JP7284943B2 - Laminate and combination of laminate and intermediate transfer recording medium - Google Patents

Description

The present invention relates to a laminate, more specifically, a laminate comprising a metal plate and a resin layer, the thickness ratio of these layers being within a specific range, and a combination of the laminate and an intermediate transfer recording medium. Regarding.

Conventionally, various thermal transfer recording methods are known, but in recent years, a thermal transfer sheet provided with a dye layer containing a sublimation dye and a receiving material provided with a receiving layer are superimposed, and then a thermal head provided in a thermal transfer printer is used. Therefore, a sublimation-type thermal transfer method is widely used in which a thermal transfer sheet is heated to cause the sublimation dye in the dye layer to migrate to a receiving layer provided on a transfer-receiving material to form an image.

However, there are cases where it is difficult to use the sublimation thermal transfer method depending on the surface shape of the material to be transferred, and in such cases, an intermediate transfer recording medium is used to form an image on the material to be transferred. (see Patent Document 1).
In forming 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, image formation is performed, and then the intermediate transfer is performed. It is carried out by heating the recording medium and transferring the receptor layer onto the transfer material.

In order to transfer the receptor layer of the intermediate transfer recording medium onto such a transfer material, high transferability is required so that no untransferred portion occurs. However, depending on the material of the material to be transferred, an untransferred portion may occur, and there is room for improvement in the transferability. The transferability problem is particularly conspicuous when the object to be transferred includes a metal plate or the like having high thermal conductivity.

In addition, the object to be transferred is required to be capable of preventing the occurrence of blocking during storage (blocking resistance).

JP-A-2005-319702

SUMMARY OF THE INVENTION An object of the present invention is to provide a laminate capable of improving the transferability of a receiving layer from an intermediate transfer recording medium and effectively preventing the occurrence of blocking during stacking and storage. .

A laminate of the present invention in a 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 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.

A laminate of the present invention in a 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-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;
The ratio of the sum of the thicknesses of the resin layers to the thickness of the metal plate (the sum of the thicknesses of the resin layers/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 higher and 60° C. or lower 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 polyester resin contained in the first resin layer preferably has a glass transition temperature of 45° C. or higher and 60° C. or lower.

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 two aspects described above, the thickness of the metal plate is preferably 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 has a receiving layer containing a vinyl resin on its outermost surface.

In the above aspect, the receptor layer preferably 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 stacking and storage can be effectively prevented.

1 is a schematic cross-sectional view of a laminate of the present invention in a first aspect; FIG. FIG. 4 is a schematic cross-sectional view of a laminate of the present invention in a second aspect; 1 is a schematic cross-sectional view of an intermediate transfer recording medium in one embodiment; FIG. 1 is a schematic cross-sectional view of an intermediate transfer recording medium in one embodiment; FIG.

(Laminate of the first aspect)
1st aspect WHEREIN: The laminated body 10 of this invention is equipped with the metal plate 11 and the resin layer 12, as shown in FIG.
In this embodiment, the laminate 10 of the present invention may have a back layer 13 on the surface of the metal plate 11 opposite to the surface on which the resin layer 12 is provided, as shown in FIG.

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 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, transferability of the receiving layer of the intermediate transfer recording medium onto the resin layer of the laminate can be improved.

(metal plate)
Metal species constituting the metal plate include, for example, iron, copper, zinc (Zn), aluminum, nickel (Ni), titanium, manganese, palladium, lead, gold, platinum and stainless steel. Of these, iron and stainless steel are preferred because they have relatively low thermal conductivity values and are easy to handle during metal blanking.
The metal plate also includes those obtained by subjecting the surface of the plate of the above metal species to plating, for example, an iron plate having the surface plated with a Zn—Ni alloy.
In the present invention, the term "stainless steel" means an alloy containing iron as a main component and further containing chromium and/or nickel.

At least one surface of the metal plate may be subjected to surface processing such as sandblasting, hairline processing, matte coating processing, and chemical etching processing from the viewpoint of improving adhesion with adjacent layers.

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 receptor layer of the intermediate transfer recording medium onto the resin layer of the laminate can be further improved.

(resin layer)
A 1st aspect WHEREIN: A resin layer contains polyester-type resin whose glass transition temperature (Tg) is 45 degreeC or more and 60 degrees C or less.
When the resin layer contains a polyester-based resin having a Tg within the above numerical range, transferability of the receiving layer of the intermediate transfer recording medium onto the resin layer of the laminate can be improved. Also, 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 (differential scanning calorimetry) in accordance with JIS K 7121 (published in 2012).
The resin layer can contain two or more of the polyester-based resins.

