JP6417685B2 - Transfer foil sheet, transfer foil sheet manufacturing method and decorative member - Google Patents

Description

  The present invention relates to a transfer foil sheet, a transfer foil sheet manufacturing method, and a decorative member.

  In the field of building materials and the like, when a member to be used is to be decorated, a decorative sheet is generally used. In consideration of decorating a complicated shape, the decorative sheet is superior in terms of workability when it is a thin film. In terms of the environment, in the field of building materials, etc., the concept of recycling members such as wood substrates and resin substrates is common, and the decorative sheet is preferably a thin film as much as possible in order not to impair the recyclability. .

  The decorative sheet is roughly classified into a non-transfer type and a transfer type, but the transfer type is preferable from the viewpoint of thinning. Patent Documents 1 and 2 have been proposed as such transfer-type decorative sheets.

Patent Document 1 discloses a transfer foil in which a siloxane resin layer and an acrylic resin layer are formed in this order on a release surface of a base sheet, and the resin of the acrylic resin layer has a glass transition point of 80 ° C. As described above, a transfer foil having a weight average molecular weight of 50,000 or more is disclosed.
Patent Document 2 includes a hard coat agent composition containing an active energy ray-curable acrylic acrylate resin having no urethane bond structure and an active energy ray-curable urethane acrylate resin on one side of a base film having a release layer. A curable hard coat layer, an active energy ray-curable acrylic acrylate resin and / or an active energy ray-curable urethane acrylate resin and a primer composition containing a polyisocyanate compound, and a curable primer layer and an adhesive layer An active energy ray-curable transfer sheet for in-mold molding is disclosed.

JP-A-8-192598 JP 2011-143719 A

  For example, in the building material field, the performance required for the transfer type decorative sheet is to follow the shape of the member to be transferred, transferability such as no cracking during transfer, adhesion of the surface protective layer, surface protective layer Coating film strength, anti-blocking properties, printability, etc. are required.

  The transfer foil of Patent Document 1 discloses that the adhesion of the surface protective layer is improved by adding a silane coupling agent. However, it is necessary to add an expensive silane coupling agent, and in the adhesion improving means of Patent Document 1, the surface protective layer is limited to a siloxane-based resin, and the versatility is low. Moreover, although the transfer foil of Patent Document 1 has a problem of scratch resistance, examination of factors affecting the coating strength of the surface protective layer is insufficient, and transfer and printing suitability and coating strength are sufficient. I cannot say that.

  In the transfer sheet of Patent Document 2, a certain study is made on the adhesion and coating strength of the surface protective layer. However, the transfer sheet of Patent Document 2 is insufficient in the examination of the primer layer that affects the adhesion, and cannot be said to have sufficient adhesion, and also affects the coating strength of the surface protective layer. Consideration of factors is insufficient and it cannot be said that the coating film strength is sufficient.

  The present invention provides a transfer foil sheet excellent in transfer suitability, adhesion of a surface protective layer, coating strength of the surface protective layer, anti-blocking property and printability, a production method thereof, and a decorative member using the transfer foil sheet The purpose is to do.

In order to solve the above problems, the present invention provides the following transfer foil sheets [1] to [9], a method for producing the same, and a decorative member using the transfer foil sheet.
[1] A transfer foil sheet having a surface protective layer and a primer layer in this order on a substrate, wherein the surface protective layer has a double bond equivalent of 250 to 800 g / eq and a weight average molecular weight of 1. A cured product of an ionizing radiation curable resin composition containing a (meth) acrylate resin having a glass transition temperature of 70 to 130 ° C. and a thickness of 2 to 10 μm, A transfer foil sheet in which the primer layer contains a cured product of a composition containing a polyol resin and an isocyanate compound.
[2] The transfer foil sheet according to [1], wherein the isocyanate compound has an ethylenically unsaturated bond group in the molecule.
[3] The transfer foil sheet according to the above [1] or [2], wherein the polyol resin is an acrylic polyol resin.
[4] The transfer foil sheet according to any one of the above [1] to [3], which has a design layer on the primer layer.
[5] The transfer foil sheet according to the above [4], which has an adhesive layer on the design layer.
[6] The transfer foil sheet according to the above [5], which has a concealing layer between the design layer and the adhesive layer.
[7] A method for producing a transfer foil sheet in which the following steps (1) to (3) are sequentially performed.
(1) Ionizing radiation curable containing an acrylate resin having a double bond equivalent of 250 to 800 g / eq, a weight average molecular weight of 1,000 to 40,000, and a glass transition temperature of 70 to 130 ° C. on a substrate. (2) Step of forming the surface protective layer by applying and drying the surface protective layer ink containing the resin composition so that the thickness after drying becomes 2 to 10 μm. (2) The ionizing radiation curable resin composition Step (3) of applying a primer layer ink containing a composition containing a polyol resin and an isocyanate compound on the surface protective layer and drying the primer layer with the uncured portion in a state where the primer layer is formed. A step of irradiating ionizing radiation from the primer layer side to advance curing of the ionizing radiation curable resin composition in the surface protective layer [8] The member to be transferred and any one of [1] to [6] above Transcription A decorative member with a base material formed by bonding a surface of the foil sheet opposite to the base material.
[9] A decorative member obtained by peeling off the base material on the surface of the decorative member with a base material according to [8].

  The transfer foil sheet of the present invention can improve transferability, adhesion of the surface protective layer, coating strength of the surface protective layer, antiblocking property, and printability. Moreover, the manufacturing method of the transfer foil sheet of this invention can manufacture the transfer foil sheet which has this performance efficiently. Moreover, the decorative member of the present invention is excellent in design without cracking of the surface protective layer, and also excellent in coating strength of the surface protective layer.

It is sectional drawing which shows one Embodiment of the transfer foil sheet of this invention. It is sectional drawing which shows other embodiment of the transfer foil sheet of this invention.

[Transfer foil sheet]
The transfer foil sheet of the present invention is a transfer foil sheet having a surface protective layer and a primer layer in this order on a substrate, and the surface protective layer has a double bond equivalent of 250 to 800 g / eq, It contains a cured product of an ionizing radiation curable resin composition containing a (meth) acrylate resin having a weight average molecular weight of 1,000 to 40,000 and a glass transition temperature of 70 to 130 ° C., and has a thickness of 2 And the primer layer contains a cured product of a composition containing a polyol resin and an isocyanate compound.

