JP2019151035A - Transfer film - Google Patents

Abstract

To provide a transfer film which can impart a design having low glossiness to a transferred body, exhibits excellent peelability between an intermediate layer and a surface layer, and has a surface layer excellent in solvent resistance.SOLUTION: A transfer film is formed of a laminate having at least a base material layer, an intermediate layer and a transfer layer in this order, in which the transfer layer has at least a surface layer in contact surface with the intermediate layer, the surface layer can be peeled from the intermediate layer, the surface layer contains an acrylic resin, and the intermediate layer is a cured product of a resin composition containing particles, a crosslinked acrylic resin and a polyfunctional amino compound.SELECTED DRAWING: None

Description

  The present invention relates to a transfer film.

  2. Description of the Related Art Conventionally, transfer films used for applications in which designs such as designs and characters are applied to a transfer object such as fabric are known.

  For example, Patent Document 1 discloses a thermal transfer film in which a substrate, a release layer, and a print forming layer made of a heat-adhesive resin are laminated. The thermal transfer film is peeled between the substrate and the peeling layer, and the peeling layer and the print forming layer are transferred to the transfer target.

  For example, in Patent Document 2, a base film made of a polyester film, a release layer, and a transfer layer (the transfer layer includes a release layer, and the release layer is in contact with the release layer) are sequentially stacked. A transfer film is disclosed. In the transfer film, the transfer layer is transferred to the transfer target so that the transfer layer is peeled between the release layer and the release layer.

Japanese Patent Laid-Open No. 9-300893 JP 2007-320147 A

  For example, a transfer film and a transfer layer are provided on a transfer film such as fabric, and the transfer layer is transferred to the transfer body, and the transfer substrate is peeled off from the transfer layer. Is done. The transfer layer includes a surface layer located on the surface after the transfer, and further, a printing layer or the like formed with colored ink is provided on the surface layer (on the side opposite to the transfer substrate). May be.

  The transfer film is required to have excellent peelability between the transfer substrate and the transfer layer in order to appropriately transfer the transfer layer to the transfer target.

  However, the thermal transfer film of Patent Document 1 described above has a very high necessary peeling force because the layer that is in contact with the peeling layer to be peeled is a base material, and cannot be practically used as a transfer film. Absent. Moreover, the transfer film of patent document 2 describes that an acrylic resin etc. can be used as a component of a mold release layer. In an acrylic resin that requires a component of the release layer, the required peeling force is very high. Therefore, the transfer film disclosed in Patent Document 2 is also not practical.

  In recent years, it has been required to apply various designs to fabrics using transfer films. For example, from the viewpoint of reducing the texture gap between the fabric and the transfer layer, the gloss of the transfer layer is reduced. Is required. However, for example, in the thermal transfer film of Patent Document 1, the glossiness of the release layer after transfer is high.

  Further, in the transfer layer of the transfer film, when a layer formed of an ink such as a printing layer is further laminated on the surface layer (on the side opposite to the transfer substrate), The surface layer and the intermediate layer are likely to be peeled off from the base material layer, which may cause a problem that the transfer layer cannot be properly transferred. For this reason, the surface layer is also required to have excellent solvent resistance.

  Under such circumstances, the present invention can impart a low-gloss design to the transfer object, exhibit excellent releasability between the intermediate layer and the surface layer, and the surface layer has excellent solvent resistance. The main object is to provide a transfer film.

  The present inventors have intensively studied to solve the above problems. As a result, it comprises a laminate comprising at least a base material layer, an intermediate layer, and a transfer layer in this order, and the transfer layer includes at least a surface layer in contact with the intermediate layer, and the surface layer Can be peeled from the intermediate layer, the surface layer contains an acrylic resin, and the intermediate layer is a cured product of a resin composition containing particles, a crosslinkable acrylic resin, and a polyfunctional amino compound. Found that a low-gloss design can be imparted to a material to be transferred such as a fabric, the intermediate layer and the surface layer have excellent releasability, and the surface layer has excellent solvent resistance. . The present invention has been completed by further studies based on such findings.

That is, the present invention includes the following.
[1] A laminate comprising at least a base material layer, an intermediate layer, and a transfer layer in this order,
The transfer layer includes at least a surface layer in contact with the intermediate layer,
The surface layer is peelable from the intermediate layer;
The surface layer includes an acrylic resin,
The said intermediate | middle layer is a transfer film which is a hardened | cured material of the resin composition containing particle | grains, a crosslinkable acrylic resin, and a polyfunctional amino compound.
[2] The transfer film according to Item 1, wherein a peeling force between the intermediate layer and the surface layer is 0.05 to 0.6 N / 25 mm.
[3] The transfer film according to Item 1 or 2, wherein a minimum film-forming temperature of the acrylic resin contained in the surface layer is 5 ° C. or lower.
[4] The transfer film according to any one of Items 1 to 3, wherein the particles are inorganic particles.
[5] The transfer film according to any one of Items 1 to 4, wherein the surface layer further contains an antistatic agent.
[6] The transfer film according to any one of Items 1 to 5, wherein the surface roughness Sa of the surface layer opposite to the intermediate layer is 0.1 μm or more.
[7] The transfer film according to any one of Items 1 to 6, wherein the 60-degree specular gloss on the opposite side of the surface layer from the intermediate layer is 60% or less.
[8] The transfer film according to any one of Items 1 to 7, wherein the surface layer has a surface resistance of 1.0 × 10 ¹³ Ω / sq or less.
[9] The transfer film according to any one of Items 1 to 8, which is used for transferring the transfer layer onto a fabric.

  According to the present invention, there is provided a transfer film composed of a laminate including at least a base material layer, an intermediate layer, and a transfer layer in this order, and a low-gloss design can be imparted to a transfer target, It is possible to provide a transfer film that exhibits excellent peelability between the surface layer and the surface layer, and further has excellent solvent resistance in the surface layer.

It is a schematic sectional drawing of an example of the transfer film of this invention. It is a schematic sectional drawing of an example of the transfer film of this invention. FIG. 2 is a schematic cross-sectional view of an example of a laminate (a transfer body with a base layer and an intermediate layer) in which the transfer film of FIG. 1 is transferred to a transfer target. FIG. 4 is a schematic cross-sectional view of an example of a transfer body obtained by peeling a base material layer and an intermediate layer from the transfer body of FIG. 3. FIG. 3 is a schematic cross-sectional view of an example of a transfer body obtained by transferring the transfer film of FIG. 2 to a transfer target body and peeling off a base material layer and an intermediate layer.

  The transfer film according to this embodiment includes a laminate including at least a base material layer, an intermediate layer, and a transfer layer in this order, and the transfer layer is at least a surface layer in contact with the intermediate layer. The surface layer is peelable from the intermediate layer, the surface layer includes an acrylic resin, and the intermediate layer includes a resin including particles, a crosslinkable acrylic resin, and a polyfunctional amino compound. It is a cured product of the composition. Hereinafter, the transfer film according to the present embodiment will be described in detail.

  In the present specification, “to” in a numerical range means the above and the following. That is, the expression α to β means α or more and β or less, or β or more and α or less, and includes α and β as a range. “(Meth) acryl” means “acryl or methacryl”, and other similar ones have the same meaning. In the present specification, the expression “acrylic resin” includes “acrylic resin and methacrylic resin”.

[Lamination structure of transfer film]
As shown in FIGS. 1 and 2, the transfer film 10 according to this embodiment has a laminated structure including at least a base material layer 1, an intermediate layer 2, and a transfer layer 11 in this order. As shown in FIG. 2, an anchor layer 8 or the like may be provided between the base material layer 1 and the intermediate layer 2. The transfer layer 11 is a layer to be transferred to a transfer medium such as a fabric, and may include a surface layer 3 to be described later and, if necessary, a smoothing layer 4, a printing layer 5, an adhesive layer 6 and the like. Good. FIG. 1 shows a transfer film 10 in which the transfer layer 11 has only the surface layer 3. FIG. 2 shows a transfer film 10 in which the transfer layer 11 has a surface layer 3, a smoothing layer 4, a printing layer 5, and an adhesive layer 6. In the transfer layer 11, the surface layer 3 is in contact with the intermediate layer 2. The surface layer 3 can be peeled off from the intermediate layer 2.

  As for the transfer film 10, the transfer layer 11 side is transcribe | transferred to the to-be-transferred body 7, the intermediate | middle layer 2 and the base material layer 1 are peeled from the transfer layer 11, and the transfer body 20 is obtained. For example, in the case of transferring the transfer film 10 of FIG. 1 to the transfer object 7, first, the transfer film 10 is transferred to the transfer object 7, and the base material layer 1 and the intermediate layer as shown in FIG. A transfer body 21 with 2 is obtained. Next, by peeling the base material layer 1 and the intermediate layer 2 from the transfer material 21 with the base material layer 1 and the intermediate layer 2, the transfer material 20 (the surface layer 3 and the material to be transferred) as shown in FIG. 7) is obtained. Similarly, when the transfer film 10 of FIG. 2 is transferred to the transfer target 7, the transfer member 20 (surface layer 3, smoothing layer 4, printing layer 5, adhesive layer 6, and transfer target as shown in FIG. 5) is obtained. 7) is obtained.

