JP2019119105A - Laminate, and combination of laminate and intermediate transfer recording medium - Google Patents

Abstract

To provide a laminate that can satisfactorily transfer a receiving layer from an intermediate transfer recording medium, and effectively prevents the occurrence of blocking during loading storage.SOLUTION: A laminate has a metal plate, and a resin layer on the metal plate. The resin layer has a polyester resin with a glass transition temperature of 45°C or more and 60°C or less. The ratio between the thickness of the resin layer and the thickness of the metal plate (resin layer thickness/metal plate) of 0.015 or more.SELECTED DRAWING: Figure 1

Description

  The present invention comprises a laminate, more specifically, a laminate comprising a metal plate and a resin layer, wherein the thickness ratio of these layers is in a specific range, and a combination of the laminate and an intermediate transfer recording medium About.

  Conventionally, various thermal transfer recording methods are known, but recently, a thermal transfer sheet provided with a dye layer containing a sublimation dye and a transfer target provided with a receiving layer are superposed, and then a thermal head provided with a thermal transfer printer Thus, a sublimation thermal transfer system is widely used, in which the thermal transfer sheet is heated to transfer the sublimable dye in the dye layer to the receiving layer provided in the transferee to form an image.

However, it may be difficult to use the sublimation thermal transfer method depending on the surface shape of the transferred object, etc. In such a case, image formation on the transferred object using the intermediate transfer recording medium is difficult. (See Patent Document 1).
In the formation of an image using an intermediate transfer recording medium, the thermal transfer sheet is heated, the sublimable dye in the dye layer of the thermal transfer sheet is transferred to the receiving layer of the intermediate transfer medium, and the image is formed. It is carried out by heating the recording medium and transferring the receiving layer onto the transfer receiving material.

  The transfer of the receptor layer provided in the intermediate transfer recording medium onto such a transfer-receiving material is required to have high transferability so as not to generate an untransferred portion. However, depending on the material of the transferred object, a non-transferred portion is generated, and there is room for improvement in the transferability. And, the problem of the transferability is particularly remarkable when the transferee is provided with a metal plate or the like having a high thermal conductivity.

  In addition, the receiving material is required to be able to prevent the occurrence of blocking during loading and storage (blocking resistance).

JP 2005-319702 A

  The problem to be solved by the present invention is to provide a laminate capable of improving the transferability of the receiving layer from the intermediate transfer recording medium and effectively preventing the occurrence of blocking during loading and storage. .

The laminate of the present invention in the first aspect comprises a metal plate, and a resin layer on the metal plate,
The resin layer contains a polyester resin having a glass transition temperature of 45 ° C. or more and 60 ° C. or less,
A ratio of the thickness of the resin layer to the thickness of the metal plate (the thickness of the resin layer / the metal plate) is 0.015 or more.

  In the said aspect, it is preferable that content of the polyester-type resin contained in a resin layer is 90 mass% or more and 100% or less.

  In the above aspect, the thickness of the resin layer is preferably 6 μm or more and 10 μm or less.

The laminate of the present invention in the second aspect comprises a metal plate, and two or more resin layers on the metal plate,
At least a first resin layer provided at a position where the two or more resin layers are in contact with the metal plate, and a second resin layer provided on the outermost surface of the laminate,
The first resin layer contains a polyester resin,
The second resin layer contains a resin material having a glass transition temperature of 45 ° C. or more and 60 ° C. or less,
It is characterized in that a ratio of the sum of the thickness of the resin layer to the thickness of the metal plate (the sum of the thickness of the resin layer / the thickness of the metal plate) is 0.015 or more.

  In the above aspect, the resin material having a glass transition temperature of 45 ° C. or more and 60 ° C. or less contained in the second resin layer is preferably a polyester resin.

  In the above aspect, the content of the resin material having a glass transition temperature of 45 ° C. or more and 60 ° C. or less in the second resin layer is preferably 90% by mass or more and 100% by mass or less.

  In the above aspect, the thickness of the second resin layer is preferably 6 μm or more and 10 μm or less.

  In the above aspect, the glass transition temperature of the polyester resin contained in the first resin layer is preferably 45 ° C. or more and 60 ° C. or less.

  In the above aspect, the content of the polyester-based resin in the first resin layer is preferably 80% by mass or more and 90% by mass or less.

  In the above aspect, the thickness of the first resin layer is preferably 1 μm or more and 3 μm or less.

  In the said 2 aspect, it is preferable that the thickness of a metal plate is 0.4 mm or more and 1.0 mm or less.

  The combination of the laminate and the intermediate transfer recording medium of the present invention is characterized in that the intermediate transfer recording medium is provided with a receiving layer containing a vinyl-based resin on the outermost surface.

  In the above aspect, the receiving layer preferably contains a vinyl chloride-vinyl acetate copolymer.

  According to the laminate of the present invention, the transferability of the receptive layer from the intermediate transfer recording medium can be improved, and the occurrence of blocking during loading and storage can be effectively prevented.

It is a schematic cross section of the laminated body of this invention in a 1st aspect. It is a schematic cross section of the laminated body of this invention in a 2nd aspect. FIG. 1 is a schematic cross-sectional view of an intermediate transfer recording medium in an embodiment. FIG. 1 is a schematic cross-sectional view of an intermediate transfer recording medium in an embodiment.

(Laminated body of the first aspect)
In the first aspect, as shown in FIG. 1, the laminate 10 of the present invention includes a metal plate 11 and a resin layer 12.
Moreover, in this aspect, as shown in FIG. 1, the laminate 10 of the present invention may have the back surface layer 13 on the surface of the metal plate 11 opposite to the surface on which the resin layer 12 is provided.

In the first aspect, the ratio of the thickness of the resin layer to the thickness of the metal plate (the thickness of the resin layer / the thickness of the metal plate) included in the laminate of the present invention is 0.015 or more Preferably, it is more preferably 0.015 or more and 0.025 or less, and still more preferably 0.016 or more and 0.022 or less.
By setting the ratio of the thickness of the resin layer to the thickness of the metal plate in the above numerical range, the transferability of the receiving layer of the intermediate transfer recording medium onto the resin layer of the laminate can be improved.