FIG. 1 is a cross-sectional view showing an embodiment of a transfer foil sheet 10 of the present invention. The transfer foil sheet 10 of FIG. 1 has a surface protective layer 12 and a primer layer 13 on a base material 11. The transfer foil sheet 10 in FIG. 2 has a surface protective layer 12 and a primer layer 13 on a substrate 11, and further has a design layer 14, a concealing layer 15 and an adhesive layer 16 on the primer layer 13. It will be.
The transfer foil sheet of FIG. 1 has a primer layer 13 side facing the member to be transferred, the primer layer 13 is bonded to an adhesive layer provided on the member to be transferred, and only the base material 11 is peeled off after bonding. The layer 13 and the surface protective layer 12 can be transferred to a member to be transferred to produce a decorative member.
The transfer foil sheet 10 of FIG. 2 adheres the adhesive layer 16 of the transfer foil sheet 10 to the member to be transferred, and peels only the base material 11 after bonding, whereby the adhesive layer 16, the concealing layer 15, and the design layer 14. The decorative layer can be produced by transferring the primer layer 13 and the surface protective layer 12 to the member to be transferred.

(Base material)
The substrate can be used without particular limitation as long as it functions as a support for various papers and plastic films, but the member to be transferred when the surface to be transferred is not flat. From the viewpoint of followability to the plastic, a plastic film is preferable.

As a plastic film, what consists of various synthetic resins is mentioned. Synthetic resins include polyethylene resin, polypropylene resin, polymethylpentene resin, polyvinyl chloride resin, polyvinylidene chloride resin, polyvinyl alcohol resin, vinyl chloride-vinyl acetate copolymer resin, ethylene-vinyl acetate copolymer resin, ethylene-vinyl. Representative examples include alcohol copolymer resin, polyethylene terephthalate resin, polybutylene terephthalate resin, polyethylene naphthalate-isophthalate copolymer resin, polymethyl methacrylate resin, polyethyl methacrylate resin, polybutyl acrylate resin, nylon 6 or nylon 66 Polyamide resin, cellulose triacetate resin, cellophane, polystyrene resin, polycarbonate resin, acrylonitrile-butadiene-styrene copolymer (ABS resin), polyarylate resin, And polyimide resins.
Among these plastic films, polyethylene terephthalate resin is suitable from the viewpoint of dimensional stability and strength, and may be stretched as necessary.
Although the thickness of a base material is not specifically limited, From a viewpoint of workability | operativity in the case of transcription | transfer, it is preferable that it is 20-100 micrometers, and it is more preferable that it is 20-60 micrometers.

  The surface protective layer, primer layer, and other layers provided as necessary on the base material are bonded to the member to be transferred, and then only the base material is peeled off, and the constituent layers of the transfer foil sheet other than the base material Is transcribed. Therefore, it is necessary to make it possible to peel between the base material and the surface protective layer. In order to make the substrate and the surface protective layer peelable, for example, the surface of the substrate on the side where the surface protective layer is provided is subjected to a release treatment with a release agent such as a silicone-based release agent to weaken the adhesive force. Or a means for selecting a combination of the material of the base material and the material of the surface protective layer so that the adhesive force is appropriate. Moreover, in order to ensure an appropriate adhesive force between the base material and the surface protective layer, an easy adhesion layer made of a resin or the like that imparts unevenness on the base material by chemical coating or sand blasting treatment or improves the adhesive force is provided. It may be formed or subjected to corona discharge treatment.

(Surface protective layer)
The surface protective layer is positioned on the outermost surface after being transferred to the transfer target member. In the present invention, the structure of the surface protective layer is a (meth) acrylate resin having a double bond equivalent of 250 to 800 g / eq, a weight average molecular weight of 1,000 to 40,000, and a glass transition temperature of 70 to 130 ° C. And a cured product of an ionizing radiation curable resin composition containing the material, and has a thickness of 2 to 10 μm.

As the (meth) acrylate resin, a resin having a (meth) acryloyl group that is an ionizing radiation-curable functional group can be used. Examples of such (meth) acrylate resins include urethane (meth) acrylate, acrylic (meth) acrylate, polyester (meth) acrylate, and epoxy (meth) acrylate.
Among these (meth) acrylate resins, acrylate resins having an acryloyl group such as urethane acrylate, acrylic acrylate, polyester acrylate, and epoxy acrylate are preferable from the viewpoint of the balance between adhesion to the primer layer and coating film strength. Among them, urethane (meth) acrylate is preferable.
The ionizing radiation means an electromagnetic wave or a charged particle beam having an energy quantum capable of polymerizing or cross-linking molecules, and usually ultraviolet (UV) or electron beam (EB) is used. Electromagnetic waves such as X-rays and γ-rays, and charged particle beams such as α-rays and ion beams can also be used. In the present invention, among the ionizing radiation curable resins, an electron beam curable resin that is cured with an electron beam is preferable. The electron beam curable resin is excellent in that curing is not inhibited even if an ultraviolet absorber is added to the surface protective layer, and it is easy to make it unnecessary.

  In the present invention, an acrylate resin having a double bond equivalent of 250 to 800 g / eq, a weight average molecular weight of 1,000 to 40,000, and a glass transition temperature of 70 to 130 ° C. is used. The thickness of the surface protective layer is 2 to 10 μm. By satisfying these conditions at the same time, the transferability, adhesion of the surface protective layer, coating strength of the surface protective layer, antiblocking property, and printability can be improved due to the synergistic effect of each condition.

When the double bond equivalent is less than 250, the degree of curing of the surface protective layer becomes too high, and cracks occur during transfer processing. Also, when the double bond equivalent is less than 250, the degree of curling due to curing shrinkage increases, resulting in hindrance to productivity, or the peel strength between the base material and the surface protective layer becomes too weak, so that the transfer to the member to be transferred There may be a problem that the base material peels off at an unintended timing, such as before the operation. When the double bond equivalent exceeds 800 g / eq, the coating strength of the surface protective layer cannot be increased, and various surface properties such as solvent resistance and scratch resistance are deteriorated.
The double bond equivalent is preferably 250 to 600 g / eq, and more preferably 300 to 600 g / eq.
The double bond equivalent can be calculated as follows.
[Double bond equivalent] = [molecular weight of repeating structural unit] / [number of double bonds in repeating structural unit]

