JP5633593B2 - Protective layer transfer sheet and intermediate transfer medium - Google Patents

Description

  The present invention relates to a protective layer transfer sheet and an intermediate transfer medium.

  Forms a thermal transfer image on the transfer material by the sublimation transfer method because it is excellent in transparency, has high reproducibility and gradation of intermediate colors, and can easily form a high-quality image equivalent to a conventional full-color photographic image. It is widely done. As a printed matter in which a thermal transfer image is formed on a transfer object, an ID card used in many fields such as a digital photograph, an identification card, a driver's license, and a membership card is known.

  For the formation of a thermal transfer image by a sublimation transfer method, a thermal transfer sheet in which a dye layer is provided on one side of a substrate and a transfer target, for example, a thermal transfer in which a receiving layer is provided on one side of another substrate An image receiving sheet is used. Then, the transferred object and the dye layer of the thermal transfer sheet are overlapped, and heat is applied from the back side of the thermal transfer sheet by the thermal head to transfer a large number of three or four color dots onto the transferred object. By doing so, it is possible to obtain a printed matter in which a thermal transfer image is formed on the transfer target. According to such a sublimation transfer method, since the amount of dye transfer can be controlled by the amount of energy applied to the thermal transfer sheet, density gradation is possible, so that the image is very clear and has transparency and halftone. Therefore, it is possible to form a high-quality printed product comparable to a full-color photographic image.

  Recently, an intermediate transfer in which a receiving layer is provided on a substrate in a peelable manner to meet the demand for obtaining a printed material on which a thermal transfer image is formed on an arbitrary transfer target other than a thermal transfer image receiving sheet. A medium has been proposed (for example, Patent Document 1). According to this intermediate transfer medium, the dye of the dye layer of the thermal transfer sheet is transferred onto the receiving layer of the intermediate transfer medium to form a thermal transfer image, and then the back side of the intermediate transfer medium is heated to form the receiving layer. The image can be transferred onto an arbitrary transfer medium, and a printed material having a thermal transfer image formed on the transfer medium can be obtained.

  A print obtained by forming a thermal transfer image on the receiving layer of the thermal transfer image-receiving sheet by the sublimation transfer method, or a thermal transfer image is formed on the receiving layer of the intermediate transfer medium by the sublimation transfer method, and this receiving layer is applied to any receiving layer. In the printed matter obtained by retransferring onto the transfer body, the receiving layer on which the thermal transfer image is formed is located on the outermost surface of the printed matter. However, although the thermal transfer image formed on the receiving layer by the sublimation transfer method is excellent in the formation of a gradation image as described above, the formed printed matter is different from the one using ordinary printing ink, and the dye is a pigment. In addition, since it is a relatively low molecular weight dye and no vehicle is present, it has the disadvantage of poor durability such as plasticizer resistance, abrasion resistance, and solvent resistance.

  Therefore, recently, the receiving layer of the thermal transfer image-receiving sheet on which the thermal transfer image is formed and the protective layer transfer sheet having the protective layer are overlapped, and the protective layer is transferred using a thermal head or a heating roll to form a thermal transfer image. A method in which a protective layer is further formed on the formed receiving layer is used. By further forming a protective layer on the receiving layer on which the thermal transfer image is thus formed, the durability of the thermal transfer image can be improved. For example, Patent Document 2 proposes an intermediate transfer medium in which a release layer, a protective layer, and a receiving layer / adhesive layer are provided on a substrate. According to this intermediate transfer medium, when the receiving layer and the protective layer on which the thermal transfer image is formed are transferred onto an arbitrary substrate, the protective layer is located on the surface of the receiving layer on which the thermal transfer image is formed. Durability can be imparted to the thermal transfer image.

JP-A-62-238791 JP 2004-351656 A

  However, when a protective layer whose main purpose is to improve durability is used, the foil of the protective layer is poor and the protective layer of the protective layer transfer sheet or the receiving layer of the intermediate transfer medium on which the thermal transfer image is formed When the protective layer is transferred onto the transfer target, tailing occurs in the transferred protective layer, or transfer failure occurs at the end of the transfer portion. Although it is conceivable to reduce the film thickness of the protective layer in order to improve the foil cutting property, when the film thickness of the protective layer is reduced, there arises a problem that durability is lowered.

  Although important features required for the protective layer include durability and foil breakability, as described above, durability and foil tearability are in a trade-off relationship, and it is intended to improve the durability of the protective layer. In such a case, the foil breakability of the protective layer is lowered. From this, it is the present condition that both durability and foil tearability cannot be satisfied with one protective layer.

  The present invention has been made in view of such a situation, and a protective layer transfer sheet that has good foil tearability of the protective layer during transfer and can impart sufficient durability to a thermal transfer image, and an intermediate layer. It is a main problem to provide a transfer medium.

