JP2015182302A - Decorative sheet and decorative resin molding - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a decorative sheet capable of imparting excellent tactile to a decorative resin molding, and having high moldability.SOLUTION: A decorative sheet has a transfer layer on a release layer of a support medium having at least a substrate layer and the release layer. In the decorative sheet, the release layer is formed of a resin composition containing a resin and synthetic resin particles having an average particle size of 2-15 μm, and the release layer contains the 40-150 pts. mass synthetic resin particles to the 100 pts. mass resin.

Description

  The present invention relates to a decorative sheet having a smooth, moist and excellent tactile sensation and having high moldability, and a decorative resin molded article 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. In addition to the molding method by injection molding, a method is also known in which a decorative sheet is attached to a molded body that has been molded in advance, such as a vacuum pressure bonding method, with heating or pressurization.

  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. After the decorative sheet is subjected to injection molding and integrally molded with the resin, the design of the transfer layer is exposed on the surface of the resin molded product by peeling the interface between the release layer and the transfer layer and removing the support. .

  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 known that a textured low gloss feeling can be expressed on a decorative sheet by forming irregularities on a transfer layer using a release layer having irregularities formed on the surface (Patent Document). 2).

  On the other hand, along with the various orientations of consumers in recent years, decorative resin molded products can not only display the design by appearance but also obtain a unique tactile sensation when actually touched by hand, For example, a smooth and moist feel is required. For example, in Patent Document 3, a transfer sheet is formed on a shaped film having a fine uneven surface formed by an inorganic filler such as silica particles, a transfer sheet is formed, the transfer sheet is molded, and a molding resin and A technique for obtaining a molded body having a suede-like touch with a moist and smooth surface is disclosed by peeling the shaped film after integrally transferring the transfer sheet (for example, Patent Document 3). (See Example 6, FIG. 5, etc.).

JP-A-8-20199 JP-A-6-171037 JP-A-5-138936

According to the technique disclosed in Patent Document 3, a molded article having excellent tactile sensation can be obtained. On the other hand, some decorative resin molded products have a complicated surface shape such as a three-dimensional curved surface, and the decorative sheet used for such a decorative resin molded product includes a decorative resin molded product. There is a demand for high three-dimensional formability that can sufficiently follow the shape. Therefore, the development of a decorative sheet having higher formability is also demanded for a decorative sheet that can impart an excellent tactile sensation to a decorative resin molded product.
Under such circumstances, the present invention can provide an excellent tactile sensation to a decorative resin molded product, a decorative sheet having a higher moldability, and a decorative resin molded product using the decorative sheet. The main purpose is to provide.

  The present inventors have intensively studied to solve the above problems. As a result, in the decorative sheet having a transfer layer on the release layer of the support having at least the base material layer and the release layer, the release layer is a resin and the synthetic resin particles having an average particle diameter of 2 to 15 μm. In the release layer, the synthetic resin fine particles are contained in an amount of 40 to 150 parts by mass with respect to 100 parts by mass of the resin, so that the decorative resin molded product is smooth. It has been found that a moist and excellent tactile sensation can be imparted, and that the decorative sheet has high moldability. 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 decorative sheet having a transfer layer on the release layer of the support having at least a base material layer and a release layer,
The release layer is formed of a resin composition containing a resin and synthetic resin particles having an average particle diameter of 2 to 15 μm,
The said release layer WHEREIN: The decorating sheet in which 40-150 mass parts of said synthetic resin microparticles | fine-particles are contained with respect to 100 mass parts of said resins.
Item 2. Item 2. The decorative sheet according to Item 1, wherein in the release layer, the resin forming the resin composition is a curable resin.
Item 3. Item 3. The decorative sheet according to Item 1 or 2, wherein the synthetic resin particles are at least one selected from the group consisting of acrylic beads, silicon beads, and urethane beads.
Item 4. Item 4. The decorative sheet according to any one of Items 1 to 3, wherein the release layer has a thickness of 0.01 to 15 µm.
Item 5. Item 5. The decorative sheet according to any one of Items 1 to 4, wherein the transfer layer includes a protective layer, and the protective layer is laminated in contact with the release layer.
Item 6. Item 6. The decorative sheet according to Item 5, wherein the protective layer is formed of an ionizing radiation curable resin.
Item 7. On the release layer of the support having at least a base material layer and a release layer, a transfer layer and a molded resin layer are sequentially provided,
The release layer is formed of a resin composition containing a resin and synthetic resin particles having an average particle diameter of 2 to 15 μm,
In the mold release layer, a decorative resin molded product with a support, wherein 40 to 150 parts by mass of the synthetic resin fine particles are included with respect to 100 parts by mass of the resin forming the resin composition.
Item 8. Item 11. A decorative resin molded product obtained by removing the support from the decorated resin molded product with a support according to Item 7.