In the present invention, the "polyester resin" means a polymer containing an ester group obtained by polycondensing a polyhydric carboxylic acid and a polyhydric alcohol.
Examples of polycarboxylic 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, citracone. 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-phenylene diacetic acid, m-phenylene Examples include diglycolic acid, p-phenyleneglycolic acid, o-phenyleneglycolic acid and p-hydroxybenzoic acid.
Examples of polyhydric alcohols include ethylene glycol such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, polyethylene glycol, propanediol, butanediol, pentanediol, hexanediol, neopentyl glycol, 1,4 -cyclohexanedimethanol, decanediol, 2-ethyl-butyl-1-propanediol, bisphenol A and the like.
Furthermore, in this specification, the polyester resin also includes modified products and copolymers thereof. Examples of modified polyester-based resins include urethane-modified polyester-based resins. In addition, the copolymer includes a copolymer obtained by polycondensing three or more kinds of the polyhydric carboxylic acid and the polyhydric alcohol, a monomer constituting the polyester resin, and other monomers (α-olefin compounds, vinyl ester compounds, vinyl ether compounds and (meth)acrylic acid ester compounds).

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, more preferably 90% by mass or more and 100% by mass or less. preferable. By setting the content of the polyester-based resin within the above numerical range, it is possible to further improve the transferability of the receptor layer of the intermediate transfer recording medium onto the resin layer of the laminate. Moreover, 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 higher and 60° C. or lower is preferably 2000 or higher and 12000 or lower, more preferably 6000 or higher and 10000 or lower. By setting the Mn of the polyester resin within the above numerical range, the transferability of the receptor layer of the intermediate transfer recording medium onto the resin layer of the laminate can be further improved. Moreover, 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 (published 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 higher and 40 mgKOH/g or lower, more preferably 10 mgKOH/g or higher and 20 mgKOH/g or lower. By setting the hydroxyl value of the polyester resin within the above numerical range, the transferability of the receptor layer of the intermediate transfer recording medium onto the resin layer of the laminate can be further improved. Moreover, 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 addition, in this invention, a hydroxyl value can be measured by the method based on JISK2501 (issued in 2003).

The resin layer may contain a resin material other than the polyester-based resin having a Tg of 45° C. or higher and 60° C. or lower (hereinafter simply referred to as other resin material in some cases) as long as the characteristics of the present invention are not impaired. Other resin materials include polyester resins with a Tg of less than 45°C, polyester resins with a 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, polyvinyl butyral and polyvinylpyrrolidone (PVP) vinyl resins, 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 cellulose acetate butyrate (CAB ), polystyrene resins such as polystyrene (PS), polycarbonate resins, and ionomer resins.
In the present invention, "(meth)acryl" includes both "acryl" and "methacryl".
In the present invention, "(meth)acrylate" includes both "acrylate" and "methacrylate".

In addition, the resin layer contains plasticizers, fillers, ultraviolet stabilizers, anti-coloring agents, fluorescent whitening agents, delustering agents, deodorant agents, flame retardant agents, and weather resistant agents, as long as the properties of the present invention are not impaired. , 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 dye.

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 of the intermediate transfer recording medium onto the resin layer of the laminate can be further improved. Moreover, 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 formed by dispersing or dissolving the above material in water or an appropriate solvent, and coating the resin layer by known means such as roll coating, reverse roll coating, gravure coating, reverse gravure coating, bar coating or rod coating. can be formed by coating a metal plate to form a coating film and drying it.

(back layer)
The laminate of the present invention may have a back layer on the surface opposite to the surface of the metal plate provided with the resin layer. By including the back layer in the laminate, the blocking resistance of the laminate can be further improved.
In addition, since the laminate has the back layer, the transportability of the laminate in the printer can be improved.

The back layer can contain a resin material such as polyolefin resin, vinyl resin, (meth)acrylic resin, cellulose resin, polyester resin, polyamide resin, polycarbonate resin, polystyrene resin and polyurethane. system resin and the like. The back layer can contain two or more of the resin materials described above.

In one embodiment, the back layer includes filler. Examples of fillers 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. Organic-inorganic hybrid fillers may also be used.

In addition, the back layer can contain the above-described additives as long as the characteristics of the present invention are not impaired.