  As a specific example of the laminated structure of the transfer film according to the present embodiment, a laminated structure in which base material layer 1 / intermediate layer 2 / surface layer 3 are laminated in order; base material layer 1 / intermediate layer 2 / surface layer 3 / smooth Layered structure in which the fluorinated layer 4 is laminated in sequence; substrate layer 1 / intermediate layer 2 / surface layer 3 / smoothing layer 4 / printed layer 5 in layered structure; substrate layer 1 / intermediate layer 2 / surface Laminated structure in which layer 3 / smoothing layer 4 / printing layer 5 / adhesive layer 6 are laminated in order; laminated structure in which base material layer 1 / intermediate layer 2 / surface layer 3 / printing layer 5 are laminated in order; 1 / intermediate layer 2 / surface layer 3 / printing layer 5 / adhesive layer 6 laminated in sequence; base material layer 1 / intermediate layer 2 / surface layer 3 / smoothing layer 4 / printing layer 5 are laminated in order Laminated structure; base material layer 1 / intermediate layer 2 / surface layer 3 / smoothing layer 4 / adhesive layer 6 laminated in order; base material layer 1 / intermediate layer 2 / surface layer 3 / adhesive layer 6 Laminated structure laminated in order; laminated structure in which base material layer 1 / anchor layer 8 / intermediate layer 2 / surface layer 3 are laminated in order; base material layer 1 / anchor layer 8 / intermediate layer 2 / surface layer 3 / smoothing Laminate structure in which layer 4 is laminated in order; Laminate structure in which base material layer 1 / anchor layer 8 / intermediate layer 2 / surface layer 3 / smoothing layer 4 / printing layer 5 are laminated in order; base material layer 1 / anchor layer 8 / intermediate layer 2 / surface layer 3 / smoothing layer 4 / printing layer 5 / adhesive layer 6 laminated in order; base material layer 1 / anchor layer 8 / intermediate layer 2 / surface layer 3 / printing layer 5 Layered structure in which base material layer 1 / anchor layer 8 / intermediate layer 2 / surface layer 3 / printing layer 5 / adhesive layer 6 are sequentially laminated; base material layer 1 / anchor layer 8 / intermediate Layer 2 / surface layer 3 / smoothing layer 4 / printing layer 5 laminated in order; base layer 1 / anchor layer 8 / intermediate layer 2 / surface layer 3 / flat Layer 4 / adhesive layer 6 is laminated structure are laminated in this order; substrate layer 1 / anchor layer 8 / intermediate layer 2 / the surface layer 3 / the adhesive layer 6 like laminated structure which are sequentially stacked. FIG. 1 is a schematic diagram of a cross-sectional structure of an embodiment of a transfer film 10 in which a base layer 1 / an intermediate layer 2 / a surface layer 3 are laminated in this order as an aspect of a laminated structure of the transfer film 10 of the present embodiment. Show. In FIG. 2, as one aspect of the laminated structure of the transfer film 10 of this embodiment, a base layer 1 / anchor layer 8 / intermediate layer 2 / surface layer 3 / smoothing layer 4 / printing layer 5 / adhesive layer 6 These show the schematic diagram of the cross-sectional structure of one form of the transfer film 10 laminated | stacked in this order.

  1 to 5, the interface between the intermediate layer 2 and the surface layer 3 and the interface between the surface layer 3 and the smoothing layer 4 are regularly arranged in semicircles and straight lines with uniform sizes. Although described in a lined shape, this schematically represents that the interface is roughened, and does not necessarily mean a regular shape as shown. Nor does it mean that the two interfaces have the same shape.

[Each layer of transfer film]
(Base material layer 1)
The base material layer 1 is formed of a resin sheet (resin film) serving as a support in the transfer film 10.

  The resin component used for the base material layer 1 is not particularly limited as long as it plays a role as a support and can transfer the transfer layer to the transfer target 7 by transfer, for example. As a resin component used for the base material layer 1, a thermoplastic resin and a thermosetting resin are mentioned, for example. Specific examples of the thermoplastic resin include polyester resins such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polypropylene terephthalate, polypropylene naphthalate, polytrimethylene terephthalate, and polybutylene terephthalate; polyethylene, polypropylene, 4-methyl Polyolefin resins such as pentene-1 polymer resins and cyclic olefin resins; polystyrene resins such as amorphous polystyrene resins and crystalline polystyrene resins; acetyl cellulose resins such as cellulose and triacetyl cellulose; polymethacrylates Acrylic resins such as polymethylmethacrylate; Thermoplastic polyurethane resins such as polyether, polyester and polycarbonate; Polycarbonate Resins, polyamide resins such as nylon 66; thermoplastic imide resins such as polyimide and polyetherimide; sulfone resins such as polysulfone and polyethersulfone; polyphenylene sulfide resins and polyetheretherketone resins; polyvinyl alcohol Examples of the resin include: vinyl resins such as polyvinyl acetate and polyvinyl chloride; polylactic acid resins; rubber resins such as butadiene resins, styrene butadiene resins, and silicone resins. Examples of the thermosetting resin include epoxy resins, phenol resins, urea resins, melamine resins, silicone resins, unsaturated polyester resins, thermosetting polyurethane resins, thermosetting imide resins, and the like. Among these, polyethylene terephthalate is preferable from the viewpoint of high strength and high heat resistance.

  As a resin component which forms the base material layer 1, only 1 type may be used and 2 or more types may be mixed and used. Moreover, the base material layer 1 may be formed with the single layer sheet | seat of these resin, and may be formed with the multilayer sheet | seat by the same kind or different kind | species resin.

  The base material layer 1 may be a layer formed from any of an unstretched film, a uniaxially stretched film, or a biaxially stretched film. From the viewpoint of heat resistance and strength, the base material layer is preferably a layer formed from a biaxially stretched film.

  The base material layer 1 may be subjected to a surface treatment as desired. As the surface treatment, for example, a surface oxidation treatment for improving adhesion with an anchor layer or an intermediate layer, which will be described later, or a back surface of the base material layer (a surface opposite to the provision of an intermediate layer, a transfer layer, etc. described later) For example, a roughening treatment for preventing side blocking may be mentioned. Examples of the surface oxidation treatment include corona discharge treatment, plasma treatment, acid treatment, flame treatment, hot air treatment, ozone treatment, ultraviolet irradiation treatment, and electron beam treatment. Examples of the unevenness treatment include sandblast treatment and solvent treatment.

  The thickness of the base material layer 1 is not particularly limited and is appropriately set, but is preferably about 10 to 200 μm, more preferably about 20 to 150 μm, and still more preferably about 35 to 120 μm. The thickness of the base material layer is measured according to JIS C 2151: 2006 using a micrometer (JIS B 7502: 1994).

(Anchor layer 8)
In the transfer film of this embodiment, the adhesiveness between the intermediate layer 2 and the base material layer 1 is increased, and it is easy to prevent a part of the intermediate layer from being peeled off from the base material layer at the time of transfer. An anchor layer 8 may be provided between the base material layer 1 and the intermediate layer 2. The anchor layer 8 may be one layer or two or more layers.

  Although it does not specifically limit as a component which comprises the anchor layer 8, For example, polyolefin resin, polyester resin, urethane resin, acrylic resin, styrene resin, cellulose resin, silicone resin, vinyl alcohol resin, Examples thereof include ethylene vinyl alcohol resins, isocyanate group-containing resins, carbodiimide resins, epoxy resins, and oxazoline group-containing resins. The components constituting the anchor layer 8 may be one type or two or more types. These resins may be introduced with a carboxyl group or a hydroxy group for the purpose of enhancing the adhesiveness with the base material layer or the intermediate layer.

Although the thickness of the anchor layer 8 is not specifically limited, 0.1-3 micrometers is preferable. The coating amount of the anchor layer 8 is not particularly limited, but is preferably 0.1 to 3 g / m ² .

  For example, the anchor layer 8 is formed by extruding or coating the surface of the base material layer 1 with a coating solution containing a solvent as it is or in addition to the components of the anchor layer 8. It can be formed by solidifying by using solidification means such as drying or energy ray irradiation alone or in combination. As the solvent, the same solvents as those exemplified in the intermediate layer 2 and the surface layer 3 described later can be used.

(Intermediate layer 2)
The intermediate layer 2 is provided between the base material layer 1 and the surface layer 3. The intermediate layer 2 is in contact with the surface layer 3 and is substantially peelable from the surface layer 3. Here, substantially peeling means that a small amount of components of the surface layer 3 are attached to the surface of the intermediate layer 2 after peeling, and that a small amount of components of the intermediate layer 2 are attached to the surface of the surface layer 3 after peeling. Is allowed to adhere. The mass ratio of the component of the trace amount of the intermediate layer 2 and the mass ratio of the component of the trace amount of the surface layer 3 are each preferably 20% by mass or less, more preferably 10 mass% of the total mass of each layer before peeling. % Or less, and more preferably 5% by mass or less.

  The intermediate layer 2 is a cured product of a resin composition containing particles, a crosslinkable acrylic resin, and a polyfunctional amino compound. In the transfer film 10, the intermediate layer 2 is a cured product of a resin composition containing particles, a crosslinkable acrylic resin, and a polyfunctional amino compound, and the surface layer 3 that is in contact with the intermediate layer 2 includes: As will be described later, by including an acrylic resin, it is possible to give a design with low gloss to the transfer body 7, and excellent peelability between the intermediate layer 2 and the surface layer 3 is exhibited, and the surface layer 3 is excellent. The solvent resistance can be exhibited.

  The particles contained in the intermediate layer 2 exist in a state where the shape of the particles is maintained. On the other hand, the crosslinkable acrylic resin constitutes the base material (matrix) of the particles together with the polyfunctional amino compound in the resin composition. Therefore, in the resin composition, the crosslinkable acrylic resin is not in the form of particles. The particles contained in the intermediate layer 2 are not particularly limited as long as the surface on the surface layer 3 side of the intermediate layer 2 can be roughened, and both inorganic particles and organic particles can be used. Moreover, inorganic-organic composite particles may be used. From the viewpoint of suppressing deformation when heat or pressure is applied during transfer and maintaining the desired roughness, and from the viewpoint of solvent resistance, inorganic particles are preferred, and the particle size distribution is uniform and desired. From the viewpoint of easily obtaining the surface roughness, organic particles are preferable. Only one type of particle may be used, or two or more types may be mixed and used.

  Specific examples of the inorganic particles include white pigments and colored pigments. For example, light calcium carbonate, heavy calcium carbonate, kaolin, calcined kaolin, talc, calcium sulfate, barium sulfate, titanium dioxide, zinc oxide, zinc sulfide, zinc carbonate, satin white, aluminum silicate, diatomaceous earth, calcium silicate, magnesium silicate Synthetic amorphous silica, colloidal silica, alumina, colloidal alumina, boehmite, pseudoboehmite, aluminum hydroxide, magnesium carbonate, magnesium hydroxide, zeolite, smectite and the like. Among these, synthetic amorphous silica is preferable because the particle diameter is uniform and the affinity between the crosslinkable acrylic resin and the polyfunctional amino compound described above and below is good. The method for producing the synthetic amorphous silica is not particularly limited, and the synthetic amorphous silica can be produced using a dry method such as a combustion method or an arc method, or a wet method such as a precipitation method or a gel method. Among these, silica produced by a wet method is preferable because it has a larger number of surface silanol groups than a product produced by a dry method, and thus a layer excellent in coating film strength and solvent resistance is easily formed.