  The decorative sheet of the present invention can impart a smooth, moist and excellent tactile sensation to a decorative resin molded product, and has high moldability. Furthermore, in the decorative sheet of this invention, the release property of the release layer from a decorative resin molded product is also favorable, and a decorative resin molded product can be manufactured with high productivity.

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 is a decorative sheet having a transfer layer on the release layer of the support having at least a base material layer and a release layer, and the release layer comprises a resin and an average. It is formed of a resin composition containing synthetic resin particles having a particle diameter of 2 to 15 μm, and in the release layer, synthetic resin fine particles are 40 to 150 parts by mass with respect to 100 parts by mass of the resin forming the resin composition. It is included. Hereinafter, the decorative sheet of the present invention will be described in detail. In the present specification, unless otherwise specified, “(meth) acrylic acid” means “acrylic acid or methacrylic acid”, and other similar notations have the same meaning. Moreover, the decorating sheet of this invention does not need to be provided with the layer which has a pattern etc., for example, may be transparent and may be comprised by the single color.

(1) Laminated structure of decorative sheet The decorative sheet of the present invention has a laminated structure having a transfer layer on a release layer of a support having at least a base material layer and a release layer. In the decorative sheet of the present invention, the base material layer and the release layer constitute a support, and the support serves as a support member for the transfer layer. That is, after integrally molding the decorative sheet of the present invention with the molding 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 may be provided with at least a decorative layer that imparts design properties to the decorative sheet. That is, the transfer layer may be a single layer composed of a decorative layer, or may be a multilayer including the decorative layer and one or more other layers.

  For example, in the transfer layer, for the purpose of protecting the decorative layer, improving stain resistance and scratch resistance, improving the peelability of the support, and the like (that is, between the release layer and the decorative layer) A protective layer may be provided as necessary as the contacting surface layer.

  Moreover, when providing a protective layer, the primer layer may be provided as needed between the protective layer and the decoration layer for the purpose of improving these adhesiveness.

  Further, 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 molding resin when integrally molding with the injection resin. May be provided

  As described above, the decorative sheet of the present invention may include at least one layer selected from the group consisting of a protective layer, a primer layer, and an adhesive layer, as necessary, in addition to the decorative layer as the transfer layer. Good. That is, as an example of the laminated structure in the decorative sheet of the present invention of the present invention, base layer / release layer / protective layer provided as necessary / primer layer provided as necessary / decoration layer / as needed And a laminated structure in which adhesive layers provided are sequentially laminated. 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 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 molding resin are integrally formed, the interface between the release layer and the transfer 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 peelability. 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 transfer layer. In the decorative sheet of the present invention, the release layer is formed of a resin composition containing a resin and synthetic resin particles having an average particle diameter of 2 to 15 μm. Furthermore, 40 to 150 parts by mass of synthetic resin fine particles are included with respect to 100 parts by mass of the resin forming the resin composition of the release layer. Thus, by setting the average particle diameter and content ratio of the synthetic resin particles used in the release layer in the above specific range, irregularities according to the shape of the synthetic resin particles can be formed in the transfer layer, The unevenness of the release layer can impart a smooth and moist and excellent tactile sensation to the transfer layer. Furthermore, in the decorative sheet of this invention, by providing such a mold release property, not only the excellent tactile sensation but also the moldability remarkably excellent at the time of manufacture of a decorative resin molded product can be provided. In addition, according to the decorative sheet of the present invention having such a release layer, the release layer from the decorative resin molded product has good releasability, and the decorative resin molded product is manufactured with high productivity. Can do.

