JP6561591B2 - Decorative sheet - Google Patents

Description

  The present invention relates to a decorative sheet that is excellent in the workability of peeling a concavo-convex protective layer from a surface layer on which fine concavo-convex shapes are formed.

  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. In recent years, with the diversification of consumer needs, decorative resin molded products having various design properties have been demanded. In order to follow the diversifying consumer needs, it is desired to develop a decorative resin molded product having a concavo-convex shape on the surface and having a good touch as well as a design feeling.

  Conventionally, in the production of a decorative resin molded product, a molding method in which a decorative sheet that has been given designability in advance is integrated with a resin by injection molding is used, and a decorative resin molded product in which an uneven shape is formed In the manufacture of the above, a decorative sheet having an uneven shape on the surface is used.

  As such a decorative sheet, for example, Patent Document 1 discloses a resin decorative film for providing a concavo-convex pattern on the surface of a molded product in film insert molding, and is provided with a concavo-convex pattern. There is disclosed a decorative film for film insert molding comprising a shape layer film and a protective layer film in close contact with the concavo-convex pattern, wherein the shaped layer film and the protective layer film are weakly bonded.

  However, in the decorative film disclosed in Patent Document 1, the peeling force necessary for peeling the protective layer film from the shaping layer film is not constant, and the peeling workability may be lowered. In addition, when selecting the resin for the decorative sheet and the protective film, it is necessary to weakly bond with a specific adhesive force, and the melting point of the resin for the protective film must be lower than the melting point of the resin for the decorative sheet. Since it is necessary to consider, there also exists a problem that the combination of resin which can be used will be limited.

JP 2013-43417 A

  The main object of the present invention is to provide a decorative sheet that is excellent in the workability of peeling the uneven protective layer from the surface layer on which fine uneven shapes are formed. Furthermore, this invention also makes it the objective to provide the decorative resin molded product using the said decorative sheet, and these manufacturing methods.

  The present inventors have intensively studied to solve the above problems. As a result, at least a base material layer, a surface layer having an uneven shape, and a peelable uneven protective layer are laminated in this order, and the surface layer is a cured product of a resin composition containing a silicone ionizing radiation curable resin. It has been found that the decorative sheet formed by is excellent in the workability of peeling the uneven protective layer from the surface layer on which the fine uneven shape is formed. 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. At least, a base material layer, a surface layer having an uneven shape, and a peelable uneven protective layer are laminated in this order,
The said surface layer is a decorating sheet | seat formed with the hardened | cured material of the resin composition containing a silicone type ionizing radiation curable resin.
Item 2. Item 2. The decorative sheet according to Item 1, wherein the uneven protective layer is formed of a cured product of an ionizing radiation curable resin composition.
Item 3. Item 2. The decorative sheet according to Item 1, wherein the uneven protective layer includes an adhesive layer and a release film in order from the surface layer side.
Item 4. Item 2. The decorative sheet according to Item 1, wherein the uneven protective layer comprises a release layer, an adhesive layer, and a release film layer in order from the surface layer side.
Item 5. Item 5. The decorative sheet according to Item 3 or 4, wherein the adhesive layer fills the concave and convex portions of the surface layer.
Item 6. Item 6. The decorative sheet according to any one of Items 1 to 5, wherein a primer layer is laminated directly under the surface layer.
Item 7. Item 7. The decorative sheet according to any one of Items 1 to 6, wherein a pattern layer is laminated between the base material layer and the surface layer.
Item 8. A first step of forming a laminate in which a surface layer made of a cured product of a resin composition having a concavo-convex shape and containing a silicone ionizing radiation curable resin is laminated on a base material layer;
A second step of forming an uneven protective layer on the surface layer of the laminate obtained in the first step;
A method for producing a decorative sheet.
Item 9. Item 9. The method for manufacturing a decorative sheet according to Item 8, wherein the second step includes the following steps.
Item 10. Process for forming a concavo-convex protective layer by applying a curable resin composition on the surface layer so as to fill the concavo-convex recesses of the surface layer. Item 9. The method for manufacturing a decorative sheet according to Item 8, wherein the second step includes the following steps.
Applying a resin composition on the surface layer and filling the concave and convex portions of the surface layer to form an adhesive layer;
Item 11 is a step of laminating a release film layer on the adhesive layer. At least, a molded resin layer, a base material layer, a surface layer having an uneven shape, and a peelable uneven protective layer are laminated in this order,
The surface layer is a decorative resin molded product with a concavo-convex protective layer, which is formed of a cured product of a resin composition containing a silicone ionizing radiation curable resin.
Item 12. The manufacturing method of the decorative resin molded product with an uneven | corrugated protective layer provided with the process of forming a molded resin layer by inject | pouring resin to the base material layer side of the decorating sheet in any one of claim | item 1 -7.
Item 13. Item 12. A method for producing a decorative resin molded product, comprising a step of peeling the concave-convex protective layer from the decorative resin molded product with a concave-convex protective layer according to Item 11.

  ADVANTAGE OF THE INVENTION According to this invention, the decorating sheet which is excellent in the peeling workability | operativity of the uneven | corrugated protective layer from the surface layer in which the fine uneven | corrugated shape was formed can be provided. Furthermore, this invention can also provide the decorative resin molded product using the said decorating sheet, and these manufacturing methods.

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 sheet of the present invention. 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-section of one form of the decorative resin molded product with an uneven | corrugated protective layer of this 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 formed by laminating at least a base material layer, a surface layer having an uneven shape, and a peelable uneven protective layer in this order, and the surface layer is made of a silicone ionizing radiation curable resin. It is formed by the hardened | cured material of the resin composition containing. 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. Further, the decorative sheet of the present invention may not have a pattern layer or the like, and may be transparent, for example.

Laminated structure of decorative sheet The decorative sheet of the present invention has a laminated structure in which at least a base material layer 1, a surface layer 2 having an uneven shape, and a peelable uneven protective layer 3 are laminated in this order.

  The uneven protective layer 3 may be a single layer, or a laminate in which the release layer 32 / release film layer 30 is laminated in order from the surface layer 2 side; the release layer 32 / adhesive layer 31 / release film. A laminated body in which the layers 30 are laminated may be used. The release layer 32 fills the concave and convex portions of the surface layer 2. When the adhesive layer 31 is formed of an adhesive, the adhesive layer 31 fills the concave and convex portions of the surface layer 2. Moreover, when the uneven | corrugated protective layer 3 has the mold release layer 32 and the adhesive layer 31 formed with the adhesive agent, in the decorating sheet | seat of this invention, the mold release layer 32 and the adhesive layer 31 are. The concave and convex portions of the surface layer 2 are filled. As will be described later, the adhesive layer 31 means an adhesive layer or an adhesive layer, and is formed of an adhesive or an adhesive.

  In the decorative sheet of the present invention, a primer layer 4 may be provided between the base material layer 1 and the surface layer 2 as necessary for the purpose of improving the adhesion between the layers.

  Moreover, you may provide the pattern layer 5 between the base material layer 1 and the surface layer 2 as needed in order to provide decorating property. When the primer layer 4 is provided, the pattern layer 5 may be provided between the base material layer 1 and the primer layer 4.

  Moreover, between the base material layer 1 and the surface layer 2, the concealing layer (not shown) may be provided as needed for the purpose of suppressing the color change and variation of the base material layer 1. If the primer layer 4 is provided, the concealing layer may be provided between the base material layer 1 and the primer layer 4, and if the pattern layer 5 is provided, the concealing layer is a base material layer. 1 and the pattern layer 5 may be provided.

  Furthermore, a transparent resin layer 6 may be provided between the base material layer 1 and the surface layer 2 as necessary for the purpose of improving scratch resistance. If the primer layer 4 is provided, the transparent resin layer 6 may be provided between the pattern layer 5 and the primer layer 4.

  Furthermore, in the decorative sheet of the present invention, the back surface of the base material layer 1 (the surface on the side opposite to the surface layer 2) for the purpose of enhancing the adhesion with the molding resin during the molding of the decorative resin molded product. May be provided with a back surface adhesive layer (not shown) as required.

