JP6232879B2 - Transfer sheet and covering member using the same - Google Patents

Description

  The present invention relates to a transfer sheet and a covering member using the transfer sheet. Specifically, the transfer sheet of the present invention comprises a transfer substrate and a transfer layer, and by transferring the transfer layer to various transferred members such as building members, the weather resistance, solvent resistance, Gives features such as decorativeness.

  Conventionally, many metal members are used as building members such as window frames and bath walls, but the demand for resin molded products is increasing for the purpose of improving heat insulation. However, resin-molded members have poor design properties, and surface properties such as weather resistance and solvent resistance are insufficient as they are.

  In order to improve the above problems, there is a method of wrapping a decorative sheet using a polyolefin resin on the surface of a resin molded member, but the organic mass of the resin molded member increases due to wrapping, which reduces nonflammability. There is a problem. Therefore, as a method for suppressing an increase in organic mass, a method of applying a surface protective layer or a design layer to a resin molded member by a transfer method has been proposed.

  However, the conventional transfer sheet (also referred to as transfer foil) has a problem that cracks are likely to occur when transferred to a resin molded member having a complicated shape. Further, when the resin molding member is a thermoplastic resin having a large thermal expansion and contraction such as a product made of vinyl chloride, there is a problem that the transfer sheet cannot follow the thermal expansion and contraction of vinyl chloride after the transfer and thus cracks are likely to occur.

  For example, Patent Documents 1 and 2 are known as conventional transfer foils.

  Patent Document 1 discloses a hard coat transfer foil. Specifically, the claim 1 states that “a hard coat layer composed of a hard ionizing radiation curable resin and a hard ion composed of a soft ionizing radiation curable resin on one surface of a peelable substrate sheet”. A hard code transfer foil characterized by laminating a coat layer in the order described here is disclosed. Further, in claim 2, “the hard coat transfer foil according to claim 1, wherein the thickness of the hard hard coat layer is 0.1 to 2 μm and the thickness of the soft hard coat layer is 1 to 50 μm”. It is disclosed. The action of the transfer foil is as follows: “Since the hard hard coat layer on the surface is thin, the cracks generated are not recognized with the naked eye and there is no problem in appearance. Further, the crack part is in close contact with the soft hard coat layer below. In addition, the substrate and the pattern to be protected are sufficiently protected because they are covered with an internal soft hard coat layer that does not cause cracks. (Lower left column on page 2).

  However, in the transfer foil of Patent Document 1, since the hard hard coat layer is thin, it is described that cracks that occur are not recognized with the naked eye and there is no problem with appearance, but even if it is an inconspicuous crack, long-term durability is achieved. In view of this, it is insufficient and there is room for improvement.

  Claim 1 of Patent Document 2 states that “a transfer foil in which a siloxane-based resin layer and an acrylic resin layer are formed in this order on the release surface of a base sheet, and the resin of the acrylic resin layer is made of glass A transfer foil having a transition point of 80 ° C. or more and a weight average molecular weight of 50,000 or more is disclosed.

  However, since the transfer foil of Patent Document 2 has a hard siloxane-based resin layer, it tends to be detached from the base sheet. In addition, in order to suppress the occurrence of cracks in the siloxane resin layer during transfer, it is disclosed that a relatively flexible acrylic resin layer is provided as a thick film and used as a buffer layer. However, the performance is still insufficient to transfer to the surface.

Japanese Patent Application No. 1-268021 Japanese Unexamined Patent Publication No. 8-195298

  An object of the present invention is to provide a transfer sheet having performances such as scratch resistance and stain resistance, and excellent in processability and long-term durability when transferred to a transfer member having a complicated shape. To do. It is another object of the present invention to provide a covering member obtained by transferring a transfer layer of a transfer sheet to a transfer target member.

  As a result of intensive studies, the present inventors have found that the above object can be achieved by a transfer sheet in which a specific surface protective layer is laminated on a transfer substrate, and have completed the present invention.