<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 moldability during the production of a decorative resin molded product while further improving the touch feeling when touching the transfer layer by hand, preferably acrylic beads, Examples thereof include urethane beads and silicone beads, more preferably urethane beads and acrylic beads, and particularly preferably urethane beads and cross-linked acrylic beads. 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 from the viewpoint of further improving the touch, moldability, and peelability, for example, 0.7 to 1.5 g / cm ³ are preferred, more preferably 0.8～1.3G / cm ^3, include 0.85~1.2g / cm ^3. Also, by satisfying such specific gravity, it becomes possible for the synthetic resin particles to localize in the surface region in the resin forming the release layer, 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 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 as long as it is in the range of 2 to 15 μm, but preferably 5 to 10 μm from the viewpoint of further improving the above-mentioned touch feeling, moldability, and peelability. 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 touch, moldability, peelability, and the like. For example, for 100 parts by mass of the resin forming the release layer Although it will not restrict | limit especially if it exists in the range of 40-150 mass parts, Preferably it is 60-100 mass parts, More preferably, 60-80 mass parts is mentioned. As described above, in the decorative sheet of the present invention, the average particle diameter of the synthetic resin particles in the release layer is in the range of 2 to 15 μm, and the content ratio of the synthetic resin particles forms the release layer. By being in the range of 40 to 150 parts by mass with respect to parts by mass, the decorative sheet is provided with a smooth and moist and excellent tactile sensation while having a remarkably excellent moldability when producing a decorative resin molded product. Can be made. Furthermore, the peelability of the release layer from the decorative resin molded product can be improved.

<Resin>
The release layer is formed of a resin composition containing the above synthetic resin particles and resin. The resin for forming the release layer is not particularly limited, and examples thereof include thermoplastic resins and curable resins. From the viewpoint of further improving the above-described tactile sensation, moldability, and peelability, preferably curable. Resin. In addition, as a thermoplastic resin, the thing similar to what was illustrated by the below-mentioned protective layer can be used.

<Curable resin>
The curable resin used for the release layer is not particularly limited with respect to the type of the curing reaction, and is a thermosetting resin, a room temperature curable resin, an ionizing radiation curable resin, a one-component reactive curable resin, or a two-component. Any of reaction curable resins and the like may be used. Among these curable resins, ionizing radiation curable resins are preferably used from the viewpoint of further improving moldability and releasability.

<Thermosetting resin, room temperature curable resin, 1 liquid reaction curable resin, or 2 liquid reaction curable resin>
Among the curable resins used for the release layer, thermosetting resins, room temperature curable resins, one-component reaction curable resins, or two-component reaction curable resins include epoxy resins and phenol resins. , Urea resin, non-thermosetting polyester resin, melamine resin, alkyd resin, polyimide resin, silicone resin, thermosetting acrylic resin, thermosetting polyurethane resin, and the like. Although there is no restriction | limiting in particular as an aspect of hardening reaction of these resin, For example, there exist the following aspects. Epoxy resin is a reaction with amine, acid catalyst, carboxylic acid, acid anhydride, hydroxyl group, dicyandiamide or ketimine; phenol resin is a reaction between base catalyst and excess aldehyde; urea resin is a polycondensation under alkaline or acidic conditions Reaction; Non-thermosetting polyester resin is a co-condensation reaction between maleic anhydride and diol; Melamine resin is a heat polycondensation reaction of methylol melamine; Alkyd resin is an air oxidation of unsaturated groups introduced into side chains, etc. Reaction with polyimide; reaction in the presence of an acid or weak alkali catalyst, or reaction with an isocyanate compound (in the case of a two-component type); condensation reaction in the presence of an acid catalyst of a silanol group; In the case of a hydroxyl-functional acrylic resin, a thermosetting acrylic resin is a reaction between a hydroxyl group and an amino resin that it has (one-pack type Or in the case of a carboxyl functional acrylic resin, a reaction between a carboxylic acid such as acrylic acid or methacrylic acid and an epoxy compound; a thermosetting urethane resin is a polyester resin, a polyether resin or an acrylic resin containing a hydroxyl group. And the like, and the reaction of an isocyanate compound or a modified product thereof. In the thermosetting resin, a crosslinking agent, a polymerization initiator, a polymerization accelerator, and the like are used as necessary in order to advance the curing reaction as necessary. These thermosetting resins may be used individually by 1 type, and may be used in combination of 2 or more type.

