially as (meth) acryl / urethane copolymer resin, For example, acrylic / urethane (polyester urethane) block copolymer resin is mentioned. Further, as the curing agent, the above-described various isocyanates are used. The ratio of the acrylic to urethane ratio in the acrylic-urethane (polyester urethane) block copolymer resin is not particularly limited. For example, the acrylic / urethane ratio (mass ratio) is 9/1 to 1/9, preferably 8 / 2 to 2/8.

  Although it does not restrict | limit especially about the thickness of a primer layer, For example, it is about 0.5-20 micrometers, Preferably, 1-5 micrometers is mentioned.

(Decoration layer)
A decoration layer is a layer provided in order to provide designability as a layer which comprises a transfer layer.

  The decoration layer is usually composed of a pattern layer and / or a concealment layer. Here, the pattern layer is a layer provided for expressing a pattern such as a pattern or characters, and the concealing layer is generally a solid layer, and is provided for concealing coloring such as injection resin. Is a layer. The concealing layer may be provided inside the picture layer to enhance the picture of the picture layer, or the decoration layer may be formed by the concealing layer alone.

  The pattern of the pattern layer is not particularly limited, and examples thereof include a pattern made of wood, stone, cloth, sand, geometric pattern, characters, and the like.

  The decoration layer is formed using a printing ink containing a colorant, a binder resin, and a solvent or dispersion medium.

  The colorant of the printing ink used for forming the decorative layer is not particularly limited, but for example, aluminum, chromium, nickel, tin, titanium, iron phosphide, copper, gold, silver, brass and other metals, alloys, or Metallic pigment composed of scale-like foil powder of metal compound; 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 carbonic acid Pearlescent pigment made of foil powder such as lead; 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 ; Inorganic pigments such as zinc white, petal, vermilion, ultramarine, cobalt blue, titanium yellow, yellow lead, carbon black Isoindolinone yellow, Hansa yellow A, quinacridone red, permanent red 4R, phthalocyanine blue, indanthrene blue RS, and organic pigments such as aniline black (including dyes) and the like. These colorants may be used alone or in combination of two or more.

  In addition, the binder resin of the printing ink used for forming the decorative layer is not particularly limited. For example, acrylic resin, styrene resin, polyester resin, urethane resin, chlorinated polyolefin resin, vinyl chloride-acetic acid Examples include vinyl copolymer resins, polyvinyl butyral resins, alkyd resins, petroleum resins, ketone resins, epoxy resins, melamine resins, fluorine resins, silicone resins, fiber derivatives, rubber resins, and the like. These binder resins may be used individually by 1 type, and may be used in combination of 2 or more type.

  Moreover, the solvent or dispersion medium of the printing ink used for forming the decorative layer is not particularly limited. For example, petroleum-based organic solvents such as hexane, heptane, octane, toluene, xylene, ethylbenzene, cyclohexane, and methylcyclohexane; Ester organic solvents such as ethyl, butyl acetate, 2-methoxyethyl acetate, and 2-ethoxyethyl acetate; alcohols such as methyl alcohol, ethyl alcohol, normal propyl alcohol, isopropyl alcohol, isobutyl alcohol, ethylene glycol, and propylene glycol Organic solvents; ketone organic solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone; ether organic solvents such as diethyl ether, dioxane, tetrahydrofuran; Emissions, carbon tetrachloride, trichlorethylene, chlorinated organic solvents such as tetrachlorethylene; water and the like. These solvents or dispersion media may be used individually by 1 type, and may be used in combination of 2 or more type.

  In addition, printing inks used to form decorative layers include anti-settling agents, curing catalysts, UV absorbers, antioxidants, leveling agents, thickeners, antifoaming agents, lubricants, etc. as necessary. It may be.

  The decorative layer can be formed on the protective layer with a printing ink using a known printing method such as gravure printing, flexographic printing, silk screen printing, or offset printing. When the decorative layer is a combination of a pattern layer and a concealing layer, one layer is laminated and dried, and then the other layer is laminated and dried.

  Although there is no restriction | limiting in particular about the thickness of a decoration layer, For example, 1-40 micrometers, Preferably it is 3-30 micrometers.