That is, the present invention relates to the following transfer sheet and a covering member using the same.
1. On the transfer substrate, as a transfer layer, at least a surface protective layer and a primer layer are laminated in that order,
(1) The surface protective layer has a thickness is 5 to 20 [mu] m, and Martens hardness 30~110N / mm are ^two der,
(2) The surface protective layer is a cured product of a coating film of a composition for forming a surface protective layer containing an ionizing radiation curable resin and a non-crosslinked acrylic polymer, and the coating film is cured by irradiation with ionizing radiation. The body,
A transfer sheet characterized by that.
2 . The non-crosslinked acrylic polymer is at least one monomer selected from the group consisting of N- (meth) acryloyloxyethylhexahydroimide, 2-hydroxy-3-phenoxypropyl (meth) acrylate and isobornyl (meth) acrylate. Item 2. The transfer sheet according to Item 1 , which is a polymer of
3 . Item 3. The transfer sheet according to Item 1 or 2 , wherein the non-crosslinked acrylic polymer has a weight average molecular weight of 4000 to 6000.
4 . Item 4. The transfer sheet according to any one of Items 1 to 3 , wherein the non-crosslinked acrylic polymer has a glass transition temperature of 10 to 75 ° C.
5 . Item 5. The transfer sheet according to any one of Items 1 to 4 , wherein the surface protective layer contains a polyester resin.
6 . Item 6. The transfer sheet according to any one of Items 1 to 5 , wherein a decorative layer is laminated on the primer layer.
7 . Item 7. The transfer sheet according to any one of Items 1 to 6 , wherein the transfer substrate contains at least one of polyethylene terephthalate and polypropylene.
8 . A covering member obtained by transferring the transfer layer of the transfer sheet according to any one of Items 1 to 7 onto a transfer member.
9 . Item 9. The covering member according to Item 8 , wherein the material of the member to be transferred is at least one selected from the group consisting of inorganic non-metallic materials, metallic materials, woody materials, and plastic materials.

  Hereinafter, the transfer sheet of the present invention and a covering member using the same will be described.

Transfer sheet The transfer sheet of the present invention, on the transfer substrate, as a transfer layer, at least a surface protective layer and a primer layer are laminated in that order,
The surface protective layer has a layer thickness of 5 to 20 μm and a Martens hardness of 30 to 110 N / mm ² .

  In the transfer sheet of the present invention, at least a surface protective layer and a primer layer are laminated in this order as a transfer layer on a transfer substrate, and the transfer layer is transferred to various shapes of transferred members (such as building materials of various materials). Then, it is used by the method of peeling a transfer base material. That is, after the transfer layer is transferred to the transfer member, the transfer substrate is peeled off, so that the surface protective layer is located on the outermost layer of the transfer layer that covers the transfer member. The transfer sheet of the present invention exhibits performance such as scratch resistance and contamination resistance by having a surface protective layer, and the surface protective layer has a specific thickness and physical properties, so that it has a complicated shape. Excellent processability and long-term durability when transferring to a transfer member.

  The layer structure of the transfer sheet of the present invention is not particularly limited as long as at least the surface protective layer and the primer layer are laminated in this order on the transfer substrate. For example, as shown in FIG. A layer configuration in which the surface protective layer 2, the primer layer 3, the pattern layer 4, and the colored hiding layer 5 are laminated in this order can be exemplified. In the description of the transfer sheet, the direction in which the surface protective layer and the primer layer are located when viewed from the transfer substrate is referred to as “up” or “front surface”, and the opposite direction as viewed from the transfer substrate. Is referred to as “bottom” or “back”.

  When transferring the transfer layer of the transfer sheet of the present invention to the member to be transferred, an adhesive layer 6 is prepared between the member to be transferred 7 and the transfer sheet, as shown in FIG. The transfer layer is transferred so that the layer 5 is in contact with the adhesive layer 6. Thereafter, the surface protective layer 2 is positioned on the outermost layer of the transfer layer that covers the member 7 to be transferred by peeling the transfer substrate 1 from the transfer layer.

  Hereinafter, for each layer constituting the transfer sheet of the present invention, as illustrated in FIG. 1, a surface protective layer, a primer layer, a pattern layer, and a colored masking layer are laminated in that order on the transfer substrate. The layer configuration will be described as an example.

(Transfer substrate)
As a transfer substrate, it has releasability, and a wide range of conventionally known transfer substrates for transfer sheets can be used. When the surface of the member to be transferred is a flat or two-dimensional uneven surface, the transfer substrate may be paper having no stretchability, but when the surface of the member to be transferred is a three-dimensional uneven surface, It is preferable to use a transfer substrate having stretchability.

  Examples of the transfer substrate having stretchability include thermoplastic polyester films such as polyethylene terephthalate film and polybutylene terephthalate film; polypropylene film, polyethylene film, polymethylpentene film, ethylene-propylene copolymer film, ethylene-propylene -Polyolefin films such as butene terpolymer films and olefin thermoplastic elastomer films; resin films (sheets) such as vinyl chloride resin films and polyamide resin films.

  These resin films may be stretched, but those having low stretching or non-stretching are preferred in that stretchability during transfer is easily obtained. As the transfer substrate, these resin films may be used alone or in combination of two or more.