  The synthetic amorphous silica may have a modified surface. As the synthetic amorphous silica whose surface has been modified, for example, within a range that does not impair the coating film strength and solvent resistance, the dispersibility in the solvent at the time of coating is improved and the coating suitability is improved. For the purpose, silanes, silicones, various waxes, various surfactants, inorganic salts and the like can be used.

  A commercially available product may be used as the synthetic amorphous silica. For example, Mizusawa Chemical Industry Co., Ltd. Mizukasil (registered trademark) series, Fuji Silysia Chemical Co., Ltd. silicia (registered trademark) series, Tosoh Silica Co., Ltd. nip seal (registered trademark) series, etc. are suitable as commercially available products. Can be used.

  As organic particles, polyamide resin, polyester resin, polycarbonate resin, polyether resin, polyolefin resin, polysulfone resin, polystyrene resin, polyurethane resin, polyacrylic resin, polyvinyl chloride resin, polyvinylidene chloride resin, Examples thereof include spherical organic particles such as ethylene-vinyl acetate copolymer resin, styrene copolymer resin, acrylic resin, and phenol resin. As a resin constituting the organic particles, a thermosetting resin or a glass transition temperature is added at the time of transfer from the viewpoint of easily suppressing the deformation and maintaining the desired roughness when heat or pressure is applied at the time of transfer. Resins higher than the temperature are preferred. Moreover, as an organic particle, although a hollow particle and a solid particle can be used, a solid particle is preferable for the same reason. The organic particle component is preferably a crosslinkable resin from the viewpoint of solvent resistance.

  The average particle diameter of the particles is not particularly limited as long as the surface of the intermediate layer 2 on the surface layer 3 side can be roughened. From the viewpoint of suitably imparting the low gloss design of the surface layer 3 while exhibiting excellent peelability between the intermediate layer 2 and the surface layer 3, the average particle diameter of the particles is preferably about 2 to 12 μm, more Preferably about 4-10 micrometers, More preferably, about 5-7 micrometers is mentioned. In addition, although inorganic particles such as synthetic amorphous silica have a structure in which primary particles form aggregates (secondary particles), the average particle size refers to the secondary particle size.

  In the present invention, the average particle diameter of the particles contained in the intermediate layer 2 is selected by randomly selecting 20 or more particles in an image obtained by observing the cross section of the intermediate layer 2 with an electron microscope. It is the average value of the maximum diameters measured for the particles.

  The particle content ratio in the intermediate layer 2 is not particularly limited as long as the surface of the intermediate layer 2 on the surface layer 3 side can be roughened. From the viewpoint of suitably imparting a low-gloss design of the surface layer 3 while exhibiting excellent peelability between the intermediate layer 2 and the surface layer 3, the content of the particles in the intermediate layer 2 is such that the particles and the crosslinkable acrylic The total mass of the resin and the polyfunctional amino compound is 100 parts by mass, preferably about 5 to 30 parts by mass, more preferably about 8 to 25 parts by mass, and still more preferably about 10 to 22 parts by mass.

  The crosslinkable acrylic resin is a resin that is a main component of the intermediate layer 2. Here, in this specification, the main component means a component having the largest contained mass in each layer. The crosslinkable acrylic resin is an acrylic resin having a functional group that forms a crosslinked structure by reacting with a polyfunctional amino compound described later. Examples of such functional groups include hydroxy groups (sometimes referred to as hydroxyl groups or hydroxyl groups), carboxy groups, amino groups, amide groups, and the like.

  The crosslinkable acrylic resin is not particularly limited as long as it can react with a polyfunctional amino compound to form a crosslinked structure, and examples thereof include acid-modified acrylic resins, polyol-type acrylic resins, and polyacrylamines.

  The acid-modified acrylic resin is a polymer obtained by modifying an acrylic resin by block polymerization or graft polymerization with an acid component such as carboxylic acid. Examples of the acid component used for modification include carboxylic acids such as maleic acid, acrylic acid, itaconic acid, crotonic acid, maleic anhydride, and itaconic anhydride, or anhydrides thereof. The acrylic resin to be modified includes a homopolymer of (meth) acrylic acid ester, a copolymer of two or more different (meth) acrylic acid ester monomers, or (meth) acrylic acid ester and other monomers. The copolymer of these is mentioned. More specifically, acid-modified acrylic resins include poly (meth) acrylate methyl, poly (meth) ethyl acrylate, poly (meth) acrylate propyl, poly (meth) acrylate butyl, and (meth) acrylic. Methyl acid-butyl (meth) acrylate copolymer, Ethyl (meth) acrylate-butyl (meth) acrylate copolymer, Ethylene-methyl methacrylate copolymer, Styrene-methyl (meth) acrylate Examples include (meth) acrylic acid esters such as copolymers.

  The polyol-type acrylic resin is an acrylic resin having a plurality of hydroxy groups. Examples of polyol-type acrylic resins include alkyl (meth) acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and octyl (meth) acrylate. And 2-hydroxyethyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate and other (meth) acrylic acid ester having a hydroxyl group in the molecule Can be obtained.

  As the form before the acrylic resin is applied, it may be dissolved in water, an organic solvent or the like, or dispersed using a dispersant such as a surfactant (emulsion), or a mixture of them. May be. Only one type of acrylic resin may be used, or two or more types may be mixed and used.

  A commercial item can also be used as a crosslinkable acrylic resin. Preferred commercial products of the crosslinkable acrylic resin include a crosslinkable acid-modified acrylic resin, DIC Corporation's ACRICID (registered trademark) series (for example, A-452), and a crosslinkable polyol-type acrylic. Examples thereof include YL-455 (manufactured by Toyo Ink Co., Ltd.), which is a resin.

  The content of the crosslinkable acrylic resin in the intermediate layer 2 is from the viewpoint of suitably imparting the low gloss design of the surface layer 3 while exhibiting excellent peelability between the intermediate layer 2 and the surface layer 3. The total mass of the crosslinkable acrylic resin and the polyfunctional amino compound is 100 parts by mass, preferably about 55 to 90 parts by mass, more preferably about 60 to 85 parts by mass, and further preferably about 65 to 80 parts by mass. . The intermediate layer 2 is a cured product of a resin composition containing particles, a crosslinkable acrylic resin, and a polyfunctional amino compound. In the intermediate layer 2, the crosslinkable acrylic resin has undergone a crosslinking reaction with the polyfunctional amino compound. It is contained in the state.

  The polyfunctional amino compound is an amino compound having a plurality of functional groups that undergo a crosslinking reaction with the crosslinkable acrylic resin. Examples of the polyfunctional amino compound include melamine resin, urea resin, benzoguanamine resin, and diamines. Examples of melamine resins include methylated melamine resins and butylated melamine resins. Examples of urea resins include methylated urea resins and butylated urea resins. Examples of benzoguanamine resins include methylated benzoguanamine resins and butylated benzoguanamine resins. Examples of diamines include ethylene diamine, tetramethylene diamine, hexamethylene diamine, N, N′-diphenylethylene diamine, and p-xylylenediamine. Among these, methylated melamine is particularly preferable.

  A commercial item can also be used as a polyfunctional amino compound. As a preferable commercial item of a polyfunctional amino compound, Nicarak (registered trademark) MW-30MLF (manufactured by Nippon Carbide Co., Ltd. (full ether type polyfunctional amino compound)), Nicarac (registered trademark) MS-001 (Nippon Carbide ( (Methylated melamine polyfunctional amino compound having imino group and methylol group)) and the like.

  The content of the polyfunctional amino compound in the intermediate layer 2 is from the viewpoint of suitably imparting the low gloss design of the surface layer 3 while exhibiting excellent peelability between the intermediate layer 2 and the surface layer 3. The total mass of the crosslinkable acrylic resin and the polyfunctional amino compound is 100 parts by mass, preferably about 5 to 20 parts by mass, more preferably about 8 to 18 parts by mass, and further preferably about 10 to 16 parts by mass. The intermediate layer 2 is a cured product of a resin composition containing particles, a crosslinkable acrylic resin, and a polyfunctional amino compound. In the intermediate layer 2, the polyfunctional amino compound has undergone a crosslinking reaction with the crosslinkable acrylic resin. It is contained in the state.

  The resin composition forming the intermediate layer 2 preferably further contains a catalyst in addition to the particles, the crosslinkable acrylic resin, and the polyfunctional amino compound. The catalyst is not particularly limited as long as it accelerates the curing of the crosslinkable acrylic resin and the polyfunctional amino compound, and a known catalyst can be used. Examples of the catalyst include acidic catalysts such as paratoluenesulfonic acid, methyl paratoluenesulfonate, ethyl paratoluenesulfonate, nbutyl paratoluenesulfonate, benzenesulfonic acid, sulfonic acid, and methanesulfonic acid.

  The content of the catalyst in the intermediate layer 2 is suitable for coating the surface layer and the like by increasing the solvent resistance of the surface layer 3 while exhibiting excellent peelability between the intermediate layer 2 and the surface layer 3. From the viewpoint of improving the quality, the total mass of the particles, the crosslinkable acrylic resin and the polyfunctional amino compound is 100 parts by mass, preferably about 0.1 to 5.0 parts by mass, more preferably 1.0 to 4. About 0 mass part is mentioned.

  In addition to the particles, the crosslinkable acrylic resin, the polyfunctional amino compound, the catalyst added if necessary, the intermediate layer 2 further includes a solvent-containing coating solution (intermediate layer coating solution) as a base material. It can be formed by coating on the surface of the layer 1 or the anchor layer 8. The solvent is not particularly limited. For example, hydrocarbons such as hexane, heptane, octane, toluene, xylene, ethylbenzene, cyclohexane, and methylcyclohexane; halogenated hydrocarbons such as dichloromethane, trichloroethane, trichloroethylene, tetrachloroethylene, and dichloropropane Alcohols such as methanol, ethanol, propanol, isopropyl alcohol, butanol, isobutyl alcohol and diacetone alcohol; ethers such as diethyl ether, diisopropyl ether, dioxane and tetrahydrofuran; acetone, methyl ethyl ketone, methyl isobutyl ketone, isophorone and cyclohexanone Ketones: methyl acetate, ethyl acetate, butyl acetate, isobutyl acetate, amyl acetate, ethyl butyrate Esters of ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether acetate and other organic solvents such as derivatives thereof Can be used. Only one type of solvent may be used, or two or more types may be mixed and used.