Considering the adhesion between the surface protective layer and the primer layer, the surface protective layer is tack-free, and the surface protective layer forms a primer layer before curing the ionizing radiation curable composition, and then ionizing radiation is applied. It is preferable to cure the surface protective layer by irradiation.
When the weight average molecular weight is less than 1,000, the tack-free property of the surface protective layer may be impaired. For example, blocking in the manufacturing process, and the surface protective layer of the back trap when forming (printing) the primer layer may be used. Phenomenon that the printability does not become good, such as peeling from the base material, and that the good coated surface state of the primer layer can not be obtained, so the ionizing radiation curable resin composition of the surface protective layer before forming the primer layer It is necessary to cure the object. When the ionizing radiation curable resin composition of the surface protective layer is cured before forming the primer layer, the adhesion between the primer layer and the surface protective layer cannot be improved.
When the weight average molecular weight exceeds 40,000, the solvent is less likely to evaporate from the surface protective layer, and the residual solvent causes cross-linking inhibition of the ionizing radiation curable resin composition, thereby increasing the coating strength of the surface protective layer. The surface physical properties such as solvent resistance and scratch resistance are reduced. Since the present invention is a transfer specification, the surface that becomes the surface after the transfer of the surface protective layer is in contact with the base material, the solvent is difficult to evaporate, and the problem of cross-linking inhibition of the surface protective layer by the residual solvent is likely to occur. It is of great significance to prevent crosslinking inhibition by setting the average molecular weight to 40,000 or less. In addition, a solvent here is contained in the ink for surface protection layers and / or the ink for primer layers mentioned later.
The weight average molecular weight is preferably 1,000 to 20,000, and more preferably 1,500 to 10,000.
In the present invention, the weight average molecular weight is a value measured by gel permeation chromatogram method and converted to polystyrene.

When the glass transition temperature is less than 70 ° C., the tack-free property of the surface protective layer is impaired, and it is necessary to cure the ionizing radiation curable resin composition of the surface protective layer before forming the primer layer. The adhesion with the surface protective layer cannot be improved. In addition, when the glass transition temperature is less than 70 ° C., blocking in the production process, peeling of the surface protective layer from the base material by the back trap when forming the primer layer, and a good coated surface state of the primer layer can be obtained. Phenomenon that printability does not become good such as disappearing occurs. When the glass transition temperature exceeds 130 ° C., the adhesion between the primer layer and the surface protective layer cannot be improved, and printability is also adversely affected.
The glass transition temperature is preferably 80 to 130 ° C, and more preferably 80 to 110 ° C.

When the thickness of the surface protective layer is less than 2 μm, the coating strength of the surface protective layer cannot be increased, and various surface properties such as solvent resistance and scratch resistance are deteriorated. When the thickness of the surface protective layer exceeds 10 μm, it may not be possible to follow the shape of the member to be transferred, or cracks may occur during transfer, and transfer aptitude cannot be made sufficient. Moreover, when the thickness of the surface protective layer exceeds 10 μm, curling occurs during the production of the transfer foil sheet, and the production stability may be insufficient. In addition, when the thickness of the surface protective layer exceeds 10 μm, the solvent is less likely to volatilize from the surface protective layer, the remaining solvent causes cross-linking inhibition of the ionizing radiation curable resin composition, and the coating strength of the surface protective layer is increased. The surface physical properties such as solvent resistance and scratch resistance are deteriorated.
The thickness of the surface protective layer is preferably 3 to 8 μm, and more preferably 3 to 5 μm.

When the ionizing radiation curable resin composition is ultraviolet curable, the ionizing radiation curable composition preferably contains additives such as a photopolymerization initiator and a photopolymerization accelerator.
Examples of the photopolymerization initiator include one or more selected from acetophenone, benzophenone, α-hydroxyalkylphenone, Michler's ketone, benzoin, benzylmethyl ketal, benzoylbenzoate, α-acyloxime ester, thioxanthones, and the like.
The photopolymerization accelerator can reduce polymerization inhibition by air during curing and increase the curing speed. For example, p-dimethylaminobenzoic acid isoamyl ester, p-dimethylaminobenzoic acid ethyl ester, etc. One or more selected may be mentioned.
Moreover, the surface protective layer may contain the base material peeling regulator, when the peeling strength (transfer strength) of a base material and a surface protective layer is weak. As the base material release modifier, a resin of the same system as the resin constituting the base material is selected, and the content thereof is 0.1 to 3 of the total resin component of the surface protective layer from the viewpoint of coating film performance and ink dispersibility. About 0.0 mass% is preferable. Accordingly, the peel strength is improved by increasing the intermolecular force between the substrate and the surface protective layer, and the peel strength can be adjusted.

The ionizing radiation curable resin composition may contain an ionizing radiation curable resin other than the acrylate resins described above. However, in order to easily exhibit the effect of the present invention described above, it is preferable to contain 50% by mass or more of the cured product of the acrylate resin described above with respect to the total solid content of the surface protective layer, and 70% by mass or more. It is more preferable to contain 90% by mass or more.
In addition, in the surface protective layer, resin components other than ionizing radiation curable resins such as thermosetting resins and thermoplastic resins, pigments, dyes, antioxidants, ultraviolet absorbers, as long as the effects of the present invention are not impaired. Etc. You may contain additives, such as.
The surface protective layer is prepared by adjusting the ink for the surface protective layer from the ionizing radiation curable resin composition, the diluting solvent, other resin components to be added as necessary, and additives, and applying and drying the ink on the substrate. Can be formed. As will be described later, from the viewpoint of adhesion between the primer layer and the surface protective layer, the timing for curing the ionizing radiation curable resin composition is preferably after the formation of the primer layer.

(Primer layer)
The primer layer is provided on the surface protective layer. In this invention, it comprises so that a primer layer may contain the hardened | cured material of the composition containing a polyol-type resin and an isocyanate type compound, and the adhesiveness of a primer layer and a surface protective layer is made favorable by this structure.

  Examples of polyol-based resins include acrylic polyol resins, polyester polyol resins, and polycarbonate polyol resins, and one or more of these can be used. Of these polyol resins, acrylic polyol resins are preferred in that they have excellent adhesion after the heat test.

  The polyol resin preferably has a weight average molecular weight of 1,000 to 100,000, more preferably 5,000 to 80,000, and still more preferably 20,000 to 50,000. By setting the molecular weight of the polyol resin to 1,000 or more, the solvent resistance of the primer layer can be easily improved, and by setting the molecular weight to 100,000 or less, the viscosity of the ink forming the primer layer is increased, It is easy to suppress gelation.