  As an example of the laminated structure of the decorative sheet of the present invention, a laminated structure in which a base material layer 1 / surface layer 2 / concave / convex protective layer 3 are laminated in order; base material layer 1 / pattern layer 5 / surface layer 2 / concave / concave protective layer 3 (adhesive layer 31 / release film layer 30) laminated in order; laminated structure in which base material layer 1 / pattern layer 5 / surface layer 2 / unevenness protective layer 3 (cured resin layer) was laminated in order A laminated structure in which a base layer 1 / a pattern layer 5 / a primer layer 4 / a surface layer 2 / a concave / convex protective layer 3 (a release layer 32 / an adhesive layer 31 / a release film layer 30) are sequentially laminated; 1 / Picture layer 5 / Primer layer 4 / Surface layer 2 / Concavity and convexity protection layer 3 (cured resin layer) laminated in order; base material layer 1 / pattern layer 5 / transparent resin layer 6 / primer layer 4 / surface Laminated structure in which layer 2 / uneven protective layer 3 (release layer 32 / adhesive layer 31 / release film layer 30) is laminated in order; base material layer / Picture layer 5 / the transparent resin layer 6 / primer layer 4 / surface layer 2 / uneven protective layer 3 (cured resin layer) can be mentioned laminated structure, etc., which are sequentially stacked. 1 and 2 show cross-sectional views of a decorative sheet in which a base material layer 1 / surface layer 2 / unevenness protective layer 3 are sequentially laminated as an embodiment of the laminated structure of the decorative sheet of the present invention. In FIG. 3, as one aspect of the laminated structure of the decorative sheet of the present invention, base material layer 1 / pattern layer 5 / transparent resin layer 6 / primer layer 4 / surface layer 2 / unevenness protective layer 3 (release layer 32 / Sectional drawing of the decorating sheet | seat in which the laminated structure in which the adhesive layer 31 / release film layer 30) was laminated | stacked in order is laminated | stacked is shown.

Composition of each layer of the decorative sheet [base material layer 1]
The base material layer 1 is a resin sheet (resin film) that plays a role as a support in the decorative sheet of the present invention. The resin component used for the base material layer 1 is not particularly limited, and may be appropriately selected according to the three-dimensional moldability, compatibility with the molding resin, and the like. Preferably, a resin film made of a thermoplastic resin is used. Can be mentioned. Specifically, as the thermoplastic resin, acrylonitrile-butadiene-styrene resin (hereinafter sometimes referred to as “ABS resin”), acrylonitrile-styrene-acrylate resin (hereinafter referred to as “ASA resin”). And acrylic resins, polyolefin resins such as polypropylene and polyethylene, polycarbonate resins, vinyl chloride resins, and polyethylene terephthalate (PET). Among these, ABS resin and acrylic resin are preferable from the viewpoint of three-dimensional moldability. Moreover, the base material layer 1 may be formed with the single layer sheet | seat of these resin, and may be formed with the multilayer sheet | seat by the same kind or different kind | species resin.

  The bending elastic modulus of the base material layer 1 is not particularly limited. For example, when the decorative sheet of the present invention is integrated with a molding resin by an insert molding method, the flexural modulus at 25 ° C. of the base material layer 1 in the decorative sheet of the present invention is 500 to 4,000 MPa, preferably 750-3,000 MPa is mentioned. Here, the flexural modulus at 25 ° C. is a value measured according to JIS K7171. When the flexural modulus at 25 ° C. is 500 MPa or more, the decorative sheet has sufficient rigidity, and even when subjected to the insert molding method, the surface characteristics and moldability are further improved. In addition, when the bending elastic modulus at 25 ° C. is 3,000 MPa or less, sufficient tension can be applied when manufacturing by roll-to-roll, and sagging does not easily occur. So that the so-called pattern registration is good.

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

  The base material layer 1 may be subjected to a treatment such as forming a known adhesive layer.

  Furthermore, the base material layer 1 may be colored with a coloring agent or may not be colored. Moreover, the base material layer 1 may be any of colorless and transparent, colored and transparent, and translucent. Although it does not restrict | limit especially as a coloring agent used for the base material layer 1, Preferably the coloring agent which does not discolor also under the temperature conditions of 150 degreeC or more is mentioned, Specifically, the existing dry color, paste color, masterbatch resin Examples thereof include compositions.

  Although the thickness of the base material layer 1 is suitably set according to the use of the decorative sheet, the molding method to be integrated with the molding resin, etc., usually about 25 to 1000 μm and about 50 to 700 μm are mentioned. More specifically, if the decorative sheet of the present invention is subjected to the insert molding method, the thickness of the base material layer 1 is usually about 50 to 1000 μm, preferably 100 to 700 μm, more preferably 100 to 500 μm. Can be mentioned. Moreover, if it is a case where the decorating sheet of this invention is used for the injection molding simultaneous decorating method, as thickness of the base material layer 1, 25-200 micrometers normally, Preferably it is 50-200 micrometers, More preferably, 70-200 micrometers is mentioned. .

[Surface layer 2]
The surface layer 2 has an uneven shape, and is formed of a cured product of a resin composition (ionizing radiation curable resin composition) containing a silicone ionizing radiation curable resin. Thus, this invention which formed the surface layer 2 which has uneven | corrugated shape with the hardened | cured material of the resin composition containing silicone type ionizing radiation-curable resin, and covered the said surface layer 2 with the uneven | corrugated protective layer 3 mentioned later. This decorative sheet is very excellent in the workability of peeling from the surface layer of the concave-convex protective layer 3 after applying the decorative sheet to a decorative resin molded product.

<Uneven shape>
The concavo-convex shape formed on the surface layer 2 is not particularly limited, and may be appropriately set according to the design feeling or the touch to be imparted. Examples of the uneven shape include a hairline pattern, a wood grain pattern, a geometric pattern (dots, stripes, carbon) and the like.

  Further, the height of the convex portion, the width of the convex portion, the pitch between the adjacent convex portions, the width of the concave portion, etc. in the concave-convex shape formed on the surface layer 2 are appropriately determined according to the design feeling or touch to be imparted. You only have to set it.

  For example, the center line average roughness (Ra) of the surface layer 2 is usually 1.0 to 20 μm, preferably 1.0 to 10 μm, more preferably from the viewpoint of imparting an excellent design feeling and touch due to the uneven shape. 1.5-5 micrometers is mentioned. When the average roughness of the center line of the surface layer 2 is 20 μm or less, when the decorative sheet is wound and stored in a roll shape, the irregularities are excessively severe, so that damage or tear during transportation, collapse of the winding It is preferable that the above does not occur.

  From the same viewpoint, the maximum height (Rmax) is usually 1.0 to 100 μm, preferably 1.0 to 80 μm, and more preferably 1.0 to 60 μm. From the same viewpoint, the ten-point average height (Rz) is usually 1.0 to 100 μm, preferably 1.0 to 80 μm, and more preferably 1.0 to 60 μm. The centerline average roughness (Ra), the maximum height (Rmax), and the ten-point average height (Rz) are values measured by the methods described in the examples.

  Moreover, as for the uneven | corrugated shape formed by the surface layer 2, the bottom part of a recessed part may be formed by the surface layer 2 like the aspect shown in FIG. 1, and in the bottom part of a recessed part like the aspect shown in FIG. The lower layer of the surface layer 2 may be exposed, and a plurality of convex portions of the surface layer 2 may be partially provided. The former is preferable from the viewpoint of protecting the surface of the decorative resin molded product. 1 and 2 show a laminated structure in which a base material layer 1, a surface layer 2, and an uneven protective layer 3 are laminated in order for convenience.

  In the decorative sheet of the present invention, the uneven shape may be formed in at least a part of the region in order to give the decorative sheet a high texture due to the uneven shape. That is, in the decorative sheet of the present invention, the uneven shape satisfying the above relationship may be formed in a part of the region, or may be formed in the entire region.

<Silicone ionizing radiation curable resin>
The silicone-based ionizing radiation curable resin used for forming the surface layer 2 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 photopolymerization initiators, and provide stable curing characteristics, so they are suitable for use in the formation of surface layers. Is done.

  Although it does not restrict | limit especially as a silicone type ionizing radiation-curable resin contained in the resin composition which forms the surface layer 2, Preferably acrylic silicone (meth) acrylate, silicone (meth) acrylate, and silicone modified urethane (meth) acrylate are preferable. Particularly preferred is acrylic silicone (meth) acrylate. In the present invention, “acrylic silicone (meth) acrylate” means “a part of the structure of the acrylic resin is substituted with a siloxane bond (Si—O) in one molecule, and the acrylic resin is a functional group. Which has two or more (meth) acryloyloxy groups at the side chain and / or main chain terminal. The term “silicone (meth) acrylate” means “modified silicone oil in which a (meth) acryloyl group is introduced into a side chain or both ends of a silicone oil having polysiloxane as a main chain”. Hereinafter, acrylic silicone (meth) acrylate, silicone (meth) acrylate, and silicone-modified urethane (meth) acrylate that are preferable as the silicone ionizing radiation curable resin will be described in detail.

(Acrylic silicone (meth) acrylate)
The acrylic silicone (meth) acrylate is not particularly limited, and a part of the structure of the acrylic resin is substituted with a siloxane bond (Si—O) in one molecule, and the side chain of the acrylic resin and / Or what is necessary is just to have two or more (meth) acryloyloxy groups (acryloyloxy group or methacryloyloxy group) in the principal chain terminal. As an example of this acrylic silicone (meth) acrylate, the structure of the acrylic resin which has a siloxane bond in a side chain as disclosed by Unexamined-Japanese-Patent No. 2007-070544 is mentioned preferably, for example.