  The solvent preferably has a surface tension at 25 ° C. of 20 mN / m or more and less than 40 mN / m, more preferably 22 mN / m or more and less than 36 N / m. If the surface tension is not less than the lower limit of the above range, application defects such as yuzu skin (orange peel) are unlikely to occur, and if the surface tension is less than the upper limit of the above range, application defects such as thick edges (framing) are unlikely to occur.

  The boiling point of the solvent is preferably 10 to 150 ° C., more preferably 20 to 120 ° C., from the viewpoint of easily improving the production efficiency of the handling property of the coating liquid. Preferred solvents include hexane, heptane, cyclohexane, benzene, toluene, ethanol, isopropyl alcohol, diisopropyl ether, tetrahydrofuran, acetone, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate and the like.

  Further, the total solid content concentration of the intermediate layer coating liquid is not particularly limited, but a viewpoint of uniformly coating the intermediate layer 2 by suitably dispersing components such as particles in the intermediate layer coating liquid. Therefore, Preferably about 10-30 mass% is mentioned.

[Dispersant]
The mid layer 2 may contain a dispersant. The dispersant is preferable because it improves dispersion of the particles in the solvent to improve the coating suitability, and improves the compatibility of the particles in the resin composition to improve the coating strength and solvent resistance. Examples of the dispersant include anionic polymer dispersants such as polycarboxylic acid partial alkyl ester, nonionic polymer dispersants such as polyether, and cationic polymer dispersants such as polyalkylene polyamine. And nonionic surfactant type dispersants such as polyhydric alcohol esters, and cationic surfactant type dispersants such as alkylpolyamines. Examples of commercially available dispersants include SN Dispersant (registered trademark) series, Nopco Spurs (registered trademark) series, SN Sparse (registered trademark) series manufactured by San Nopco Corporation. Only one type of dispersant may be used, or two or more types of dispersants may be mixed and used. The content of the dispersant in the intermediate layer 2 is preferably 0.01 to 5 with the total mass of the particles, the crosslinkable acrylic resin, and the polyfunctional amino compound being 100 parts by mass from the viewpoint of easily obtaining good dispersibility. About 0.0 parts by mass, more preferably about 0.1 to 3.0 parts by mass.

〔Additive〕
The intermediate layer 2 may contain at least one additive as long as it does not impair the effects of the present invention. Examples of the additive include adhesives, antioxidants, ultraviolet absorbers, lubricants, plasticizers, flame retardants, colorants, viscosity modifiers, antifoaming agents, antistatic agents, and the like. Only one type of additive may be used, or two or more types may be mixed and used.

  Although it does not specifically limit as an adhesive agent, For example, a thermoplastic resin, a thermosetting resin, etc. are mentioned. An adhesive agent can be used 1 type or in combination of 2 or more types.

  Adhesive thermoplastic resins include polyamide, polyolefin (eg, polyethylene, polypropylene, etc.), polycarbonate, polyester (eg, polyethylene terephthalate, polyethylene naphthalate, etc.), polystyrene, polyphenylene sulfide, polyvinyl chloride, acrylonitrile-butadiene-styrene. Examples include copolymer resin (ABS resin), acrylonitrile-styrene copolymer resin, polyacetal, polyvinyl alcohol, polyvinylidene chloride, polyetherimide, acetylcellulose, nitrocellulose, cellulose propionate, and ethylcellulose.

  Examples of the thermosetting resin for the adhesive include phenol resin, epoxy resin, urea resin, unsaturated polyester resin, thermosetting polyurethane resin, silicone resin, diallyl phthalate resin and the like.

  The antioxidant is not particularly limited. For example, 2,6-di-tert-butyl-p-cresol (generic name: BHT), phenolic, hindered amine, phosphite, lactone and tocopherol An antioxidant is mentioned. Specifically, dibutylhydroxytoluene, pentaerythritol tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 1,3,5-trimethyl-2,4,6-tris ( 3,5-di-t-butyl-4hydroxy) benzene and tris (2,4-di-t-butylphenyl) phosphite.

  Although it does not specifically limit as a ultraviolet absorber, For example, benzotriazole (Tinuvin 328 etc. made from BASF), benzophenone (Cytec UV-531 etc. made from Cytec), hydroxybenzoate (UV-CHEK-AM-340 etc. made from Ferro) etc. are mentioned, It is done.

  Although it does not specifically limit as a lubricant, For example, low molecular weight polyolefins, such as polyethylene, a polypropylene, polybutene; Silicones which have a softening point by heating; Fatty acids, such as oleic acid amide, erucic acid amide, ricinoleic acid amide, stearic acid amide Amides; plant waxes such as carnauba wax, rice wax, candelilla wax, tree wax, jojoba oil; animal waxes such as beeswax; montan wax, ozokerite, ceresin, paraffin wax, microcrystalline wax, Fischer-Tropsch wax, etc. And synthetic waxes such as mineral waxes, petroleum waxes and ester waxes.

  Although it does not specifically limit as a plasticizer, For example, a citric acid ester, dibutyl phthalate, polyethyleneglycols, propylene glycol, glycerol etc. are mentioned.

  Examples of the colorant include various colored dyes, colored pigments, and fluorescent dyes.

  Although it does not specifically limit as a flame retardant, For example, a halogen compound, aluminum hydroxide, magnesium hydroxide, a phosphate, a borate, an antimony oxide, etc. are mentioned.

  The viscosity modifier is not particularly limited, and examples thereof include starch, cellulose, modified cellulose, pectin, carrageenan, guar gum, locust bean gum, tamarind gum, xanthan gum, curdlan and the like.

  Although it does not specifically limit as an antifoamer, For example, a silicone type antifoamer, a polyether type antifoamer, a fatty acid ester antifoamer, a fluorine type antifoamer etc. are mentioned.

  As the antistatic agent, those similar to those used for the surface layer 3 can be used.

The coating amount of the intermediate layer 2 is not particularly limited, but from the viewpoint of suitably exhibiting the low gloss design of the surface layer 3 while exhibiting excellent peelability between the intermediate layer 2 and the surface layer 3. preferably 0.5 to 3.0 g / m ^2, more preferably about 0.7 to 2.5 g / m ^2, and more preferably about include about 1.0 to 2.0 g / m ^2.

  In addition, the thickness of the intermediate layer 2 is not particularly limited, but from the viewpoint that the low gloss design of the surface layer 3 is suitably achieved while exhibiting excellent peelability between the intermediate layer 2 and the surface layer 3. Preferably about 0.5-3.0 micrometers, More preferably, about 0.7-2.5 micrometers, More preferably, about 1.0-2.0 micrometers is mentioned. Here, the thickness is the thickness of the coating layer when the cross section of the film is observed with an electron microscope. In addition, since the coating layer is roughened, the coating surface is not flat. Therefore, the coating layer thickness is calculated as an average value of the thicknesses measured at arbitrary 10 points randomly selected in the visual field.

  The peeling force between the intermediate layer 2 and the later-described surface layer 3 is preferably about 0.05 to 0.6 N / 25 mm, more preferably from the viewpoint of exhibiting excellent peelability between the intermediate layer 2 and the surface layer 3. About 0.1 to 0.55 N / 25 mm, more preferably about 0.2 to 0.50 N / 25 mm, and particularly preferably about 0.25 to 0.45 N / 25 mm.

  Moreover, as hardening conditions of the resin composition which forms the intermediate | middle layer 2, hardening temperature about 70-170 degreeC and hardening time about 0.1-10 minutes are mentioned.

  The peel force between the intermediate layer 2 and the surface layer 3 of the transfer film 10 is a value measured using a peel tester, and is specifically measured by the method described in the examples.

<Transfer layer 11>
The transfer layer 11 is a layer that is transferred from the transfer film 10 to the transfer target 7. By transferring the transfer layer 11 to the transfer body 7, for example, a design such as a pattern or a shape included in the transfer layer 11 can be applied to the transfer body 7 to manufacture the transfer body 20. As described above, the transfer layer 11 includes the surface layer 3 provided so as to be in contact with the intermediate layer 2, and further, the smoothing layer 4, the print layer 5, the adhesive layer 6, and the like as necessary. You may have. Hereinafter, each layer of the transfer layer 11 will be described in detail.

(Surface layer 3)
The surface layer 3 is provided on the opposite side of the intermediate layer 2 from the base material layer 1 side. The surface layer 3 is in contact with the intermediate layer 2 and can be peeled off from the intermediate layer 2.

  The surface layer 3 is characterized by containing an acrylic resin. As described above, in the transfer film 10, the intermediate layer 2 is a cured product of a resin composition containing particles, a crosslinkable acrylic resin, and a polyfunctional amino compound, and the surface is in contact with the intermediate layer 2. When layer 3 contains an acrylic resin, a design with low gloss can be imparted to transferred object 7, excellent peelability between intermediate layer 2 and surface layer 3 is exhibited, and surface layer 3 is excellent. The solvent resistance can be exhibited.

  The low gloss design can be imparted to the transfer body 7 because the surface of the intermediate layer 2 containing particles is roughened by the irregular shape of the particles, Since the surface layer 3 is formed on the surface layer 3, the uneven shape corresponding to the uneven shape of the intermediate layer 2 is formed on the surface of the surface layer 3 on the intermediate layer 2 side (that is, the outermost surface of the transfer body 20 after transfer). Because it is. Due to the uneven shape of the surface layer 3, the transfer body 20 can exhibit a low gloss design.

  In the transfer film 10, the intermediate layer 2 is a cured product of a resin composition containing particles, a crosslinkable acrylic resin, and a polyfunctional amino compound, and the surface layer 3 is in contact with the intermediate layer 2. However, by including an acrylic resin, the adhesive strength between the intermediate layer 2 and the surface layer 3 is appropriately adjusted, and excellent peelability between the intermediate layer 2 and the surface layer 3 is exhibited (specifically, With peel force (N / 25 mm).