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

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

(Laminate of the second aspect)
In a second aspect, the laminate 20 of the present invention comprises a metal plate 21 and two or more resin layers 22, as shown in FIG. 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.
In this aspect, the laminate 20 of the present invention may have a back layer 25 on the surface opposite to the surface of the metal plate 21 provided with the resin layer, as shown in FIG.

In the second aspect, the ratio of the sum of the thicknesses of the two or more resin layers provided in the laminate of the present invention to the thickness of the metal plate (the sum of the thicknesses of the two or more resin layers / the thickness of the metal plate thickness) is preferably 0.015 or more, 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, it is possible to improve the transferability of the receptor layer of the intermediate transfer recording medium onto the resin layer of the laminate. .

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

(resin layer)
2nd aspect WHEREIN: The laminated body of this invention is equipped with two or more resin layers.
The resin layer contains a polyester resin, 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 higher and 60 ° C. or lower, and is provided on the outermost surface of the laminate. and a second resin layer.

The sum of the thicknesses of the resin layers is preferably 7 μm or more and 28 μm or less, 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, it is possible to further improve the transferability of the receiving layer of the intermediate transfer recording medium onto the resin layer of the laminate.

The first resin layer may contain one or more polyester 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-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-based resin within the above numerical range, the adhesion of the first resin layer to the metal plate can be further improved.

The first resin layer may contain a resin material other than the polyester-based resin, such as the other resin materials described above, and additives, as long as the characteristics of the present invention are not impaired.

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 receptor layer of the intermediate transfer recording medium onto the resin layer of the laminate can be improved. Also, 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 these resin materials.

Examples of resin materials having a Tg of 45° C. or higher and 60° C. or lower include polyester-based resins, polyamide-based resins, polyolefin-based resins, vinyl-based resins, (meth)acrylic-based resins, polyimide-based resins, cellulose-based resins, and polystyrene-based resins. resins, polycarbonate resins, ionomer resins, and the like.
Among these, polyester-based resins are preferable from the viewpoint of transferability and blocking resistance.
Further, when the laminate is composed of a metal plate, a first resin layer, and a second resin layer, a polyester-based 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 is 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 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 can be formed on the resin layer of the laminate. Transferability can be further improved. Moreover, the blocking resistance of the laminate can be further improved.

The second resin layer may contain a resin material with a Tg of less than 45° C., a resin material with a Tg of more than 60° C., and the above-mentioned additives, 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, 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 receptor layer of the intermediate transfer recording medium onto the resin layer of the laminate can be further improved. Moreover, 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 other resin layers).
Other resin layers are made of polyolefin resin, vinyl resin, (meth)acrylic resin, cellulose resin, etc. depending on the required functions (plasticizer resistance, solvent resistance, light resistance, heat resistance, moisture resistance, etc.). Resin materials such as resins, polyester-based resins, polyamide-based resins, polycarbonate-based resins, polystyrene-based resins, and polyurethane-based resins can be included.
In addition, the above additives can be included within a range that does not impair the characteristics of the present invention.

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

Each layer constituting the resin layer can be formed by dispersing or dissolving the above materials in water or an appropriate solvent, and performing a roll coating method, reverse roll coating method, gravure coating method, reverse gravure coating method, bar coating method, rod coating method, or the like. It can be formed by coating a metal plate or the like by a known means to form a coating film, and drying the film.

(back layer)
Since the resin, thickness, etc. forming the back layer are the same as those in the first embodiment, the description is omitted here.

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

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

(Base material)
The substrate has heat resistance to withstand thermal energy applied during thermal transfer (for example, heat from a thermal head), and has mechanical strength capable of supporting a receiving layer or the like provided on the substrate.
Examples of substrates include paper substrates such as woodfree 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 resins such as naphthalate (PEN), 1,4-polycyclohexylene dimethylene terephthalate, terephthalic acid-cyclohexanedimethanol-ethylene glycol copolymer, polyamide 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 polyvinylpyrrolidone (PVP) Vinyl resins, (meth)acrylic resins such as polyacrylate, polymethacrylate and polymethyl methacrylate, polyimide resins such as polyimide and polyetherimide, cellophane, cellulose acetate, nitrocellulose, cellulose acetate propionate (CAP ) and cellulose-based resins such as cellulose acetate butyrate (CAB), polystyrene-based resins such as polystyrene (PS), polycarbonate-based resins, ionomer-based resins, etc. (hereinafter simply referred to as “resin films”). Available. 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 that has been uniaxially or biaxially stretched.