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

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

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

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

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

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

  Moreover, it is preferable that the average molecular weight between crosslinking points of acrylic silicone (meth) acrylate is 100-2,500. If the average molecular weight between crosslinking points is 100 or more, it is preferable from the viewpoint of three-dimensional formability, and if it is 2,500 or less, it is preferable from the viewpoint of chemical resistance and scratch resistance. From the same viewpoint, the average molecular weight between crosslinking points of the acrylic silicone (meth) acrylate is more preferably 100 to 1,500, still more preferably 100 to 1,000.

(Silicone (meth) acrylate)
The silicone (meth) acrylate is not particularly limited as long as it is a modified silicone oil in which a (meth) acryloyl group is introduced into a side chain or both ends of a silicone oil having a polysiloxane as a main chain. (Meth) acrylate and polyfunctional (trifunctional or higher) silicone (meth) acrylate can be used.

  As the monofunctional or bifunctional silicone (meth) acrylate, conventionally known ones can be used, and any modified silicone oil having an organic group of (meth) acrylic group and having one or two organic groups is particularly limited. Not. The structure of the modified silicone oil is roughly divided into a side chain type, a both-end type, a single-end type, and a side-chain both-end type depending on the bonding position of the organic group to be substituted. There is no particular limitation. As such a silicone (meth) acrylate, the weight average molecular weight is preferably 1000 to 6000, more preferably 3000 to 6000, and the functional group equivalent (weight average molecular weight / functional group number) is preferably 500 to 3000, more preferably 1500 to Those having a condition of 3000 are used.

  As the polyfunctional (trifunctional or higher) silicone (meth) acrylate used for the silicone (meth) acrylate, conventionally known ones can be used, and the organic group is a (meth) acrylic group, and a plurality of the organic groups are preferable. Is not particularly limited as long as it is a modified silicone oil having 4 or more, and further 4 to 6. The structure of the modified silicone oil is roughly divided into a side chain type, a both-end type, a single-end type, and a side-chain both-end type depending on the bonding position of the organic group to be substituted. There is no particular limitation. As such a silicone (meth) acrylate, the weight average molecular weight is preferably 3000 to 100,000, more preferably 10,000 to 30000, and the functional group equivalent (weight average molecular weight / number of functional groups) is preferably 750 to 25000, more preferably 3000 to Those having a condition of 6000 are used.

  In addition, the weight average molecular weight of silicone (meth) acrylate in this specification is a value measured with polystyrene as a standard substance by gel permeation chromatography.

(Silicone-modified urethane (meth) acrylate)
The silicone-modified urethane (meth) acrylate is not particularly limited, and examples thereof include compounds in which a part of the side chain of the urethane (meth) acrylate is modified with silicone. Silicone-modified urethane (meth) acrylate is obtained, for example, by reacting a urethane prepolymer having an isocyanate group with a silicone compound having a silanol group together with hydroxy (meth) acrylate.

  Regarding the number of functional groups and molecular weight of the silicone-modified urethane (meth) acrylate, for example, the number of functional groups per molecule is 1 to 10, preferably 2 to 8, more preferably 3 to 6, and the weight average molecular weight is 1000 to 1000. What is 50000, Preferably it is 3000-30000, More preferably, it is 5000-10000.

  The ratio of the silicone ionizing radiation curable resin in the resin composition forming the surface layer 2 is preferably about 1 to 10% by mass, more preferably about 1 to 5% by mass, and further preferably 3 to 5% by mass. %.

  The resin composition forming the surface layer 2 preferably contains other ionizing radiation curable resin in addition to the silicone ionizing radiation curable resin. Other ionizing radiation curable resins are as follows.

(Other ionizing radiation curable resins)
The other ionizing radiation curable resin used for forming the surface layer 2 refers to a resin that is cross-linked and cured by irradiating with ionizing radiation, like the aforementioned silicone ionizing radiation curable resin.

  Specific examples of the other ionizing radiation curable resins include those obtained by appropriately mixing prepolymers, oligomers, and / or monomers having polymerizable unsaturated bonds or epoxy groups in the molecule.

  As the oligomer used as the other ionizing radiation curable resin, a (meth) acrylate oligomer having a radical polymerizable unsaturated group in the molecule is preferable, and in particular, two or more polymerizable unsaturated bonds are contained in the molecule. A polyfunctional (meth) acrylate oligomer having (bifunctional or higher) is preferred. Examples of the polyfunctional (meth) acrylate oligomer include polycarbonate (meth) acrylate, urethane (meth) acrylate, epoxy (meth) acrylate, polyester (meth) acrylate, polyether (meth) acrylate, polybutadiene (meth) acrylate, Examples include oligomers having a cationically polymerizable functional group in the molecule (for example, novolac type epoxy resin, bisphenol type epoxy resin, aliphatic vinyl ether, aromatic vinyl ether, etc.). Here, the polycarbonate (meth) acrylate is not particularly limited as long as it has a carbonate bond in the polymer main chain and a (meth) acrylate group in the terminal or side chain. It can be obtained by esterification with acrylic acid. 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. Urethane (meth) acrylate can be obtained, for example, by esterifying a polyurethane oligomer obtained by reaction of polyether polyol or polyester polyol and polyisocyanate with (meth) acrylic acid. Epoxy (meth) acrylate can be obtained, for example, by reacting (meth) acrylic acid with an oxirane ring of a relatively low molecular weight bisphenol type epoxy resin or novolak type epoxy resin and esterifying it. Also, a carboxyl-modified epoxy (meth) acrylate obtained by partially modifying this epoxy (meth) acrylate with a dibasic carboxylic acid anhydride can be used. Polyester (meth) acrylate is obtained by esterifying the hydroxyl group of a polyester oligomer having hydroxyl groups at both ends obtained by condensation of a polyvalent carboxylic acid and a polyhydric alcohol with (meth) acrylic acid, for example, or It can be obtained by esterifying the terminal hydroxyl group of an oligomer obtained by adding an alkylene oxide with (meth) acrylic acid. The polyether (meth) acrylate can be obtained by esterifying the hydroxyl group of the polyether polyol with (meth) acrylic acid. Polybutadiene (meth) acrylate can be obtained by adding (meth) acrylic acid to the side chain of the polybutadiene oligomer. These oligomers may be used individually by 1 type, and may be used in combination of 2 or more type.

  Moreover, as said monomer used as other ionizing radiation curable resin, the (meth) acrylate monomer which has a radically polymerizable unsaturated group in a molecule | numerator is suitable, and a polyfunctional (meth) acrylate monomer is especially 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 monomer include ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, and 1,6-hexanediol diene. (Meth) acrylate, neopentyl glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, hydroxypivalic acid 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) Chryrate, 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, in combination with silicone ionizing radiation curable resins, it is preferable from the viewpoint of imparting an excellent design feeling and touch feeling while further facilitating the peeling operation of the uneven protective layer. Is an oligomer having a polymerizable unsaturated bond or epoxy group in the molecule, particularly preferably polycarbonate (meth) acrylate.

  When a silicone ionizing radiation curable resin and polycarbonate (meth) acrylate are used in combination, these ratios may be set in consideration of the molecular weight, the number of functional groups, etc., for example, a silicone ionizing radiation curable resin. And the mass ratio of the polycarbonate (meth) acrylate (silicone ionizing radiation curable resin: polycarbonate (meth) acrylate) is preferably about 50:50 to 1:99, more preferably about 20:80 to 1:99, particularly Preferably about 15:85 to 1:99 is mentioned.

  Below, the polycarbonate (meth) acrylate used suitably as an ionizing radiation curable resin for forming the surface layer 2 is explained in full detail.

If the polycarbonate (meth) acrylate used in combination with the polycarbonate (meth) acrylate silicone ionizing radiation curable resin has a carbonate bond in the polymer main chain and has a (meth) acrylate in the terminal or side chain, For example, urethane (meth) acrylate having a polycarbonate skeleton may be used. The (meth) acrylate is preferably 2 to 6 functional groups per molecule from the viewpoint of improving crosslinking and curing. The polycarbonate (meth) acrylate is preferably a polyfunctional polycarbonate (meth) acrylate having two or more (meth) acrylates at the terminals or side chains. Polycarbonate (meth) acrylate may be used individually by 1 type, and may be used in combination of 2 or more types.

  The polycarbonate (meth) acrylate is obtained, for example, by converting 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.

