JP2022100333A - Laminate and combination of laminate and intermediate transfer recording medium - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a combination of a laminate which can satisfactorily transfer a reception layer from an intermediate transfer recording medium and can effectively prevent occurrence of blocking in loading storage, and the intermediate transfer recording medium.

SOLUTION: There is provided a combination of a laminate as a transferred body and an intermediate transfer recording medium, in which the laminate includes a metal plate and two or more layers of resin layers on the metal plate; the two or more layers of the resin layers include at least a first resin layer provided at a position containing the metal plate and a second resin layer provided on the outermost surface of the laminate; the first resin layer contains a polyester-based resin; the second resin layer contains a resin material having a glass transition temperature of 45°C or higher and 60°C or lower; a thickness of the metal plate is 0.1 mm or more and 0.4 mm or less; a ratio (sum of thickness of resin layers/thickness of metal plate) of the sum of the thicknesses of the resin layers to the thickness of the metal plate is 0.015 or more; and the intermediate transfer recording medium has a reception layer containing a vinyl-based resin on the outermost surface.

SELECTED DRAWING: Figure 1

COPYRIGHT: (C)2022,JPO&INPIT

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 within a specific range, and a combination of the laminate and an intermediate transfer recording medium. Regarding.

Conventionally, various thermal transfer recording methods have been known, but in recent years, a thermal transfer sheet having a dye layer containing a sublimation dye and a transfer target having a receiving layer are superposed, and then a thermal head provided in a thermal transfer printer. Therefore, a sublimation type thermal transfer method is widely used in which the sublimation dye in the dye layer is transferred to the receiving layer provided in the transferred body to form an image by heating the thermal transfer sheet.

However, depending on the surface shape of the transferred object, it may be difficult to use the sublimation thermal transfer method. In such a case, an image is formed on the transferred object using an intermediate transfer recording medium. (See Patent Document 1).
To form an image using an intermediate transfer recording medium, the thermal transfer sheet is heated, the sublimation dye in the dye layer of the thermal transfer sheet is transferred to the receiving layer of the intermediate transfer medium, image formation is performed, and then intermediate transfer is performed. This is done by heating the recording medium and transferring the receiving layer onto the transferee.

The transfer of the receptor layer included in the intermediate transfer recording medium on such a transfer target is required to have high transferability without generating an untransferred portion. However, depending on the material of the transferred body, an untransferred portion is generated, and there is room for improvement in its transferability. The problem of transferability was particularly remarkable when the transferred body was provided with a metal plate or the like having a high thermal conductivity.

Further, the transferred body is required to be able to prevent the occurrence of blocking during loading and storage (blocking resistance).

Japanese Unexamined Patent Publication No. 2005-319702

An object 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 higher and 60 ° C. or lower.
The ratio of the thickness of the resin layer to the thickness of the metal plate (thickness of the resin layer / metal plate) is 0.015 or more.

In the above aspect, the content of the polyester resin contained in the resin layer is preferably 90% by 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.
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 and contains
The second resin layer contains a resin material having a glass transition temperature of 45 ° C. or higher and 60 ° C. or lower.
The ratio of the sum of the thicknesses of the resin layers to the thickness of the metal plate (sum of the thicknesses of the resin layers / the thickness of the metal plate) is 0.015 or more.

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

In the above aspect, the content of the resin material in the second resin layer having a glass transition temperature of 45 ° C. or higher and 60 ° C. or lower 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 higher and 60 ° C. or lower.

In the above aspect, the content of the polyester 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 above two aspects, the thickness of the metal plate is preferably 0.4 mm or more and 1.0 mm or less.

The combination of the above-mentioned 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 resin on the outermost surface.

In the above embodiment, it is preferable that the receiving layer contains a vinyl chloride-vinyl acetate copolymer.

According to the laminate of the present invention, the transferability of the receiving 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 sectional drawing of the laminated body of this invention in 1st aspect. It is a schematic sectional drawing of the laminated body of this invention in 2nd aspect. It is a schematic sectional view of the intermediate transfer recording medium in one Embodiment. It is a schematic sectional view of the intermediate transfer recording medium in one Embodiment.