  In the present invention, among these resin films, a transfer substrate containing at least one of polyethylene terephthalate and polypropylene is preferable, and the transfer substrate may be stretched as necessary.

  The thickness of the transfer substrate is not limited, but is usually preferably about 10 to 200 μm, more preferably about 20 to 60 μm.

  If necessary, the transfer substrate may be provided with a known release layer in order to improve the peelability on the side where the transfer layer is laminated. Examples of the component of the release layer include silicone resin, melamine resin, polyamide resin, urethane resin, polyolefin resin, and wax. These components can be used alone or in admixture of two or more. The release layer can be formed by applying the peelable resin component to the surface of the transfer substrate. The component and thickness of the release layer can be appropriately set according to the characteristics of the transfer sheet of the final product.

(Surface protective layer)
A surface protective layer is laminated on the transfer substrate. In the present invention, the surface protective layer has a layer thickness of 5 to 20 μm and a Martens hardness of 30 to 110 N / mm ² . When the transfer sheet has a decorative layer, the surface protective layer is preferably transparent so that the decorative layer can be visually recognized through the surface protective layer after the transfer layer is transferred.

The resin constituting the surface protective layer is not particularly limited as long as the surface protective layer having a film thickness of 5 to 20 μm and a Martens hardness of 30 to 110 N / mm ² can be formed. For example, an ionizing radiation curable resin A two-component curable urethane resin can be used. These resins can be used alone or in admixture of two or more. When using at least one of an ionizing radiation curable resin and a two-component curable urethane resin, it is easy to ensure effects such as scratch resistance and contamination resistance.

  The ionizing radiation curable resin is not particularly limited, and a prepolymer (including an oligomer) and / or a monomer containing a functional group capable of undergoing a polymerization and crosslinking reaction by irradiation with ionizing radiation such as ultraviolet rays and electron beams as a main component. A transparent resin can be used. These prepolymers or monomers can be used alone or in combination. The curing reaction is usually a cross-linking curing reaction.

  Specifically, as the prepolymer or monomer, a compound having in the molecule a radically polymerizable unsaturated group such as a (meth) acryloyl group or (meth) acryloyloxy group, or a cationically polymerizable functional group such as an epoxy group. Is mentioned. Further, a polyene / thiol prepolymer based on a combination of polyene and polythiol is also preferable. Here, the (meth) acryloyl group means an acryloyl group or a methacryloyl group, and the same applies to other portions described as (meth).

  Examples of the prepolymer having a radically polymerizable unsaturated group include polyester (meth) acrylate, urethane (meth) acrylate, epoxy (meth) acrylate, melamine (meth) acrylate, triazine (meth) acrylate, and silicone (meth) acrylate. Etc. These molecular weights are usually 250 or more and less than 3000.

  As a monomer which has a radically polymerizable unsaturated group, methyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, phenoxyethyl (meth) acrylate etc. are mentioned as a monofunctional monomer, for example. Examples of the polyfunctional monomer include diethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane ethylene oxide tri (meth) acrylate, dipentaerythritol tetra ( And (meth) acrylate, dipentaerythritol penta (meth) acrylate, and dipentaerythritol hexa (meth) acrylate.

  Examples of the prepolymer having a cationic polymerizable functional group include prepolymers of epoxy resins such as bisphenol type epoxy resins and novolac type epoxy compounds, and vinyl ether type resins such as fatty acid type vinyl ethers and aromatic vinyl ethers. Examples of the thiol include polythiols such as trimethylolpropane trithioglycolate and pentaerythritol tetrathioglycolate. Examples of the polyene include those in which allyl alcohol is added to both ends of polyurethane by diol and diisocyanate.

  As the ionizing radiation used for curing the ionizing radiation curable resin, electromagnetic waves or charged particles having energy capable of causing a curing reaction of molecules in the ionizing radiation curable resin (composition) are used. Usually, ultraviolet rays or electron beams may be used, but visible light, X-rays, ion rays, or the like may be used.

  As the ultraviolet light source, for example, a light source such as an ultra-high pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc lamp, a black light, a metal halide lamp can be used. As a wavelength of ultraviolet rays, 190 to 380 nm is usually preferable.

  As the electron beam source, for example, various electron beam accelerators such as a cockcroft Walton type, a bandegraft type, a resonant transformer type, an insulated core transformer type, a linear type, a dynamitron type, and a high frequency type can be used. Among these, those capable of irradiating electrons having energy of 100 to 1000 keV, preferably 100 to 300 keV are preferable.