<Other additives>
Moreover, various additives can be mix | blended with the resin composition used for formation of the surface layer 2 according to the desired physical property with which the surface layer 2 is equipped. Examples of such additives include weather resistance improvers such as ultraviolet absorbers and light stabilizers, wear resistance improvers, polymerization inhibitors, crosslinking agents, infrared absorbers, antistatic agents, adhesion improvers, and leveling agents. , Thixotropic agent, coupling agent, plasticizer, antifoaming agent, filler, solvent, colorant and the like. 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 surface layer 2>
Although it does not restrict | limit especially about the thickness after hardening of the surface layer 2, For example, 0.01-20 micrometers, Preferably it is 0.01-15 micrometers, More preferably, 0.01-12 micrometers is mentioned. By satisfying the thickness in such a range, the uneven shape can be more effectively expressed, and an excellent design feeling and hand feeling can be provided. In addition, the thickness of the surface layer 2 means the thickness of the convex part of the surface layer 2.

<Formation of surface layer 2>
The surface layer 2 may be formed on a predetermined layer so that the cured product of the resin composition containing the silicone ionizing radiation curable resin has an uneven shape, and the specific method is particularly limited. is not. Examples of a method for providing the surface layer 2 with a concavo-convex shape include a method of embossing, a method of applying and curing the resin composition forming the surface layer 2 only on the portion where the convex portion is formed, and the like. However, a method of embossing is preferable.

  Specific examples of the method for forming the surface layer 2 having an uneven shape include the following first to third methods.

1st method: The base material layer 1 and the other layer provided as needed are laminated | stacked in order, the sheet | seat which has other than the surface layer 2 is prepared, and the embossing is carried out on the side which laminates | stacks the surface layer 2 of the said sheet | seat. A method of applying the resin composition used for forming the surface layer 2 and curing the resin composition after the application.

Second method: The base material layer 1 and other layers provided as necessary are laminated in order to prepare a sheet having other than the surface layer 2, and the surface layer 2 on the side on which the surface layer 2 of the sheet is laminated. A method of embossing the surface layer 2 side after applying the resin composition used for forming the resin and curing the resin composition.

Third method: The base material layer 1 and other layers provided as necessary are sequentially laminated to prepare a sheet having other than the surface layer 2, and the convex portion on the side where the surface layer 2 of the sheet is laminated is prepared. A method of curing the resin composition by applying a resin composition used for forming the surface layer 2 only to a portion to be formed.

  The method for applying the resin composition used for forming the surface layer 2 on the predetermined layer is not particularly limited, and examples thereof include gravure coating, bar coating, roll coating, reverse roll coating, and comma coating. A gravure coat is preferable.

  In this way, the resin composition (uncured resin layer) containing the silicone ionizing radiation curable resin applied on the predetermined layer is irradiated with ionizing radiation such as an electron beam and ultraviolet rays to thereby apply the resin composition. The surface layer 2 is formed by curing. 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. 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.

[Unevenness protection layer 3]
The concave / convex protective layer 3 is a layer provided on the surface layer 2 so as to be in contact with the surface layer 2, and is laminated so as to be peelable from the interface with the surface layer 2, and is integrally formed with the molding resin. It is a layer that is peeled off after a long time. The uneven protective layer 3 may be a single layer or multiple layers. As the uneven protective layer 3 in the case of multiple layers, for example, a laminate in which the release layer 32 / release film layer 30 is laminated in order from the surface layer 2 side, and an adhesive layer 31 / release film layer 30 are laminated. The laminated body and the laminated body by which the mold release layer 32 / adhesive-adhesive layer 31 / release film layer 30 were laminated | stacked are mentioned. When the release layer 32 or the adhesive layer 31 formed of an adhesive is laminated, each of these layers fills the concave and convex portions of the surface layer 2. When the uneven | corrugated protective layer 3 has both the mold release layer 32 and the adhesive layer 31 formed with the adhesive agent, in the decorating sheet | seat of this invention, the mold release layer 32 and the adhesive layer 31 are the same. The concave and convex portions of the surface layer 2 are filled.

  In this invention, when the adhesive layer 31 of the uneven | corrugated protective layer 3 is formed with the adhesive agent, it can form by apply | coating an adhesive agent on the surface layer 2 which has an uneven | corrugated shape. For this reason, the formation of the adhesive layer 31 does not require heating by extrusion molding or thermal lamination. Therefore, when the adhesive layer 31 is formed of an adhesive, the concave / convex protective layer 3 is formed to protect the concave / convex shape of the surface layer 2 while suitably maintaining the fine concave / convex shape of the surface layer 2. can do.

  Moreover, when the uneven | corrugated protective layer 3 is a single layer, the uneven | corrugated protective layer 3 may be formed with the cured resin layer formed of the hardened | cured material of curable resin, and may be formed with the thermoplastic resin. .

(Peeling film layer 30)
When the uneven protective layer 3 is a multi-layer, the release film layer 30 forms the uneven protective layer 3 together with at least one of the release layer 32 and the adhesive layer 31, and the surface during vacuum molding or injection molding of the decorative sheet This is a layer provided to suppress deformation and disappearance of the uneven shape of the layer 2. Moreover, the uneven | corrugated protective layer 3 may consist only of the peeling film layer 30, and the peeling film layer 30 has filled the uneven | corrugated shaped recessed part of the surface layer 2 in this case.

  The material for the release film layer 30 is not particularly limited, and can be formed of, for example, a thermoplastic resin film. The thermoplastic resin constituting the thermoplastic resin film is not particularly limited, and acrylonitrile-butadiene-styrene resin (hereinafter sometimes referred to as “ABS resin”); acrylonitrile-styrene-acrylate resin; acrylic resin; Polyolefin resins such as polypropylene and polyethylene; polycarbonate resins; vinyl chloride resins; polyethylene terephthalate (PET) resins, polybutylene terephthalate (PBT) resins, and the like. One kind of thermoplastic resin may be contained alone, or two or more kinds may be contained.

  Although it does not restrict | limit especially as thickness of the peeling film layer 30, Preferably it is about 5-100 micrometers, More preferably, about 20-50 micrometers is mentioned. Moreover, the peeling film layer 30 may consist of multiple layers.

  Although the formation method of the peeling film layer 30 is not specifically limited, From a viewpoint of suppressing that the uneven | corrugated shape of the surface layer 2 deform | transforms or lose | disappears at the time of formation of the peeling film layer 30, the adhesive layer 31 mentioned later is formed. Then, it is preferable to laminate | stack the film formed beforehand by the adhesive force or adhesive force of the adhesive layer 31. FIG. In the case where the adhesive layer 31 is not provided, a method of laminating a film formed in advance on the surface layer 2 or the release layer 32 by thermal lamination, or a resin for forming the release film layer 30 is used. The method of laminating by extrusion molding is exemplified. In addition, in the decorating sheet of this invention, since the surface layer 2 is formed with the hardened | cured material of an ionizing radiation curable resin composition, compared with the decorating sheet which has the thermoplastic resin film in which the uneven | corrugated shape was provided on the surface Even when the release film layer 30 is laminated by thermal lamination or extrusion, deformation of the concavo-convex shape is suppressed.

(Adhesive layer 31)
The adhesive layer 31 is provided together with the release film layer 30 as necessary, and constitutes the uneven protective layer 3. The adhesive layer 31 is formed of an adhesive or a pressure-sensitive adhesive. As an adhesive used for the adhesive layer 31, it can be applied so as to fill the uneven shape of the surface layer 2 and can be peeled off from the surface of the surface layer 2 together with the release film layer 30. There is no particular limitation, and a curable resin is preferably used. Examples of the curable resin include urethane adhesives, acrylic adhesives, epoxy adhesives, rubber adhesives, etc. Among them, urethane adhesives can maintain a sufficient adhesive force even during injection molding. This is preferable in that it can be peeled off from the surface of the surface layer 2. Such urethane adhesives include two-component curable urethane resin adhesives, and two-component curable urethane resin adhesives include various hydroxyl groups such as polyether polyol, polyester polyol, and acrylic polyol. It is an adhesive using a two-component curable urethane resin containing a containing compound and various polyisocyanate compounds such as tolylene diisocyanate and hexamethylene diisocyanate.

  Moreover, when using an adhesive for the adhesive layer 31, the adhesive sheet by which the adhesive was apply | coated on the above-mentioned peeling film layer 30 can be used. Examples of such an adhesive sheet include a general polypropylene base material coated with an acrylic adhesive.

  Although it does not restrict | limit especially as thickness of the adhesive layer 31, Preferably it is about 5-70 micrometers, More preferably, about 15-60 micrometers is mentioned. In addition, the thickness of the adhesive layer 31 is the thickness of the part located on the convex part of the layer (surface layer 2 or the mold release layer 32) located below.

  When the adhesive layer 31 is formed of an adhesive, the adhesive layer 31 is formed by applying the above-described adhesive on a layer (surface layer 2 or release layer 32) located below the adhesive layer 31. It can be formed by coating. Specifically, the adhesive is applied to the surface of the surface layer 2 by a method such as gravure coating, bar coating, roll coating, reverse roll coating, comma coating, etc. It may be applied to the surface).