(Metal plate)
Examples of metal species constituting the metal plate include iron, copper, zinc (Zn), aluminum, nickel (Ni), titanium, manganese, palladium, lead, gold, platinum, stainless steel and the like. Among these, iron and stainless steel are preferable because they have relatively low thermal conductivity and are easy to handle during metal sheet punching.
Moreover, what metal-plated the board surface of the said metal seed | species is included in a metal plate, for example, what plated Zn-Ni alloy on the surface of an iron plate is mentioned.
In the present invention, stainless steel means an alloy containing iron as a main component and further containing chromium and / or nickel.

  From at least one surface of the metal plate, surface processing such as sand blasting processing, hair line processing, mat coating processing and chemical etching processing may be performed from the viewpoint of improving adhesion with the adjacent layer.

  The thickness of the metal plate is preferably 0.1 mm or more and 1 mm or less, and more preferably 0.2 mm or more and 0.5 mm or less. By setting the thickness of the metal plate within the above numerical range, the transferability of the receiving layer provided on the intermediate transfer recording medium onto the resin layer provided on the laminate can be further improved.

(Resin layer)
In the first aspect, the resin layer contains a polyester resin having a glass transition temperature (Tg) of 45 ° C. or more and 60 ° C. or less.
When the resin layer contains a polyester-based resin having a Tg within the above numerical range, the transferability of the receiving layer of the intermediate transfer recording medium onto the resin layer of the laminate can be improved. In addition, the blocking resistance of the laminate can be improved. Furthermore, the adhesion of the resin layer to the metal plate can be improved.
In the present invention, “glass transition temperature (Tg)” is a value determined by DSC (indication scanning calorimetry) in accordance with JIS K 7121 (issued in 2012).
The resin layer can contain two or more of the polyester resins.

In the present invention, "polyester resin" means a polymer containing an ester group obtained by polycondensation of polyvalent carboxylic acid and polyvalent alcohol.
Examples of polyvalent carboxylic acids include oxalic acid, malonic acid, succinic acid, adipic acid, sebacic acid, cyclohexanedicarboxylic acid, terephthalic acid, isophthalic acid, orthophthalic acid, phthalic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid Acid, 4,4'-diphenyldicarboxylic acid, 2,5-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, naphthalenetricarboxylic acid, pyrenetricarboxylic acid, pyrenetetracarboxylic acid, azelaic acid , Decanedicarboxylic acid, azelaic acid, dodecanedicarboxylic acid, glutaric acid, trimellitic acid, pyromellitic acid, phthalic anhydride, tetrachlorophthalic acid, nitrophthalic acid, p-carboxyphenylacetic acid, p-phenylenediacetic acid, m-pheny Range glycolic acid, p- E d glycol acid, o- phenylene glycolic acid and p- hydroxybenzoic acid, and the like.
Examples of polyhydric alcohols include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, ethylene glycol such as polyethylene glycol, propanediol, butanediol, pentanediol, hexanediol, neopentyl glycol, 1,4 -Cyclohexanedimethanol, decanediol, 2-ethyl-butyl-1-propanediol, bisphenol A and the like can be mentioned.
Furthermore, in the present specification, the polyester-based resin also includes its modified products and copolymers. Examples of modified polyester resins include, for example, urethane-modified polyester resins. Further, in the copolymer, a copolymer obtained by polycondensation of three or more of the polyvalent carboxylic acid and the polyvalent alcohol, a monomer constituting the polyester resin, and other monomers (α-olefin) Included are copolymers with compounds, vinyl ester compounds, vinyl ether compounds, (meth) acrylic acid ester compounds and the like.

  The content of the polyester resin having a Tg of 45 ° C. or more and 60 ° C. or less in the resin layer is preferably 80% by mass or more and 100% by mass or less, and more preferably 90% by mass or more and 100% by mass or less preferable. By setting the content of the polyester resin within the above numerical range, it is possible to further improve the transferability of the receiving layer provided on the intermediate transfer recording medium onto the resin layer provided on the laminate. In addition, the blocking resistance of the laminate can be further improved. Furthermore, the adhesion of the resin layer to the metal plate can be further improved.

The number average molecular weight (Mn) of the polyester resin having a Tg of 45 ° C. or more and 60 ° C. or less is preferably 2000 or more and 12000 or less, and more preferably 6000 or more and 10000 or less. By setting the Mn of the polyester resin within the above numerical range, the transferability of the receiving layer of the intermediate transfer recording medium onto the resin layer of the laminate can be further improved. In addition, the blocking resistance of the laminate can be further improved. Furthermore, the adhesion of the resin layer to the metal plate can be further improved.
In the present invention, "number average molecular weight (Mn)" means a value measured by gel permeation chromatography using polystyrene as a standard substance, and is measured by a method according to JIS K 7252-1 (2008). it can.

The hydroxyl value of the polyester resin having a Tg of 45 ° C. or more and 60 ° C. or less is preferably 5 mg KOH / g or more and 40 mg KOH / g or less, and more preferably 10 mg KOH / g or more and 20 mg KOH / g or less. By setting the hydroxyl value of the polyester resin within the above numerical range, the transferability of the receiving layer of the intermediate transfer recording medium onto the resin layer of the laminate can be further improved. In addition, the blocking resistance of the laminate can be further improved. Furthermore, the adhesion of the resin layer to the metal plate can be further improved.
In the present invention, the hydroxyl value can be measured by a method in accordance with JIS K 2501 (issued in 2003).