<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 release 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 polycarbonate (meth) acrylate, acrylic silicone (meth) acrylate, urethane (meth) acrylate oligomer, epoxy (meth) acrylate oligomer, polyester (meth) acrylate oligomer, Examples include polyether (meth) acrylate oligomers and polybutadiene (meth) acrylate oligomers. 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 further improving the moldability, an oligomer having a polymerizable unsaturated bond or an epoxy group in the molecule, more preferably polycarbonate (meth) acrylate and / or acrylic. Examples include silicone (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 (meth) acrylate may be, for example, urethane (meth) acrylate having a polycarbonate skeleton. The urethane (meth) acrylate having a polycarbonate skeleton can be obtained, for example, by reacting a polycarbonate polyol, a polyvalent isocyanate compound, and hydroxy (meth) acrylate.

  The polycarbonate polyol is a polymer having a carbonate bond in the polymer main chain and having 2 or more, preferably 2 to 50, more preferably 3 to 50 hydroxyl groups in the terminal or side chain. A typical method for producing the polycarbonate polyol includes a method by a polycondensation reaction from a diol compound (A), a trihydric or higher polyhydric alcohol (B), and a compound (C) to be a carbonyl component.

The diol compound (A) used as a raw material for the polycarbonate polyol is represented by the general formula HO—R ¹ —OH. Here, R ¹ is a 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 this specification is
This 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, 0.01-15 micrometers, Preferably it is 0.01-12 micrometers, More preferably, 0.01-10 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 applying it onto the base material layer. For example, when a curable resin is used as the resin for forming the release layer, the release layer can be formed by crosslinking and curing the applied resin composition.

  For example, in the case of using a thermoplastic resin, the thermoplastic resin may be heated and melted, mixed with various additives as necessary, and then applied to the surface of the base material layer.

  If a thermosetting resin, a room temperature curable resin, a one-component reaction curable resin, or a two-component reaction curable resin is used, a resin composition in which these resins and various additives are mixed as necessary. The resin composition may be cured by applying the product to the base material layer by a method such as gravure coating, bar coating, roll coating, reverse roll coating, comma coating, and heating as necessary. .

  If ionizing radiation curable resin is used, or if ionizing radiation curable resin and thermoplastic resin are used in combination, ionizing radiation curable resin, and optionally thermoplastic resin, and if necessary The resin composition mixed with various additives is applied to the base material layer by a method such as gravure coating, bar coating, roll coating, reverse roll coating, comma coating, and the resin composition is irradiated with ionizing radiation. Can be cured. In addition, the viscosity of the said resin composition should just be a viscosity which can apply | coat a resin composition to the surface of a base material with the below-mentioned application system. 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, etc. 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. Although it does not restrict | limit especially as an ultraviolet source, For example, a high pressure mercury lamp, a low pressure mercury lamp, a metal halide lamp, a carbon arc lamp, an ultraviolet light emitting diode (LED-UV) etc. are mentioned.