(Release layer 32)
The concave / convex protective layer 3 may include a release layer 32 for the purpose of improving the peelability between the concave / convex protective layer 3 and the surface layer 2. In the concave / convex protective layer 3, the release layer 32 is provided on the outermost surface on the surface layer 2 side. Moreover, when the uneven | corrugated protective layer 3 has the mold release layer 32 and the adhesive layer 31 formed with the adhesive agent, in the decorating sheet | seat of this invention, the mold release layer 32 and the adhesive layer 31 are. The concave and convex portions of the surface layer 2 are filled.

  The material for forming the release layer 32 is not particularly limited as long as it can be applied so as to fill the uneven shape of the surface layer 2 and can be peeled from the surface of the surface layer 2 as the uneven protective layer 3. However, the release layer 32 is preferably formed of a cured product of the ionizing radiation curable resin composition. As a result, it is possible to more effectively suppress deformation and disappearance of the uneven shape of the surface layer 2 during vacuum molding or injection molding, and to impart an excellent design feeling and hand feeling to the decorative resin molded product.

<Ionizing radiation curable resin in release layer 32>
The types and preferred ones of the ionizing radiation curable resin used for forming the release layer 32 are the same as those used for forming the surface layer 2. In particular, among the ionizing radiation resins, the combination of the ionizing radiation curable resin (1) and the ionizing radiation curable resin (2) exemplified in the section of the surface layer 2 is the surface layer during vacuum molding or injection molding. 2 is preferably used in the release layer 32 because it can be provided not only with an effect of suppressing deformation and disappearance of the uneven shape 2 but also with ease of peeling after being integrally molded with the molding resin. As the ionizing radiation curable resin in the release layer 32, trifunctional pentaerythritol acrylate is preferable. The ionizing radiation curable resin used for forming the release layer 32 and the ionizing radiation curable resin used for forming the surface layer 2 may be the same type or different types. .

<Other additive components>
In addition to the ionizing radiation curable resin, the ionizing radiation curable resin composition used for forming the release layer 32 contains other resin components as necessary for improving moldability. May be. Examples of the resin component other than the ionizing radiation curable resin include 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 polypropylene, styrene resin such as polystyrene and α-methylstyrene, polyamide, polycarbonate, acetal resin such as polyoxymethylene, fluorine resin such as ethylene-4 fluoroethylene copolymer, polyimide, polylactic acid, polyvinyl Acetal resin; thermoplastic resin such as liquid crystalline polyester resin. These resin components may be used individually by 1 type, and may be used in combination of 2 or more type.

  In addition to the ionizing radiation curable resin composition, the release layer 32 includes a silicone resin, a fluorine resin, an acrylic resin (for example, an acrylic-melamine resin), a polyester resin, a polyolefin resin, and polystyrene. Resin, polyurethane resin, cellulose resin, vinyl chloride-vinyl acetate copolymer resin, thermoplastic resin such as nitrified cotton, copolymer of monomers forming the thermoplastic resin, or these resins (meta ) Those modified with acrylic acid or urethane can be formed by using a resin composition singly or in combination. Among these, acrylic resins, polyester resins, polyolefin resins, polystyrene resins, copolymers of monomers that form these resins, and those obtained by urethane modification thereof are more preferable. More specifically, acrylic-melamine Resin, acrylic-melamine resin-containing composition, polyester resin and ethylene / acrylic acid copolymer modified with urethane, acrylic resin / styrene / acrylic copolymer And a resin composition mixed with the above emulsion. Among these, it is particularly preferable that the release layer 32 is composed of an acrylic-melamine resin alone or a composition containing 50% by mass or more of the acrylic-melamine resin.

  Various additives can be blended into the resin composition forming the release layer 32 in consideration of desired physical properties to be provided in the uneven protective layer 3. Examples of the additive include a weather resistance improver such as an ultraviolet absorber and a light stabilizer, an abrasion resistance improver, a polymerization inhibitor, a crosslinking agent, an infrared absorber, an antistatic agent, an adhesion improver, a leveling agent, Examples include a thixotropic agent, a coupling agent, a plasticizer, an antifoaming agent, a filler, a solvent, and a colorant. These additives can be appropriately selected from those commonly used. In addition, as the ultraviolet absorber or light stabilizer, a reactive ultraviolet absorber or light stabilizer having a polymerizable group such as a (meth) acryloyl group in the molecule can be used.

  Although it does not restrict | limit especially as thickness of the mold release layer 32, Preferably it is about 1-40 micrometers, More preferably, about 5-15 micrometers is mentioned. The thickness of the release layer 32 is the thickness of the portion located on the convex portion of the surface layer 2.

  The release layer 32 can be formed by applying the above-described resin composition on the surface layer 2. Specifically, the resin composition may be applied to the surface of the surface layer 2 by a method such as gravure coating, bar coating, roll coating, reverse roll coating, or comma coating.

(Cured resin layer)
Moreover, when the uneven | corrugated protective layer 3 is formed with the cured resin layer formed with the hardened | cured material of the curable resin composition, the cured resin layer can be formed by one layer. At this time, the cured resin layer fills the concave portion of the surface layer 2. The curable resin composition for forming the curable resin layer is preferably the ionizing radiation curable resin composition exemplified for the release layer 32 described above.

<Total thickness of the uneven protective layer 3>
Although it does not restrict | limit especially about the total thickness of the uneven | corrugated protective layer 3, For example, 5-150 micrometers is mentioned. Further, from the viewpoint of making it easy to peel the uneven protective layer after being integrated with the molding resin, the total thickness of the uneven protective layer 3 is preferably 10 to 100 μm, more preferably 15 to 100 μm. In addition, the total thickness of the uneven | corrugated protective layer 3 means the thickness of the protective layer after hardening, when using cured resin here. The total thickness of the uneven protective layer 3 is the thickness of the portion located on the convex portion of the surface layer 2.

[Primer layer 4]
The primer layer 4 has a pattern layer 5 when the pattern layer 5 is provided between the base layer 1 and the surface layer 2 for the purpose of making it difficult for fine cracks and whitening to occur in the stretched portion of the surface layer 2. And / or the surface layer 2 and / or between the base material layer 1 and the pattern layer 5 as necessary.

  From the viewpoint of enhancing the adhesion between the surface layer 2 and the layer located therebelow, it is preferable that the primer layer 4 is provided immediately below the surface layer 2.

  Primer compositions constituting the primer layer 4 include urethane resin, (meth) acrylic resin, (meth) acrylic-urethane copolymer resin, vinyl chloride-vinyl acetate copolymer, polyester resin, butyral resin, chlorinated polypropylene. Those using chlorinated polyethylene as a binder resin are preferably used, and these resins can be used alone or in combination of two or more. Among these, urethane resin, (meth) acrylic resin, and (meth) acrylic-urethane copolymer resin are preferable.

  As the urethane resin, polyurethane having a polyol (polyhydric alcohol) as a main ingredient and an isocyanate as a crosslinking agent (curing agent) can be used. As the polyol, one having two or more hydroxyl groups in the molecule, for example, polyester polyol, polyethylene glycol, polypropylene glycol, acrylic polyol, polyether polyol and the like are used. Examples of the isocyanate include polyvalent isocyanate having two or more isocyanate groups in the molecule, aromatic isocyanate such as 4,4-diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated diphenylmethane diisocyanate. Aliphatic (or alicyclic) isocyanates such as are used. It is also possible to mix urethane resin and butyral resin.

  From the viewpoints of adhesion with the surface layer 2 after crosslinking, difficulty in interaction after laminating the surface layer 2, physical properties, and moldability, an acrylic polyol or polyester polyol as a polyol, and hexamethylene diisocyanate as a crosslinking agent, It is preferable to combine with 4,4-diphenylmethane diisocyanate, and it is particularly preferable to use acrylic polyol and hexamethylene diisocyanate in combination.

  (Meth) acrylic resins include (meth) acrylic acid ester homopolymers, copolymers of two or more different (meth) acrylic acid ester monomers, or (meth) acrylic acid esters and other monomers. Polymers, specifically, poly (meth) methyl acrylate, poly (meth) ethyl acrylate, poly (meth) acrylate propyl, poly (meth) acrylate butyl, methyl (meth) acrylate- (Meth) butyl acrylate copolymer, (meth) ethyl acrylate- (meth) butyl acrylate copolymer, ethylene- (meth) methyl acrylate copolymer, styrene- (meth) methyl acrylate copolymer A (meth) acrylic resin made of a homopolymer or a copolymer containing a (meth) acrylic acid ester such as the above is preferably used.

  As the (meth) acryl-urethane copolymer resin, for example, an acrylic-urethane (polyester urethane) block copolymer resin is preferable. As the curing agent, the above-mentioned various isocyanates are used. The acrylic-urethane (polyester urethane) block copolymer resin adjusts the acrylic / urethane ratio (mass ratio) in the range of preferably 9/1 to 1/9, more preferably 8/2 to 2/8, if desired. It is preferable.