The resin layer may contain a resin material other than a polyester resin having a Tg of 45 ° C. or more and 60 ° C. or less (hereinafter, sometimes simply referred to as another resin material) as long as the characteristics of the present invention are not impaired. Other resin materials include polyester resins having Tg of less than 45 ° C., polyester resins having Tg of more than 60 ° C., polyamide resins such as nylon 6 and nylon 6, 6, polyethylene (PE), polypropylene (PP) and Polyolefin resins such as polymethylpentene, polyvinyl chloride, polyvinyl alcohol (PVA), polyvinyl acetate, vinyl chloride-vinyl acetate copolymer, vinyl resins such as polyvinyl butyral and polyvinyl pyrrolidone (PVP), polyacrylates, poly (Meth) acrylic resins such as methacrylate and polymethyl methacrylate, polyimide resins such as polyimide and polyetherimide, cellophane, cellulose acetate, nitrocellulose, cellulose acetate propionate (CAP) and cerulo Scan acetate butyrate (CAB) and cellulose-based resins, polystyrene (PS) or the like of polystyrene resin, polycarbonate resin, and ionomer resins.
In the present invention, “(meth) acrylic” includes both “acrylic” and “methacrylic”.
In the present invention, "(meth) acrylate" includes both "acrylate" and "methacrylate".

  In addition, the resin layer is a plasticizer, a filler, an ultraviolet light stabilizer, a coloring prevention material, a fluorescent whitening material, a matting material, a deodorant material, a flame retardant material, a weather resistant material, as long as the characteristics of the present invention are not impaired. An additive such as an antistatic material, a yarn friction reducing material, a slip material, an antioxidant, an ion exchange material, a dispersing material, an ultraviolet absorbing material, and a coloring material such as a pigment or a dye can be included.

  The thickness of the resin layer is preferably 5 μm or more and 25 μm or less, more preferably 6 μm or more and 10 μm or less, and particularly preferably 7 μm or more and 9 μm or less. By setting the thickness of the resin layer in the above numerical range, the transferability of the receiving layer provided on the intermediate transfer recording medium onto the resin layer provided in the laminate can be further improved. In addition, the blocking resistance of the laminate can be further improved. Furthermore, the adhesion of the resin layer to the metal plate can be further improved.

  The resin layer is obtained by dispersing or dissolving the above-described material in water or a suitable solvent, and using known methods such as roll coating, reverse roll coating, gravure coating, reverse gravure coating, bar coating or rod coating. It forms by apply | coating on a metal plate, forming a coating film, and making it dry.

(Back layer)
The laminate of the present invention may have a back surface layer on the surface opposite to the surface on which the resin layer of the metal plate is provided. By providing the back layer on the laminate, the blocking resistance of the laminate can be further improved.
In addition, when the laminate includes the back surface layer, the transportability of the laminate in the printer can also be improved.

  The back surface layer can contain a resin material, and for example, polyolefin resin, vinyl resin, (meth) acrylic resin, cellulose resin, polyester resin, polyamide resin, polycarbonate resin, polystyrene resin and polyurethane Examples include resin-based resins. The back surface layer can contain two or more of the above-described resin materials.

  In one embodiment, the back layer comprises a filler. Examples of the filler include organic fillers such as (meth) acrylic particles, polyamide particles and polyethylene wax, and inorganic fillers such as silicon dioxide particles, calcium carbonate particles and titanium oxide particles. Alternatively, organic-inorganic hybrid fillers may be used.

  Moreover, the back surface layer can contain the said additive in the range which does not impair the characteristic of this invention.

  The thickness of the back surface layer is not particularly limited, and can be, for example, 1 μm or more and 2 μm or less.

  The back layer is obtained by dispersing or dissolving the above-mentioned material in water or a suitable solvent, and using known methods such as roll coating, reverse roll coating, gravure coating, reverse gravure coating, bar coating or rod coating. It forms by apply | coating on a metal plate, forming a coating film, and making it dry.

(Laminated body of the second aspect)
In the second embodiment, as shown in FIG. 2, the laminate 20 of the present invention comprises a metal plate 21 and two or more resin layers 22, and the resin layer 22 is a first resin as described later. A layer 23 and a second resin layer 24 are provided.
Although FIG. 2 shows a laminate including two resin layers, the laminate 20 of the present invention may include three or more resin layers.
Moreover, in this aspect, as shown in FIG. 2, the laminate 20 of the present invention may have the back surface layer 25 on the surface opposite to the surface on which the resin layer of the metal plate 21 is provided.

In the second aspect, the laminate of the present invention has a ratio of the sum of the thicknesses of two or more resin layers to the thickness of the metal plate (sum of the thicknesses of two or more resin layers / metal plate The thickness) is preferably 0.015 or more, and more preferably 0.015 or more and 0.035 or less.
By setting the ratio of the sum of the resin layer thickness to the thickness of the metal plate within the above numerical range, the transferability of the receiving layer provided on the intermediate transfer recording medium onto the resin layer provided on the laminate can be improved. .

(Metal plate)
The metal type, thickness and the like constituting the metal plate are the same as in the first embodiment, and thus the description thereof is omitted here.

(Resin layer)
In a second aspect, the laminate of the present invention comprises two or more resin layers.
The resin layer contains a polyester resin, includes a first resin layer provided at a position in contact with the metal plate, and a resin material having a Tg of 45 ° C. or more and 60 ° C. or less, and is provided on the outermost surface of the laminate. And at least a second resin layer.

  The sum of the thicknesses of the resin layers is preferably 7 μm or more and 28 μm or less, and more preferably 7 μm or more and 13 μm or less. By setting the sum of the thicknesses of the resin layers within the above numerical range, the transferability of the receiving layer provided on the intermediate transfer recording medium onto the resin layer provided on the laminate can be further improved.

The first resin layer can contain one or more polyester resins.
The Tg of the polyester resin is preferably 80 ° C. or more and 120 ° C. or less, and more preferably 80 ° C. or more and 100 ° C. or less. By setting the Tg of the polyester resin within the above numerical range, the adhesion of the first resin layer to the metal plate can be further improved.