The polyol resin preferably has a hydroxyl value of 30 to 130 mgKOH / g, more preferably 50 to 130 mgKOH / g, and still more preferably 60 to 120 mgKOH / g. By setting the hydroxyl value of the polyol resin to 30 mgKOH / g or more, the crosslinking density of the primer layer can be increased, and cohesive failure when the primer layer is impacted can be easily suppressed. In addition, by setting the hydroxyl value to 130 mgKOH / g or less, the flexibility of the primer layer is ensured, and as a result of being difficult to break during transfer, it becomes easy to prevent the adhesion between the primer layer and the surface protective layer from being impaired.
The hydroxyl value can be measured by an acetylation method using acetic anhydride.

The isocyanate compound mainly has a role of reacting with the polyol resin to increase the coating strength of the primer layer.
As the isocyanate compound, a compound having one or more isocyanate groups in the molecule can be used. From the viewpoint of increasing the coating film strength, a compound having two or more isocyanate groups in the molecule is suitable. Examples of the polyvalent isocyanate having two or more isocyanate groups in the molecule include aromatic isocyanates such as xylylene diisocyanate and 4,4-diphenylmethane diisocyanate, or hexamethylene diisocyanate, isophorone diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated diphenylmethane. Aliphatic (or alicyclic) isocyanates such as diisocyanate are listed.

In the present invention, among the isocyanate compounds, those having an ethylenically unsaturated bond group in the molecule are preferable. The isocyanate compound having an ethylenically unsaturated bond group in the molecule is crosslinked and cured together with the ionizing radiation curable resin composition by irradiation with ionizing radiation when the ionizing radiation curable resin composition of the surface protective layer is crosslinked, The coating strength of the primer layer can be increased, and the ionizing radiation curable resin composition of the surface protective layer can also be cross-linked during the cross-linking and curing to improve the adhesion between the primer layer and the surface protective layer. it can.
Examples of the ethylenically unsaturated bond group include a (meth) acryloyl group, a vinyl group, and an allyl group.
Examples of the isocyanate compound having an ethylenically unsaturated bond group in the molecule include β-isocyanatoethyl (meth) acrylate (eg, Showen Denko Co., Ltd .: Karenz MOI), (meth) acrylate and (meth) acrylamides having a hydroxyl group. And a compound in which an isocyanate group of a polyvalent isocyanate is connected by a urethane bond.

  The polyol-based resin and the isocyanate-based compound are preferably used at a blending ratio in which the equivalent ratio of the isocyanate group of the isocyanate-based compound to the hydroxyl group of the polyol-based resin is 0.5 to 5.0. It is more preferable to use at a blending ratio of 0.

  In the primer layer, you may contain the component used as solid content other than the polyol-type resin and isocyanate type compound which were mentioned above. However, in order to easily exhibit the effects of the present invention described above, it is preferable to contain 50% by mass or more of the components derived from the above-described polyol-based resin and isocyanate-based compound with respect to the total solid content of the primer layer. It is preferably contained in an amount of not less than mass%, more preferably not less than 90% by mass. In addition, the component derived from a polyol resin and an isocyanate compound means the reaction product of a polyol resin, the reaction product of an isocyanate compound, the unreacted polyol resin and the unreacted isocyanate compound.

The primer layer may contain other resin components, pigments, dyes, antioxidants, ultraviolet absorbers and the like as long as the effects of the present invention are not impaired.
The primer layer is prepared by adjusting the primer layer ink from a composition containing a polyol resin and an isocyanate compound, a diluting solvent, and an additive to be added as necessary, and applying and drying the ink on the surface protective layer. Can be formed.
The primer layer contains a cured product of a composition containing a polyol resin and an isocyanate compound, that is, a reaction product of a polyol resin and an isocyanate compound. Formation of the reaction product (cured product) also proceeds by heat when the primer layer is dried, but it is preferable to proceed by aging treatment after forming the primer layer, as will be described later.

(Design layer)
The design layer is provided on the primer layer as necessary for the purpose of improving the design of the member to be transferred. The design layer may be formed so as to have concealment properties, but may be formed in a transparent color and take advantage of the pattern of the member to be transferred. Further, the design layer may not be concealed, and the pattern and color of the member to be transferred may be concealed by a concealment layer described later.
As a design layer, metal layers, such as metal foil and a metal vapor deposition film, a colored layer, a pattern layer, etc. are mentioned.

Gold, silver, copper, aluminum, etc. can be used for the metal which comprises metal foil.
The metal vapor deposition film can be formed of various metal materials by physical vapor deposition or chemical vapor deposition. Physical vapor deposition methods include vacuum vapor deposition, ion plating, sputtering, etc. Chemical vapor deposition methods include plasma CVD using plasma and catalytic chemical vapor that thermally decomposes a material gas using a heated catalyst body. Examples thereof include a phase growth method (Cat-CVD).
Examples of the metal-based material used for vapor deposition include gold, silver, copper, aluminum, magnesium, zinc, tin, nickel, titanium, and the like; or oxides, carbides, and nitrides thereof; or a mixture thereof.

  The colored layer is a solid layer and is formed by printing or the like. As the ink used for forming the colored layer, an ink obtained by appropriately mixing a binder, a colorant such as a pigment or a dye, an extender pigment, a solvent, a stabilizer, a plasticizer, a catalyst, or a curing agent is used. The binder is not particularly limited. For example, acrylic resin, styrene resin, polyester resin, urethane resin, chlorinated polyolefin resin, vinyl chloride-vinyl acetate copolymer resin, polyvinyl butyral resin, alkyd resin, Examples include petroleum resins, ketone resins, epoxy resins, melamine resins, fluorine resins, silicone resins, fiber derivatives, rubber resins, and the like. These resins can be used alone or in admixture of two or more. When heat is applied to the transfer foil sheet during lamination, for example, mixing of an acrylic resin and a vinyl chloride-vinyl acetate copolymer resin is preferable.

  The pattern layer is formed by printing or the like. Pattern patterns (pattern patterns) include wood grain patterns, marble patterns (for example, travertine marble patterns), stone patterns that simulate the surface of rocks, fabric patterns that simulate cloth and cloth-like patterns, tiled patterns, There are brickwork patterns, etc., and there are also patterns such as marquetry and patchwork that combine these. These patterns are formed by multicolor printing with the usual yellow, red, blue and black process colors, as well as by multicolor printing with special colors prepared by preparing the individual color plates that make up the pattern. Is done. As the ink using the pattern layer, the same ink as the colored layer can be used.