In the transfer sheet of the present invention, the surface protective layer has a thickness of 5 to 20 μm, and preferably 5 to 15 μm. The Martens hardness of the surface protective layer is 30 to 110 N / mm ² , and 70 to 110 N / mm ² is preferable among them.

  The Martens hardness can be appropriately set by 1) mixing two or more ionizing radiation curable resins having different hardnesses, 2) mixing an elastomer with the ionizing radiation curable resin, and the like. It is also possible to adjust the Martens hardness to a desired value by changing the number of polymerizable functional groups in one molecule or using a mixture of ionizing radiation curable resins having different functional groups. it can.

In addition, the Martens hardness in this specification is a value measured using a surface film physical property tester (PICODENTOR HM-500, manufactured by Fisher Instruments Co., Ltd.), and a specific measurement method is as follows. is there. In this measurement method, using the diamond indenter (Vickers indenter) shown in Fig. 3 (a), the diamond indenter was pushed into the measurement sample as shown in Fig. 3 (b), and the diagonal line of the pyramid-shaped depression formed on the surface The surface area A (mm ² ) is calculated from the length of and the hardness is obtained by dividing the test load F (N). As shown in FIG. 3 (c), the indentation conditions were as follows. First, a load of 0 to 5 mN was applied for 10 seconds, then 5 mN was maintained for 5 seconds, and finally 5 Unloading to ~ 0 mN in 10 seconds. And the hardness calculated | required by F / A based on the surface area A and the test load F is the said Martens hardness. In addition, in this specification, in order to avoid the influence of the hardness of layers other than a surface protective layer, the Martens hardness of the cross section of the surface protective layer was measured. At this time, the transfer sheet is embedded with a resin (cold-curing type epoxy two-component curable resin), allowed to stand at room temperature for 24 hours or more and cured, and then the cured embedded sample is mechanically polished to provide a surface protective layer. The cross section was exposed, and the Martens hardness of the cross section was measured by pushing a diamond indenter into the cross section (at a position avoiding the fine particles such as inorganic filler in the surface protective layer).

  In the present invention, since the surface protective layer has a specific layer thickness and Martens hardness, not only has the basic performance as a surface protective layer such as scratch resistance and stain resistance, but also a member having a complicated shape. It also has excellent processability and long-term durability when transferring the transfer layer. That is, when the transfer layer is transferred to a transfer member having a complicated shape, the surface protection layer is not easily cracked, and the followability of the surface protection layer is excellent even when the transfer member is thermally expanded and contracted after transfer. Cracks do not easily occur during thermal expansion and contraction of the transfer member, and are excellent in long-term durability.

  The surface protective layer preferably contains a polyester resin as necessary. By containing a polyester resin, the intermolecular force between the surface protective layer and the transfer substrate is increased and the adhesion is improved. Therefore, even when the transfer layer is transferred to a substrate having a complicated shape, the surface protective layer Foil spills and cracks are less likely to occur at the bent part of

  The content of the polyester resin is not limited, but when using untreated PET (PET that has not been subjected to surface treatment such as corona treatment) as a transfer substrate, the ionizing radiation curable resin contained in the surface protective layer and About 0.1 to 3.0 parts by mass is preferable with respect to 100 parts by mass of the total mass of the non-crosslinked acrylic polymer. If the polyester resin content exceeds 3 parts by mass, the adhesion strength between the surface protective layer and the transfer substrate may exceed the adhesion strength between the surface protective layer and the primer layer, which may make transfer processing difficult. is there.

  In addition, the surface protective layer may contain known additives such as anti-mold agents (ultraviolet absorbers, light stabilizers), plasticizers, stabilizers, fillers, dispersants, dyes, pigments and the like, and solvents. Good.

  Examples of weathering agents (ultraviolet absorbers) include benzophenone ultraviolet absorbers, benzotriazole ultraviolet absorbers, and triazine ultraviolet absorbers. As the light stabilizer, for example, a hindered amine light stabilizer is suitable. The content of these weathering agents is not limited, but both the ultraviolet absorber and the light stabilizer may be about 1000 to 10,000 mass ppm in the surface protective layer.

  The surface protective layer is formed by, for example, applying an ionizing radiation curable resin (or a resin composition containing an ionizing radiation curable resin) onto a transfer substrate by a known coating method such as gravure coating or roll coating, followed by ionization. It can be formed by curing the resin by irradiation with radiation.