  The content of the polyester-based resin in the first resin layer is preferably 80% by mass or more and 90% by mass or less. By setting the content of the polyester resin within the above numerical range, the adhesion of the first resin layer to the metal plate can be further improved.

  In the range which does not impair the characteristic of the present invention, the first resin layer may contain resin materials other than polyester resins such as the above-mentioned other resin materials, additives, and the like.

  The thickness of the first resin layer is preferably 1 μm or more and 3 μm or less. By setting the thickness of the first resin layer within the above numerical range, the adhesion of the first resin layer to the metal plate can be further improved.

The second resin layer contains a resin material having a Tg of 45 ° C. or more and 60 ° C. or less. By setting the Tg of the resin material contained in the second resin layer within the above numerical range, the transferability of the receiving layer provided on the intermediate transfer recording medium onto the resin layer provided on the laminate can be improved. In addition, the blocking resistance of the laminate can be improved.
The resin layer provided on the outermost surface of the laminate can contain two or more of the resin materials.

Examples of resin materials having a Tg of 45 ° C. to 60 ° C. include polyester resins, polyamide resins, polyolefin resins, vinyl resins, (meth) acrylic resins, polyimide resins, cellulose resins, and polystyrene resins. And resins such as polycarbonate resins and ionomer resins.
Among these, polyester resins are preferable from the viewpoint of transferability and blocking resistance.
In addition, when the laminate comprises a metal plate, a first resin layer, and a second resin layer, a polyester resin is preferable from the viewpoint of the adhesion of the second resin layer to the first resin layer. .

  The content of the resin material having a Tg of 45 ° C. or more and 60 ° C. or less in the second resin layer is preferably 80% by mass or more and 100% by mass or less, and 90% by mass or more and 100% by mass or less Is more preferred. By setting the content of the resin material having a Tg of 45 ° C. or more and 60 ° C. or less in the second resin layer in the above numerical range, the receiving layer provided on the intermediate transfer recording medium on the resin layer provided on the laminate Transferability can be further improved. In addition, the blocking resistance of the laminate can be further improved.

  The second resin layer may contain a resin material having a Tg of less than 45 ° C., a resin material having a Tg of more than 60 ° C., and the additive as long as the characteristics of the present invention are not impaired.

  The thickness of the second resin layer is preferably 6 μm or more and 25 μm or less, and more preferably 6 μm or more and 10 μm or less. By setting the thickness of the second resin layer within the above numerical range, the transferability of the receiving layer provided on the intermediate transfer recording medium onto the resin layer provided on the laminate can be further improved. In addition, the blocking resistance of the laminate can be further improved.

One or more resin layers may be further provided between the first resin layer and the second resin layer (hereinafter, sometimes referred to as another resin layer).
The other resin layers are polyolefin resins, vinyl resins, (meth) acrylic resins, cellulose resins according to the required functions (plasticizer resistance, solvent resistance, light resistance, heat resistance, moisture resistance, etc.) A resin material such as a resin, a polyester resin, a polyamide resin, a polycarbonate resin, a polystyrene resin, and a polyurethane resin can be included.
Moreover, the said additive can be included in the range which does not impair the characteristic of this invention.

  The thickness of the other resin layer is preferably changed appropriately according to the required function, but can be, for example, 0.1 μm or more and 20 μm or less.

  Each layer constituting the resin layer is obtained by dispersing or dissolving the above-mentioned material in water or a suitable solvent, and using roll coating, reverse roll coating, gravure coating, reverse gravure coating, bar coating, rod coating, etc. It can form by apply | coating on a metal plate etc. by a well-known means, forming a coating film, and drying this.

(Back layer)
The resin, thickness and the like constituting the back surface layer are the same as in the first embodiment, and thus the description thereof is omitted here.

(Combination of laminate and intermediate transfer recording medium)
The combination of the laminate of the present invention and an intermediate transfer recording medium is characterized in that the intermediate transfer recording medium has a receiving layer containing a vinyl-based resin on the outermost surface.

(Intermediate transfer recording medium)
In one embodiment, as shown in FIG. 3, the intermediate transfer recording medium 30 comprises a substrate 31 and a receiving layer 32.
In one embodiment, as shown in FIG. 4, the intermediate transfer recording medium 30 includes a protective layer 33 between the base 31 and the receiving layer 32.
In one embodiment, as shown in FIG. 4, the intermediate transfer recording medium 30 is provided with a release layer 34 between the base 31 and the receiving layer 32. The release layer 34 may be provided between the base 31 and the protective layer 33.
In one embodiment, as shown in FIG. 4, the intermediate transfer recording medium 30 includes an adhesive layer 35 between the receiving layer 32 and the protective layer 33.
In one embodiment, as shown in FIG. 4, the intermediate transfer recording medium 30 includes a back layer 36 on the side opposite to the side on which the receiving layer 32 is provided.

(Base material)
The substrate has heat resistance that can withstand thermal energy (for example, heat by a thermal head) applied during thermal transfer, and has mechanical strength capable of supporting a receiving layer or the like provided on the substrate.
As the substrate, for example, paper substrates such as high-quality paper, art paper, coated paper, resin-coated paper, cast-coated paper, paperboard, synthetic paper and impregnated paper, polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethylene Polyester-based resins such as naphthalate (PEN), 1,4-polycyclohexylene dimethylene terephthalate, terephthalic acid-cyclohexanedimethanol-ethylene glycol copolymer, polyamide-based resins such as nylon 6 and nylon 6, 6, polyethylene ( PE), polyolefin resins such as polypropylene (PP) and polymethylpentene, polyvinyl chloride, polyvinyl alcohol (PVA), polyvinyl acetate, vinyl chloride-vinyl acetate copolymer, polyvinyl butyral and polyvinyl pyrrolidone (PVP) (Meth) acrylic resins such as vinyl resins, polyacrylates, polymethacrylates and polymethyl methacrylates, polyimide resins such as polyimides and polyetherimides, cellophane, cellulose acetate, nitrocellulose, cellulose acetate propionate Films comprising a cellulose resin such as CAP) and cellulose acetate butyrate (CAB), a polystyrene resin such as polystyrene (PS), a polycarbonate resin, an ionomer resin (hereinafter referred to simply as “resin film”) Can be used. The resin film may be a stretched film or an unstretched film, but from the viewpoint of strength, it is preferable to use a stretched film stretched in a uniaxial direction or a biaxial direction.