  The thickness of the design layer can be appropriately adjusted within a range of about 0.1 to 20 μm in consideration of the form of the design layer and the target design properties. The design layer may contain additives such as an antioxidant and an ultraviolet absorber as long as the effects of the present invention are not impaired.

(Hidden layer)
The concealing layer is provided on the design layer as necessary in order to conceal the pattern and color of the transferred member and improve the design.
As the ink used for forming the concealing layer, an ink in which a binder, a colorant such as a pigment or a dye, an extender pigment, a solvent, a stabilizer, a plasticizer, a catalyst, or a curing agent is appropriately mixed is used. There is no restriction | limiting as this binder, The thing similar to what was illustrated as a binder of a colored layer can be used.

The colorant may be appropriately selected from the use of the decorative sheet and the color compatibility with the pattern layer. For example, carbon black (black), iron black, titanium white, antimony white, yellow lead, titanium yellow, and petal , Inorganic pigments such as cadmium red, ultramarine, and cobalt blue, organic pigments or dyes such as quinacridone red, isoindolinone yellow, and phthalocyanine blue, metal pigments made of scaly foil pieces such as aluminum and brass, titanium dioxide-coated mica, base And nacreous (pearl) pigments composed of scaly foil pieces such as conductive lead carbonate.
The thickness of the masking layer is preferably 0.5 to 20 μm, and more preferably 1 to 10 μm. The concealing layer may contain additives such as an antioxidant and an ultraviolet absorber as long as the effects of the present invention are not impaired.

(Adhesive layer)
The adhesive layer is provided as necessary for transferring to the transfer member. When the transfer foil sheet does not have a design layer or a concealing layer, the adhesive layer is provided on the primer layer. When the transfer foil sheet has a design layer and does not have a masking layer, the adhesive layer is provided on the design layer, and when the transfer foil sheet has a design layer and a masking layer, the adhesive layer is on the masking layer. Provided.
In addition, when an adhesive layer is formed on a member to be transferred by applying an adhesive to the member to be transferred, a constituent layer other than the base material is provided on the member to be transferred without providing an adhesive layer on the transfer foil sheet. Can be transferred. However, even in this case, an adhesive layer may be provided on the member to be transferred.
The adhesive layer may be a laminate of two or more layers. For example, multiple layers of adhesive layers having the same composition or multiple layers of adhesive layers having different compositions can be used.

  As the adhesive used for the adhesive layer, a thermosetting adhesive or a hot melt adhesive is preferable. A hot-melt adhesive is preferable in that it can be produced without providing a separator on the adhesive layer because it exhibits adhesiveness by heating.

  As the thermosetting adhesive, those including a composition having a property of causing a chemical reaction by heat to cause crosslinking are preferable. For example, a two-component curable urethane adhesive, a polyester urethane adhesive, and a polyether urethane adhesive. Examples thereof include an adhesive, an acrylic adhesive, a polyester adhesive, a polyamide adhesive, a polyvinyl acetate adhesive, an epoxy adhesive, and a rubber adhesive.

A hot-melt adhesive is a heat-melt adhesive that is made of a thermoplastic material that exhibits fluidity when heated and develops adhesive strength when it is solidified by cooling (expresses heat-sealability).
Examples of hot melt adhesives include ethylene-vinyl acetate, vinyl chloride-vinyl acetate, polyolefin, polyamide, nylon, polyester, rubber, acrylic, urethane, cellulose, and reactive hot melt. And a mixture of two or more types can be used as necessary. In particular, it is preferable to use a mixture of an acrylic resin and a urethane resin. These resins are preferably selected according to the member to be transferred. Specifically, from the viewpoint of improving the adhesion to the member to be transferred, it is preferable to use a material of the same system as the resin constituting the member to be transferred.

  Moreover, in order to improve the adhesiveness after cooling and solidification, when using a hot melt adhesive, a tackifier, a plasticizer, etc. may be further added to the adhesive layer. Examples of the tackifier include (modified) rosin, terpene, hydrocarbon resin and the like. Examples of the plasticizer include phthalate, glycolate, fatty alcohol, mineral oil and the like.

The adhesive layer preferably contains an isocyanate curing agent. The isocyanate curing agent may be a polyvalent isocyanate having two or more isocyanate groups in the molecule, for example, an aromatic isocyanate such as xylylene diisocyanate or 4,4-diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, Examples thereof include aliphatic (or alicyclic) isocyanates such as hydrogenated tolylene diisocyanate and hydrogenated diphenylmethane diisocyanate. Among these, non-yellowing materials such as hexamethylene diisocyanate are preferable from the viewpoint of suppressing yellowing of the adhesive layer.
Moreover, when taking the transfer method by a heating, it is preferable to use block isocyanate as an isocyanate type hardening | curing agent. When an isocyanate curing agent other than blocked isocyanate is used, the strength of the adhesive layer may change due to the progress of the reaction, which may result in lack of transfer stability. Since the isocyanate group can be regenerated by applying heat and applying heat, better adhesion can be expressed.

The masking agent of the blocked isocyanate can be used without any particular limitation, for example, phenolic, alcoholic, active methylene, mercaptan, acid amide, acid imide, lactam, imidazole, urea, Examples include oxime-based, amine-based, imide-based, and hydrazine compounds. Specifically, phenol, cresol, 2-hydroxypyridine, butyl cellosolve, propylene glycol monomethyl ether, ethylene glycol, benzyl alcohol, ethanol, dimethyl malonate, diethyl malonate, ethyl acetoacetate, acetylacetone, butyl mercaptan, acetanilide, acetic acid amide Succinimide, ε-caprolactam, imidazole, urea, thiourea, acetoaldoxime, acetone oxime, cyclohexaneoxime, diphenylamine, aniline, carbazole, ethyleneimine, dimethylhydrazine and the like.
The dissociation temperature of the mask agent is not particularly limited as long as it is not higher than the heating temperature when transferring the transfer foil sheet to the transfer material and is higher than the drying temperature of the layer containing the blocked isocyanate and the layer formed after the layer. Although not performed, 80 to 140 ° C. is preferable from the viewpoint of workability and heat resistance of the substrate.