  Although it does not restrict | limit especially about the thickness of the primer layer 4, For example, it is about 0.5-20 micrometers, Preferably, 1-5 micrometers is mentioned.

  The primer layer 4 is a gravure coat, a gravure reverse coat, a gravure offset coat, a spinner coat, a roll coat, a reverse roll coat, a kiss coat, a wheeler coat, a dip coat, a solid coat with a silk screen, a wire bar coat, It is formed by a normal coating method such as flow coating, comma coating, flow coating, brush coating, spray coating, or transfer coating method. Here, the transfer coating method is a method in which a primer layer or an adhesive layer is formed on a thin sheet (film substrate) and then the surface of the target layer in the decorative sheet is coated.

[Picture layer 5]
The pattern layer 5 is provided between the base material layer 1 and the surface layer 2 or between the base material layer 1 and the primer layer 4 or a concealing layer when the primer layer 4 is provided for the purpose of imparting decorativeness to the decorative sheet. Is provided between the concealing layer and the surface layer 2 as necessary.

  The picture layer 5 can be a layer in which a desired picture is formed using an ink composition, for example. As the ink composition used for forming the pattern layer 5, a binder and a colorant such as a pigment and a dye, an extender pigment, a solvent, a stabilizer, a plasticizer, a catalyst, and a curing agent are appropriately mixed. .

  The binder used in the ink composition is not particularly limited. For example, polyurethane resin, vinyl chloride / vinyl acetate copolymer resin, vinyl chloride / vinyl acetate / acrylic copolymer resin, chlorinated polypropylene resin, acrylic resin , Polyester resin, polyamide resin, butyral resin, polystyrene resin, nitrocellulose resin, cellulose acetate resin and the like. These binders may be used individually by 1 type, and may be used in combination of 2 or more type.

  The colorant used in the ink composition is not particularly limited. For example, carbon black (black), iron black, titanium white, antimony white, yellow lead, titanium yellow, petal, cadmium red, ultramarine, cobalt blue Inorganic pigments such as: organic pigments or dyes such as quinacridone red, isoindolinone yellow, phthalocyanine blue; metal pigments composed of scaly foils such as aluminum and brass; scaly foils such as titanium dioxide-coated mica and basic lead carbonate Examples include pearlescent (pearl) pigments composed of pieces.

  The pattern formed by the pattern layer 5 is not particularly limited. For example, a pattern that simulates the surface of a rock, such as a wood grain pattern, a marble pattern (for example, a travertine marble pattern), a cloth pattern, or a cloth-like pattern is imitated. Examples include fabric patterns, tiled patterns, brickwork patterns, and the like, which may be a pattern such as a parquet or patchwork that is a combination of these, or may be a solid color (so-called solid solid). These patterns are formed by multicolor printing with normal yellow, red, blue, and black process colors, but also by multicolor printing with special colors performed by preparing individual color plates constituting the pattern. Can be formed.

  Although the thickness in particular of the pattern layer 5 is not restrict | limited, For example, 1-30 micrometers, Preferably 1-20 micrometers is mentioned.

  Further, the pattern layer 5 may be a metal thin film layer. Examples of the metal forming the metal thin film layer include tin, indium, chromium, aluminum, nickel, copper, silver, gold, platinum, zinc, and alloys containing at least one of these. The method for forming the metal thin film layer is not particularly limited, and examples thereof include a vapor deposition method such as a vacuum vapor deposition method, a sputtering method, and an ion plating method using the above-described metal. The metal thin film layer may be provided on the entire surface or may be provided partially. Moreover, in order to improve adhesiveness with an adjacent layer, you may provide the primer layer using well-known resin in the surface and back surface of a metal thin film layer.

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

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

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

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

  The concealing layer is a normal printing method such as gravure printing, offset printing, silk screen printing, printing from a transfer sheet, inkjet printing, etc .; gravure coating, gravure reverse coating, gravure offset coating, spinner coating, roll coating, reverse roll It is formed by a normal coating method such as a coat.

[Transparent resin layer 6]
For the purpose of improving chemical resistance and scratch resistance, the transparent resin layer 6 is provided between the base material layer 1 and the surface layer 2. When the primer layer 4 is provided, the transparent resin layer 6 is provided between the base material layer 1 and the primer layer 4. 5 is provided between the pattern layer 5 and the surface layer 2, or when the primer layer 4 and the pattern layer 5 are provided in this order on the base material layer 1, between the primer layer 4 and the pattern layer 5 as required. It is a layer provided. The transparent resin layer 6 is a layer suitably provided in a decorative sheet that is integrated with a molding resin by an insert molding method.

  The resin component forming the transparent resin layer 6 is appropriately selected according to transparency, three-dimensional formability, shape stability, chemical resistance, etc., but a thermoplastic resin is usually used. The thermoplastic resin is not particularly limited, and examples thereof include acrylic resins, polyolefin resins such as polypropylene and polyethylene, polycarbonate resins, ABS resins, polyester resins such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), and vinyl chloride resins. Etc. are used. Among these thermoplastic resins, from the viewpoint of chemical resistance, scratch resistance, etc., preferably acrylic resins, polyolefin resins, polycarbonate resins, polyester resins; more preferably acrylic resins, polyester resins; more preferably polyesters. Resin.

  The transparent resin layer 6 is subjected to a physical or chemical surface treatment such as an oxidation method or an unevenness method on one side or both sides as necessary in order to improve the adhesion with other layers that are in contact with each other. May be. These physical or chemical surface treatments are the same as the surface treatments applied to the base material layer.

  Although it does not restrict | limit especially about the thickness of the transparent resin layer 6, For example, 10-200 micrometers, Preferably 15-150 micrometers is mentioned.

  The transparent resin layer 6 may be laminated via an adhesive, or may be laminated directly without using an adhesive. When laminating via an adhesive, examples of the adhesive used include polyester resin, polyether resin, polyurethane resin, epoxy resin, phenol resin resin, polyamide resin, polyolefin resin, and polyresin. Examples thereof include vinyl acetate resin, cellulose resin, (meth) acrylic resin, polyimide resin, amino resin, rubber, and silicon resin. Moreover, when laminating | stacking without using an adhesive agent, it can carry out by methods, such as an extrusion method, a sand lamination method, and a thermal lamination method.

[Back adhesive layer]
A back surface adhesive layer (not shown) is provided on the back surface (surface opposite to the surface layer 2) of the base material layer 1 for the purpose of improving the adhesion with the molding resin when molding a decorative resin molded product. The layer is provided as necessary.

  A thermoplastic resin or a curable resin is used for the back surface adhesive layer depending on the molding resin used for the decorative resin molded product.

  Examples of the thermoplastic resin used for forming the back surface adhesive layer include an acrylic resin, an acrylic-modified polyolefin resin, a chlorinated polyolefin resin, a vinyl chloride / vinyl acetate copolymer, a thermoplastic urethane resin, a thermoplastic polyester resin, and a polyamide. Examples thereof include resins and rubber resins. These thermoplastic resins may be used individually by 1 type, and may be used in combination of 2 or more type.

  Moreover, as a thermosetting resin used for formation of a back surface adhesive layer, 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.

Manufacturing method of decorating sheet The decorating sheet of this invention can be manufactured through the following 1st process and 2nd process, for example.

A first step of forming a laminate on which a surface layer made of a cured product of a resin composition having a concavo-convex shape and including a silicone ionizing radiation curable resin is laminated on the base material layer was obtained in the first step. A second step of forming an uneven protective layer on the surface layer of the laminate.

  In the first step and the second step, the components used for forming each layer, the specific conditions for the method for forming each layer, the method for forming the uneven shape of the surface layer 2, and the like are as described in the section for the composition of each layer. It is.

When forming the uneven | corrugated protective layer 3 with the laminated body of the adhesive layer 31 and the peeling film layer 30 which were formed with the adhesive agent, a 2nd process can be performed by the following processes, for example.
Applying a resin composition constituting an adhesive on the surface layer 2 and filling the concave and convex portions of the surface layer 2 to form the adhesive layer 31;
A step of laminating a release film layer 30 on the adhesive layer 31;

Moreover, when forming the uneven | corrugated protective layer 3 with the laminated body of the mold release layer 32 and the peeling film layer 30, a 2nd process can be performed by the following processes, for example.
A step of applying a resin composition constituting the release layer 32 on the surface layer 2 and filling the concave and convex portions of the surface layer 2 to form the release layer 32;
A step of laminating a release film layer 30 on the release layer 32;

Furthermore, when forming the uneven | corrugated protective layer 3 with the laminated body of the mold release layer 32, the adhesive bond layer 31, and the peeling film layer 30, a 2nd process can be performed by the following processes, for example.
A step of applying a resin composition constituting the release layer 32 on the surface layer 2 and filling the concave and convex portions of the surface layer 2 to form the release layer 32;
A step of applying the resin composition constituting the adhesive on the release layer 32 and filling the concave and convex portions of the surface layer 2 to form the adhesive layer 31;
A step of laminating a release film layer 30 on the adhesive layer 31;

Moreover, when forming the uneven | corrugated protective layer 3 with the above-mentioned cured resin layer, a 2nd process can be performed by the following processes, for example.
A step of applying a curable resin composition for forming a cured resin layer on the surface layer 2 and forming a concavo-convex protective layer so as to fill the concavo-convex recesses of the surface layer 2.