In addition, a laminate formed of only the above-described paper substrate, a laminate formed of only a resin film, or a laminate of a paper substrate and a resin film can be used as a substrate.
These laminates can be produced by using a dry lamination method, a wet lamination method, an extrusion method or the like.

  The thickness of the substrate is not particularly limited, and can be, for example, 5 μm or more and 30 μm or less.

(Receptive layer)
The intermediate transfer recording medium is provided with a receiving layer on the outermost surface thereof, and the receiving layer contains a vinyl-based resin.
Examples of vinyl resins include polyvinyl chloride, PVA, polyvinyl acetate, vinyl chloride-vinyl acetate copolymer, polyvinyl butyral, and PVP. Moreover, you may use the monomer which comprises the said vinyl resin, and other monomers (an alpha-olefin compound, a (meth) acrylic acid ester compound, etc.) as vinyl-type resin (ethylene-vinyl acetate copolymer etc.).
Among these, a vinyl chloride-vinyl acetate copolymer is preferable from the viewpoint of transferability to a resin layer included in the laminate.

  The Mn of the vinyl resin is preferably 5000 or more and 50000 or less, and more preferably 10000 or more and 20000 or less. By setting the Mn of the vinyl resin within the above numerical range, the transferability to the resin layer included in the laminate can be further improved.

  The content of the vinyl-based resin in the receiving layer is more preferably 90% by mass or more and 100% by mass or less. By making content of vinyl-type resin into the said numerical range, the transferability to the resin layer with which the said laminated body is equipped can be improved more.

  In one embodiment, the receptive layer comprises a thermoplastic resin which softens by heating and exhibits adhesiveness. As a thermoplastic resin, for example, polyester resin, (meth) acrylic resin, (meth) acrylic resin, polyurethane resin, cellulose resin, melamine resin, polyamide resin, polyolefin resin, and styrene resin Etc.

In one embodiment, the receptive layer comprises a release material. Thereby, the releasability from the thermal transfer sheet at the time of image formation can be improved, and a good image can be formed on the receiving layer.
Examples of the release agent include solid waxes such as polyethylene wax, amide wax and Teflon (registered trademark) powder, fluorine-based surfactants, phosphate ester-based surfactants, silicone oil and the like.
Among the above, silicone oil is preferable from the viewpoint of releasability from the thermal transfer sheet.
The receptive layer can include two or more of the above-described release agents.

As silicone oil, for example, straight silicone oil such as dimethyl silicone oil and methyl phenyl silicone oil, and amino modified silicone oil, epoxy modified silicone oil, carboxy modified silicone oil, methacryl modified silicone oil, mercapto modified silicone oil, carbinol modified Examples thereof include modified silicone oils such as silicone oils, fluorine-modified silicone oils, methylstyryl-modified silicone oils and polyether-modified silicone oils.
Among the above, from the viewpoint of releasability from the thermal transfer sheet, epoxy-modified silicone oil is preferable.

  The content of the release agent in the receiving layer is preferably 0.5% by mass or more and 15% by mass or less. By setting the content of the release agent in the receptive layer within the above numerical range, the releasability of the receptive layer can be further improved.

  To the extent the properties of the present invention are not impaired, the receiving layer can contain the above additives.

  The thickness of the receptive layer is preferably 2 μm or more and 10 μm or less. By setting the thickness of the receptive layer in the above numerical range, the transferability to the resin layer provided in the laminate can be improved.

  The receiving layer is prepared by dispersing or dissolving the above-mentioned material in water or a suitable solvent, and using known methods such as roll coating, reverse roll coating, gravure coating, reverse gravure coating, bar coating or rod coating. The composition is applied onto a substrate or the like to form a coating film, which can be formed by drying.

(Protective layer)
The intermediate transfer recording medium of the present invention can comprise a protective layer between the substrate and the receiving layer. The protective layer is a layer to be transferred onto the resin layer included in the laminate together with the receptive layer, and is a layer having a function of protecting the image formed on the receptive layer.

  In one embodiment, the protective layer is made of (meth) acrylic resin, polyester resin, cellulose resin, polystyrene resin, polyamide resin, acetal resin, polycarbonate resin, thermosetting resin, active light curing resin, etc. including.

  In one embodiment, the protective layer comprises a filler. Examples of the filler include organic fillers, inorganic fillers, and organic-inorganic hybrid fillers. The filler may be in the form of powder or sol, but it is preferable to use powder because the selectivity of the solvent in preparing the coating liquid is broad.

The filler contained in the protective layer preferably has an average particle diameter of 1 nm or more and 200 nm or less, more preferably 1 nm or more and 50 nm or less, and still more preferably 7 nm or more and 25 nm or less. The transferability of the protective layer can be improved by setting the average particle size of the filler within the above numerical range.
In the present invention, “average particle diameter” means volume average particle diameter, and using a particle size distribution / particle size distribution measuring device (Nanotrac particle size distribution measuring device manufactured by Nikkiso Co., Ltd.), JIS Z It can measure according to 8819-2 (issued in 2001).

  Examples of the powdery organic filler include acrylic particles such as non-crosslinked acrylic particles and crosslinked acrylic particles, polyamide particles, fluorine particles, polyethylene wax and the like. Moreover, as an inorganic filler of powder, metal oxide particles, such as a calcium carbonate particle, a silica particle, and a titanium oxide, etc. can be mentioned. Moreover, as an organic-inorganic hybrid type filler, what mixed the silica particle with acrylic resin, etc. are mentioned. Furthermore, examples of the sol-like filler include silica sol-based and organosol-based fillers and the like. These fillers may be used alone or in combination of two or more.