(Laminated body of the first aspect)
In the first aspect, the laminated body 10 of the present invention includes a metal plate 11 and a resin layer 12 as shown in FIG.
Further, in the embodiment, as shown in FIG. 1, the laminated body 10 of the present invention may be provided with 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 (thickness of the resin layer / thickness of the metal plate) provided in the laminate of the present invention is 0.015 or more. It is more preferably 0.015 or more and 0.025 or less, and further 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 within the above numerical range, the transferability of the receiving layer provided in the intermediate transfer recording medium on the resin layer provided in the laminate can be improved.

(Metal plate)
Examples of the metal species constituting the metal plate include iron, copper, zinc (Zn), aluminum, nickel (Ni), titanium, manganese, palladium, lead, gold, platinum and stainless steel. Among these, iron and stainless steel are preferable because the value of thermal conductivity is relatively small and they are easy to handle during metal plate punching.
Further, the metal plate includes a plate surface of the above metal type plated, and examples thereof include a metal plate plated with a Zn—Ni alloy on the surface of the iron plate.
In the present invention, the stainless steel means an alloy containing iron as a main component and further containing chromium and / or nickel.

From the viewpoint of improving the adhesion to the adjacent layer, at least one surface of the metal plate may be subjected to surface treatment such as sandblasting, hairline processing, matte coating processing, and chemical etching processing.

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 included in the intermediate transfer recording medium on the resin layer included in 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 higher and 60 ° C. or lower.
By including the polyester resin having Tg within the above numerical range in the resin layer, the transferability of the receiving layer included in the intermediate transfer recording medium on the resin layer provided in the laminate can be improved. In addition, the blocking resistance of the laminated body can be improved. Further, the adhesion of the resin layer to the metal plate can be improved.
In the present invention, the "glass transition temperature (Tg)" is a value obtained by DSC (differential scanning calorimetry) in accordance with JIS K 7121 (issued in 2012).
The resin layer can contain two or more kinds of the polyester-based resin.

In the present invention, the "polyester resin" means a polymer containing an ester group obtained by polycondensing a polyvalent carboxylic acid and a polyhydric alcohol.
Examples of the polyvalent carboxylic acid 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, and citracon. Acid, 4,4'-diphenyldicarboxylic acid, 2,5-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, naphthalenetricarboxylic acid, pyrentricarboxylic acid, pyrenetetracarboxylic acid, azelaic acid , Decandicarboxylic acid, azelaic acid, dodecanedicarboxylic acid, glutaric acid, trimellitic acid, pyromellitic acid, phthalic acid anhydride, tetrachlorophthalic acid, nitrophthalic acid, p-carboxyphenylacetic acid, p-phenylene diacetic acid, m-pheni Examples thereof include range glycolic acid, p-phenylene glycolic acid, o-phenylene glycolic acid and p-hydroxybenzoic acid.
Examples of the polyhydric alcohol include ethylene glycol such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol and polyethylene glycol, propanediol, butanediol, pentanediol, hexanediol, neopentylglycol, 1,4. -Cyclohexanedimethanol, decanediol, 2-ethyl-butyl-1-propanediol, bisphenol A and the like can be mentioned.
Further, in the present specification, the polyester resin also includes a modified product thereof and a copolymer thereof. Examples of the modified polyester resin include urethane modified polyester resin and the like. Further, the copolymer includes a copolymer obtained by polycondensing the polyvalent carboxylic acid and the polyhydric alcohol in three or more kinds, a monomer constituting a polyester resin, and other monomers (α-olefin). A copolymer with a compound, a vinyl ester compound, a vinyl ether compound, a (meth) acrylic acid ester compound, etc.) is included.

The content of the polyester resin having a Tg of 45 ° C. or higher and 60 ° C. or lower 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, the transferability of the receiving layer included in the intermediate transfer recording medium on the resin layer provided in the laminate can be further improved. In addition, the blocking resistance of the laminated body can be further improved. Further, 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 higher and 60 ° C. or lower 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 included in the intermediate transfer recording medium on the resin layer provided in the laminate can be further improved. In addition, the blocking resistance of the laminated body can be further improved. Further, 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 based on JIS K 7252-1 (issued in 2008). can.