  Furthermore, when the surface layer 3 contains an acrylic resin, the action of the solvent contained in the ink used for forming the printing layer 5 and the like can be obtained even when the printing layer 5 and the like described later are laminated on the surface layer 3. Thus, the surface layer 3 is effectively prevented from being unintentionally peeled off from the intermediate layer 2 (that is, peeled off except when the transfer layer 11 is transferred). In addition, the penetration of the solvent from the surface layer 3 to the intermediate layer 2 is also suppressed, and unintentional peeling of the intermediate layer 2 from the base material layer 1 due to the penetration of the solvent (peeling other than when transferring the transfer layer 11) is also caused. Effectively suppressed. That is, when the surface layer 3 contains an acrylic resin, excellent peelability between the intermediate layer 2 and the surface layer 3 is exhibited, and the solvent resistance of the surface layer 3 is suitably enhanced.

  The minimum film-forming temperature of the acrylic resin is preferably 5 ° C. or less, more preferably 2 ° C. or less, from the viewpoint of further improving the peelability and solvent resistance. The minimum film forming temperature of the acrylic resin is preferably −10 ° C. or higher with respect to the lower limit.

  In the present invention, the minimum film-forming temperature refers to the minimum temperature at which an emulsion polymer is fused to form a film (film-forming) when the dispersion solvent evaporates. The minimum film-forming temperature is measured by a method based on ISO 2115, and for example, a film-forming temperature (MFT) test apparatus manufactured by Imoto Seisakusho Co., Ltd. can be used.

  The acrylic resin is not particularly limited. For example, a homopolymer of (meth) acrylic acid ester, a copolymer of two or more different (meth) acrylic acid ester monomers, or (meth) acrylic acid ester and other Examples thereof include a copolymer with a monomer. More specifically, as the acrylic resin, poly (meth) methyl acrylate, poly (meth) ethyl acrylate, poly (meth) acrylate propyl, poly (meth) acrylate butyl, (meth) acrylate methyl- ( (Meth) butyl acrylate copolymer, (meth) ethyl acrylate- (meth) butyl acrylate copolymer, ethylene- (meth) methyl acrylate copolymer, styrene- (meth) methyl acrylate copolymer, etc. (Meth) acrylic acid ester and the like. As the form before the acrylic resin is applied, it may be dissolved in water, an organic solvent or the like, or dispersed using a dispersant such as a surfactant (emulsion), or a mixture of them. May be. Only one type of acrylic resin may be used, or two or more types may be mixed and used.

  The content of the acrylic resin in the surface layer 3 suitably imparts a low-gloss design of the surface layer 3 while exhibiting excellent peelability between the intermediate layer 2 and the surface layer 3, and further improves solvent resistance. From the standpoint of exhibiting, the total component contained in the surface layer 3 is 100 parts by mass, preferably about 80 to 97 parts by mass, more preferably about 82 to 95 parts by mass, and still more preferably about 86 to 93 parts by mass.

  In the transfer film 10, from the viewpoint of suitably imparting the low gloss design of the surface layer 3, the surface roughness Sa on the side opposite to the intermediate layer 2 side of the surface layer 3 is preferably about 0.1 μm or more, more Preferably about 0.14-0.5 micrometer, More preferably, about 0.17-0.4 micrometer, More preferably, about 0.19-0.35 micrometer is mentioned.

  In the transfer film 10, the surface roughness Sa on the side opposite to the intermediate layer 2 side of the surface layer 3 is a value measured using an optical interference type non-contact surface shape measuring instrument. Is a value measured by the method described in 1.

  Further, in the transfer film 10, from the viewpoint of suitably imparting the low gloss design of the surface layer, the 60 degree specular gloss on the side opposite to the intermediate layer 2 side of the surface layer 3 is preferably about 60% or less, More preferably, it is about 1 to 60%, more preferably about 5 to 50%, and particularly preferably about 10 to 40%.

  In the transfer film 10, the 60 degree specular glossiness of the surface layer 3 on the side opposite to the intermediate layer 2 side is a value measured by a method in accordance with the provisions of JIS-Z8741: 1997 (Method 3). Is a value measured by the method described in Examples.

  Furthermore, the 60-degree specular gloss of the surface layer 3 after the transfer film 10 is transferred to the transfer body 7 (that is, the 60-degree specular gloss on the intermediate layer 2 side) is preferably about 20% or less, more preferably Is about 1 to 20%, more preferably about 1 to 15%, and particularly preferably about 2 to 10%.

  The 60-degree specular gloss of the surface layer 3 after the transfer film 10 is transferred to the transfer body 7 (that is, the 60-degree specular gloss on the intermediate layer 2 side) is stipulated in JIS-Z8741: 1997 (Method 3). It is a value measured by a compliant method, specifically a value measured by the method described in the examples.

  The surface layer 3 preferably further contains an antistatic agent in addition to the acrylic resin. When the surface layer 3 contains the antistatic agent, the surface resistance of the transfer body 20 after the transfer can be reduced and the generation of static electricity can be suppressed, and the workability during transfer and the transfer layer 11 are transferred. The feeling of use of the transfer body 20 (for example, fabric) can be improved.

  The antistatic agent is not particularly limited, and known ones can be used. From the viewpoint of excellent coating suitability and effectively suppressing the surface resistance of the surface layer 3, preferably an anionic surfactant, a cationic surfactant, an amphoteric surfactant, a nonionic surfactant, etc. Surfactants are preferred, and anionic surfactants are more preferred. Only one type of antistatic agent may be used, or two or more types may be mixed and used. In order to prevent aggregation of the antistatic agent in the layer and to exhibit excellent antistatic properties, an antistatic agent and an auxiliary component may be used in combination. Examples of auxiliary components include higher alcohols such as lauryl alcohol and octadecyl alcohol.

  Anionic surfactants can be classified by focusing on the connecting part of their hydrophobic and hydrophilic groups. Fatty acid salt type, sulfonic acid type (sulfonate type), sulfate ester type (sulfate type), phosphate ester type (phosphate) Type). Specific examples of the fatty acid salt type include laurate and stearate. Specific examples of the sulfonic acid type include linear alkylbenzene sulfonate, α-sulfo fatty acid methyl ester salt, α-olefin sulfonate, alkane sulfonate, and the like. Examples of the sulfate ester type include alkyl sulfate ester salts and alkyl ether sulfate ester salts. Examples of the phosphate ester type include monoalkyl phosphate ester salts. Examples of the salt include sodium salt and potassium salt. Of these, the sulfuric acid ester type and the phosphoric acid ester type are preferable because of excellent antistatic properties, and the phosphoric acid ester type is particularly preferable.

  Examples of the cationic surfactant include amine salts and quaternary ammonium salts. Examples of amine salts include N-methylbishydroxyethylamine fatty acid ester salts. As the quaternary ammonium salt, alkyltrimethylammonium salt, alkylbenzyldimethylammonium salt, alkyldihydroxyethylmethylammonium salt, dialkyldimethylammonium salt, tetraalkylammonium salt, N, N-di (polyoxyethylene) dialkylammonium salt, Examples thereof include N-alkylalkanamide ammonium salts. Examples of the salt include hydrochloride and sulfate.

  Nonionic surfactants include ether forms such as alkyl polyoxyethylene ether and p-alkylphenyl polyoxyethylene ether; fatty acid sorbitan polyoxyethylene ether, fatty acid sorbitol polyoxyethylene ether, fatty acid glycerin polyoxyethylene ether, etc. Ether ester form; fatty acid polyoxyethylene ester, monoglyceride, diglyceride, sorbitan ester, sucrose ester, dihydric alcohol ester, borate ester, etc .; fatty acid alkanolamide, N, N-di (polyoxyethylene) alkanamide Etc. can be exemplified.

  Amphoteric surfactants include amino acid forms such as monoaminocarboxylate and polyaminocarboxylate; N-alkyl-β- such as N-alkylaminopropionate and N, N-di (carboxyethyl) alkylamine salts. Alanine form; betaine forms such as N-alkylbetaine, N-alkylamidobetaine, N-alkylsulfobetaine, N, N-di (polyoxyethylene) alkylbetaine, imidazolinium betaine; 1-carboxymethyl-1-hydroxy Examples thereof include alkylimidazoline derivatives such as -1-hydroxyethyl-2-alkyl-2-imidazoline and 1-sulfoethyl-2-alkyl-2-imidazoline.

  Commercially available products can be used as the antistatic agent. For example, electro stripper (registered trademark) ME-2 (sulfuric ester type anionic surfactant manufactured by Kao Corporation), electro stripper (registered trademark) F (Phosphate-type anionic surfactant manufactured by Kao Corporation), Electro Stripper (registered trademark) QN (Cationic surfactant manufactured by Kao Corporation), Electro Stripper (registered trademark) AC (Amphoteric manufactured by Kao Corporation) Ionic surfactant).

  As the content of the antistatic agent in the surface layer 3, the low-gloss design of the surface layer 3 is suitably imparted while exhibiting excellent peelability between the intermediate layer 2 and the surface layer 3, and excellent solvent resistance. From the viewpoint of effectively reducing the surface resistance of the surface layer 3, the total component contained in the surface layer 3 is 100 parts by mass, preferably about 2 to 15 parts by mass, more preferably 3 to 12 parts. About part by mass, more preferably about 5 to 11 parts by mass.

In the transfer film 10, the surface resistance of the surface layer 3 is preferably about 1.0 × 10 ¹³ Ω / sq or less, more preferably about 1.0 × 10 ¹² Ω / sq or less, and still more preferably 1. For example, about 0 × 10 ¹¹ Ω / sq or less. The surface resistance is preferably about 1.0 × 10 ⁹ Ω / sq or more. Note that the surface resistance of the surface layer 3 may be measured on any surface of the surface layer 3. That is, the surface layer 3 may be measured on the surface opposite to the intermediate layer 2 side, and the surface layer is exposed by peeling the base material layer 1 and the intermediate layer 2 by transferring the transfer layer to a cloth or the like. 3 may be measured on the surface of the intermediate layer 2 side. Both measured values show almost the same value.