  The content of the filler in the protective layer is preferably 5% by mass or more and 60% by mass or less, and more preferably 20% by mass or more and 50% by mass or less. Thereby, the durability of the protective layer can be improved.

  The thickness of the protective layer is preferably 1 μm or more and 15 μm or less, and more preferably 2 μm or more and 8 μm or less. By setting the thickness of the protective layer in the above numerical range, the durability of the protective layer can be improved.

  The protective layer is prepared by dispersing or dissolving the above-described material in water or a suitable solvent, and using a known means such as a roll coater, reverse roll coater, gravure coater, reverse gravure coater, bar coater and rod coater. To form a coating film, which is then dried and, if necessary, irradiated with an actinic ray to cure.

(Peeling layer)
The intermediate transfer recording medium of the present invention can comprise a release layer between the substrate and the receptive layer, or between the substrate and the protective layer. By providing the intermediate transfer recording medium with the release layer, the transferability of the receiving layer can be improved. In addition, the peeling layer peels from the base material at the time of thermal transfer, and is transferred onto the resin layer included in the laminate.

In one embodiment, the release layer contains a cellulose resin, a vinyl resin, a polyurethane resin, a silicone resin, a fluorine resin, a fluorine modified resin, a wax and the like.
Examples of the wax include microcrystalline wax, carnauba wax, paraffin wax, Fischer Tropsch wax, various low molecular weight polyethylenes, wood wax, beeswax, bees wax, bamboo wax, wool wax, shellac wax, candelilla wax, petrolactam, some Modified wax, fatty acid ester, fatty acid amide and the like can be mentioned. Among these, polyethylene wax is particularly preferred.

  The thickness of the release layer is not particularly limited, and can be, for example, 0.1 μm or more and 5 μm or less.

  The release layer is obtained by dispersing or dissolving the above-mentioned material in water or a suitable solvent, and applying it onto the substrate by a known means such as roll coater, reverse roll coater, gravure coater, reverse gravure coater, bar coater and rod coater. Can be formed by forming a coating film and drying it.

(Adhesive layer)
If the intermediate transfer recording medium comprises a protective layer, an adhesive layer can be provided between the receptive layer and the protective layer. By providing the intermediate transfer recording medium with the adhesive layer, the adhesion between the receiving layer and the protective layer can be improved.

  The adhesive layer contains a thermoplastic resin which is softened by heating and exhibits adhesiveness. For example, polyester resins, vinyl resins such as vinyl chloride, vinyl acetate and ethylene-vinyl acetate copolymer, And (meth) acrylic resins, (meth) acrylic resins, polyurethane resins, cellulose resins, melamine resins, polyamide resins, polyolefin resins, and styrene resins.

  The thickness of the adhesive layer is not particularly limited, and can be, for example, 0.1 μm or more and 5 μm or less.

  The adhesive layer is prepared by dispersing or dissolving the above-mentioned material in water or a suitable solvent, and using known methods such as roll coating, reverse roll coating, gravure coating, reverse gravure coating, bar coating or rod coating. It forms by apply | coating on a protective layer, forming a coating film, and making it dry.

(Back layer)
The intermediate transfer recording medium may be provided with a back layer on the side of the substrate not provided with the receiving layer. By providing the back layer on the intermediate transfer recording medium, it is possible to prevent the occurrence of sticking and wrinkles due to heating at the time of thermal transfer.

  EXAMPLES The present invention will next be described in more detail by way of examples, which should not be construed as limiting the invention thereto.

Example 1
The coating liquid for resin layer formation of the following composition was apply | coated to one side of the iron plate of thickness 0.4 mm, and it dried, the resin layer of thickness 6 micrometers was formed, and the laminated body was produced.
<Coating fluid for resin layer formation>
-30 parts by mass of polyester resin A (manufactured by Unitika Co., Ltd., Eletel (registered trademark) UE 3300, Tg 45 ° C., Mn 8000, hydroxyl value 18 mg KOH / g)
· 70 parts by mass of cyclohexanone

Example 2
A laminate was produced in the same manner as in Example 1 except that the thickness of the resin layer was changed to 8 μm.

Example 3
A laminate was produced in the same manner as in Example 1 except that the thickness of the resin layer was changed to 10 μm.

Example 4
A laminate was prepared in the same manner as in Example 1, except that polyester resin A was changed to polyester resin B (manufactured by Unitika Co., Ltd., Eletel (registered trademark) UE3380, Tg 60 ° C., Mn 8000, hydroxyl value 15 mg KOH / g). Was produced.

Example 5
A laminate was produced in the same manner as in Example 1 except that the iron plate was changed to a stainless steel plate.

Example 6
A laminate was produced in the same manner as in Example 5 except that the polyester resin A was changed to a polyester resin B.

Example 7
A laminate was produced in the same manner as in Example 1 except that the coating liquid for forming a resin layer was changed to the following composition.
<Coating fluid for resin layer formation>
· Polyester resin A 27 parts by mass · (Meth) acrylic resin 3 parts by mass (Mitsubishi Chemical Co., Ltd., Dianal (registered trademark) BR-64, Tg 55 ° C, Mn 65000, acid value 2 mg KOH / g)
· 70 parts by mass of cyclohexanone

Example 8
A laminate was produced in the same manner as in Example 1 except that the coating liquid for forming a resin layer was changed to the following composition.
<Coating fluid for resin layer formation>
· Polyester resin A 24 parts by mass · (Meth) acrylic resin 6 parts by mass (Mitsubishi Chemical Co., Ltd. product, Dianal (registered trademark) BR-64, Tg 55 ° C, Mn 65000, acid value 2 mg KOH / g)
· 70 parts by mass of cyclohexanone

Example 9
A coating solution for forming a first resin layer having the following composition is applied to one surface of an iron plate having a thickness of 0.4 mm, and dried to form a first resin layer having a thickness of 2 μm, and then the first resin layer is formed thereon. The coating liquid for forming a second resin layer having the following composition was applied and dried to form a second resin layer having a thickness of 6 μm, whereby a laminate was produced.
<First resin layer forming coating liquid>
Polyester-based resin C (Tg 90 ° C.) 27 parts by mass Isocyanate-based curing agent 3 parts by mass Cyclohexanone 70 parts by mass <coating liquid for forming a second resin layer>
· Polyester resin B 30 parts by mass · Cyclohexanone 70 parts by mass

Example 10
A laminate was produced in the same manner as Example 9, except that the thickness of the second resin layer was changed to 10 μm.