The hydroxyl value of the polyester resin having a Tg of 45 ° C. or higher and 60 ° C. or lower is preferably 5 mgKOH / g or more and 40 mgKOH / g or less, and more preferably 10 mgKOH / g or more and 20 mgKOH / g or less. By setting the hydroxyl value of the polyester resin within the above numerical range, the transferability of the receiving layer included in the intermediate transfer recording medium on the resin layer provided in the laminate can be further improved. In addition, the blocking resistance of the laminated body can be further improved. Further, 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 according to JIS K 2501 (issued in 2003).

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

Further, the resin layer is a plastic material, a filler, an ultraviolet stabilizing material, a coloring inhibitor, a fluorescent whitening material, a matte material, a deodorant material, a flame retardant material, and a weather resistant material as long as the characteristics of the present invention are not impaired. , Antistatic material, thread friction reducing material, slip material, antioxidant material, ion exchange material, dispersant material, ultraviolet absorber, and additive material such as coloring material such as pigment and 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 within the above numerical range, the transferability of the receiving layer included in the intermediate transfer recording medium on the resin layer provided in the laminate can be further improved. In addition, the blocking resistance of the laminated body can be further improved. Further, the adhesion of the resin layer to the metal plate can be further improved.

The resin layer is formed by dispersing or dissolving the above-mentioned material in water or an appropriate solvent, and using a known means such as a roll coating method, a reverse roll coating method, a gravure coating method, a reverse gravure coating method, a bar coating method or a rod coating method. , It can be formed by applying it on a metal plate to form a coating film and drying it.

(Back layer)
The laminate of the present invention may be provided with 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 surface layer of the laminated body, the blocking resistance of the laminated body can be further improved.
Further, since the laminated body includes the back surface layer, the transportability of the laminated body in the printer can be improved.

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

In one embodiment, the back surface 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 diate particles, calcium carbonate particles and titanium oxide particles. Further, an organic-inorganic hybrid type filler may be used.

Further, the back surface layer may contain the above-mentioned additive as long as the characteristics of the present invention are not impaired.

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

The back surface layer is formed by dispersing or dissolving the above-mentioned material in water or an appropriate solvent, and using a known means such as a roll coating method, a reverse roll coating method, a gravure coating method, a reverse gravure coating method, a bar coating method or a rod coating method. , It can be formed by applying it on a metal plate to form a coating film and drying it.

(Laminated body of the second aspect)
In the second aspect, as shown in FIG. 2, the laminate 20 of the present invention includes 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 having two resin layers, the laminate 20 of the present invention may have three or more resin layers.
Further, in the embodiment, as shown in FIG. 2, the laminated body 20 of the present invention may be provided with 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 ratio of the sum of the thicknesses of the two or more resin layers and the thickness of the metal plate (the sum of the thicknesses of the two or more resin layers / the metal plate) provided in the laminate of the present invention. 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 thicknesses of the resin layers to the thickness of the metal plate within the above numerical range, the transferability of the receiving layer provided in the intermediate transfer recording medium on the resin layer provided in the laminate can be improved. ..

(Metal plate)
Since the metal type, thickness, and the like constituting the metal plate are the same as those in the first aspect, the description thereof is omitted here.

(Resin layer)
In the second aspect, the laminate of the present invention comprises two or more resin layers.
The resin layer contains a first resin layer containing a polyester resin and provided at a position in contact with a metal plate, and a resin material having a Tg of 45 ° C. or higher and 60 ° C. or lower, and is provided on the outermost surface of the laminate. It also includes 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 included in the intermediate transfer recording medium on the resin layer provided in the laminate can be further improved.

The first resin layer can contain one kind or two or more kinds of polyester-based resins.
The Tg of the polyester resin is preferably 80 ° C. or higher and 120 ° C. or lower, and more preferably 80 ° C. or higher and 100 ° C. or lower. 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 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.