  In the transfer film 10, the surface resistance of the surface of the surface layer 3 opposite to the intermediate layer 2 side is a value measured by the method described in the examples.

  The surface layer 3 is formed by applying a coating liquid (surface layer coating liquid) containing a solvent to the surface of the intermediate layer 2 in addition to an acrylic resin and an antistatic agent added as necessary. can do. It does not restrict | limit especially as a solvent, It selects according to components, such as an acrylic resin to be used. For example, when the water-insoluble acrylic resin is used, the intermediate layer 2 similar to that illustrated can be used. When water-soluble or water-dispersible materials are used as the acrylic resin, water; alcohols such as methanol, ethanol, propanol, isopropyl alcohol, butanol, isobutyl alcohol, diacetone alcohol; solvents such as acetone are used. be able to. Only one type of solvent may be used, or two or more types may be mixed and used. Further, the total solid content concentration of the surface layer coating liquid is not particularly limited, but preferably from about 5 to 25% by mass from the viewpoint of uniformly coating the surface layer 3.

Although it does not restrict | limit especially as a coating amount of the surface layer 3, While giving the outstanding peelability of the intermediate | middle layer 2 and the surface layer 3, the low gloss design of the surface layer 3 is provided suitably, Furthermore, it is excellent. From the viewpoint of exhibiting high solvent resistance, it is preferably about 0.5 to 3.0 g / m ² , more preferably about 0.7 to 2.5 g / m ² , and still more preferably 1.0 to 2.0 g / m ^2. m ² or so.

  Although it does not restrict | limit especially as thickness of the surface layer 3, giving the design of the low glossiness of the surface layer 3 suitably, exhibiting the outstanding peelability of the intermediate | middle layer 2 and the surface layer 3, and also excellent resistance From the standpoint of exhibiting solvent properties, it is preferably about 0.5 to 3.0 μm, more preferably about 0.7 to 2.5 μm, and still more preferably about 1.0 to 2.0 μm. Here, the thickness of the surface layer 3 is a coating layer thickness when the cross section of the film is observed with an electron microscope. In addition, since the coating layer is roughened, the coating surface is not flat. Therefore, the coating layer thickness is calculated as an average value of the thicknesses measured at arbitrary 10 points randomly selected in the visual field.

When the thickness of the surface layer 3 is T _S (μm) and the thickness of the intermediate layer 2 is T _M (μm), 0.5 ≦ T _S / T _M ≦ 2 is preferable, and 0.8 ≦ T _S / T _M ≦ 1.5 is more preferable. Further, when the coating amount of the surface layer 3 is Q _S (g / m ² ) and the coating amount of the intermediate layer 2 is Q _M (g / m ² ), 0.5 ≦ Q _S / Q _M ≦ 2 is preferable. 0.8 ≦ Q _S / Q _M ≦ 1.5 is more preferable. When the ratio T _S / T _M between the thickness of the surface layer 3 and the thickness of the intermediate layer 2 and / or the ratio Q _S / Q _M between the thickness of the surface layer 3 and the coating amount of the intermediate layer 2 is within the above range. Since the uneven shape caused by the particles contained in the intermediate layer 2 is well formed on the surface of the surface layer 3 on the intermediate layer 2 side, the low gloss design of the transfer body 20 and the intermediate layer 2 are formed. Both of the peeling forces at the time of delamination between the surface layer 3 and the surface layer 3 are good.

〔Additive〕
If necessary, the surface layer 3 may contain at least one additive as long as the effects of the present invention are not impaired. Examples of the additive include an adhesive, an antioxidant, an ultraviolet absorber, a lubricant, a plasticizer, a flame retardant, a colorant, a viscosity modifier, an antifoaming agent, and the like, similar to the intermediate layer 2.

  The surface layer 3 may contain an anti-blocking agent for the purpose of suppressing the occurrence of blocking when the transfer film is laminated, if necessary. As an antiblocking agent, the particle | grains used for an intermediate | middle layer are mentioned, for example. From the viewpoint of improving the transparency of the surface layer and improving the visibility of the printed layer and the like, the anti-blocking agent is preferably about 10 parts by mass or less, more preferably 5 parts, based on 100 parts by mass of all components contained in the surface layer 3. It is about 1 part by mass or less, more preferably about 1 part by mass or less, and particularly preferably about 0.5 part by mass or less.

(Smoothing layer 4)
In the transfer layer 11, the smoothing layer 4 is provided on the side opposite to the intermediate layer 2 side of the surface layer 3 as necessary. By providing the smoothing layer 4 on the opposite side of the surface layer 3 from the intermediate layer 2 side, for example, when the printing layer 5 or the like is further formed thereon, the printing layer 5 can be formed on a smooth surface. And high-definition printing can be performed. The smooth layer may also have a role of protecting the printing layer 5 from components in the atmosphere such as sunlight, ultraviolet rays, sulfurous acid gas and ozone, such as scratches.

  If the smoothing layer 4 fills the rough surface of the surface layer 3 on the side of the intermediate layer 2 and forms a smooth surface to the extent that printing dot omission in the printing layer described later can be suppressed, the material and the like are not limited to the same. . The smoothing layer 4 can be formed of, for example, a thermoplastic resin such as an acrylic resin, a urethane resin, a nylon resin, or a polyester resin, or a thermosetting resin. The smoothing layer may contain particles for the purpose of improving the adhesion with the printing layer described later. Specifically, it can be formed by, for example, applying a coating solution containing a thermoplastic resin smoothly on the surface of the surface layer 3.

  The thickness of the smoothing layer 4 is not particularly limited as long as the smooth surface can be formed by filling the rough surface of the surface layer 3 on the intermediate layer 2 side, and is, for example, about 1 to 100 μm, preferably about 3 to 80 μm. Preferably about 5-60 micrometers is mentioned.

(Print layer 5)
In the transfer layer 11, the printing layer 5 is provided on the side opposite to the intermediate layer 2 side of the surface layer 3 as necessary. By providing the printing layer 5 on the side opposite to the intermediate layer 2 side of the surface layer 3, a design such as a design or characters can be imparted to the transferred object 7.

  The print layer 5 is formed using, for example, an ink (coating liquid) containing a colorant, a binder resin, and a solvent. As described above, since the surface layer 3 contains an acrylic resin, the transfer film 10 has an appropriate peeling force with respect to the intermediate layer 2 and is used for forming the printing layer 5. The ink is excellent in resistance to the solvent, and the printing layer 5 can be suitably formed.

  The colorant of the ink used for forming the printing layer 5 is not particularly limited, but for example, metals such as aluminum, chromium, nickel, tin, titanium, iron phosphide, copper, gold, silver, brass, alloys, or Metallic pigment composed of scale-like foil powder of metal compound; mica-like iron oxide, titanium dioxide coated mica, titanium dioxide coated bismuth oxychloride, bismuth oxychloride, titanium dioxide coated talc, fish scale foil, colored titanium dioxide coated mica, basic carbonic acid Pearlescent pigment made of foil powder such as lead; fluorescent pigments such as strontium aluminate, calcium aluminate, barium aluminate, zinc sulfide, calcium sulfide; white inorganic pigments such as titanium dioxide, zinc white, antimony trioxide ; Colored inorganic face such as zinc white, petal, vermilion, ultramarine, cobalt blue, titanium yellow, yellow lead, carbon black ; Isoindolinone yellow, Hansa yellow A, quinacridone red, permanent red 4R, phthalocyanine blue, indanthrene blue RS, and organic pigments such as aniline black (including dyes) and the like. These colorants may be used alone or in combination of two or more.

  The ink binder resin used for forming the printing layer 5 is not particularly limited, and examples thereof include acrylic resins, styrene resins, polyester resins, urethane resins, chlorinated polyolefin resins, and vinyl chloride-acetic acid. Examples include vinyl copolymer resins, polyvinyl butyral resins, alkyd resins, petroleum resins, ketone resins, epoxy resins, melamine resins, fluorine resins, silicone resins, fiber derivatives, rubber resins, and the like. These binder resins may be used individually by 1 type, and may be used in combination of 2 or more type.

  Moreover, the solvent of the ink used for forming the printing layer 5 is not particularly limited. For example, petroleum organic solvents such as hexane, heptane, octane, toluene, xylene, ethylbenzene, cyclohexane, and methylcyclohexane; ethyl acetate, acetic acid Ester-based organic solvents such as butyl, 2-methoxyethyl acetate and 2-ethoxyethyl acetate; alcohol-based organic solvents such as methyl alcohol, ethyl alcohol, normal propyl alcohol, isopropyl alcohol, isobutyl alcohol, ethylene glycol and propylene glycol; Ketone organic solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone; ether organic solvents such as diethyl ether, dioxane, tetrahydrofuran; dichloromethane, carbon tetrachloride , Trichlorethylene, chlorinated organic solvents tetrachlorethylene and the like; water and the like. These solvents may be used individually by 1 type, and may be used in combination of 2 or more type.

  Further, the ink used for forming the printing layer 5 includes an anti-settling agent, a curing catalyst, an ultraviolet absorber, an antioxidant, a leveling agent, a thickener, an antifoaming agent, a lubricant, and the like as necessary. It may be.

  The printing layer 5 can be formed on the layer forming the printing layer 5 by a known printing method such as gravure printing, flexographic printing, silk screen printing, and offset printing.

  Although it does not restrict | limit especially about the thickness of the printing layer 5, For example, about 3-100 micrometers, Preferably it is about 5-50 micrometers, More preferably, about 8-30 micrometers is mentioned.

(Adhesive layer 6)
In the transfer layer 11, the adhesive layer 6 is provided on the side opposite to the intermediate layer 2 side of the surface layer 3 as necessary. By providing the adhesive layer 6 on the opposite side of the surface layer 3 from the intermediate layer 2 side, the transfer layer 11 can be suitably transferred to the transfer body 7. Examples of the transfer include pressure transfer (transfer by pressure) and thermal transfer (transfer by heat and pressure). Examples of pressure transfer include adhesion and adhesion. Examples of thermal transfer include thermal bonding and welding.