(Adhesive layer)
An adhesive layer is provided as needed as a layer which forms the outermost surface on the opposite side to a support body in the decorating sheet of this invention. It is preferable to provide an adhesive layer from the viewpoint of enhancing the adhesion between the injection resin and the decorative sheet when performing integral molding with the injection resin.

  The resin forming the adhesive layer is appropriately set according to the injection resin used for the decorative resin product, and examples thereof include those used as heat-sensitive adhesives and pressure adhesives. Specific examples of resins that form the adhesive layer include acrylic resins, acrylic-modified polyolefin resins, chlorinated polyolefin resins, polyvinyl chloride, vinyl chloride / vinyl acetate copolymers, thermoplastic urethane resins, thermoplastic polyester resins, and polyamides. Examples thereof include resins, rubber resins, curable urethane resins, and epoxy resins. These resins may be used individually by 1 type, and may be used in combination of 2 or more type.

  The adhesive layer is formed by applying the resin in a form that can be applied in the form of a solution or emulsion, and applying and drying it using gravure printing, screen printing, reverse coating using a gravure plate, etc. Is done.

  The thickness of the adhesive layer is not particularly limited, but is preferably about 0.1 to 6 μm from the viewpoint of efficiently transferring the decorative sheet to the decorative molded product with good adhesiveness.

(3) Manufacturing method of decorating sheet The decorating sheet of this invention can be manufactured through the following 1st-4th process, for example.
A first step of obtaining a laminate in which a release layer is laminated on a base material layer by applying and curing a resin composition containing synthetic resin particles and an ionizing radiation curable resin on the base material layer;
The release layer and the protective layer are sequentially laminated on the base material layer by applying and curing a resin composition containing an ionizing radiation curable resin on the release layer of the laminate obtained in the first step. A second step of obtaining a laminated body,
On the protective layer of the laminate obtained in the second step, a primer layer is formed as necessary, and then a decorative layer is formed. According to the third step of obtaining a laminate in which the primer layer and the decorative layer are sequentially laminated, and by forming an adhesive layer as necessary on the decorative layer of the laminate obtained in the third step The 4th process of obtaining the laminated body on which the mold release layer, the protective layer, the primer layer, the decoration layer as needed, and the contact bonding layer as needed were laminated | stacked in order on the base material layer.

  In the first to fourth steps, the components used for forming each layer, the specific conditions of the method for forming each layer, and the like are as described in the section of the composition of each layer.

2. With supports decorated resin molded article of the support with a decorative resin molded article the present invention is formed it is molded by integrating the injected resin to the decorative sheet of the present invention. That is, the decorative resin molded product with a support of the present invention has a protective layer, a decorative layer, and an injection resin layer in this order on the release layer of the support having at least a base material layer and a release layer. The release layer is formed from a cured product of a resin composition containing synthetic resin particles and an ionizing radiation curable resin, and the protective layer is formed from a cured product of a resin composition containing an ionizing radiation curable resin. It is formed. In FIG. 2, the cross-sectional structure is shown about the suitable one aspect | mode of the decorative resin molded product with a support body of this invention.

  Specifically, the decorative resin molded product with a support layer of the present invention is prepared by using the decorative sheet of the present invention, such as an insert molding method, an injection molding simultaneous decorating method, a blow molding method, a gas injection molding method, and the like. It is produced by various injection molding methods. Among these injection molding methods, an insert molding method and an injection molding simultaneous decorating method are preferable.

  In the insert molding method, first, in the vacuum forming process, 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 extra 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 making it, a decorative resin molded product with a support is produced.

More specifically, the decorative resin molded product with a support of the present invention is produced 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 excess portions of the vacuum-decorated decorative sheet to obtain a molded sheet, and inserting the molded sheet obtained in the above process into an injection mold, closing the injection mold, and molding the fluid resin The process of injecting the resin and the molded sheet.

  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 with a support is produced.

More specifically, the decorative resin molded product with a support of the present invention is produced by an injection molding simultaneous decorating method including the following steps.
After the decorative sheet of the present invention is installed so that the base material 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 and softened. And vacuum suction from the movable mold side, the step of preforming the decorative sheet by adhering the softened decorative sheet along the molding surface of the movable mold,
After clamping the movable mold and the fixed mold having the decorative sheet adhered along the molding surface, the resin molding material in a fluid state is injected and filled into the cavity formed by both molds. An injection molding process in which the formed resin molded body and the decorative sheet are laminated and integrated by solidification, and a movable molded mold is separated from the fixed mold, and the entire decorative sheet is laminated. The process of taking out.