As long as the characteristics of the present invention are not impaired, the first resin layer may contain a resin material other than the polyester-based resin such as the above-mentioned other resin materials, an additive, 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 higher and 60 ° C. or lower. 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 included in the intermediate transfer recording medium on the resin layer provided in the laminate can be improved. In addition, the blocking resistance of the laminated body can be improved.
The resin layer provided on the outermost surface of the laminate may contain two or more kinds of the resin material.

Examples of the resin material having a Tg of 45 ° C. or higher and 60 ° C. or lower include polyester-based resin, polyamide-based resin, polyolefin-based resin, vinyl-based resin, (meth) acrylic-based resin, polyimide-based resin, cellulose-based resin, and polystyrene-based resin. Examples thereof include resins, polycarbonate resins and ionomer resins.
Among these, polyester resins are preferable from the viewpoint of transferability and blocking resistance.
When the laminate is composed of a metal plate, a first resin layer, and a second resin layer, a polyester resin is preferable from the viewpoint of adhesion of the second resin layer to the first resin layer. ..

The content of the resin material having a Tg of 45 ° C. or higher and 60 ° C. or lower 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 preferable. By setting the content of the resin material having a Tg of 45 ° C. or higher and 60 ° C. or lower in the second resin layer within the above numerical range, the receiving layer of the intermediate transfer recording medium on the resin layer of the laminate can be used. Transferability can be further improved. In addition, the blocking resistance of the laminated body can be further improved.

As long as the characteristics of the present invention are not impaired, 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 above-mentioned additive.

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 included in the intermediate transfer recording medium on the resin layer provided in the laminate can be further improved. In addition, the blocking resistance of the laminated body can be further improved.

One or more resin layers may be further provided between the first resin layer and the second resin layer (hereinafter, referred to as other resin layers in some cases).
Other resin layers are polyolefin-based resin, vinyl-based resin, (meth) acrylic-based resin, cellulose-based, depending on the required functions (plasticizer resistance, solvent resistance, light resistance, heat resistance, moisture resistance, etc.). Resin materials such as resins, polyester resins, polyamide resins, polycarbonate resins, polystyrene resins and polyurethane resins can be included.
Further, the above-mentioned additive can be contained as long as the characteristics of the present invention are not impaired.

The thickness of the other resin layers is preferably changed as appropriate according to the required functions, but can be, for example, 0.1 μm or more and 20 μm or less.

Each layer constituting the resin layer is prepared by dispersing or dissolving the above-mentioned material in water or an appropriate solvent, and using a roll coating method, a reverse roll coating method, a gravure coating method, a reverse gravure coating method, a bar coating method, a rod coating method, or the like. It can be formed by applying it on a metal plate or the like to form a coating film by a known means and drying it.

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

(Combination of laminated body and intermediate transfer recording medium)
The combination of the above-mentioned laminate of the present invention and the intermediate transfer recording medium is characterized in that the intermediate transfer recording medium is provided with a receiving layer containing a vinyl resin on the outermost surface.

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

(Base material)
The base material has heat resistance that can withstand the thermal energy applied during thermal transfer (for example, heat from a thermal head), and has mechanical strength that can support a receiving layer or the like provided on the base material.
Examples of the base material include paper base materials 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), and polyethylene. Polyester resin such as naphthalate (PEN), 1,4-polycyclohexylene methylene terephthalate, terephthalic acid-cyclohexanedimethanol-ethylene glycol copolymer, polyamide resin 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 polyvinylpyrrolidone (PVP), etc. (Meta) acrylic resins such as vinyl resins, polyacrylates, polymethacrylates and polymethylmethacrylates, polyimide resins such as polyimide and polyetherimide, cellophane, cellulose acetate, nitrocellulose, cellulose acetate propionate (CAP). ) And a cellulose-based resin such as cellulose acetate butyrate (CAB), a polystyrene-based resin such as polystyrene (PS), a polycarbonate-based resin, an ionomer-based resin, and the like (hereinafter, simply referred to 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 the uniaxial direction or the biaxial direction.

Further, the above-mentioned laminate made of the paper base material alone, the laminate made of the resin film alone, or the laminate made of the paper base material and the resin film can be used as the base material.
These laminates can be produced by using a dry lamination method, a wet lamination method, an extraction method, or the like.