2. Uneven protective layer-decorated resin molded article uneven protective layer-decorated resin molded article of the present invention is formed is molded by integrally molding a resin in the decorative sheet of the present invention. That is, in the decorative resin molded product with an uneven protective layer of the present invention, at least the molded resin layer 7, the base material layer 1, the surface layer 2 having an uneven shape, and the peelable uneven protective layer 3 are laminated in this order. Thus, the surface layer 2 is formed of a cured product of a resin composition containing a silicone ionizing radiation curable resin. In FIG. 4, the cross-sectional structure is shown about the one aspect | mode of the decorative resin molded product with an uneven | corrugated protective layer of this invention.

  The decorative resin molded product with a concavo-convex protective layer of the present invention is, for example, various injection moldings such as insert molding, simultaneous injection molding, blow molding, and gas injection molding using the decorative sheet of the present invention. It is produced by the method. The decorative sheet of the present invention is subjected to various injection molding methods to produce a decorative resin molded product with a concave-convex protective layer, thereby exhibiting the above-described effect of suppressing the concave-convex shape from being damaged during injection molding. Therefore, as a suitable example of the molded resin layer 7 constituting the decorative resin molded product with a concave-convex protective layer of the present invention, an injection resin layer formed by injection molding can be given. 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, a resin in a fluid state is injected into the mold and solidified, and at the same time as the injection molding, a decorative sheet is formed on the outer surface of the resin molded product. By integrating the material layer 1 side, a decorative resin molded product with an uneven protective layer is produced.

  More specifically, the decorative resin molded product with an uneven protective layer 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 the vacuum forming step in the insert molding method, the decorative sheet may be heated and molded. The heating temperature at this time is not particularly limited, and may be appropriately selected depending on the type of resin constituting the decorative sheet, the thickness of the decorative sheet, and the like, for example, when an ABS resin film is used as the base material layer. For example, the temperature is usually about 100 to 250 ° C, preferably about 130 to 200 ° C. Moreover, in the integration step, the temperature of the resin in a fluid state is not particularly limited, but is usually about 180 to 320 ° C, preferably about 220 to 280 ° C.

  In addition, in the simultaneous injection molding decoration method, the decorative sheet of the present invention is placed in a female mold that also serves as a vacuum forming mold provided with a suction hole for injection molding, and preliminary molding (in-line preliminary molding) is performed with this female mold. After the injection mold is clamped, the resin in a fluid state is injected and filled into the mold and solidified, and the base material layer of the decorative sheet of the present invention is formed on the outer surface of the resin molding simultaneously with the injection molding By integrating the one side, a decorative resin molded product with a concavo-convex protective layer is produced.

  More specifically, the decorative resin molded product with a concavo-convex protective layer 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. In the injection molding process, the temperature of the resin in the fluidized state is not particularly limited, but is usually about 180 to 320 ° C, preferably about 220 to 280 ° C.

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

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

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

  In the decorative resin molded product with a concave-convex protective layer of the present invention, the molded resin layer may be formed by selecting a molded resin according to the application. The molding resin 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 concave / convex protective layer from the decorative resin molded product with the concave / convex protective layer of the present invention. In addition, in a decorative resin molded product with a concavo-convex protective layer, the concavo-convex protective layer plays a role as a protective sheet for the decorative resin molded product, so it is stored as it is without being peeled after manufacturing, 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. Decorative resin molded product By removing the concavo-convex protective layer 3 from the decorative resin molded product with the concavo-convex protective layer, a decorative resin molded product having a concavo-convex shape on the surface is obtained. When the support is peeled and removed from the decorative resin molded product with a concave-convex protective layer, the surface layer 2 appears on the surface of the decorative resin molded product, and an excellent design feeling and touch feeling are expressed by the concave-convex shape. In FIG. 5, the cross-sectional structure is shown about the one aspect | mode of the decorative resin molded product from which the uneven | corrugated protective layer 3 was removed.

  Since the decorative resin molded product of the present invention has an excellent design feeling and touch feeling due to the uneven shape, for example, interior or exterior materials for vehicles such as automobiles; It can be used as fittings 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; containers and the like.

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

[Manufacture of decorative sheets]
Example 1
An ABS resin film (thickness: 200 μm) was used as the base material layer. A woodgrain pattern layer (thickness: 5 μm) was formed on the base material layer by gravure printing using an ink composition containing an acrylic resin. A primer layer resin composition comprising a binder resin composed of a two-component curable resin containing 100 parts of a main agent (acrylic polyol / urethane, mass ratio 9/1) and 7 parts of a curing agent (hexamethylene diisocyanate) on a pattern layer. It was applied and dried to form a primer layer having a thickness of 2 μm, and a laminate in which a base material layer / picture layer / primer layer was laminated in order was obtained.

  Embossing was performed on the primer layer side of the laminate obtained above to form a concavo-convex shape of a dot pattern on the primer layer. The embossed plate depth (height from the bottom of the concave portion to the top surface of the convex portion) of the embossed plate used for embossing is 60 μm. Next, the ionizing radiation curable resin composition (EB2) shown in Table 1 was applied on the primer layer on which the uneven shape was formed so that the thickness after curing was 8 μm. This resin composition was cured by irradiation with an acceleration voltage of 165 kV and an irradiation dose of 50 kGy (5 Mrad) to form a surface layer having an uneven shape.

  Next, the ionizing radiation curable resin composition (EB3) described in Table 1 was applied on the surface layer having an uneven shape so that the thickness after curing was 10 μm. This resin composition was cured by irradiation with an acceleration voltage of 165 kV and an irradiation dose of 50 kGy (5 Mrad) to form a release layer on the surface layer.

  Next, an adhesive made of a polyester resin composition is applied onto the release layer so that the thickness after curing is 30 μm, and the concave and convex portions of the surface layer are filled so that the adhesive layer Formed. Next, a release film layer (polyethylene film, thickness 30 μm) is laminated on the adhesive layer, and then a base layer / picture layer / primer layer / surface layer with uneven shape / uneven protective layer (release) Layer / adhesive layer / release film layer) was laminated in order to obtain a decorative sheet having a laminated structure.

Example 2
In the same manner as in Example 1, a surface layer having a concavo-convex shape was formed on a laminate in which a base material layer / picture layer / primer layer were laminated in order. Next, a release layer was laminated on the surface layer in the same manner as in Example 1. Furthermore, a pressure-sensitive adhesive sheet (thickness 75 μm) made of a polypropylene base material coated with an acrylic pressure-sensitive adhesive is laminated thereon, and a base material layer / picture layer / primer layer / surface layer with concave / convex shape / concave / convex protection A decorative sheet having a laminated structure in which layers (release layer / adhesive sheet) were sequentially laminated was obtained.

Example 3
In the same manner as in Example 1, a surface layer having a concavo-convex shape was formed on a laminate in which a base material layer / picture layer / primer layer were laminated in order. Next, the ionizing radiation curable resin composition (EB3) shown in Table 1 was applied on the surface layer so that the thickness after curing was 10 μm. The resin composition is irradiated with an acceleration voltage of 165 kV and an irradiation dose of 50 kGy (5 Mrad) to be cured to form a concavo-convex protective layer (cured resin layer). A decorative sheet having a laminated structure in which protective layers (cured resin layers) were sequentially laminated was obtained.

Example 4
In the same manner as in Example 1, a surface layer having a concavo-convex shape was formed on a laminate in which a base material layer / picture layer / primer layer were laminated in order. Next, a polyethylene layer is formed on the surface layer having an uneven shape by extrusion, so that the base layer / the pattern layer / the primer layer / the surface layer having the uneven shape / the uneven protective layer (polyethylene layer) are sequentially formed. A decorative sheet having a laminated structure was obtained. In addition, as conditions for extrusion molding, the temperature under the die of the extruder was 230 to 250 ° C., and the thickness of the polyethylene layer was 50 μm.

Comparative Example 1
An acrylic resin film (thickness 75 μm) was used as the surface layer. A woodgrain pattern layer (thickness: 5 μm) was formed on the surface layer by gravure printing using an ink composition containing an acrylic resin. An ABS resin film (thickness: 200 μm) as a base material layer was laminated on the pattern layer. Next, the surface on the surface layer side of the obtained laminate was embossed using the same emboss plate as in Example 1 to form a concavo-convex shape of a dot pattern on the surface layer. Next, as in Example 4, a concavo-convex protective layer (polyethylene layer) is formed on the concavo-convex surface layer, and the base layer / the pattern layer / the concavo-convex surface layer / the concavo-convex protective layer are sequentially laminated. A decorative sheet having a laminated structure was obtained.