Further, a laminate consisting of the above-mentioned paper substrate alone, a laminate consisting of a resin film alone, or a laminate of a paper substrate and a resin film can also be used as the 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 has a receiving layer on its outermost surface, and the receiving layer contains a vinyl resin.
Vinyl resins include polyvinyl chloride, PVA, polyvinyl acetate, vinyl chloride-vinyl acetate copolymer, polyvinyl butyral, PVP and the like. Further, monomers constituting the vinyl resin and other monomers (α-olefin compounds, (meth)acrylic acid ester compounds, etc.) may be used as vinyl resins (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.

Mn of the vinyl-based 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 resin within the above numerical range, the transferability to the resin layer included in the laminate can be further improved.

More preferably, the content of the vinyl-based resin in the receiving layer is 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 included in the laminate can be further improved.

Also, in one embodiment, the receiving layer comprises a thermoplastic resin that is softened by heating and exhibits adhesiveness. Examples of thermoplastic resins include polyester resins, (meth)acrylic resins, (meth)acrylic resins, polyurethane resins, cellulose resins, melamine resins, polyamide resins, polyolefin resins, and styrene resins. etc.

In one embodiment, the receptive layer includes a release material. This makes it possible to improve releasability from the thermal transfer sheet during image formation, and form a good image on the receiving layer.
Examples of the release material include solid waxes such as polyethylene wax, amide wax, and Teflon (registered trademark) powder, fluorosurfactants, phosphate ester 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 release materials.

Examples of silicone oils include straight silicone oils such as dimethyl silicone oil and methylphenyl silicone oil, amino-modified silicone oils, epoxy-modified silicone oils, carboxy-modified silicone oils, methacryl-modified silicone oils, mercapto-modified silicone oils, and carbinol-modified silicone oils. Examples 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 releasing agent in the receiving layer within the above numerical range, the releasability of the receiving layer can be further improved.

The receptive layer can contain the above-described additives 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 included in the laminate can be improved.

The receiving layer is formed by dispersing or dissolving the above materials in water or an appropriate solvent and applying the coating by known means such as roll coating, reverse roll coating, gravure coating, reverse gravure coating, bar coating, rod coating, and the like. , to form a coating film on a substrate or the like, and then drying the film.

(protective layer)
The intermediate transfer recording medium of the present invention can have a protective layer between the substrate and the receiving layer.
The protective layer is a layer that is transferred onto the resin layer of the laminate together with the receiving layer, and has a function of protecting the image formed on the receiving 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, actinic radiation curable resin, and the like. including.

In one embodiment, the protective layer includes fillers. Fillers 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 of the wide selectivity of the solvent when preparing the coating liquid.

The average particle size of the filler contained in the protective layer is preferably 1 nm or more and 200 nm or less, more preferably 1 nm or more and 50 nm or less, and even more preferably 7 nm or more and 25 nm or less. By setting the average particle size of the filler within 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, using a particle size distribution / particle size distribution measuring device (manufactured by Nikkiso Co., Ltd., Nanotrack particle size distribution measuring device), JIS Z 8819-2 (published 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. Examples of powdery inorganic fillers include calcium carbonate particles, silica particles, and metal oxide particles such as titanium oxide. Further, examples of organic-inorganic hybrid fillers include those obtained by hybridizing acrylic resin with silica particles. Furthermore, examples of sol-like fillers include silica sol-based and organosol-based fillers. These fillers may be used alone or in combination of two or more.

The filler content 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 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 formed by dispersing or dissolving the above material in water or an appropriate solvent, and coating it on a substrate or the like by 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. to form a coating film, which is then dried and, if necessary, irradiated with actinic rays for curing.

(Release layer)
The intermediate transfer recording medium of the present invention can have a release layer between the substrate and the receiving layer or between the substrate and the protective layer. By providing the release layer to the intermediate transfer recording medium, the transferability of the receiving layer and the like can be improved. Moreover, the peeling layer is peeled off from the base material during thermal transfer and transferred onto the resin layer included in the laminate.

In one embodiment, the release layer includes 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, or the like.
Waxes include, for example, microcrystalline wax, carnauba wax, paraffin wax, Fischer-Tropsch wax, various low-molecular-weight polyethylenes, wood wax, beeswax, whale wax, ivory wax, wool wax, shellac wax, candelilla wax, petrolactam, and some modified waxes, fatty acid esters, fatty acid amides, and the like;
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 formed by dispersing or dissolving the above material in water or an appropriate solvent, and coating the base material with 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. It can be formed by drying to form a coating film.