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

(Receptive layer)
The intermediate transfer recording medium has a receiving layer on the outermost surface thereof, and the receiving layer contains a vinyl resin.
Examples of the vinyl resin include polyvinyl chloride, PVA, polyvinyl acetate, vinyl chloride-vinyl acetate copolymer, polyvinyl butyral, PVP and the like. Further, the monomer constituting the vinyl resin and other monomers (α-olefin compound, (meth) acrylic acid ester compound, etc.) may be used as the vinyl resin (ethylene-vinyl acetate copolymer, etc.).
Among these, a vinyl chloride-vinyl acetate copolymer is preferable from the viewpoint of transferability to the resin layer provided in the laminate.

The Mn of the vinyl resin is preferably 5,000 or more and 50,000 or less, and more preferably 10,000 or more and 20,000 or less. By setting the Mn of the vinyl-based resin within the above numerical range, the transferability to the resin layer provided in the laminated body can be further improved.

The content of the vinyl resin in the receiving layer is more preferably 90% by mass or more and 100% by mass or less. By setting the content of the vinyl-based resin within the above numerical range, the transferability to the resin layer provided in the laminate can be further improved.

Further, in one embodiment, the receiving layer contains a thermoplastic resin that is softened by heating and exhibits adhesiveness. Examples of the thermoplastic resin include polyester resin, (meth) acrylic resin, (meth) acrylic resin, polyurethane resin, cellulose resin, melamine resin, polyamide resin, polyolefin resin, and styrene resin. And so on.

In one embodiment, the receiving layer comprises a mold release material. As a result, 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 material include solid waxes such as polyethylene wax, amide wax, and Teflon (registered trademark) powder, fluorine-based surfactants, phosphoric acid ester-based surfactants, and silicone oils.
Among the above, silicone oil is preferable from the viewpoint of releasability from the thermal transfer sheet.
The receiving layer can contain two or more of the above-mentioned release materials.

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

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 receiving layer within the above numerical range, the release property of the receiving layer can be further improved.

The receiving layer may contain the above-mentioned additive as long as the characteristics of the present invention are not impaired.

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

The receiving layer is prepared by dispersing or dissolving the above-mentioned material in water or an appropriate solvent, and using a known means such as a roll coating method, a reverse roll coating method, a gravure coating method, a reverse gravure coating method, a bar coating method or a rod coating method. It can be formed by applying it on a substrate or the like to form a coating film and drying it.

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

In one embodiment, the protective layer is a (meth) acrylic resin, a polyester resin, a cellulose resin, a polystyrene resin, a polyamide resin, an acetal resin, a polycarbonate resin, a thermosetting resin, an active photocurable resin, or the like. including.

In one embodiment, the protective layer comprises a filler. Examples of the filler include an organic filler, an inorganic filler, and an organic-inorganic hybrid type filler. Further, the filler may be a powder or a sol, but it is preferable to use a powder because the selectivity of the filler when adjusting the coating liquid is wide.

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

Examples of the organic filler of the powder include non-crosslinked acrylic particles, acrylic particles such as crosslinked acrylic particles, polyamide particles, fluorine particles, polyethylene wax and the like. Examples of the powder inorganic filler include calcium carbonate particles, silica particles, metal oxide particles such as titanium oxide, and the like. Examples of the organic-inorganic hybrid type filler include a hybrid of acrylic resin and silica particles. Further, examples of the sol-like filler include silica sol-based fillers and organosol-based fillers. 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. This makes it possible to improve the durability of the protective layer.

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

The protective layer is obtained by dispersing or dissolving the above-mentioned material in water or a suitable solvent, and using known means such as a roll coater, a reverse roll coater, a gravure coater, a reverse gravure coater, a bar coater, and a rod coater, on a substrate or the like. It can be formed by applying it to a coating film to form a coating film, then drying the coating film, irradiating it with active light as necessary, and curing it.

(Release layer)
The intermediate transfer recording medium of the present invention may include a release layer between the base material and the receiving layer, or between the base material and the protective layer. When the intermediate transfer recording medium includes a release layer, the transferability of the receiving layer and the like can be improved. Further, the peeled layer is peeled from the base material during thermal transfer and transferred onto the resin layer provided in the laminate.