Comparative Example 2
In the same manner as in Comparative Example 1, a laminate in which a base layer / a pattern layer / a surface layer having an uneven shape was sequentially laminated was obtained. Next, an adhesive composed of a polyester resin composition is applied onto the surface layer so that the thickness after curing is 50 μm, and the concave and convex portions of the surface layer are filled to form an adhesive layer. Formed. Next, the release film layer is laminated from above the adhesive layer, and the base layer / the pattern layer / the surface layer having an uneven shape / the uneven protective layer (adhesive layer / release film layer) in this order. A decorative sheet having a laminated structure was obtained.

Comparative Example 3
In the same manner as in Example 1 except that the surface layer was formed using the ionizing radiation curable resin composition (EB1) shown in Table 1, the surface layer having the base material layer / picture layer / primer layer / uneven shape was formed in this order. A laminated body was obtained. Next, as in Comparative Example 2, a pressure-sensitive adhesive layer and a release film layer were laminated on the surface layer, and a base layer / picture layer / primer layer / surface layer having an uneven shape / uneven protective layer (adhesion) A decorative sheet having a layered structure in which (layering layer / release film layer) was sequentially laminated was obtained.

[Manufacture of decorative resin molded products]
Each decorative sheet was heated to 160 ° C. with an infrared heater and softened. Next, vacuum forming was performed using a vacuum forming die (maximum draw ratio: 100%), preformed along the internal shape of the die, and clamped. Thereafter, a mixed resin of polycarbonate and ABS was injected into the cavity of the mold, and the decorative sheet and the molding resin were integrally molded to obtain a decorative resin molded product with an uneven protective layer. Subsequently, the decorative resin molded product was obtained by peeling the concave / convex protective layer by hand from the obtained decorative resin molded product with the uneven protective layer.

<Evaluation of uneven shape>
In order to evaluate the uneven shape of the surface of the decorative resin molded product, the center line average roughness (Ra), maximum, using a surface roughness / contour shape measuring machine (Hardy Surf E-35A manufactured by Tokyo Seimitsu Co., Ltd.) The height (Rmax) and the ten-point average height (Rz) were measured. The results are shown in Table 1.

<Evaluation of uneven shape of decorative sheet>
In the manufacturing process of the decorative sheet of the example and the comparative example, the unevenness feeling was evaluated visually and by hand with respect to the change in the uneven shape of the surface layer before and after forming the unevenness protection layer. In addition, peeling of the uneven | corrugated protective layer from a decorating sheet was performed by peeling an uneven | corrugated protective layer from a decorating sheet by hand. The evaluation criteria are as follows. The results are shown in Table 1.
◯: Almost no change in unevenness.
(Triangle | delta): Although the uneven | corrugated feeling changed, even if it peels after forming an uneven | corrugated protective layer, an uneven | corrugated feeling is felt.
X: A feeling of unevenness is greatly changed, and the feeling of unevenness is not felt after the unevenness protection layer is peeled off.

<Evaluation of uneven shape of decorative resin molded product>
About the change of the uneven | corrugated shape before and behind manufacturing a decorative resin molded product from each decorative sheet, the uneven | corrugated feeling was evaluated visually and the touch. The evaluation criteria are as follows. The results are shown in Table 1.
◯: Even after making a decorative resin molded product, there is almost no change in the uneven feeling, and the uneven feeling is strongly felt.
(Triangle | delta): After setting it as a decorative resin molded product, although the uneven | corrugated feeling changed, the decorative resin molded product can also feel an unevenness | corrugation.
X: After making a decorative resin molded product, the uneven feeling greatly changes, and the decorative resin molded article does not feel the unevenness.

<Peeling workability of uneven protective layer>
The workability when the concave / convex protective layer was peeled off from the decorative resin molded product with the concave / convex protective layer was evaluated according to the following criteria.
(Double-circle): By applying a fixed force, the uneven | corrugated protective layer could be peeled in the state of one film | membrane, and all the uneven | corrugated protective layers could be peeled easily by one peeling operation | work.
A: By applying a certain force, the concave / convex protective layer could be peeled in a single film state, and all the concave / convex protective layers could be peeled off by a single peeling operation.
X: Although the uneven | corrugated protective layer was able to be peeled by applying a fixed force, the uneven | corrugated protective layer was not able to be peeled in the state of one film | membrane, but the peeling operation | work of multiple times was required.

  In Table 1, “-” in the item of adhesion between the surface layer and the uneven protective layer indicates that the surface layer and the uneven protective layer are directly laminated, and “in the surface roughness item of the decorative resin molded product”. “-” Indicates that no measurement was performed.

EB1
Bifunctional polycarbonate acrylate (weight average molecular weight; 10,000): 95 parts by mass Tetrafunctional urethane acrylate oligomer (weight average molecular weight; 6,000): 5 parts by mass
EB2
Bifunctional polycarbonate acrylate (weight average molecular weight; 8,000): 95 parts by mass Bifunctional silicone acrylate oligomer (weight average molecular weight; 6,000): 5 parts by mass
EB3
Trifunctional pentaerythritol acrylate (weight average molecular weight; 300): 30 parts by mass Acrylic polymer (weight average molecular weight 120,000): 70 parts by mass
Polyester resin composition for adhesive layer Polyester polyol: isocyanate = 100: 10
Extruded grade low density PE extruded in Example 4 and Comparative Example 1
Polyethylene film heat-laminated in Comparative Example 3 Low density PE film

DESCRIPTION OF SYMBOLS 1 Base material layer 2 Surface layer 3 Concavity and convexity protective layer 4 Primer layer 5 Picture layer 6 Transparent resin layer 7 Molding resin layer 30 Peeling film layer 31 Adhesive layer 32 Release layer

Claims (14)

At least, a base material layer, a surface layer having an uneven shape, and a peelable uneven protective layer are laminated in this order,
The surface layer is formed of a cured product of a resin composition containing a silicone ionizing radiation curable resin ,
The silicone-based ionizing radiation curable resin, Ru least one der silicone (meth) acrylate and a silicone-modified urethane (meth) acrylate, the decorative sheet.   The decorative sheet according to claim 1, wherein the uneven protective layer is formed of a cured product of an ionizing radiation curable resin composition.   The decorative sheet according to claim 1, wherein the uneven protective layer includes an adhesive layer and a release film in order from the surface layer side.   The decorative sheet according to claim 1, wherein the uneven protective layer includes a release layer, an adhesive layer, and a release film layer in order from the surface layer side.   The decorative sheet according to claim 3 or 4, wherein the adhesive layer fills the concave and convex portions of the surface layer.   The decorative sheet according to any one of claims 1 to 5, wherein a primer layer is laminated directly under the surface layer.   The decorative sheet according to any one of claims 1 to 6, wherein a pattern layer is laminated between the base material layer and the surface layer. The decorating sheet according to any one of claims 1 to 7, wherein a ratio of the silicone ionizing radiation curable resin in the resin composition forming the surface layer is 1 to 10% by mass. A first step of forming a laminate in which a surface layer made of a cured product of a resin composition having a concavo-convex shape and containing a silicone ionizing radiation curable resin is laminated on a base material layer;
A second step of forming an uneven protective layer on the surface layer of the laminate obtained in the first step;
Equipped with a,
The silicone-based ionizing radiation curable resin, Ru least one der silicone (meth) acrylate and a silicone-modified urethane (meth) acrylate, method of manufacturing the decorative sheet. The method for producing a decorative sheet according to claim 9 , wherein the second step includes the following steps.
A step of forming a concavo-convex protective layer by applying a curable resin composition on the surface layer and filling the concavo-convex recesses of the surface layer. The method for producing a decorative sheet according to claim 9 , wherein the second step includes the following steps.
Applying a resin composition on the surface layer and filling the concave and convex portions of the surface layer to form an adhesive layer;
A step of laminating a release film layer on the adhesive layer At least, a molded resin layer, a base material layer, a surface layer having an uneven shape, and a peelable uneven protective layer are laminated in this order,
The surface layer is formed of a cured product of a resin composition containing a silicone ionizing radiation curable resin ,
The silicone-based ionizing radiation curable resin, silicone (meth) acrylate and Ru at least one Der silicone-modified urethane (meth) acrylate, uneven protective layer-decorated resin molded article. The manufacturing method of the decorative resin molded product with an uneven | corrugated protective layer provided with the process of forming a molded resin layer by injecting resin in the base material layer side of the decorating sheet in any one of Claims 1-8 . The manufacturing method of a decorative resin molded product provided with the process of peeling an uneven | corrugated protective layer from the decorative resin molded product with an uneven | corrugated protective layer of Claim 12 .