  The resin for forming the adhesive layer 6 is not particularly limited as long as it can improve the adhesiveness and tackiness between the transfer film 10 and the transfer object 7, and for example, a thermoplastic resin or a thermosetting resin. Resin is used. Examples of the thermoplastic resin include polyolefins such as polyethylene and polypropylene; acrylic resins, acrylic modified polyolefin resins, chlorinated polyolefin resins, vinyl chloride-vinyl acetate copolymers, thermoplastic urethane resins, thermoplastic polyester resins, polyamides, and rubbers. Based resins and the like. A thermoplastic resin may be used individually by 1 type, and may be used in combination of 2 or more types. Moreover, as a thermosetting resin, a thermosetting polyurethane, an epoxy resin, etc. are mentioned, for example. A thermosetting resin may be used individually by 1 type, and may be used in combination of 2 or more types.

  Although it does not restrict | limit especially about the thickness of the contact bonding layer 6, For example, about 5-200 micrometers, Preferably it is about 10-150 micrometers, More preferably, about 20-100 micrometers is mentioned.

[Transfer Film Manufacturing Method]
A method for manufacturing the transfer film 10 according to this embodiment will be described. According to the said manufacturing method, said transfer film 10 can be manufactured suitably. However, the manufacturing method of the transfer film 10 is not limited to the following manufacturing method.

  The transfer film 10 is obtained by laminating each layer so that a laminate including at least the base material layer 1, the intermediate layer 2, and the transfer layer 11 is obtained in this order. The details of the base material layer 1, the intermediate layer 2, and the transfer layer 11 are as described above.

  As a specific example of the manufacturing method of the transfer film 10, first, the intermediate layer 2 is laminated on one surface of the base material layer 1. At this time, the intermediate layer 2 can be formed by applying the intermediate layer coating liquid for forming the intermediate layer 2 to the surface of the base layer 1. Next, the surface layer 3 is laminated on the intermediate layer 2. At this time, the surface layer 3 can be formed by applying the surface layer coating liquid for forming the surface layer 3 to the surface of the intermediate layer 2. Through the above steps, a laminate including at least the base material layer 1, the intermediate layer 2, and the transfer layer 11 in this order is obtained.

  When the smoothing layer 4, the printing layer 5, the adhesive layer 6 and the like are further provided on the transfer layer 11 in addition to the surface layer 3, these layers may be further laminated on the surface layer 3. .

(Transfer member 7)
In this embodiment, the transfer body 20 is obtained by transferring the transfer layer 11 of the transfer film 10 to the transfer body 7.

  The transfer target 7 is not particularly limited as long as the transfer layer 11 can be transferred by transfer or the like. Examples of the material 7 to be transferred include those provided on the surface with fabric, paper, resin, wood, stone, metal, and the like.

  For example, the transfer object 7 having a cloth on the surface includes clothes, curtains, bags, shoes, rugs, bedding, chairs, interior items (wallpaper, curtains, etc.), car interior items (sheet covering materials, ceiling covering materials, And a wide range of items that are required to be designed, such as a console covering material, a pillar garnish covering material, a sun visor covering material, a floor mat, and the like.

  In addition, as the material of the fibers constituting the fabric, synthetic fibers such as polyethylene terephthalate, polybutylene terephthalate, nylon, polypropylene, polyethylene, vinylon, rayon, acrylic, acetate, polyvinyl chloride; cotton, hemp, silk, paper, etc. Natural fibers; these mixed fibers and the like. The fabric may be a woven fabric or a non-woven fabric.

(Transfer 20)
The transfer body 20 is a laminated body of the transfer layer 11 and the transfer body 7 as described above. The details of the transfer layer 11 and the transfer target 7 are as described above.

  The temperature and pressure when the transfer layer 11 of the transfer film 10 is transferred to the transfer body 7 may be appropriately adjusted according to the material of the transfer layer 11 and the transfer body 7, respectively. ˜200 ° C., pressure 0.1 KPa˜10 MPa.

  By peeling the base material layer 1 and the intermediate layer 2 from the transfer material 7 (the transfer material 21 with the base material layer 1 and the intermediate layer 2) on which the transfer film 10 is laminated, the transfer layer 11 and the transfer material 7 are separated. A laminated transfer body 20 is obtained.

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

Each material shown in Table 1 is as follows.
(Pigment)
Synthetic Amorphous Silica A: Silicia (registered trademark) 370 Fuji Silysia Chemical Ltd. average particle size 6.7 μm
Synthetic amorphous silica B: Silicia (registered trademark) 450 manufactured by Fuji Silysia Chemical Ltd. Average particle size 8.0 μm
Synthetic amorphous silica C: Silicia (registered trademark) 310 manufactured by Fuji Silysia Chemical Ltd. Average particle size: 2.7 μm

(Middle layer resin)
・ Acid-modified acrylic resin (crosslinkable): manufactured by ACRIDIC (registered trademark) A-4525 DIC Corporation ・ Polyol type acrylic resin (crosslinkable): YL-455 manufactured by Toyo Ink Co., Ltd. ・ Long chain alkyl group Containing resin (non-crosslinkable): Pyroyl 1010S manufactured by Lion Specialty Chemicals Co., Ltd.

(Curing agent for intermediate layer)
・ Methylated melamine A: Nicarac (registered trademark) MW-30MLF Nippon Carbide Co., Ltd. full ether type polyfunctional amino compound ・ Methylated melamine B: Nicarac (registered trademark) MS-001 Nippon Carbide Co., Ltd. imino group And methylated melamine having a methylol group Polyfunctional amino compound / polyisocyanate: Takenate (registered trademark) D110N manufactured by Mitsui Chemicals, Inc.

(Intermediate layer acidic catalyst)
・ P-Toluenesulfonic acid: Dryer (registered trademark) 900 Hitachi Chemical Co., Ltd.

(Surface layer resin)
Acrylic resin A: Bonron (registered trademark) XHS-50 Acrylic resin emulsion manufactured by Mitsui Chemicals Co., Ltd. Minimum film forming temperature 0 ° C.
Acrylic resin B: KE-1062 Styrene PMC emulsion made by Starlight PMC Co., Ltd. Minimum film-forming temperature 55 ° C

(Antistatic agent for surface layer)
・ Phosphate ester type anionic surfactant: Electro Stripper (registered trademark) F manufactured by Kao Corp. ・ Sulfate ester type anionic surfactant: Electro stripper (registered trademark) ME-2 manufactured by Kao Corp. ・Zwitterionic surfactant: Electrostripper (registered trademark) AC manufactured by Kao Corporation; Cationic surfactant: Electrostripper (registered trademark) QN manufactured by Kao Corporation

<Example 1>
By the following procedures, the coating liquid for forming an intermediate | middle layer and the coating liquid for forming a surface layer were each prepared, and the transfer film was manufactured. The compositions of the intermediate layer and the surface layer are as shown in Table 1.

(Preparation of coating solution for forming the intermediate layer)
In a mixed solvent of toluene: methyl ethyl ketone (MEK) = 1: 1 (mass ratio), synthetic amorphous silica A (Silicia (registered trademark) 370 manufactured by Fuji Silysia Chemical Ltd.) (average particle size = 6.7 μm) as inorganic particles. )) 12 parts by mass, 75 parts by mass of acid-modified acrylic resin (Acridic (registered trademark) A-452 manufactured by DIC Corporation) as a resin, and methylated melamine A (Nicalac (registered trademark)) as a polyfunctional amino compound as a curing agent ) MW-30MLF Nippon Carbide Co., Ltd. full ether type) 13 parts by mass, acidic catalyst (Hitachi Chemical Co., Ltd. dryer 900, p-toluenesulfonic acid 50% by mass solution) 1.5 parts by mass are mixed and stirred. Using a machine (Shinto Kagaku Co., Ltd. Three-One Motor BL3000), the mixture was stirred at a rotation speed of 1500 rpm for 30 minutes to obtain a dispersion. Next, the solid content concentration of the dispersion liquid was measured, and the above mixed solvent was added to the dispersion liquid to obtain an intermediate layer coating liquid in which the total solid content concentration was adjusted to 20% by mass. The total solid concentration of the dispersion and the intermediate layer coating liquid was measured by weighing about 5 g of the dispersion liquid and the intermediate layer coating liquid, respectively, and then drying in a 100 ° C. explosion-proof dryer for 30 minutes. And calculated from the weight values before and after drying.

(Preparation of coating solution for forming surface layer)
Acrylic resin A (Bonlon (registered trademark) XHS-50, an acrylic resin manufactured by Mitsui Chemicals, Inc.) having a minimum film-forming temperature of 0 ° C. as an acrylic resin in a mixed solvent of water: isopropyl alcohol (IPA) = 8: 2 (mass ratio) Emulsion) 90 parts by mass, antistatic agent (phosphate ester type anionic surfactant: Electro Stripper (registered trademark) F manufactured by Kao Corporation) 10 parts by mass are mixed, and a stirrer (Shinto Kagaku Co., Ltd.). Using a three-one motor BL3000), the mixture was stirred at a rotation speed of 800 rpm for 15 minutes to obtain a mixed solution. Next, the solid content concentration of the mixed solution was measured, and the above mixed solvent was added to the mixed solution to obtain a surface layer coating solution in which the solid content concentration was adjusted to 15% by mass. In addition, the solid content concentration of the mixed solution and the surface layer coating solution was measured in the same manner as the intermediate layer coating solution.

(Manufacture of transfer film)
A biaxially stretched polyethylene terephthalate film (E5100 manufactured by Toyobo Co., Ltd.) having a thickness of 100 μm was prepared as a base material layer. Next, on one surface of the base material layer, the coating amount (dry mass) of the intermediate layer coating liquid is set using a Mayer bar (shaft diameter: 6.35 mmφ manufactured by Yasuda Seiki Seisakusho Co., Ltd.). The coating was applied to 1.2 g / m ² and dried in an explosion-proof dryer at 150 ° C. for 60 seconds to obtain a laminate of the base material layer and the intermediate layer. In addition, the coating amount (dry mass) for the intermediate layer is the mass difference (g) between the base material before coating and the laminate after coating in a state where the humidity is adjusted for 6 hours or more in an environment of 23 ° C. and 50%. And a coating area (m ² ), a value calculated by “mass difference ÷ coating area”.