  In the decorative resin molded product with a support of the present invention, the injection resin layer may be formed by selecting an injection resin according to the application. The injection resin may be a thermoplastic resin or a thermosetting resin.

  Examples of the thermoplastic resin used as the injection resin include polyolefin resins such as polyethylene and polypropylene, ABS resin, styrene resin, polycarbonate resin, acrylic resin, and vinyl chloride resin. 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 used as injection 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.

  A decorative resin molded product can be obtained by peeling and removing the support from the decorated resin molded product with a support of the present invention. In addition, in the decorative resin molded product with a support, the base material layer in the support plays a role as a protective sheet for the decorative resin molded product. The support may be peeled off. By using in such a mode, it is possible to prevent the decorative resin molded product from being damaged due to rubbing during transportation.

3. Decorated resin molded product The decorated resin molded product of the present invention is obtained by peeling and removing a support from the decorated resin molded product with a support. When the support is peeled and removed from the decorative resin molded product with the support, the interface between the release layer and the protective layer is peeled off, and the base material layer and the release layer are removed together. That is, the decorative resin molded product of the present invention has at least an injection resin layer, a decorative layer, and a protective layer in order, and the protective layer is formed of a cured product of a resin composition containing an ionizing radiation curable resin. It is characterized by. In FIG. 3, the cross-sectional structure is shown about the suitable one aspect | mode of the decorative resin molded product of this invention.

  The decorative resin molded product of the present invention has a design that expresses a rich and low gloss feeling with a texture, can be molded into complex shapes, and has excellent scratch resistance. , For example, interior materials or exterior materials of vehicles such as automobiles; construction members such as baseboards and rims; fittings such as window frames and door frames; interior materials of buildings such as walls, floors, and ceilings; television receivers; It can be used as a casing or container for home appliances such as an air conditioner.

  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.

[Manufacture of decorative sheets]
Examples 1 to 4 and Comparative Example 4
As the base material layer, a polyethylene terephthalate film (thickness 50 μm) having an easy-adhesive layer formed in the direction was used. On the surface of the easy adhesive layer of the polyethylene terephthalate film, a fat composition for forming a release layer having the composition shown in Table 1 was applied with a bar coder so that the thickness after curing was 3 μm, and a release layer was formed A coating film was formed. A release layer was formed on the substrate layer by irradiating an electron beam with an acceleration voltage of 165 kV and an irradiation dose of 50 kGy (5 Mrad) from the coating film to cure the release layer forming coating film. Next, the protective layer-forming resin composition having the composition shown in Table 1 is coated on the release layer with a bar coder so that the thickness after curing is 10 μm, thereby forming a protective layer-forming coating film. did. An electron beam with an acceleration voltage of 165 kV and an irradiation dose of 50 kGy (5 Mrad) was irradiated from above the coating film to cure the protective layer-forming coating film, thereby forming a protective layer. On this protective layer, a polyurethane two-component curable resin (containing an acrylic polymer polyol and xylylene diisocyanate as a curing agent so that the NCO equivalent and OH equivalent are the same amount; uncured acrylic polymer polyol) A resin composition for forming a primer layer containing a glass transition temperature Tg at the time of 100 ° C.) was applied by gravure printing to form a primer layer (thickness 1.5 μm). Further, on the primer layer, a decorative layer is formed containing an acrylic resin and a vinyl chloride-vinyl acetate copolymer resin as a binder resin (acrylic resin 50 mass%, vinyl chloride-vinyl acetate copolymer resin 50 mass%). A hairline decorative layer (thickness 5 μm) was formed by gravure printing using the black ink composition for printing. Furthermore, a base material layer is formed by forming an adhesive layer (thickness: 4 μm) on the decorative layer by gravure printing using a resin composition for forming an adhesive layer containing an acrylic resin (softening temperature: 125 ° C.). A decorative sheet in which / release layer / protective layer / primer layer / decoration layer / adhesion layer was laminated in order was produced.

Comparative Examples 1-3
Using the resin composition for forming the release layer shown in Table 1, the same conditions as in Example 1 above, except that the release layer was formed by gravure printing so that the thickness was 3 μm. The decorative sheet was manufactured.