[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 sheet is peeled and removed after integrally molding the decorative sheet and the molding resin of the present invention, the transfer layer forms a surface layer of the decorative resin molded product, and is excellent in being smooth and moist on the decorative resin molded product. A tactile sensation is imparted.

  The transfer layer includes a protective layer, a decorative layer, a primer layer, and an adhesive layer.

  In the decorative sheet of the present invention, on the support side of the transfer layer, irregularities are formed so as to follow the irregular shape of the release layer, and when this is actually touched, it is smooth and moist. You can feel the excellent touch. In addition, the unevenness expresses a low gloss feeling with a texture apart from the design properties of the decorative layer.

(Protective layer)
The protective layer is provided as necessary as a layer constituting the transfer layer as a layer in contact with the support. A protective layer is a layer provided as needed between a mold release layer and a decoration layer, when the decorating sheet of this invention is provided with a decoration layer. In the case where the decorative sheet of the present invention includes a protective layer, the protective layer is formed with unevenness by the uneven shape of the release layer, and gives a smooth and moist feel to the decorative resin molded product. From the viewpoints of protecting the decorative layer and other layers, improving the stain resistance and scratch resistance, and improving the peelability of the support, it is preferable to provide a protective layer in the decorative sheet of the present invention.

  It does not restrict | limit especially as a resin component used for a protective layer, A well-known resin can be used. For example, the protective layer may be a layer formed of a thermoplastic resin, or may be a layer formed by curing a curable resin. The protective layer may be a single layer or may be a laminate of two or more layers.

  Hereinafter, the thermoplastic resin and curable resin used for forming the protective layer will be described.

<Thermoplastic resin>
The type of the thermoplastic resin used for forming the protective layer is not particularly limited. For example, acrylic resin; polyvinyl acetal (butyral resin) such as polyvinyl butyral; polyester resin such as polyethylene terephthalate and polybutylene terephthalate; vinyl 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 ethylene-tetrafluoroethylene copolymer; 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 tactile sensation, moldability, and peelability. 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.

  Although there is no restriction | limiting in particular about the weight average molecular weight of the thermoplastic resin used for formation of a protective layer, For example, 10,000-250,000, Preferably it is 100,000-200,000, More preferably, 100,000-170,000 is mentioned. 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.

  Moreover, when using crosslinkable resin components, such as polyethylene and an ethylene-type copolymer, as a thermoplastic resin, you may perform a crosslinking process to the said thermoplastic resin as needed.

<Curable resin>
The curable resin used for the protective layer is not particularly limited with respect to the type of the curing reaction, and is a thermosetting resin, a room temperature curable resin, an ionizing radiation curable resin, a one-part reaction curable resin, or a two-part reaction. Any of curable resins and the like may be used. Among these curable resins, the viewpoint of further improving the moldability and surface physical properties, and the uneven shape formed by the release layer are easy to maintain even after molding, and the decorative resin molded product has an excellent tactile sensation. From the viewpoint of imparting, an ionizing radiation curable resin is preferable. As curable resin used for a protective layer, what was illustrated by the mold release layer is mentioned.

  Further, as the ionizing radiation curable resin used for the protective layer, from the viewpoint of further improving the above-mentioned touch feeling, moldability, and peelability, the molecular weight is preferably 175 to 1000, more preferably 200 to 800. And a polyfunctional (meth) acrylate monomer having two or more functional groups, more preferably pentaerythritol tri (meth) acrylate. In addition, polycarbonate (meth) acrylate and / or acrylic silicone (meth) acrylate is also preferably used from the viewpoint of further improving the above-mentioned tactile sensation, moldability, peelability, and surface properties.

  When forming a protective layer using ionizing radiation curable resin, you may use it as mixed resin which combined the said thermoplastic resin with ionizing radiation curable resin. That is, a preferred embodiment of the protective layer includes a cured product of a resin composition containing an ionizing radiation curable resin and a thermoplastic resin. Such a resin composition is suitable when a molded product is obtained using the simultaneous injection molding method.