The present invention for solving the above problems is a protective layer transfer sheet in which a protective layer that can be peeled off from the base material is provided on one surface of the base material, and the protective layer has a glass transition temperature (Tg). ) Exceeding 80 ° C. and having a hydroxyl value of 10 mgKOH / g or more and 100 mgKOH / g or less .

  The acrylic polyol resin may have a weight average molecular weight (Mw) in the range of 8000 to 70000. The acrylic polyol resin may be a curable acrylic polyol resin obtained by curing an acrylic polyol resin having a glass transition temperature (Tg) exceeding 80 ° C. with a curing agent.

  In addition, the curing agent may be an isocyanate curing agent selected from the group of XDI, HMDI, and IPDI.

Further, the present invention for solving the above problems is an intermediate transfer medium in which a protective layer that can be peeled off from the base material and a receiving layer are laminated on one surface of the base material, and the protective layer is made of glass. It is characterized by containing an acrylic polyol resin having a transition temperature (Tg) exceeding 80 ° C. and a hydroxyl value of 10 mgKOH / g to 100 mgKOH / g .

  According to the protective layer transfer sheet and the intermediate transfer medium of the present invention, the protective layer transfer sheet and the protective layer included in the intermediate transfer medium are provided with both the foil breakability and durability that are in a trade-off relationship. In the protective layer transfer sheet, the foil of the protective layer is good when the protective layer is transferred onto the receiving layer on which the thermal transfer image is formed, and the printed matter on which the thermal transfer image is formed is high. Durability can be imparted. In addition, in the intermediate transfer medium, the receiving layer on which the thermal transfer image was formed and the protective layer had good foil breakability when transferred onto an arbitrary substrate, and were formed on the receiving layer. High durability can be imparted to the thermal transfer image.

It is a schematic sectional drawing which shows an example of the protective layer transfer sheet of this invention. It is a schematic sectional drawing which shows an example of the protective layer transfer sheet of this invention. 1 is a schematic cross-sectional view illustrating an example of an intermediate transfer medium of the present invention. 1 is a schematic cross-sectional view illustrating an example of an intermediate transfer medium of the present invention.

<< Protective layer transfer sheet >>
Below, the protective layer transfer sheet 10 of this invention is demonstrated in detail. FIG. 1 is a schematic cross-sectional view showing an example of the protective layer transfer sheet of the present invention. As shown in FIGS. 1 and 2, the protective layer transfer sheet 10 of the present invention has a configuration in which a protective layer 2 that can be peeled off from the base material 1 is provided on one surface of the base material 1. The base material 1 and the protective layer 2 are essential components in the protective layer transfer sheet 10 of the present invention. In addition to these essential components, the protective layer transfer sheet 10 of the present invention may be provided with an arbitrary layer as shown in FIG. In FIG. 2, a release layer 3 which is an arbitrary layer is provided between the base material 1 and the protective layer 2, and an adhesive layer 4 which is an optional layer is provided on the protective layer 2. On the other surface of the substrate 1, a back layer 5 which is an arbitrary layer is provided. Hereinafter, each structure of the protective layer transfer sheet 10 of this invention is demonstrated concretely.

(Base material)
The base material 1 is an indispensable structure in the protective layer transfer sheet 10 of the present invention. The protective layer 2 or the release layer 3 arbitrarily provided between the base material 1 and the protective layer 2 and the other of the base material 1 are provided. It is provided to hold the back layer 5 that is optionally provided on the surface. The material of the base material 1 is not particularly limited, but it is desirable that the material has mechanical characteristics that can withstand heat applied when the protective layer 2 is transferred onto the transfer target and does not hinder handling. Examples of such a substrate 1 include polyesters such as polyethylene terephthalate, polyarylate, polycarbonate, polyurethane, polyimide, polyetherimide, cellulose derivatives, polyethylene, ethylene / vinyl acetate copolymer, polypropylene, polystyrene, acrylic, polychlorinated. Vinyl, polyvinylidene chloride, polyvinyl alcohol, polyvinyl butyral, nylon, polyether ether ketone, polysulfone, polyether sulfone, tetrafluoroethylene / perfluoroalkyl vinyl ether, polyvinyl fluoride, tetrafluoroethylene / ethylene, tetrafluoroethylene / hexa Various plastic films such as fluoropropylene, polychlorotrifluoroethylene, and polyvinylidene fluoride Mention may be made of the beam or sheet. Moreover, the thickness of the base material 1 can be appropriately set according to the material so that the strength and heat resistance thereof are appropriate, and is generally about 2.5 to 100 μm.