In the present invention, the surface protective layer may be a single layer or may be a multilayered structure of two or more layers. For example, in the case of a two-layer configuration, the surface protective layer may be formed by laminating the first surface protective layer and the second surface protective layer from the transfer substrate side. In the case of a plurality of laminates of two or more layers, the Martens hardness of each surface protective layer is 30 to 110 N / mm ² and the total thickness of each surface protective layer is 5 to 20 μm. Set.

  When the surface protective layer has a two-layer structure, the first surface protective layer has a Martens hardness that is greater than the Martens hardness of the second surface protective layer. Characteristics can be imparted, and processability characteristics can be imparted to the second surface protective layer.

  In the present invention, when an ionizing radiation curable resin is used as the resin constituting the surface protective layer, it further contains a non-crosslinked acrylic polymer in terms of improving transfer sheet manufacturing efficiency and transfer sheet flexibility. Is preferred. In this case, the surface protective layer is obtained by obtaining a coating film of the composition for forming a surface protective layer containing an ionizing radiation curable resin and a non-crosslinked acrylic polymer, and then curing the coating film by irradiation with ionizing radiation. Can be formed. That is, the non-crosslinked acrylic polymer already exists as a polymer in the composition for forming the surface protective layer, and is present around the non-crosslinked acrylic polymer in the ionizing radiation irradiation step for completing the surface protective layer. The ionizing radiation curable resin as the matrix to be cured is cured (crosslinked).

  Examples of non-crosslinked acrylic polymers include polymers obtained by polymerizing monomers having radically polymerizable unsaturated groups such as (meth) acryloyl groups and (meth) acryloyloxy groups in the molecule, and polyester (meth) acrylates. , Urethane (meth) acrylate, epoxy (meth) acrylate, melamine (meth) acrylate, triazine (meth) acrylate, silicone (meth) acrylate and the like polymerized. Among these, at least one monomer selected from the group consisting of N- (meth) acryloyloxyethyl hexahydroimide, 2-hydroxy-3-phenoxypropyl (meth) acrylate and isobornyl (meth) acrylate is polymerized. Is preferred.

  When the surface protective layer contains the non-crosslinked acrylic polymer, the adhesion between the surface protective layer and the primer layer laminated thereon can be further improved. In addition, the flexibility of the transfer sheet can be improved to improve the processability during transfer. Moreover, since the tack (viscosity) of the coating film of the composition for forming a surface protective layer that has not been cured (before irradiation with ionizing radiation) can be reduced by containing a non-crosslinked acrylic polymer, ionizing radiation curable resin When laminating two or more layers, there is no need to irradiate each layer with ionizing radiation, and after laminating multiple layers of coatings and the primer layer thereon, inline, multiple layers of ionizing radiation by one ionizing radiation irradiation This is preferable in that the radiation curable resin layer can be cured.

  The content of the non-crosslinked acrylic polymer is not limited as long as the above effects can be obtained. In particular, the ionizing radiation curable resin and the non-crosslinked acrylic polymer have the effect of reducing the tack of the uncured coating film. The total mass is 100% by mass, preferably 40% by mass or more, and more preferably 40-60% by mass.

  The non-crosslinked acrylic polymer preferably has a weight average molecular weight of 4000 to 6000, and more preferably 4000 to 5000. Further, the non-crosslinked acrylic polymer preferably has a glass transition temperature (Tg) of 10 to 75 ° C, more preferably 10 to 60 ° C. By using a non-crosslinked acrylic polymer having a weight average molecular weight and a glass transition temperature within such a range, the effect of alleviating the tack of the coating film can be easily obtained.

(Primer layer)
A primer layer for facilitating adhesion between the surface protective layer and the member to be transferred or the decorative layer is laminated on the surface protective layer.

  The primer layer can be formed by applying a known primer agent to the surface protective layer. Examples of the primer agent include a urethane resin primer agent made of acrylic modified urethane resin, a primer agent made of urethane-cellulose resin (for example, a resin made by adding hexamethylene diisocyanate to a mixture of urethane and nitrified cotton), and the like. Is mentioned. Among these, when the ionizing radiation curable resin of the surface protective layer contains an acrylic polymer, the primer agent is methyl ethyl ketone (MEK), ethyl acetate or the like in terms of further improving the adhesion between the surface protective layer and the primer layer. It is preferable that it contains a solvent.

  Although the thickness of a primer layer is not specifically limited, Usually, 0.1-10 micrometers, Preferably it is about 1-5 micrometers.

  A decorative layer can be formed on the primer layer. Examples of the decorative layer include a pattern layer and / or a colored hiding layer. Hereinafter, the decorative layer will be described.