Comparative Example 1
A laminate in the same manner as in Example 1 except that polyester resin A was changed to polyester resin D (manufactured by Unitika Co., Ltd., Eletel (registered trademark) UE 3980, Tg 63 ° C., Mn 8000, hydroxyl value 17 mg KOH / g). Was produced.

Comparative example 2
A laminate was produced in the same manner as in Example 1 except that the thickness of the iron plate was changed to 0.5 mm.

Comparative example 3
A laminate was produced in the same manner as in Comparative Example 2 except that the iron plate was changed to a stainless steel plate.

Comparative example 4
A laminate in the same manner as in Example 1 except that polyester resin A was changed to polyester resin E (manufactured by Unitika Co., Ltd., Eletel (registered trademark) UE3320, Tg 40 ° C., Mn 1800, hydroxyl value 60 mg KOH / g). Was produced.

  The following tests were performed and evaluated about the layered product produced in each example and each comparative example.

<< transferability test >>
An image was formed on the receiving layer of the intermediate transfer recording medium produced as described below, using the thermal transfer sheet produced as follows. For the image formation, a sublimation thermal transfer printer (CX-D80, manufactured by G. PRINTEC CO., LTD.) Was used.
After image formation, the same printer is used to transfer the peeling layer, the protective layer, the adhesive layer and the receptive layer of the intermediate transfer recording medium onto the resin layer of the laminate prepared in each of the examples and comparative examples. Transferability was evaluated according to the following evaluation criteria. The evaluation results are summarized in Tables 1 and 2.
(Evaluation criteria)
A: There was no untransferred area, and the image was completely transferred from the laminate transfer start end.
B: There was a slight untransferred area in the range of less than 1 mm from the laminate transfer start end.
NG: There was an untransferred area in the range of 1 mm or more from the end of the laminate transfer start.

(Preparation of intermediate transfer recording medium)
A coating solution for forming a release layer having the following composition was applied to one surface of a PET film having a thickness of 12 μm and dried to form a release layer having a thickness of 1 μm. Next, on the release layer, a coating solution for forming a protective layer having the following composition was applied and dried to form a protective layer having a thickness of 2 μm. Furthermore, on the protective layer, a coating solution for forming an adhesive layer having the following composition was applied and dried to form an adhesive layer having a thickness of 1 μm. Finally, a coating liquid for forming a receptive layer having the following composition is applied onto the adhesive layer, and dried to form a 2.5 μm thick receptive layer, whereby a release layer, a protective layer, and an adhesive layer are formed on the PET film. Thus, an intermediate transfer recording medium was obtained in which the receiving layer was laminated in this order.

<Coating fluid for release layer formation>
-(Meth) acrylic resin 95 parts by mass (Mitsubishi Chemical Corporation, Dianal (registered trademark) BR-87)
-5 parts by mass of polyester resin (Toyobo Co., Ltd., Byron (registered trademark) 200)
-Toluene 200 parts by mass-Methyl ethyl ketone (MEK) 200 parts by mass

<Coating fluid for forming protective layer>
-Styrene-acrylic copolymer 150 parts by mass (Mitsui Chemical Co., Ltd. product, Muticle PP320P)
-Polyvinyl alcohol 100 parts by mass (C-318, manufactured by DNP Fine Chemical Co., Ltd.)
・ 25 parts by mass of water ・ 50 parts by mass of ethanol

<Coating fluid for adhesive layer formation>
・ Polyester resin 33 parts by mass (Toyobo Co., Ltd. product, Byron (registered trademark) 200)
-Vinyl chloride-vinyl acetate copolymer 27 parts by mass (Nisshin Chemical Co., Ltd. product, Solvaine (registered trademark) CNL, Mn 12000)
・ Isocyanate curing agent 15 parts by mass (Mitsui Chemical Co., Ltd., XEL curing agent)
-Toluene 50 parts by mass-MEK 50 parts by mass

<Coating fluid for receiving layer formation>
-Vinyl chloride-vinyl acetate copolymer 95 parts by mass (Nisshin Chemical Co., Ltd. product, Solvaine (registered trademark) CNL, Mn 12000)
-Epoxy modified silicone 5 parts by mass (Shin-Etsu Chemical Co., Ltd. product, KP-1800U)
-Toluene 200 parts by mass-MEK 200 parts by mass

(Preparation of thermal transfer sheet)
The coating liquid for back surface layer formation of the following composition was apply | coated to one side of a 4.5-micrometer-thick PET film, and it dried, and formed a 0.8 μm-thick back surface layer.
<Coating fluid for back layer formation>
-Polyvinyl butyral 2.0 parts by mass (manufactured by Sekisui Chemical Co., Ltd., Eslek (registered trademark) BX-1)
-Polyisocyanate 9.2 parts by mass (manufactured by DIC Corporation, Bernock (registered trademark) D750)
-Phosphate ester surfactant 1.3 parts by mass (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., Plysurf (registered trademark) A208N)
-Talc 0.3 parts by mass (manufactured by Nippon Talc Industrial Co., Ltd., Micro Ace (registered trademark) P-3)
-Toluene 43.6 parts by mass-MEK 43.6 parts by mass