  The combination mode of the ionizing radiation curable resin and the thermoplastic resin is not particularly limited, but is preferably a polyfunctional (meth) acrylate monomer and an acrylic resin, more preferably pentaerythritol tri (meth) acrylate and (meth) acrylic acid. An acrylic resin having an ester monomer as a structural unit is exemplified.

  Further, when a mixed resin of an ionizing radiation curable resin and a thermoplastic resin is used, the mixing ratio thereof is not particularly limited. 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 such a range is satisfied, unevenness for providing an excellent tactile sensation can be effectively formed on the protective layer in a form that follows the uneven shape of the release layer. Furthermore, excellent moldability can be exhibited by satisfying the thickness in such a range. Here, the thickness of the protective layer means the thickness of the protective layer after curing when a curable resin is used.

<Formation of protective layer>
The protective layer may be formed by a method corresponding to the type of resin used.

  For example, in the case of using a thermoplastic resin, the thermoplastic resin may be heated and melted, mixed with various additives as necessary, and then applied to the surface of the release layer.

  If a thermosetting resin, a room temperature curable resin, a one-component reaction curable resin, or a two-component reaction curable resin is used, a resin composition in which these resins and various additives are mixed as necessary. The resin composition may be cured by applying the product to the release layer by a method such as gravure coating, bar coating, roll coating, reverse roll coating, comma coating, and heating if necessary. .

  If ionizing radiation curable resin is used, or if ionizing radiation curable resin and thermoplastic resin are used in combination, ionizing radiation curable resin, and optionally thermoplastic resin, and if necessary The resin composition mixed with various additives is applied to the release layer by gravure coating, bar coating, roll coating, reverse roll coating, comma coating, etc., and the resin composition is irradiated with ionizing radiation. Can be cured. 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 provided as necessary between the protective layer and the decorative layer when a protective layer is provided as a layer constituting the transfer layer. That is, the primer layer is preferably provided with a protective layer in the decorative sheet of the present invention from the viewpoint 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 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 usually a solid layer and is provided for concealing the coloring of the molded resin or the like. 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 by a known printing method such as gravure printing, flexographic printing, silk screen printing, or offset printing with a printing ink on the release layer or, if a protective layer is provided, on the protective layer. . 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)
The adhesive layer is provided as needed as a surface layer on the side opposite to the support as a layer constituting the transfer layer. That is, 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. From the viewpoint of improving the adhesion between the molding resin and the decorative sheet when performing integral molding with the molding resin, it is preferable to provide an adhesive layer.

  The resin forming the adhesive layer is appropriately set according to the molding resin used in 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) Method for producing decorative sheet The decorative sheet of the present invention can be produced, for example, through the following first and second steps.
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; and A second step of forming a transfer layer on the release layer of the laminate obtained in the first step;

  In the first and second 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 integrally molding a resin in the decorative sheet of the present invention. That is, the decorative resin molded product with a support of the present invention has a transfer layer and a molded resin layer in this order on the release layer of the support having at least a base material layer and a release layer. The mold layer is formed from a cured product of a resin composition containing synthetic resin particles and an ionizing radiation curable resin. 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 according to the present invention uses the decorative sheet of the present invention, and various types such as an insert molding method, a simultaneous injection molding decorating method, a blow molding method, and a gas injection molding method. It is produced by an injection molding method. Among these injection molding methods, an insert molding method and an injection molding simultaneous decorating method are preferable. Moreover, the decorative resin molded product with a support of the present invention is a process in which the decorative sheet of the present invention is bonded onto 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 decoration method.

  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 preforming step of the simultaneous injection molding method, the heating temperature of the decorative sheet is not particularly limited, and may be appropriately selected depending on the type of resin constituting the decorative sheet, the thickness of the decorative sheet, etc. If a polyester resin film or an acrylic resin film is used as the base material layer, the temperature can usually be about 70 to 130 ° C. Moreover, in the injection molding process, the temperature of the resin in a fluid state is not particularly limited, but can usually be about 180 to 320 ° C.