In one embodiment, the release layer contains a cellulose-based resin, a vinyl-based resin, a polyurethane-based resin, a silicone-based resin, a fluorine-based resin, a fluorine-modified resin, a wax, and the like.
Examples of waxes include microcrystalline wax, carnauba wax, paraffin wax, fisher tropus wax, various low molecular weight polyethylenes, wood wax, beeswax, whale wax, ibota wax, wool wax, celac wax, candelilla wax, petrolactam, and some. Examples thereof include modified waxes, fatty acid esters, and fatty acid amides.
Of these, polyethylene wax is particularly preferable.

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 coated on the substrate by a known means such as a roll coater, a reverse roll coater, a gravure coater, a reverse gravure coater, a bar coater and a rod coater by dispersing or dissolving the above material in water or a suitable solvent. It can be formed by forming a coating film and drying it.

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

The adhesive layer contains a thermoplastic resin that is softened by heating and exhibits adhesiveness, and is, for example, a polyester resin, a vinyl chloride resin such as vinyl chloride, vinyl acetate and an ethylene-vinyl acetate copolymer, (. Examples thereof include (meth) acrylic resin, (meth) acrylic resin, polyurethane resin, cellulose resin, melamine resin, polyamide resin, polyolefin resin, and styrene resin.

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

The adhesive layer is formed by dispersing or dissolving the above-mentioned material in water or an appropriate solvent, and using a known means such as a roll coating method, a reverse roll coating method, a gravure coating method, a reverse gravure coating method, a bar coating method or a rod coating method. , It can be formed by applying it on a protective layer to form a coating film and drying it.

(Back layer)
The intermediate transfer recording medium may be provided with a back layer on the surface of the substrate on which the receiving layer is not provided. Since the intermediate transfer recording medium is provided with a back layer, it is possible to prevent sticking, wrinkles, and the like due to heating during thermal transfer.

Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

Example 1
A coating liquid for forming a resin layer having the following composition was applied to one surface of an iron plate having a thickness of 0.4 mm and dried to form a resin layer having a thickness of 6 μm to prepare a laminated body.
<Coating liquid for forming a resin layer>
30 parts by mass of polyester resin A (manufactured by Unitika Ltd., Elitel (registered trademark) UE3300, Tg45 ° C., Mn8000, hydroxyl value 18 mgKOH / g)
・ Cyclohexanone 70 parts by mass

Example 2
A laminated body 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 laminated body 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
Laminated product in the same manner as in Example 1 except that the polyester resin A was changed to the polyester resin B (manufactured by Unitika Ltd., Elitel (registered trademark) UE3380, Tg60 ° C., Mn8000, hydroxyl value 15 mgKOH / g). Was produced.

Example 5
A laminated body 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 laminated body was produced in the same manner as in Example 5 except that the polyester-based resin A was changed to the polyester-based resin B.

Example 7
A laminated body was produced in the same manner as in Example 1 except that the coating liquid for forming the resin layer was changed to the following composition.
<Coating liquid for forming a resin layer>
-Polyester resin A 27 parts by mass- (Meta) acrylic resin 3 parts by mass (Mitsubishi Chemical Corporation, Dianal (registered trademark) BR-64, Tg55 ° C, Mn65000, acid value 2 mgKOH / g)
・ Cyclohexanone 70 parts by mass

Example 8
A laminated body was produced in the same manner as in Example 1 except that the coating liquid for forming the resin layer was changed to the following composition.
<Coating liquid for forming a resin layer>
-Polyester resin A 24 parts by mass- (Meta) acrylic resin 6 parts by mass (Mitsubishi Chemical Corporation, Dianal (registered trademark) BR-64, Tg55 ° C, Mn65000, acid value 2 mgKOH / g)
・ Cyclohexanone 70 parts by mass

Example 9
A coating liquid 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. A 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 to prepare a laminated body.
<Coating liquid for forming the first resin layer>
-Polyester 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 laminated body was produced in the same manner as in Example 9 except that the thickness of the second resin layer was changed to 10 μm.