(adhesion layer)
When the intermediate transfer recording medium has a protective layer, it can have an adhesive layer between the receiving layer and the protective layer. Adhesion between the receiving layer and the protective layer can be improved by providing the intermediate transfer recording medium with the adhesive layer.

The adhesive layer contains a thermoplastic resin that softens and exhibits adhesiveness when heated, and includes, for example, polyester resins, vinyl resins such as vinyl chloride, vinyl acetate and ethylene-vinyl acetate copolymer, ( Examples include 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 formed by dispersing or dissolving the above material in water or an appropriate solvent, and coating the adhesive layer by known means such as roll coating, reverse roll coating, gravure coating, reverse gravure coating, bar coating or rod coating. can be formed by coating the protective layer to form a coating film and drying the film.

(back layer)
The intermediate transfer recording medium may have a backing layer on the side of the substrate not provided with the receiving layer. By providing the intermediate transfer recording medium with the back layer, it is possible to prevent the occurrence of sticking, wrinkles, etc. due to heating during thermal transfer.

EXAMPLES 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 resin layer-forming coating liquid having the following composition was applied to one surface of a 0.4 mm-thick iron plate and dried to form a 6 μm-thick resin layer to prepare a laminate.
<Coating solution for resin layer formation>
· Polyester resin A 30 parts by mass (Unitika Ltd., Elitel (registered trademark) UE3300, Tg 45 ° C., Mn 8000, hydroxyl value 18 mgKOH / g)
・ Cyclohexanone 70 parts by mass

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
Laminate in the same manner as in Example 1, except that polyester resin A was changed to polyester resin B (Elitel (registered trademark) UE3380, manufactured by Unitika Ltd., Tg 60 ° C., Mn 8000, hydroxyl value 15 mgKOH / g). was made.

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 polyester resin A was changed to polyester resin B.

Example 7
A laminate was produced in the same manner as in Example 1, except that the composition of the resin layer-forming coating liquid was changed to that shown below.
<Coating solution for resin layer formation>
- Polyester resin A 27 parts by mass - (Meth) acrylic resin 3 parts by mass (manufactured by Mitsubishi Chemical Corporation, Dianal (registered trademark) BR-64, Tg 55 ° C., Mn 65000, acid value 2 mgKOH / g)
・ Cyclohexanone 70 parts by mass

Example 8
A laminate was produced in the same manner as in Example 1, except that the composition of the resin layer-forming coating liquid was changed to that shown below.
<Coating solution for resin layer formation>
・Polyester resin A 24 parts by mass ・(Meth)acrylic resin 6 parts by mass (manufactured by Mitsubishi Chemical Corporation, Dianal (registered trademark) BR-64, Tg 55 ° C., Mn 65000, acid value 2 mgKOH / g)
・ Cyclohexanone 70 parts by mass

Example 9
A coating solution for forming a first resin layer having the following composition was applied to one surface of a 0.4 mm thick iron plate 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, thereby producing a laminate.
<Coating liquid for forming the first resin layer>
・Polyester resin C (Tg 90°C) 27 parts by mass ・Isocyanate curing agent 3 parts by mass ・Cyclohexanone 70 parts by mass <Coating liquid for forming the 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 in Example 9, except that the thickness of the second resin layer was changed to 10 μm.

Comparative example 1
Laminate in the same manner as in Example 1, except that polyester resin A was changed to polyester resin D (Elitel (registered trademark) UE3980, manufactured by Unitika Ltd., Tg 63 ° C., Mn 8000, hydroxyl value 17 mgKOH / g). was made.

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
Laminate in the same manner as in Example 1, except that polyester resin A was changed to polyester resin E (Elitel (registered trademark) UE3320, manufactured by Unitika Ltd., Tg 40 ° C., Mn 1800, hydroxyl value 60 mgKOH / g). was made.

The laminates produced in each example and each comparative example were subjected to the following tests and evaluated.

<<Transfer test>>
An image was formed on the receiving layer of the intermediate transfer recording medium prepared as described below using a 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, using the same printer, the release layer, protective layer, adhesive layer and receiving layer provided in the intermediate transfer recording medium are transferred onto the resin layer provided in the laminate prepared in each example and each comparative example, 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 layer was completely transferred from the transfer start end.
B: There was a slight untransferred area within a range of less than 1 mm from the laminate transfer start end.
NG: There was an untransferred area in a range of 1 mm or more from the laminate transfer start end.