  In the vacuum bonding method, first, the decorative sheet and the resin molded body of the first pressure chamber located on the upper side and the second vacuum chamber located on the lower side in the vacuum pressure bonding machine, the decorative sheet is the first. The vacuum chamber side is placed in a vacuum press so that the resin molded body is on the second vacuum chamber side, and the base material layer 1 side of the decorative sheet faces the resin molded body side, and the two vacuum chambers are in a vacuum state. To do. The resin molding is installed on a lifting platform that is provided on the second vacuum chamber side and can be moved up and down. Next, while pressurizing the first vacuum chamber, the molded body is pressed against the decorative sheet using an elevator, and the resin molded body is stretched while stretching the decorative sheet using the pressure difference between the two vacuum chambers. Adhere to the surface. Finally, the two vacuum chambers are opened to atmospheric pressure, and the decorated resin molded product with a support of the present invention can be obtained.

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

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

  Examples of the thermoplastic resin used as the molding resin include polyolefin resins such as polyethylene and polypropylene, ABS resins, styrene resins, polycarbonate resins, acrylic resins, and vinyl chloride resins. These thermoplastic resins may be used individually by 1 type, and may be used in combination of 2 or more type.

  Examples of the thermosetting resin used as the molding resin include urethane resins and epoxy resins. 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 transfer layer is peeled off, and the base material layer and the release layer are removed together. The step of peeling and removing the support may be performed at the time of use as described above, may be included in the various molding processes described above, or immediately after the molding process. May be. 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 smooth, moist and excellent tactile sensation, and can be molded into a complicated shape, for example, an interior material or exterior material of a vehicle such as an automobile; Construction materials such as skirting boards and curbs; Furniture such as window frames and door frames; Interior materials for buildings such as walls, floors, and ceilings; Housings for home appliances such as television receivers and air conditioners; can do.

  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, 2, 4 to 9 and Comparative Examples 1 to 4
As a base material layer, a polyethylene terephthalate film (thickness 50 μm) having an easy-adhesive layer formed on one surface was used. On the surface of the easy adhesive layer of the polyethylene terephthalate film, the release layer forming resin composition having the composition shown in Table 1 was applied with a bar coater so that the thickness after curing was 9 μm, and the release layer was formed. A coating film was formed. A release layer was formed on the substrate 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, a protective layer-forming resin composition having the composition shown in Table 1 is applied on the release layer with a bar coater 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.

Example 3
As a resin fat composition for forming a protective layer, using a thermoplastic resin shown in Table 1, it was applied by gravure printing to a thickness of 10 μm and dried to form a protective layer, and a primer layer was formed. A decorative sheet was produced under the same conditions as in Example 1 except that there was not.

Examples 10 and 11
As the resin composition for forming the release layer, the protective layer is applied by gravure printing so as to have a thickness of 10 μm using the one-component curable resin or the two-component curable resin listed in Table 1, and cured. A decorative sheet was produced under the same conditions as in Example 1 except that the film was formed and the primer layer was not formed.

[Manufacture of decorative resin molded products]
Each decorative sheet obtained in the above examples and comparative examples is placed in a mold, heated with an infrared heater at 350 ° C. for 7 seconds, 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 resin molded product with a support. Subsequently, the decorative resin molded product was obtained by peeling and removing the support (base material layer and release layer) from the decorative resin molded product with the support.

[Performance evaluation of each decorative sheet]
About the decorative sheet obtained by each Example and the comparative example, three-dimensional moldability, tactile sense, and peelability 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)
○: No cracking or whitening was observed in the surface protective layer, and the shape of the mold was satisfactorily followed.
(Triangle | delta): The fine coating-film crack or whitening was recognized by a part of three-dimensional shape part or the largest extending | stretching part.
X: Remarkable coating cracking and whitening were observed in the surface protective layer without following the shape of the mold.