The adhesive layer may contain additives such as pigments, dyes, antioxidants, and ultraviolet absorbers as long as the effects of the present invention are not impaired.
The thickness of the adhesive layer is preferably 0.1 to 30 μm from the viewpoint of scratch resistance. By setting the thickness of the adhesive layer to 0.1 μm or more, it is easy to ensure the adhesion to the member to be transferred, and by setting the thickness to 30 μm or less, the coating strength of the surface protective layer is impaired, and scratch resistance It is easy to prevent the deterioration of the property.

  In the transfer foil sheet of the present invention, the transmittance of UVA (light with a wavelength of 315 to 400 nm) of the constituent layers excluding the substrate is preferably 3% or less in order to prevent deterioration of the transferred member. % Or less is more preferable.

The transfer foil sheet of the present invention may have other functional layers such as an antistatic layer.
The transfer foil sheet of the present invention as described above is an interior or exterior material for buildings such as walls, ceilings, floors, window frames, doors, handrails, skirting boards, edges, moldings, etc., kitchens, furniture, Home appliances, OA equipment, vehicle interior materials, exterior materials, and the like can be used for these decorations as transferred members. Since the transfer foil sheet of the present invention is excellent in followability, it can be used even if the member to be transferred has a non-planar shape such as one having an uneven shape, one having a curved surface, one having a corner, and the like. Moreover, since the transfer foil sheet of the present invention is a thin film and excellent in recyclability, it can be suitably used for joinery in which the concept of recycling is generalized.

[Method for producing transfer foil sheet]
The manufacturing method of the transfer foil sheet of this invention performs the process of the following (1)-(3) in order.
(1) Ionizing radiation curable containing an acrylate resin having a double bond equivalent of 250 to 800 g / eq, a weight average molecular weight of 1,000 to 40,000, and a glass transition temperature of 70 to 130 ° C. on a substrate. (2) Step of forming the surface protective layer by applying and drying the surface protective layer ink containing the resin composition so that the thickness after drying is 2 to 10 μm. (2) The ionizing radiation fat curable resin composition A step of forming a primer layer by applying and drying a primer layer ink containing a composition containing a polyol resin and an isocyanate compound on the surface protective layer in a state where the product has an uncured portion (3) ) Irradiating ionizing radiation from the primer layer side to advance the curing of the ionizing radiation curable resin composition in the surface protective layer

In the step (1), an ionization containing an acrylate resin having a double bond equivalent of 250 to 800 g / eq, a weight average molecular weight of 1,000 to 40,000, and a glass transition temperature of 70 to 130 ° C. on the substrate. A surface protective layer is formed by applying and drying an ink for a surface protective layer containing the radiation curable resin composition so that the thickness after drying is 2 to 10 μm.
In the step (1), it is preferable that the surface protective layer is kept dry until the ionizing radiation curable resin composition is not cured by irradiation with ionizing radiation. By doing in this way, when forming a primer layer by the below-mentioned process (2), since the ionizing radiation curable resin composition is in an uncured state, the adhesion between the primer layer and the surface protective layer is improved. Can be good. In addition, as the acrylate resin contained in the ionizing radiation curable resin composition, since the weight average molecular weight and the glass transition temperature are in a specific range, the surface protective layer is in a tack-free state, which will be described later. The workability at the time of forming the primer layer in the step (2) can be improved. In addition, as long as the ionizing radiation curable resin composition has an irradiation dose that does not completely cure, it may be irradiated with ionizing radiation in the step (1) or (2), but the effect of the present invention is further improved. In order to make it favorable, it is preferable not to irradiate ionizing radiation in the step (1) or (2).

The ink for the surface protective layer can be adjusted with an ionizing radiation curable resin composition, a diluting solvent, other resin components added as necessary, additives, and the like.
Examples of means for applying the surface protective layer ink include known coating means such as dip coating, roll coating, bar coating, die coating, gravure coating, blade coating, and air knife coating.
The drying conditions for the surface protective layer are about 40 to 80 ° C. and about 5 to 60 seconds.

In the step (2), a primer layer ink comprising a composition containing a polyol resin and an isocyanate compound on a surface protective layer in a state where the ionizing radiation fat curable resin composition has an uncured portion. Apply and dry to form a primer layer.
As described above, in the step (2), the surface protective layer is in an uncured state of the ionizing radiation curable resin composition and is in a tack-free state. Adhesiveness can be improved, and workability when forming the primer layer can be improved.

The primer layer ink can be adjusted with a polyol-based resin, an isocyanate-based compound, a diluting solvent, other resin components added as necessary, and additives.
Examples of means for applying the primer layer ink include known coating means such as dip coating, roll coating, bar coating, die coating, gravure coating, blade coating, and air knife coating.
The drying condition of the primer layer is about 40 to 80 ° C. and about 5 to 60 seconds.

  It is preferable that the composition containing the polyol resin and the isocyanate compound is finally sufficiently reacted with the polyol resin and the isocyanate compound so that the cured product is contained in the primer layer. Although formation of this hardened | cured material advances also by drying of a process (2), it is preferable to advance by performing an aging process after completion | finish of a process (3). The aging treatment is performed at 40 to 60 ° C. for about 4 to 24 hours.

In the step (3), ionizing radiation is irradiated from the primer layer side to advance the curing of the ionizing radiation curable resin composition in the surface protective layer.
As described above, by promoting the curing of the ionizing radiation curable resin composition in the surface protective layer after the steps (1) and (2), the adhesion between the surface protective layer and the primer layer is improved. The coating strength of the surface protective layer can be increased.
The irradiation amount of ionizing radiation can be appropriately adjusted based on the theoretical value of the amount of ionizing radiation necessary for the ionizing radiation curable resin composition to be completely cured.
In addition, when forming other layers, such as a design layer and a concealment layer, on a primer layer, in order to fully reach ionizing radiation to a surface protective layer, performing process (3) before forming other layers Is preferred.

[Coating material with base material, decorative material]
The decorative member with a substrate of the present invention is formed by adhering a member to be transferred and a surface opposite to the substrate of the transfer foil sheet of the present invention described above. When the transfer foil sheet has an adhesive layer, the transfer member and the transfer foil sheet may be bonded using the adhesive layer. When the transfer foil sheet does not have the adhesive layer, What is necessary is just to adhere | attach by apply | coating an adhesive agent to a transfer member. Even when the transfer foil sheet has an adhesive layer, the adhesive may be applied to the member to be transferred.
The material of the member to be transferred is not particularly limited, and examples thereof include plastic, metal, wood, and ceramic materials. In addition, the shape of the member to be transferred may be a flat shape, or may be a non-planar shape such as an uneven shape, a curved surface, or a corner.
Such a base-equipped decorative member is preferable in that the transferred layer can be protected when an operation such as transportation is performed after the transfer foil sheet is bonded to the member to be transferred.
The decorative member of the present invention is formed by peeling only the base material on the surface of the decorative member with a base material of the present invention described above.

  EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited at all by this example.

(Evaluation method)
The transfer foil sheets obtained in each example and comparative example were evaluated by the following methods. In addition, since the transfer foil sheet of Comparative Example 1 was remarkably inferior in adhesion, no other evaluation was performed.
(1) Adhesion UV lamp (trade name “M04-L21WB / SUV”, manufactured by Iwasaki Electric Co., Ltd.), lamp jacket (trade name “WJ50-SUV”, manufactured by Iwasaki Electric Co., Ltd.) and illuminometer (trade name “UVD-365PD” And a super accelerated weathering test apparatus (trade name “I Super UV Tester SUV-W131”, manufactured by Iwasaki Electric Co., Ltd.) equipped with “Iwasaki Electric Co., Ltd.”. The decorative member was irradiated for 20 hours under conditions of a black panel temperature of 63 ° C. and an illuminance of 60 mW / cm ² , and then the cycle of condensation for 4 hours was repeated, and the adhesion between the surface protective layer and the primer layer after 50 hours. Was evaluated by the following method.
[Adhesion evaluation method]
A cellophane tape (cellophane adhesive tape manufactured by Nichiban Co., Ltd., “Cerotape (registered trademark)” 25 mm width) is firmly attached to the surface protective layer of the decorative member at room temperature, and in a direction of 45 degrees with the surface of the decorative member, The cellophane tape was forcibly peeled off. The surface condition of the decorative member was evaluated.
A: The cellophane tape was peeled off at the same place 5 times or more, but the surface protective layer was not peeled off.
B: No peeling of the surface protective layer was observed at the first time, but peeling was observed at a part of the cellophane tape adhesion portion after the second time.
C: The cellophane tape is peeled off partly or entirely.

(2) Printability When forming the design layer and the concealing layer in the transfer foil sheet, it was visually confirmed whether or not the surface protective layer was peeled off from the substrate.
A: No peeling of the surface protective layer from the release substrate was observed, and printing was possible without problems.
B: Peeling of the surface protective layer was observed from the release substrate in part (peeling was less than 50%).
C: The surface protective layer was partially peeled from the peeling substrate (peeling was 50% or more).
D: Peeling of the surface protective layer from the peeling substrate occurred on the entire surface.
(3) Blocking prevention property Two samples of a predetermined size formed up to the surface protective layer of the transfer foil sheet are stacked and allowed to stand at room temperature under the weight of the transfer foil sheet for about 24 hours, and then the situation is observed. did.
A: Generation | occurrence | production of blocking was not seen.
B: Although some blocking was seen, when peeling off each sample, the surface protective layer did not peel from a peeling base material.
C: Blocking was observed, and when the samples were peeled off, the surface protective layer was partially peeled from the peeling substrate.
D: Blocking was observed, and when the respective samples were peeled, the surface protective layer was peeled from the entire surface of the peeling substrate.

(4) Solvent resistance Ethyl acetate was soaked in a cotton cloth, the surface of the decorative member was rubbed 20 times with a load of 500 g / cd, and the state of the surface protective layer was observed.
A: No major change in appearance was observed.
B: Appearance change such as slight gloss change was observed.
C: A significant change in gloss occurred, and a large change in appearance was observed.
D: Coating film dissolution was observed.
(5) Workability After transferring the constituent layers other than the base material of the transfer foil sheet to the transferred member having an L-shaped cross section, the corners of the decorative member were visually observed.
A: No change in appearance was observed at the corners.
B: Very slight cracks were observed at the corners.
C: Large cracks were observed at the corners, and there was a problem level as a decorative member.

[Example 1]
A double bond equivalent, a weight average molecular weight, and a glass transition temperature are displayed on a release treatment surface of a 24 μm-thick polyethylene terephthalate (hereinafter referred to as PET) film (Mitsubishi Resin Co., Ltd.) whose one surface is release treatment. An electron beam curable urethane acrylate satisfying the condition 1 and an ink for a surface protective layer containing a diluting solvent are applied and dried so that the thickness after drying becomes the thickness shown in Table 1, and the uncured electron beam A curable surface protective layer was formed.
Thereafter, an acrylic polyol resin (hydroxyl value 80 mg KOH / g, weight average molecular weight 30,000, glass transition temperature 90 ° C.), containing an isocyanate compound having a (meth) acryloyl group (glass transition temperature 60 ° C.) and a diluting solvent are contained. The primer layer ink was applied by gravure printing so that the thickness after drying was 2 μm to form a primer layer. Next, an electron beam curable urethane acrylate is cured by irradiating an uncured electron beam curable resin layer with an acceleration voltage of 125 KeV and 5 Mrad in an environment having an oxygen concentration of 200 ppm from the surface on the primer layer side. I let you.
Next, a 2 μm-thick pattern layer is formed on the primer layer with a printing ink comprising an acrylic resin, a vinyl chloride-vinyl acetate copolymer system resin, a colorant and a diluent solvent. A concealing layer was formed with a printing ink comprising a vinyl-vinyl acetate copolymer resin, a colorant, and a diluent solvent to prepare a transfer foil sheet.

[Examples 2-7, 10, 11], [Comparative Examples 2-7, 9, 10]
A transfer foil sheet was produced in the same manner as in Example 1 except that the electron beam curable urethane acrylate was changed to one satisfying the conditions in Table 1 and the thickness of the surface protective layer was changed to the conditions shown in Table 1.

[Example 8]
Example 1 except that the electron beam curable urethane acrylate was changed to one satisfying the conditions of Table 1, and the timing of irradiating the electron beam was changed after the primer layer formation but before the surface protective layer formation and before the primer layer formation. A transfer foil sheet was prepared in the same manner as described above.

[Example 9]
A transfer foil sheet was prepared in the same manner as in Example 1 except that the electron beam curable urethane acrylate was changed to an electron beam curable acrylic acrylate that satisfies the conditions in Table 1.

[Example 12]
The electron beam curable urethane acrylate is an electron beam curable acrylic acrylate that satisfies the conditions in Table 1 and a urethane acrylate having a double bond equivalent of 3,000 g / eq, a weight average molecular weight of 20,000, and a glass transition temperature of 30 ° C. : A transfer foil sheet was produced in the same manner as in Example 1 except that the mixture was changed to 30 mixture.