Comparative Example 1
Laminated product in the same manner as in Example 1 except that the polyester resin A was changed to the polyester resin D (manufactured by Unitika Ltd., Elitel (registered trademark) UE3980, Tg63 ° C., Mn8000, hydroxyl value 17 mgKOH / g). Was produced.

Comparative Example 2
A laminated body 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 laminated body 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
Laminated product in the same manner as in Example 1 except that the polyester resin A was changed to the polyester resin E (manufactured by Unitika Ltd., Elitel (registered trademark) UE3320, Tg40 ° C., Mn1800, hydroxyl value 60 mgKOH / g). Was produced.

The following tests were performed on the laminates prepared in each Example and each Comparative Example and evaluated.

<< Transcription test >>
An image was formed on the receiving layer of the intermediate transfer recording medium prepared as described below by using the thermal transfer sheet prepared as described below. A sublimation thermal transfer printer (CX-D80, manufactured by G-Printec Co., Ltd.) was used for image formation.
After image formation, the same printer was used to transfer the release layer, protective layer, adhesive layer, and receiving layer of the intermediate transfer recording medium onto the resin layer of the laminates produced in each example and each comparative example. The transferability was evaluated according to the following evaluation criteria. The evaluation results are summarized in Table 1 and Table 2.
(Evaluation criteria)
A: There was no untransferred region, and the laminate was completely transferred from the transfer start end.
B: There was a slight untransferred region within a range of less than 1 mm from the transfer start end of the laminate.
NG: There was an untransferred region within a range of 1 mm or more from the transfer start end of the laminate.

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

<Coating liquid for forming a release layer>
-(Meta) acrylic resin 95 parts by mass (manufactured by Mitsubishi Chemical Corporation, Dianal (registered trademark) BR-87)
・ Polyester resin 5 parts by mass (manufactured by Toyobo Co., Ltd., Byron (registered trademark) 200)
・ Toluene 200 parts by mass ・ Methyl ethyl ketone (MEK) 200 parts by mass

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

<Coating liquid for forming an adhesive layer>
-Polyester resin 33 parts by mass (manufactured by Toyobo Co., Ltd., Byron (registered trademark) 200)
-Vinyl chloride-vinyl acetate copolymer 27 parts by mass (manufactured by Nissin Chemical Industry Co., Ltd., Solveine (registered trademark) CNL, Mn12000)
15 parts by mass of isocyanate curing agent (Mitsui Chemicals, Inc., XEL curing agent)
・ 50 parts by mass of toluene ・ 50 parts by mass of MEK

<Coating liquid for forming a receiving layer>
-Vinyl chloride-vinyl acetate copolymer 95 parts by mass (manufactured by Nissin Chemical Industry Co., Ltd., Solveine (registered trademark) CNL, Mn12000)
・ Epoxy-modified silicone 5 parts by mass (manufactured by Shin-Etsu Chemical Co., Ltd., KP-1800U)
・ Toluene 200 parts by mass ・ MEK 200 parts by mass

(Preparation of thermal transfer sheet)
A coating liquid for forming a back surface layer having the following composition was applied to one surface of a PET film having a thickness of 4.5 μm and dried to form a back surface layer having a thickness of 0.8 μm.
<Coating liquid for forming the back surface layer>
-Polyvinyl butyral 2.0 parts by mass (Sekisui Chemical Co., Ltd., Eslek (registered trademark) BX-1)
-Polyisocyanate 9.2 parts by mass (manufactured by DIC Corporation, Barnock (registered trademark) D750)
-Phosphoric acid ester-based 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 Industry Co., Ltd., Micro Ace (registered trademark) P-3)
・ Toluene 43.6 parts by mass ・ MEK 43.6 parts by mass