(Pattern pattern layer)
A pattern layer can be formed on the primer.

  The design pattern layer imparts design properties with a desired design to the transfer sheet, and the type of design is not particularly limited. Examples thereof include a wood grain pattern, a stone pattern, a grain pattern, a tiled pattern, a brickwork pattern, a cloth pattern, a leather pattern, a geometric figure, a character, a symbol, and an abstract pattern.

  The method for forming the pattern layer is not particularly limited. For example, a colored ink or coating obtained by dissolving (or dispersing) a known colorant (dye or pigment) in a solvent (or dispersion medium) together with a binder resin. What is necessary is just to form by the printing method etc. which used the agent.

  Examples of colorants include inorganic pigments such as carbon black, titanium white, zinc white, dial, bitumen, cadmium red; azo pigments, lake pigments, anthraquinone pigments, quinacridone pigments, phthalocyanine pigments, isoindolinone pigments, dioxazine pigments. Organic pigments such as aluminum powder, metal powder pigments such as bronze powder, pearlescent pigments such as titanium oxide-coated mica and bismuth oxide chloride; fluorescent pigments; These colorants can be used alone or in admixture of two or more. These colorants may further contain fillers such as silica, extender pigments such as organic beads, neutralizing agents, surfactants and the like.

  Examples of the binder resin include acrylic resin, styrene resin, polyester resin, urethane resin, chlorinated polyolefin resin, vinyl chloride-vinyl acetate copolymer resin, polyvinyl butyral resin, alkyd resin, petroleum Resin, ketone resin, epoxy resin, melamine resin, fluorine resin, silicone resin, fiber derivative, rubber resin and the like. These resins can be used alone or in combination of one or more.

  Examples of the solvent (or dispersion medium) include petroleum organic solvents such as hexane, heptane, octane, toluene, xylene, ethylbenzene, cyclohexane, and methylcyclohexane; ethyl acetate, butyl acetate, acetic acid-2-methoxyethyl, acetic acid-2 -Ester-based organic solvents such as ethoxyethyl; alcohol-based organic solvents such as methyl alcohol, ethyl alcohol, normal propyl alcohol, isopropyl alcohol, isobutyl alcohol, ethylene glycol, propylene glycol; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone Organic solvents; ether organic solvents such as diethyl ether, dioxane, tetrahydrofuran; dichloromethane, carbon tetrachloride, trichloroethylene, tetrachloroethylene, etc. Chlorinated organic solvents; inorganic solvents such as water. These solvents (or dispersion media) can be used alone or in admixture of two or more.

  Examples of the printing method used for forming the pattern layer include a gravure printing method, an offset printing method, a screen printing method, a flexographic printing method, an electrostatic printing method, and an inkjet printing method. When forming a solid pattern pattern layer, for example, roll coating method, knife coating method, air knife coating method, die coating method, lip coating method, comma coating method, kiss coating method, flow coating method, dip coating Various coating methods such as a coating method may be mentioned. In addition, the hand-drawn method, the ink-sink method, the photographic method, the transfer method, the laser beam drawing method, the electron beam drawing method, the metal partial evaporation method, the etching method, etc. may be used or combined with other forming methods. Good.

  The thickness of the pattern layer is not particularly limited and can be set as appropriate according to product characteristics. The layer thickness at the time of coating is about 1 to 15 μm, and the layer thickness after drying is about 0.1 to 10 μm.

(Colored hiding layer)
A colored masking layer may be formed on the primer layer or the pattern layer, if necessary. The colored concealment layer is provided when it is desired to conceal the background color of the member to be transferred with the transfer sheet.

  As the ink for forming the colored masking layer, an ink for forming a pattern layer and capable of masking coloring can be used. The colored hiding layer preferably contains a relatively soft binder resin from the viewpoint of processability of the transfer sheet.

  The method for forming the colored concealment layer is preferably a method that can be formed so as to cover the entire base sheet (entirely solid). For example, the roll coating method, knife coating method, air knife coating method, die coating method, lip coating method, comma coating method, kiss coating method, flow coating method, dip coating method and the like described above are preferable.

  The thickness of the colored concealing layer is not particularly limited and can be appropriately set according to product characteristics. The layer thickness at the time of coating is about 0.2 to 10 μm, and the layer thickness after drying is about 0.1 to 5 μm.

Transfer Member The transfer sheet of the present invention can constitute a transfer member by transferring the transfer layer to a transfer member.