[Manufacture of decorative resin molded products]
Each decorative sheet obtained in the above examples and comparative examples is put into a mold, heated at 350 ° C. for 7 seconds with an infrared heater, pre-formed to conform to the shape in the mold by vacuum forming, and clamped. (Maximum draw ratio: 100%). Thereafter, the injection resin was injected into the cavity of the mold, and the decorative sheet and the injection resin were integrally molded to obtain a decorative molded product with a support. Subsequently, the decorative molded product was obtained by peeling and removing the support (base material layer and release layer) from the decorative molded product with the support.

[Performance evaluation of each decorative sheet]
About the decorative sheet obtained by each Example and the comparative example, the three-dimensional moldability, the low gloss effect, and the surface state were evaluated by the method shown below.

<Evaluation of three-dimensional formability>
After the preformed decorative sheet in the production of the decorative resin molded product was cooled, it was released from the mold, and the three-dimensional formability was evaluated according to the following criteria.
(Three-dimensional formability criteria)
A: No cracking or whitening was observed in the surface protective layer, and the shape of the mold was satisfactorily followed.
○: Although a fine coating crack or whitening was observed in a part of the three-dimensional shape portion or the maximum stretched portion, there was no practical problem.
(Triangle | delta): Although the coating-film crack and whitening were seen in the surface protective layer only in the largest extending part, it was favorable in the other part.
X: Remarkable coating cracking and whitening were observed in the surface protective layer without following the shape of the mold.

<Evaluation of peelability of support before injection molding>
The support (base material layer and release layer) was peeled off from each decorative sheet, and the release layer and the protective layer were dissociated. The force required for peeling and removing the support and the surface of the decorative resin molded product after peeling the support were evaluated according to the following criteria.
(Criteria for peelability of support)
○: The peel strength is sufficiently heavy.
Δ: Peel strength is light, but foil spillage is small enough to cause no problem during processing and molding.
X: Since peel strength is too light, foil spillage is very large during processing and molding.

<Evaluation of peelability of support after injection molding>
About the decorative molded product with a support obtained using each decorative sheet, immediately after molding, the support (base material layer and release layer) was peeled and removed, and the release layer and the protective layer were dissociated. . The force required for peeling and removing the support and the surface of the decorative resin molded product after peeling the support were evaluated. The determination criteria are the same as in the case of the evaluation of the peelability of the support before the injection molding.
(Criteria for peelability of support)
(Double-circle): The peeling strength of a support body is moderate, a support body can be peeled and removed by light force, and a peeling trace does not remain on the surface of a decorative resin molded product after peeling of a support body.
○: The peel strength of the support is slightly strong, but no peeling marks remain on the surface of the decorative resin molded product after the support is peeled off.
X: The peeling strength of the support is strong, and a peeling mark remains on the surface of the decorative resin molded product after peeling of the support.
XX: The peel strength of the support is extremely strong and the support cannot be peeled off.

<Low gloss effect>
About the surface of the molded article after the decorative sheet molding, a 60 ° gloss value was measured using a gloss meter in accordance with JIS K 7105.
<Surface properties>
The feel of the surface of each decorative sheet was confirmed by touch, and the surface properties were evaluated according to the following criteria.
(Criteria for surface properties)
(Double-circle): The nonuniformity of the ink which forms a pattern layer is not recognized, but the design property is very favorable.
◯: Some unevenness of the ink forming the pattern layer is observed, but the overall design is good.
(Triangle | delta): The nonuniformity of the ink which forms a pattern layer is recognized, and design property is bad.
X: Remarkable unevenness is recognized in the ink forming the pattern layer, and the design is remarkably bad.