On the other surface of the PET film, a coating liquid for forming a yellow dye layer, a coating liquid for forming a magenta dye layer, and a coating liquid for forming a cyan dye layer having the following compositions were sequentially applied and dried, and each had a thickness of 0. A thermal transfer sheet was obtained by forming a .6 μm yellow dye layer, magenta dye layer and cyan dye layer.
<Coating liquid for forming a yellow dye layer>
-Yellow dye (HD137) 7.0 parts by mass-Polyvinyl acetal acetal 3.0 parts by mass (Sekisui Chemical Co., Ltd., Eslek (registered trademark) KS-5)
・ 45 parts by mass of toluene ・ 45 parts by mass of MEK <Coating liquid for forming magenta dye layer>
-Magenta dye (KC-27) 7.0 parts by mass-Polyvinyl acetal acetal 3.0 parts by mass (Sekisui Chemical Co., Ltd., Eslek (registered trademark) KS-5)
-Toluene 45 parts by mass-MEK 45 parts by mass <Cyan dye layer forming coating liquid>
-Cyan dye (HSB-2194) 7.0 parts by mass-Polyvinyl acetal acetal 3.0 parts by mass (Sekisui Chemical Co., Ltd., Eslek (registered trademark) KS-5)
・ 45 parts by mass of toluene ・ 45 parts by mass of MEK

<< Blocking resistance test >>
Two of the laminates produced in each Example and each Comparative Example were laminated so that the surface on the resin layer side and the surface on the metal plate faced each other, a pressure of 0.5 MPa was applied, and the mixture was allowed to stand at 45 ° C. for 96 hours. Placed. After standing, the resin layer and the metal plate were peeled off, and the blocking resistance of the laminated body was evaluated according to the following evaluation criteria. The evaluation results are summarized in Table 1 and Table 2.
(Evaluation criteria)
A: The resin layer and the metal plate were peeled off without resistance, and no change in the shape of the surface of the resin layer was observed.
B: There was some resistance when the resin layer and the metal plate were peeled off, but no change in the shape of the surface of the resin layer was observed.
NG: There was resistance when the resin layer and the metal plate were peeled off, and it was confirmed that the shape of the resin layer surface changed.

<< Adhesion test >>
In order to evaluate the adhesion of the resin layer to the metal plate, the wear resistance test of the resin layer provided in the laminates produced in each Example and Comparative Example was carried out in accordance with ANSI-INCITS322-2002, 5.9 Surface Abrasion. A 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 Table 1 and Table 2. The wear ring was polished every 250 cycles.
(Evaluation criteria)
A: No change in the shape of the surface of the resin layer was observed, and it was found that the adhesion of the resin layer to the metal plate was high.
B: There was almost no change in the shape of the surface of the resin layer, but some scratches were observed.
C: It was found that the shape change was large due to the wear of the surface of the resin layer, and the adhesion of the resin layer to the metal plate was 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: Substrate, 32: Receptive layer, 33: Protective layer, 34: Peeling layer, 35: Adhesive layer, 36: Back layer

Claims (8)

It is a combination of a laminated body as a transfer target and an intermediate transfer recording medium.
The laminate includes 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 and contains
The second resin layer contains a resin material having a glass transition temperature of 45 ° C. or higher and 60 ° C. or lower.
The thickness of the metal plate is 0.1 mm or more and 0.4 mm or less.
The ratio of the sum of the thicknesses of the resin layers to the thickness of the metal plate (sum of the thicknesses of the resin layers / the thickness of the metal plate) is 0.015 or more.
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. The combination according to claim 1, wherein the resin material having a glass transition temperature of 45 ° C. or higher and 60 ° C. or lower contained in the second resin layer is a polyester resin. The combination according to claim 1 or 2, wherein the content of the resin material having a glass transition temperature of 45 ° C. or higher and 60 ° C. or lower in the second resin layer is 90% by mass or more and 100% by mass or less. The combination according to any one of claims 1 to 3, wherein the thickness of the second resin layer is 6 μm or more and 10 μm or less. The combination according to any one of claims 1 to 4, wherein the glass transition temperature of the polyester resin contained in the first resin layer is 80 ° C. or higher and 120 ° C. or lower. The combination according to any one of claims 1 to 5, wherein the content of the polyester resin in the first resin layer is 80% by mass or more and 90% by mass or less. The combination according to any one of claims 1 to 6, wherein the thickness of the first resin layer is 1 μm or more and 3 μm or less. The combination according to any one of claims 1 to 7, wherein the receiving layer contains a vinyl chloride-vinyl acetate copolymer.

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