(Production of intermediate transfer recording medium)
A release layer forming coating liquid 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 solution 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 on the protective layer and dried to form an adhesive layer having a thickness of 1 μm. Finally, on the adhesive layer, a coating solution for forming a receiving layer having the following composition was applied and dried to form a receiving layer having a thickness of 2.5 μm, thereby forming a release layer, a protective layer, and an adhesive layer on the PET film. , receiving layers were laminated in this order to obtain an intermediate transfer recording medium.

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

<Coating solution for forming protective layer>
・Styrene-acrylic copolymer 150 parts by mass (Muticle PP320P, manufactured by Mitsui Chemicals, Inc.)
・ Polyvinyl alcohol 100 parts by mass (C-318, manufactured by DNP Fine Chemicals Co., Ltd.)
・Water 25 parts by mass ・Ethanol 50 parts by mass

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

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

(Production of thermal transfer sheet)
On one side of a PET film having a thickness of 4.5 μm, a coating solution for forming a back layer having the following composition was applied and dried to form a back layer having a thickness of 0.8 μm.
<Coating solution for forming back surface layer>
・ Polyvinyl butyral 2.0 parts by mass (Sekisui Chemical Co., Ltd., S-Lec (registered trademark) BX-1)
· Polyisocyanate 9.2 parts by mass (DIC Corporation, Barnock (registered trademark) D750)
· Phosphate ester surfactant 1.3 parts by mass (Plysurf (registered trademark) A208N, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.)
・ Talc 0.3 parts by mass (Micro Ace (registered trademark) P-3, manufactured by Nippon Talc Industry Co., Ltd.)
・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 having the following compositions were sequentially applied and dried to form a film having a thickness of 0. A thermal transfer sheet was obtained by forming a yellow dye layer, a magenta dye layer and a cyan dye layer of 0.6 μm.
<Coating liquid for forming yellow dye layer>
・ Yellow dye (HD137) 7.0 parts by mass ・ Polyvinyl acetoacetal 3.0 parts by mass (Sekisui Chemical Co., Ltd., S-Lec (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 (Sekisui Chemical Co., Ltd., S-Lec (registered trademark) KS-5)
・Toluene 45 parts by mass ・MEK 45 parts by mass <Coating liquid for forming cyan dye layer>
・ Cyan dye (HSB-2194) 7.0 parts by mass ・ Polyvinyl acetoacetal 3.0 parts by mass (Sekisui Chemical Co., Ltd., S-Lec (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 were superimposed so that the surface on the resin layer side and the surface of the metal plate faced each other, a pressure of 0.5 MPa was applied, and the mixture was left at 45°C for 96 hours. placed. After standing still, 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 were peeled off without resistance, and no shape change was observed on the surface of the resin layer.
B: There was some resistance when the resin layer and the metal plate were peeled off, but no shape change was observed on the surface of the resin layer.
NG: There was resistance when the resin layer and the metal plate were peeled off, and a shape change on the surface of the resin layer was 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 provided in the laminate produced in each example and comparative example was performed at 50 in accordance with ANSI-INCITS322-2002, 5.9 Surface Abrasion. A cycle was performed (wear wheel: CS-10F, load: 500 g). After the test, the state of the resin layer surface was visually observed, 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 ground every 250 cycles.
(Evaluation criteria)
A: No shape change was observed on the surface of the resin layer, indicating that the adhesion of the resin layer to the metal plate was high.
B: There was almost no shape change on the surface of the resin layer, but some scratches were observed.
C: It was found that the shape change due to abrasion of the resin layer surface was large, 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 layer, 23: first resin layer, 24: second resin layer, 30: intermediate transfer recording medium , 31: substrate, 32: receiving layer, 33: protective layer, 34: release layer, 35: adhesive layer, 36: backing layer

Claims (3)

A combination of a laminate as a transfer target and an intermediate transfer recording medium,
The laminate 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 having a glass transition temperature of 80° C. or more and 120° C. or less , and the thickness of the first resin layer is 1 μm or more and 3 μm or less,
The second resin layer contains a polyester resin having a glass transition temperature of 45° C. or higher and 60° C. or lower, and the content of the polyester resin 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, and the thickness of the second resin layer is 6 μm or more and 10 μm or less,
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 (the sum of the thicknesses of the resin layers/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 has a receiving layer containing a vinyl resin on the outermost surface thereof. The combination according to claim 1, wherein the content of the polyester-based resin in the first resin layer is 80% by mass or more and 90% by mass or less. A combination according to claim 1 or 2 , wherein the receiving layer comprises a vinyl chloride-vinyl acetate copolymer.

Images