  As a member to be transferred, for example, a member made of various materials such as a building member, which needs to be provided with characteristics such as weather resistance, solvent resistance, and decorativeness can be cited. The material of the member to be transferred is not limited, and examples thereof include at least one selected from the group consisting of inorganic non-metallic materials, metallic materials, woody materials, and plastic materials.

  Specifically, in inorganic non-metallic systems, for example, papermaking cement, extruded cement, slag cement, ALC (lightweight cellular concrete), GRC (glass fiber reinforced concrete), pulp cement, wood chip cement, asbestos cement, calcium oxalate, Non-ceramic ceramic materials such as gypsum and gypsum slag, ceramic materials such as earthenware, ceramics, porcelain, setware, glass, and glazing.

  In a metal system, metal materials (metal steel plate), such as iron, aluminum, and copper, are mentioned, for example.

  In the woody system, for example, veneer, plywood, particle board, medium density fiber board (MDF), laminated timber and the like made of cedar, straw, straw, lawan, teak and the like can be mentioned.

  In the plastic system, for example, resin materials such as polypropylene, ABS resin, and phenol resin can be used.

  The shape of the member to be transferred is not particularly limited, and not only a planar member but also a member having three-dimensional unevenness can be used as the member to be transferred. In the present invention, the transfer layer of the transfer sheet can be transferred even to a transfer member having a complicated shape such as a three-dimensional unevenness, and the processability and long-term stability are excellent.

  When transferring the transfer layer of the transfer sheet to the transfer member, a known adhesive can be used. For example, adhesives mainly composed of acrylic resin, vinyl resin, polyester resin, urethane resin (PUR hot melt resin, etc.), polyamide resin, epoxy resin, rubber resin, ionomer resin, etc. are widely used. Can be used.

  The method of applying the adhesive is not particularly limited, and examples thereof include roll coating, curtain flow coating, wire bar coating, reverse coating, gravure coating, gravure reverse coating, air knife coating, kiss coating, blade coating, smooth coating, and comma coating. The method can be adopted.

  Although the thickness of an adhesive agent is not specifically limited, About 0.1-50 micrometers is preferable and about 1-10 micrometers is more preferable.

  After transferring the transfer layer, the transfer member of the present invention is obtained by peeling the transfer substrate.

  In the transfer sheet of the present invention, at least a surface protective layer and a primer layer are laminated in this order as a transfer layer on a transfer substrate, and the transfer layer is transferred to various shapes of transferred members (such as building materials of various materials). Then, it is used by the method of peeling a transfer base material. That is, after the transfer layer is transferred to the transfer member, the transfer substrate is peeled off, so that the surface protective layer is located on the outermost layer of the transfer layer that covers the transfer member. The transfer sheet of the present invention has performances such as scratch resistance and stain resistance due to the surface protective layer having specific physical properties, and has processability when transferred to a member having a complicated shape, and Excellent long-term durability.

It is a schematic diagram (an example) of the transfer sheet of the present invention. It is a schematic diagram (an example) which shows the procedure which transfers the transfer layer of the transfer sheet of this invention to a to-be-transferred member. It is a figure which shows the diamond indenter (a) used for the measurement of the Martens hardness in this specification, the schematic diagram (b) of pushing operation, and an example (c) of pushing load and displacement. 6 is a schematic diagram showing a state where a transfer layer is transferred to a transfer target member used in Test Example 1. FIG.

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

Examples 1 to 13 and Comparative Examples 1 to 5
PET film (thickness: 24μm) as a transfer substrate, manufactured by Mitsubishi Plastics Co., Ltd., with a resin composition for forming a surface protective layer (see Table 1 below for the composition) on the product name “E-130”. The film was applied to a thickness of 5 μm and dried to form an uncured coating film.

  Next, in an atmosphere with an oxygen concentration of 100 ppm, the uncured coating film was irradiated with an electron beam under the conditions of an acceleration voltage of 175 KeV and 5 Mrad (50 kGy) to cure the uncured coating film.

  Next, a primer layer (thickness: 2 μm) was formed on the surface protective layer. As the primer agent, a two-component curable urethane resin (acrylic-urethane copolymer) was used.

  Next, a woodgrain pattern layer (thickness 2 μm) was formed on the primer layer, and a colored concealing layer (thickness 3 μm) was formed on the woodgrain pattern layer, thereby preparing a transfer sheet.