<Evaluation results>
The results are shown in Table 1. As is clear from the results of Examples 1 to 4, a support having a base material layer and a release layer and a transfer layer having at least a protective layer are laminated with the release layer and the protective layer being in contact with each other. In the decorated sheet, the release layer is formed from a cured product of a resin composition containing synthetic resin particles and an ionizing radiation curable resin, and the protective layer is made of a resin composition containing an ionizing radiation curable resin. By forming it from a cured product, a rich, low-gloss feel with a texture is realized, and the support and transfer layer are made to have an appropriate peel strength, so that peeling marks of the support are formed on the surface of the decorative resin molded product. It was confirmed that it can be suppressed. In addition, the decorative sheets of Examples 1 to 4 have good peelability of the support of the decorative sheet before injection molding, so there is no foil spillage during processing molding, and machine contamination can be prevented. It was also excellent in performance. In addition, when acrylic beads were used as the synthetic resin particles, it was also confirmed that the three-dimensional moldability and surface properties were extremely good (Example 1). On the other hand, when the release layer is formed of a resin other than the ionizing radiation curable resin, the peel strength between the support and the transfer layer becomes too strong to be practically used (Comparative Examples 1 to 3). ). Further, even when the release layer was formed of an ionizing radiation curable resin, the low gloss effect was insufficient when no synthetic resin particles were blended in the release layer (Comparative Example 4).

[Footnotes in Table 1]
In Table 1, the abbreviations of the types of resin components used in the resin composition for forming the release layer are as follows.
(EB1)
Bifunctional polycarbonate acrylate (weight average molecular weight; 10,000): 94 parts by mass Hexafunctional urethane acrylate oligomer (weight average molecular weight; 6,000): 6 parts by mass Polyolefin wax: 6 parts by mass (EB2)
Bifunctional polycarbonate acrylate (weight average molecular weight; 10,000): 100 parts by mass Polyolefin wax: 6 parts by mass (two-component curable resin)
Two-component curable resin (acrylic resin A) that cures by mixing the main agent and curing agent
Mixed resin (acrylic resin B) containing acrylic resin and melamine resin in a weight ratio of 9: 1
Acrylic resin (polyester)
Polyester resin

The abbreviations of the contained particles in the ionizing radiation curable resin composition for forming the release layer in the compounded particle table 1 are as follows.
Acrylic: Crosslinked acrylic beads Silicone: Crosslinked silicone particles Urethane: Urethane resin beads (specific gravity 1.1-1.2 g / cm ³ , glass transition point -20-30 ° C)

In Table 1, abbreviations relating to the resin composition for forming the protective layer are as follows.
(EB3)
Trifunctional pentaerythritol acrylate (weight average molecular weight; 300): 40 parts by mass Acrylic polymer (weight average molecular weight 120,000): 60 parts by mass

DESCRIPTION OF SYMBOLS 1 Base material layer 2 Release layer 3 Protective layer 4 Primer layer 5 Decoration layer 6 Adhesive layer 7 Injection resin layer 10 Support body 11 Transfer layer

Claims (9)

A support sheet having at least a base material layer and a release layer, and a transfer layer having at least a protective layer and a decoration layer are decorative sheets laminated in a state where the release layer and the protective layer are in contact with each other. ,
The release layer is formed from a cured product of a resin composition containing synthetic resin particles and an ionizing radiation curable resin, and the protective layer is formed from a cured product of a resin composition containing an ionizing radiation curable resin. Has been
The decorative sheet, wherein the ionizing radiation curable resin used for forming the release layer is polycarbonate (meth) acrylate and / or acrylic silicone (meth) acrylate . The decorative sheet according to claim 1, wherein the ionizing radiation curable resin used for forming the protective layer is a polyfunctional (meth) acrylate monomer. The decorative sheet according to claim 1 or 2 , wherein the synthetic resin particles are at least one selected from the group consisting of acrylic beads, silicone beads, and urethane beads. The decorative sheet according to any one of claims 1 to 3 , wherein the release layer contains 1 to 70 parts by mass of synthetic resin particles per 100 parts by mass of the ionizing radiation curable resin. The decorative sheet according to any one of claims 1 to 4 , wherein an average particle diameter of the synthetic resin particles is 0.5 to 25 µm. The decorative sheet according to any one of claims 1 to 5 , wherein the release layer has a thickness of 0.01 to 5 µm. The primer layer between the protective layer and the decorative layer is provided, the decorative sheet according to any one of claims 1-6. On the release layer of the support having at least a base material layer and a release layer, a protective layer, a decorative layer, and an injection resin layer are sequentially provided.
The release layer is formed from a cured product of a resin composition containing synthetic resin particles and an ionizing radiation curable resin, and the protective layer is formed from a cured product of a resin composition containing an ionizing radiation curable resin. A decorated resin molded product with a support, which is characterized in that A decorative resin molded product obtained by removing the support from the decorated resin molded product with a support according to claim 8 .