On the other side of the PET film, a coating solution for forming a yellow dye layer, a coating solution for forming a magenta dye layer, and a coating solution for forming a cyan dye layer are applied surface-sequentially to the other surface of the following composition and dried. A thermal transfer sheet was obtained by forming a 6 .mu.m yellow dye layer, a magenta dye layer and a cyan dye layer.
<Coating fluid for forming yellow dye layer>
-Yellow dye (HD 137) 7.0 parts by mass-Polyvinyl acetoacetal 3.0 parts by mass (manufactured by Sekisui Chemical Co., Ltd., Eslec (registered trademark) KS-5)
Toluene 45 parts by mass MEK 45 parts by mass <coating liquid for forming magenta dye layer>
-Magenta dye (KC-27) 7.0 parts by mass-Polyvinyl acetoacetal 3.0 parts by mass (manufactured by Sekisui Chemical Co., Ltd., Eslec (registered trademark) KS-5)
Toluene 45 parts by mass MEK 45 parts by mass <coating liquid for forming a cyan dye layer>
-Cyan dye (HSB-2194) 7.0 parts by mass-Polyvinyl acetoacetal 3.0 parts by mass (manufactured by Sekisui Chemical Co., Ltd., Eslec (registered trademark) KS-5)
-Toluene 45 parts by mass-MEK 45 parts by mass

<< blocking resistance test >>
Two laminates prepared in each example and each comparative example are stacked so that the surface on the resin layer side and the surface of the metal plate face each other, a pressure of 0.5 MPa is applied, and the laminate is static for 96 hours at 45 ° C. Placed. After standing, the resin layer and the metal plate were peeled off, and the blocking resistance of the laminate was evaluated according to the following evaluation criteria. The evaluation results are summarized in Tables 1 and 2.
(Evaluation criteria)
A: The resin layer and the metal plate peeled off without resistance, and no change in the shape of the resin layer surface was observed.
B: Although there was some resistance when the resin layer and the metal plate were peeled off, no change in the shape of the resin layer surface was observed.
NG: There was resistance when the resin layer and the metal plate were peeled off, and the shape change of the surface of the resin layer could be confirmed.

<< Adhesion test >>
In order to evaluate the adhesion of the resin layer to the metal plate, the abrasion resistance test of the resin layer included in the laminate prepared in each example and comparative example is 50 according to ANSI-INCITS 322-2002, 5.9 Surface Abrasion. The cycle was carried out (wear wheel: CS-10F, load: 500 g). After the test, the state of the surface of the resin layer was visually confirmed, and the adhesion of the resin layer to the metal plate was evaluated according to the following evaluation criteria. The evaluation results are summarized in Tables 1 and 2. The wear wheel was polished every 250 cycles.
(Evaluation criteria)
A: The shape change of the resin layer surface was not seen, but it turned out that the adhesiveness of the resin layer to a metal plate is high.
B: There was almost no change in the shape of the resin layer surface, but some scratches were observed.
C: It turned out that the shape change by abrasion of the resin layer surface is large, and the adhesiveness of the resin layer with respect to a metal plate is low.

  10, 20: laminate, 11, 21: metal plate, 12, 22: resin layer, 13, 25: back surface layer, 23: first resin layer, 24: second resin layer, 30: intermediate transfer recording medium 31: base material 32: receptive layer 33: protective layer 34: release layer 35: adhesive layer 36: back layer

Claims (13)

A laminate comprising a metal plate and a resin layer on the metal plate,
The resin layer contains a polyester resin having a glass transition temperature of 45 ° C. or more and 60 ° C. or less,
A laminate, wherein the ratio of the thickness of the resin layer to the thickness of the metal plate (the thickness of the resin layer / metal plate) is 0.015 or more.   The layered product according to claim 1 whose content of said polyester system resin contained in said resin layer is 90 mass% or more and 100 mass% or less.   The layered product according to claim 1 or 2 whose thickness of said resin layer is 6 micrometers or more and 10 micrometers or less. A laminate comprising a metal plate and two or more resin layers on the metal plate,
The two or more resin layers include at least a first resin layer provided at a position in contact with the metal plate and a second resin layer provided on the outermost surface of the laminate.
The first resin layer contains a polyester resin,
The second resin layer contains a resin material having a glass transition temperature of 45 ° C. or more and 60 ° C. or less,
A laminate, wherein the ratio of the sum of the thickness of the resin layer to the thickness of the metal plate (the sum of the thickness of the resin layer / the thickness of the metal plate) is 0.015 or more.   The laminate according to claim 4, wherein the resin material having a glass transition temperature of 45 ° C. or more and 60 ° C. or less contained in the second resin layer is a polyester resin.   The layered product according to claim 4 or 5 whose content of resin material of said glass transition temperature 45 ° C or more and 60 ° C or less in said 2nd resin layer is 90 mass% or more and 100 mass% or less.   The layered product according to any one of claims 4 to 6 whose thickness of said 2nd resin layer is 6 micrometers or more and 10 micrometers or less.   The layered product according to any one of claims 4 to 7 whose glass transition temperature of polyester system resin contained in said 1st resin layer is 80 ° C or more and 120 ° C or less.   The layered product according to any one of claims 4 to 8 whose content of polyester system resin in said 1st resin layer is 80 mass% or more and 90 mass% or less.   The layered product according to any one of claims 4 to 9 whose thickness of said 1st resin layer is 1 micrometer or more and 3 micrometers or less.   The layered product according to any one of claims 1 to 10 whose thickness of said metal plate is 0.4 mm or more and 1 mm or less. A combination of the laminate according to any one of claims 1 to 11 and an intermediate transfer recording medium,
A combination of a laminate and an intermediate transfer recording medium, wherein the intermediate transfer recording medium is provided with a receiving layer containing a vinyl resin on the outermost surface.   13. A combination according to claim 12, wherein the receiving layer comprises vinyl chloride-vinyl acetate copolymer.