[In Table 1, the details of the non-crosslinked acrylic polymer are as follows.
Polymer A: N- (meth) acryloyloxyethyl hexahuman alloy polymer, weight average molecular weight 4000, Tg17 ° C
Polymer B: 2-Hydroxy-3-phenoxyfluoro (meth) acrylate polymer, weight average molecular weight 5000, Tg 56 ° C.
Polymer C: Isobornyl (meth) acrylate polymer, weight average molecular weight 6000, Tg 75 ° C.)
[In Table 1, the polyester resin is Aron Melt PES310S30, manufactured by Toagosei Co., Ltd., and the content of the polyester resin is part by mass relative to 100 parts by mass of the total mass of the ionizing radiation curable resin and the non-crosslinked acrylic polymer. ]

Test example 1
After the transfer sheets prepared in Examples and Comparative Examples were transferred to a vinyl chloride transfer member using a PUR hot melt adhesive (KLEIBERIT PUR 704, thickness 15 μm), the transfer substrate was peeled off. Thus, a covering member was produced. The member to be transferred made of vinyl chloride has the shape shown in FIG. 4, and the transfer layer was transferred as shown by the black border in FIG. Hereinafter, bending workability, presence / absence of cracks, surface performance (scratch resistance) and contamination resistance were examined.

The test results are shown in Table 2.
≪Bending workability≫
The surface state of the convex part and the concave part during the production of the covering member was observed with the naked eye.

The evaluation criteria were as follows.
○: No cracks are observed Δ: Minor cracks are observed ×: Significant cracks are observed

≪Presence of cracks≫
The coated member was subjected to a heating and cooling cycle (20 cycles) of 80 ° C. × 2 hours to −20 ° C. × 2 hours, and the surface state after 20 cycles was observed with the naked eye. The vinyl chloride member (made of hard vinyl chloride containing no plasticizer), which is a member to be transferred, has a heat-resistant temperature of 70 ° C., and shrinks by about 3% when placed in an 80 ° C. oven for 24 hours.

The evaluation criteria were as follows.
A: Appearance change is not observed even after 20 cycles. B: Appearance change is observed after 10 cycles and less than 20 cycles. X: Cracks are observed after 10 cycles.

≪Surface performance: scratch resistance≫
The coated member was subjected to a pencil dent test in accordance with JIS K5400. Specifically, while applying a load of 500 g, a pencil core having a hardness of 3B to F was tested on the transfer layer of the covering member, and the state of the wound was observed with the naked eye.

The evaluation criteria were as follows.
A: No whitening damage was observed with F. B: Whitening damage was not observed with HB. Δ: Whitening damage was not observed with B. X: Whitening damage was observed with B.

≪Stain resistance≫
A red ink manufactured by Pilot Co., Ltd. was applied on the coated member, covered with a watch glass for 6 hours, wiped with ethanol, and the contamination state was observed with the naked eye.

The evaluation criteria were as follows.
○: No contamination residue is observed Δ: Light contamination residue is observed ×: Significant contamination residue is recognized

1. 1. Transfer substrate 2. Surface protective layer Primer layer 4. Pattern layer 5 5. Colored hiding layer 6. Adhesive layer Transferee member

Claims (9)

On the transfer substrate, as a transfer layer, at least a surface protective layer and a primer layer are laminated in that order,
(1) The surface protective layer has a thickness is 5 to 20 [mu] m, and Martens hardness 30~110N / mm are ^two der,
(2) The surface protective layer is a cured product of a coating film of a composition for forming a surface protective layer containing an ionizing radiation curable resin and a non-crosslinked acrylic polymer, and the coating film is cured by irradiation with ionizing radiation. The body,
A transfer sheet characterized by that. The non-crosslinked acrylic polymer is at least one monomer selected from the group consisting of N- (meth) acryloyloxyethylhexahydroimide, 2-hydroxy-3-phenoxypropyl (meth) acrylate and isobornyl (meth) acrylate. it is a polymer, a transfer sheet according to claim 1. The non-crosslinked acrylic polymer has a weight average molecular weight of 4000 to 6000, transfer sheet according to claim 1 or 2. The transfer sheet according to any one of claims 1 to 3 , wherein the non-crosslinked acrylic polymer has a glass transition temperature of 10 to 75 ° C. The surface protective layer contains a polyester resin, a transfer sheet according to any one of claims 1-4. On the primer layer, the decorative layer is laminated, transfer sheet according to any one of claims 1-5. The transfer sheet according to any one of claims 1 to 6 , wherein the transfer substrate contains at least one of polyethylene terephthalate and polypropylene. A covering member obtained by transferring the transfer layer of the transfer sheet according to any one of claims 1 to 7 to a member to be transferred. 9. The covering member according to claim 8 , wherein the material of the member to be transferred is at least one selected from the group consisting of inorganic non-metallic materials, metallic materials, woody materials, and plastic materials.

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