Next, on the surface of the intermediate layer of the obtained laminate, the coating liquid for the surface layer was applied (dry mass) using Mayer Bar (shaft diameter: 6.35 mmφ manufactured by Yasuda Seiki Seisakusho Co., Ltd.). Was 1.2 g / m ² and dried in an explosion-proof dryer at 150 ° C. for 60 seconds to obtain a transfer film. In addition, the coating amount (dry mass) of the surface layer is the mass difference (g) between the laminate before coating and the transfer film after coating in a state where the humidity is adjusted for 6 hours or more in an environment of 23 ° C. and 50%. From the coating area (m ² ), it is a value calculated by “mass difference ÷ coating area”.

<Examples 2-9 and Comparative Examples 1-7>
The intermediate layer coating solution and the surface layer coating solution are prepared so as to have the composition, total solid concentration (%), and coating amount (g / m ² ) of the intermediate layer and surface layer described in Table 1, respectively. A transfer film was produced in the same manner as in Example 1. The base material layer is the same as in Example 1.

[Glossiness]
About each transfer film obtained above, according to JIS-Z8741: 1997 (method 3) using the variable angle gloss meter GM-3D type made by Murakami Color Research Laboratory Co., Ltd., the 60-degree mirror surface of the surface layer Gloss was measured. In addition, the measurement of glossiness is the total obtained by measuring the vertical direction and the horizontal direction of the transfer film at any three locations on the surface layer (opposite the intermediate layer side), respectively. It is an average value of six measured values. The results are shown in Table 1.

[Glossiness after transfer]
Each transfer film obtained above was cut and cut into a size of 8 cm wide × 10 cm long. Next, on the surface layer of the transfer film, an acrylic dry lamination adhesive (TM-550 solid content concentration 70 mass% manufactured by Toyo Morton Co., Ltd.), a curing agent (CAT-RT37-2K solid manufactured by Toyo Morton Co., Ltd.) A smoothing layer paint obtained by mixing a mixture of ethyl acetate (special grade, manufactured by Wako Pure Chemical Industries, Ltd.) at a mass ratio of 18/2 / 21.5 with a fraction of 95% by mass of Myacebar (Co., Ltd.) Using a shaft diameter of 6.35 mmφ manufactured by Yasuda Seiki Seisakusho, the coating amount (dry mass) was applied to 4 g / m ² , dried at 130 ° C. for 60 seconds in an explosion-proof dryer, and brought to room temperature. And left to cool for 1 minute to provide a smoothing layer. On the coated surface of the smoothing layer after cooling, a polyethylene film (PE dust pack (black) manufactured by Thermo Co., Ltd., 30 μm thick) with a width of 8 cm and a length of 10 cm is stacked as an adhesive layer, and a 2 kg roller is reciprocated twice. Affixed by. Next, on the white cotton cloth (JIS-L-0803: 2011 compliant), the transfer film adhesive layer (polyethylene film) side is overlapped, and the transfer film is heated to a surface temperature of 155 ° C. on the substrate layer side ( (Mass 2 kg) was allowed to stand for 20 seconds, and heated and pressurized. After heating and pressurization, a laminate of white cotton cloth and transfer film (white cotton cloth / adhesive layer / smoothing layer / surface layer / intermediate layer / substrate layer laminated in order) is allowed to stand at room temperature for 10 minutes. The intermediate layer and the base material layer were peeled from the cooled laminate, and the surface of the surface layer opposite to the smoothing layer side was exposed to obtain a test sample. For Examples 1-9 and Comparative Examples 1-7, three test samples were prepared, and the glossiness of the exposed surface layer (glossiness after transfer) was measured using the same measuring device as the above glossiness. An average value of a total of six measurement values obtained by measuring the test sample in the vertical direction and the horizontal direction was defined as the glossiness after transfer. The results are shown in Table 1.

[Surface roughness]
Measured under the following conditions using an optical interference type non-contact surface shape measuring instrument (manufactured by Ryoka System Co., Ltd., non-contact surface / layer cross-sectional shape measurement system, VertScan (registered trademark) 2.0 (model: R5500GML)) did. The results are shown in Table 1.
Measurement mode: WAVE
Filter: 530 white
Objective lens magnification: × 10
Field of view: 470.92 μm × 353.16 μm (640 × 480 pixels)
Number of measurements: measured at any 5 points on the film surface

(Image processing)
The following image processing was performed using the analysis software “VS-Viewer” for the measurement data at the five locations.
Complement: Complete noise removal processing: Median filter processing (5 × 5 pixels)
Roughness component extraction processing: Gaussian filter processing (cut-off value of 30 μm or more)
For each image of the five surface shape data obtained by image processing as described above, using the analysis software “VS-Viewer”, the surface roughness (Sa: arithmetic average of the absolute value of the height data) Value).

[Peeling force]
Each transfer film obtained above was cut and cut into a size of 8 cm wide × 15 cm long. Next, on the surface layer, an acrylic pressure-sensitive adhesive (Olivein BPS6163 manufactured by Toyo Morton Co., Ltd., solid content concentration: 37% by mass) and Mayer bar (Shaft diameter: 6.35 mmφ manufactured by Yasuda Seiki Co., Ltd.) The coating was applied so that the coating amount (dry mass) was 4 g / m ² and dried at 130 ° C. for 60 seconds in an explosion-proof dryer. It was allowed to cool at room temperature for 1 minute, and a biaxially stretched polyethylene terephthalate film (E5100 manufactured by Toyobo Co., Ltd.) having a width of 8 cm × length of 15 cm and a thickness of 100 μm was layered on the cooled adhesive-coated surface. It stuck by making a roller reciprocate twice. Next, a weight was placed so as to obtain a load of 5 kPa, and the plate was allowed to stand at 70 ° C. for 20 hours for heat treatment. Note that a hot air dryer was used for the heat treatment. After the heat treatment, a test sample was obtained by allowing to stand at 23 ° C. in an environment of 50% humidity for 30 minutes. For each of Examples 1 to 9 and Comparative Examples 1 to 7, two test samples were prepared. Two test pieces each having a width of 25 mm and a length of 120 mm were cut out for each of the two test samples so as not to include the end portions of the obtained test samples, and a total of four test pieces were obtained. Next, the upper end 20 mm of the test piece is peeled (substantially peeled between the intermediate layer and the surface layer) to form a grip portion, and a peel tester (Kyowa Interface Science Co., Ltd. Adhesive / film peel analysis device VPA-) 2). A T-peel peel test was performed at a speed of 1000 mm / min, and a length of 70 mm was peeled (substantially peeled between the intermediate layer and the surface layer), and the peel force at that time was measured. The average value of the peeling force of 25 mm to 70 mm from the starting point was measured. The said measurement was performed about four test pieces and the average value was made into peeling force. The results are shown in Table 1.

[Surface resistance value]
Each transfer film obtained above was cut and cut into a size of 10 cm width × 10 cm length. Next, the transfer film was allowed to stand for 24 hours in an environment of 23 ° C. and 50% humidity. About the surface layer side of the transfer film after standing, the surface resistance value (Ω / sq) was measured using a digital insulation meter (DSM-8103 manufactured by Toago DKK Co., Ltd.). The measurement was performed three times, and the average value was defined as the surface resistance value. sq is also expressed as □. (The unit of surface resistance value is conventionally square per Ω (Ω / sq or Ω / □, ohms per square) to avoid confusion with electrical resistance.)
(Measurement condition)
Measurement voltage: 100V
Integration time: 160 milliseconds Charge: 40 seconds Measurement time: 20 seconds

[Solvent resistance]
Each transfer film obtained above was allowed to stand for 24 hours in an environment of 50% humidity at 23 ° C. The surface layer side of the transfer film after standing was 200 g while appropriately supplying toluene so that the white cotton cloth for friction was always kept in a wet state by using a friction tester (Gakuken type) in accordance with JIS L 0849: 2013. The load was rubbed 50 times. The state of the surface layer and intermediate layer after rubbing was determined as follows.
AA: Peeling is not seen in the intermediate layer and the surface layer, and it can be used satisfactorily A: Peeling is seen in the intermediate layer and the surface layer having an area of less than 5% of the scratched area, but it can be used B: Separation is observed in the intermediate layer and surface layer having an area of 5% or more and less than 90%, and cannot be used.

In Table 1, for example, “7.4E + 10 Ω / sq” of the surface resistance value of Example 1 means “7.4 × 10 ¹⁰ Ω / sq”, and the description in other Examples and Comparative Examples is also used. It is the same.

DESCRIPTION OF SYMBOLS 1 Base material layer 2 Intermediate layer 3 Surface layer 4 Smoothing layer 5 Print layer 6 Adhesive layer 7 Transfer object 10 Transfer film 11 Transfer layer 20 Transfer body 21 Transfer material with base material layer and intermediate layer

Claims (9)

It consists of a laminate comprising at least a base material layer, an intermediate layer, and a transfer layer in this order,
The transfer layer includes at least a surface layer in contact with the intermediate layer,
The surface layer is peelable from the intermediate layer;
The surface layer includes an acrylic resin,
The said intermediate | middle layer is a transfer film which is a hardened | cured material of the resin composition containing particle | grains, a crosslinkable acrylic resin, and a polyfunctional amino compound.   The transfer film according to claim 1, wherein a peeling force between the intermediate layer and the surface layer is 0.05 to 0.6 N / 25 mm.   The transfer film according to claim 1 or 2, wherein a minimum film-forming temperature of the acrylic resin contained in the surface layer is 5 ° C or lower.   The transfer film according to claim 1, wherein the particles are inorganic particles.   The transfer film according to claim 1, wherein the surface layer further contains an antistatic agent.   The transfer film according to claim 1, wherein the surface roughness Sa of the surface layer opposite to the intermediate layer is 0.1 μm or more.   The transfer film according to any one of claims 1 to 6, wherein a 60-degree specular gloss on the opposite side of the surface layer from the intermediate layer side is 60% or less. The transfer film according to claim 1, wherein the surface layer has a surface resistance of 1.0 × 10 ¹³ Ω / sq or less.   The transfer film according to any one of claims 1 to 8, which is used for transferring the transfer layer onto a fabric.