[Example 13]
On the masking layer, acrylic resin (molecular weight 40,000, glass transition temperature 30 ° C.), urethane resin (molecular weight 80,000, glass transition temperature −20 ° C.) and block isocyanate (Asahi Kasei Chemicals Corporation, Duranate MF-K60X, dissociation temperature) The hot melt adhesive layer ink containing 90 ° C. is applied by gravure printing so that the thickness after drying is 2 μm, dried at 60 ° C. for 30 seconds, and the hot melt adhesive layer (heat A transfer foil sheet was produced in the same manner as in Example 1 except that the seal layer was formed.

[Comparative Example 1]
The electron beam curable urethane acrylate was changed to those satisfying the conditions in Table 1, the thickness of the surface protective layer was changed to the conditions shown in Table 1, and the acrylic polyol resin and isocyanate compound of the primer layer were changed to acrylic-urethane co-polymer. A transfer foil sheet was produced in the same manner as in Example 1 except that the polymerization resin was used.

[Comparative Example 8]
A transfer foil sheet was prepared in the same manner as in Example 1 except that the electron beam curable urethane acrylate was changed to an electron beam curable acrylic acrylate that satisfies the conditions in Table 1.

(Production of decorative members)
A polyurethane hot melt adhesive (KLEIBERIT PUR704) heated to 130 ° C. is applied on the concealing layer of the transfer foil sheets prepared in Examples 1 to 12 and Comparative Examples 1 to 10 to form an adhesive layer having a thickness of 20 μm. Then, before the hot-melt adhesive is solidified, the transfer foil sheet thus prepared is transferred to the transfer member made of vinyl chloride having an L-shaped cross section, and the transfer foil sheet has the adhesive layer side on the transfer member side. The member to be transferred and the transfer foil sheet were bonded to follow the shape of the member to be transferred. Subsequently, only the base material was peeled off to obtain a decorative member.
For the transfer member made of vinyl chloride having an L-shaped cross section, the transfer foil sheet produced in Example 13 is followed so that the hot melt adhesive layer side faces the transfer member, and the shape of the transfer member is followed. The member to be transferred and the transfer foil sheet were adhered while heating the temperature of the dryer and the heated rubber roll to 95 ° C. or higher. Subsequently, only the base material was peeled off to obtain a decorative member.

  As is clear from the results in Table 1, the transfer foil sheets of Examples 1 to 13 were excellent in transfer suitability, adhesion of the surface protective layer, coating strength of the surface protective layer, antiblocking property, and printability. It was.

(6) Additional evaluation of adhesiveness Additional evaluation of adhesiveness was performed on the decorative members obtained from the transfer foil sheets of Example 1 and Example 13. In the additional evaluation, using the same super-accelerated weather resistance test apparatus as the adhesive evaluation in (1) above, the decorative member was irradiated with a black panel temperature of 63 ° C. and an illuminance of 60 mW / cm ² for 20 hours. Thereafter, a cycle of condensation for 4 hours was repeated, and the adhesion between the surface protective layer and the primer layer after 70 hours was evaluated by the same method as in (1) above. As a result, the adhesion of Example 1 was “B”, and the adhesion of Example 13 was “A”. From this result, it can be seen that when the blocked isocyanate is contained in the adhesive layer, the adhesion can be improved.

  The transfer foil sheet of the present invention can be used for interior or exterior materials of buildings such as walls, ceilings and floors, window frames, doors, handrails, skirting boards, edges, moldings and other fittings, kitchens, furniture, home appliances, OA equipment. An interior material or exterior material of a vehicle can be used as a member to be transferred for these decorations. Since the transfer foil sheet of the present invention is excellent in followability, it can be used even if the member to be transferred has a non-planar shape such as one having an uneven shape, one having a curved surface, one having a corner, and the like. Moreover, since the transfer foil sheet of the present invention is a thin film and excellent in recyclability, it can be suitably used for joinery in which the concept of recycling is generalized.

10: transfer foil sheet 11: substrate 12: surface protective layer 13: primer layer 14: design layer 15: concealment layer 16: adhesive layer

Claims (9)

A transfer foil sheet having a surface protective layer and a primer layer in this order on a substrate, wherein the surface protective layer has a double bond equivalent of 250 to 800 g / eq, and a weight average molecular weight of 1,000 to 1,000. 40,000, containing a cured product of an ionizing radiation curable resin composition containing a (meth) acrylate resin having a glass transition temperature of 70 to 130 ° C., and having a thickness of 2 to 10 μm, the primer layer there will contain a cured product of a composition comprising a polyol resin and an isocyanate compound, the weight average molecular weight of the polyol resin is 20,000 to 50,000, and hydroxyl value is 30~130mgKOH / g Transfer foil sheet.   The transfer foil sheet according to claim 1, wherein the isocyanate compound has an ethylenically unsaturated bond group in the molecule.   The transfer foil sheet according to claim 1, wherein the polyol resin is an acrylic polyol resin.   The transfer foil sheet according to claim 1, further comprising a design layer on the primer layer.   The transfer foil sheet according to claim 4, further comprising an adhesive layer on the design layer.   The transfer foil sheet according to claim 5, further comprising a concealing layer between the design layer and the adhesive layer. The manufacturing method of the transfer foil sheet which performs the process of the following (1)-(3) in order.
(1) Ionizing radiation curable containing an acrylate resin having a double bond equivalent of 250 to 800 g / eq, a weight average molecular weight of 1,000 to 40,000, and a glass transition temperature of 70 to 130 ° C. on a substrate. (2) Step of forming the surface protective layer by applying and drying the surface protective layer ink containing the resin composition so that the thickness after drying is 2 to 10 μm. (2) The ionizing radiation fat curable resin composition things while having a uncured portion, on the surface protective layer, the weight average molecular weight of 20,000 to 50,000 and a hydroxyl value and a polyol resin and an isocyanate compound is 30~130mgKOH / g Step of applying and drying primer layer ink containing composition and forming primer layer (3) Ionizing radiation in surface protective layer by irradiating ionizing radiation from primer layer side Step to advance the cure of resistant resin composition   The decorative member with a base material which adhere | attaches a to-be-transferred member and the surface on the opposite side to the base material of the transfer foil sheet in any one of Claims 1-6.   The decorative member formed by peeling the base material of the surface of the decorative member with a base material of Claim 8.

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