<Evaluation of tactile sensation>
A tentacle evaluation survey was conducted on ten evaluators, and the number of respondents who answered that the tactile impression was “smooth and moist” was counted.
○: 8 or more responding “smooth and moist” Δ: 4-7 responding “smooth and moist”
×: The number of people who answered “smooth and moist” is 3 or less

<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 according to the following criteria.
A: The peel strength of the support is moderate, the support can be peeled and removed with a light force, and no peeling marks remain on the surface of the decorative resin molded product after the support is peeled off.
Δ: The peel strength of the support is somewhat strong, but no peel marks remain on the surface of the decorative resin molded product after the support is peeled off.
X: The peel strength of the support is extremely strong, and the support cannot be peeled off.

<Evaluation results>
The results are shown in Table 1. From this result, in the decorative sheet having at least a release layer and a transfer layer in order, the release layer is formed of a resin composition containing synthetic resin particles having an average particle diameter in the range of 2 to 15 μm, and In the mold release layer, 40 to 150 parts by mass of the synthetic resin fine particles are contained with respect to 100 parts by mass of the resin forming the resin composition, thereby giving an excellent tactile sensation to the decorative resin molded product. Moreover, it became clear that the said decorative sheet has high three-dimensional moldability (Examples 1-11). Moreover, the said decorative sheet was also excellent in the peelability of the support body after injection molding. On the other hand, in the decorative sheet including a release layer in which either the average particle size or the content of the synthetic resin particles does not satisfy the above range, at least one of three-dimensional formability or touch is inferior, It could not be put into practical use in industrial production. Further, in Comparative Example 5 in which silica was added to the release layer, the three-dimensional formability was inferior and could not be put into practical use in commercial production.

[Footnotes in Tables 1-3]
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)
Acrylic polyol: hexamethylene diisocyanate = 1: 1 (equivalent ratio of OH group and NCO group)
(One-part curable resin)
Acrylic resin: melamine resin 9: 1 (mass ratio)

Regarding the abbreviations of the contained particles in the ionizing radiation curable resin composition for forming the release layer in the compounded particle table 1,
It is as follows.
Urethane: Urethane resin beads (specific gravity 1.1-1.2g / cm ³ , glass transition point -20-30 ° C)
Acrylic: Cross-linked acrylic beads Silica: Silica particles (no surface treatment)

In Table 1, abbreviations relating to the resin composition for forming the protective layer are as follows.
(acrylic resin)
Acrylic polymer

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

Claims (8)

A decorative sheet having a transfer layer on the release layer of the support having at least a base material layer and a release layer,
The release layer is formed of a resin composition containing a resin and synthetic resin particles having an average particle diameter of 2 to 15 μm,
The said release layer WHEREIN: The decorating sheet in which 40-150 mass parts of said synthetic resin microparticles | fine-particles are contained with respect to 100 mass parts of said resins.   The decorative sheet according to claim 1, wherein in the release layer, the resin is a curable resin.   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, silicon beads, and urethane beads.   The decorative sheet according to any one of claims 1 to 3, wherein the release layer has a thickness of 0.01 to 15 µm.   The decorative sheet according to any one of claims 1 to 4, wherein a protective layer is included in the transfer layer, and the protective layer is laminated in a state of being in contact with the release layer.   The decorative sheet according to claim 5, wherein the protective layer is formed of an ionizing radiation curable resin. On the release layer of the support having at least a base material layer and a release layer, a transfer layer and a molded resin layer are sequentially provided.
The release layer is formed of a resin composition containing a resin and synthetic resin particles having an average particle diameter of 2 to 15 μm,
A decorative resin molded product with a support, wherein the release layer includes 40 to 150 parts by mass of the synthetic resin fine particles with respect to 100 parts by mass of the resin.   A decorative resin molded product obtained by removing the support from the decorated resin molded product with a support according to claim 7.