(Protective layer)
A protective layer 2 that can be peeled off from the base material 1 is provided on one surface of the base material 1. The protective layer 2 is an essential component in the protective layer transfer sheet 10 of the present invention, and is a layer that is peeled off from the substrate 1 and transferred to a transfer target during thermal transfer.

  In the present invention, the protective layer 2 contains an acrylic polyol resin. The acrylic polyol resin in the present specification means an acrylic resin having a hydroxyl group. For example, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl One or more (meth) acrylic acid alkyl esters such as (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meta) ) By copolymerizing one or more (meth) acrylic acid ester having a hydroxyl group in the molecule such as acrylate and, if necessary, one or more other polymerizable monomers such as styrene. An acrylic polyol resin obtained by the above method can be mentioned. Specific examples include methyl (meth) acrylate-2 hydroxyethyl (meth) acrylate copolymer, octyl (meth) acrylate-ethylhexyl (meth) acrylate-2 hydroxyethyl (meth) acrylate copolymer, methyl (meth) acrylate. -Butyl (meth) acrylate-2 hydroxyethyl (meth) acrylate-styrene copolymer etc. can be mentioned. (Meth) acrylate means acrylate or methacrylate.

  The glass transition temperature (Tg) of the acrylic polyol resin is closely related to the durability imparted to the protective layer 2 containing the acrylic polyol resin, and the foil breakability. When the protective layer 2 contains only an acrylic polyol resin having a glass transition temperature (Tg) of 80 ° C. or less, the protective layer has heat resistance, wear resistance, plasticizer resistance, solvent resistance, etc. The durability (hereinafter simply referred to as durability) cannot be sufficiently imparted. In particular, when the acrylic polyol resin having a glass transition temperature (Tg) of 80 ° C. or lower is an uncured acrylic polyol resin or a curable acrylic polyol resin having a low degree of curing with a curing agent, protection is required. The durability imparted to the layer 2 is extremely low, and sufficient durability cannot be imparted to the thermal transfer image to which the protective layer has been transferred.

  On the other hand, when the acrylic polyol resin having a glass transition temperature (Tg) of 80 ° C. or less is a curable acrylic polyol resin having a high degree of curing with a curing agent, it is uncured or has a low degree of curing. The durability of the protective layer containing the curable acrylic polyol resin can be improved as compared with the polyol resin. However, in order to impart sufficient heat resistance and durability to the protective layer using an acrylic polyol resin having a glass transition temperature (Tg) of 80 ° C. or lower, the glass transition temperature (Tg) is 80 ° C. or lower. Although it is necessary to sufficiently increase the degree of curing of the acrylic polyol resin, the transferability of the protective layer decreases as the degree of curing progresses. Further, as the degree of curing of the acrylic polyol resin having a glass transition temperature (Tg) of 80 ° C. or lower increases, the protective layer containing the acrylic polyol resin becomes brittle, and the protective layer at the time of transferring the protective layer The foil breakability will be significantly reduced. Moreover, it cannot be said that durability is sufficient.

  Furthermore, even when an acrylic polyol resin having a glass transition temperature (Tg) of 80 ° C. or lower is sufficiently cured, durability such as wear resistance, plasticizer resistance, solvent resistance, etc. The temperature (Tg) is lower than that of the acrylic polyol resin exceeding 80 ° C.

  That is, in the case where the protective layer 2 contains an acrylic polyol resin having a glass transition temperature (Tg) of 80 ° C. or lower, if the acrylic polyol resin is cured by a curing agent, the foil breakage However, when it is uncured, the durability requirement cannot be satisfied. In other words, when an acrylic polyol resin having a glass transition temperature (Tg) of 80 ° C. or lower is contained in the protective layer without using an acrylic polyol resin having a glass transition temperature (Tg) exceeding 80 ° C. However, it is not possible to sufficiently satisfy both the requirements of durability and tearability.

  Therefore, in the present invention, the protective layer 2 contains an acrylic polyol resin having a glass transition temperature (Tg) exceeding 80 ° C. Hereinafter, unless otherwise specified, an acrylic polyol resin having a glass transition temperature (Tg) exceeding 80 ° C. may be simply referred to as an acrylic polyol resin in the present invention. Further, in the present specification, the glass transition temperature (Tg) is a temperature (Kelvin (K)) obtained based on Fox's theoretical calculation formula converted to Celsius (° C.).

  According to the protective layer 2 containing an acrylic polyol resin in the present invention, regardless of whether the acrylic polyol resin is cured by a curing agent, and regardless of the degree of curing by the curing agent, the protective layer. 2 can be provided with sufficient durability and foil breakability. That is, according to the protective layer 2 containing the acrylic polyol resin in the present invention, it is possible to satisfy both the requirements of durability and foil breakage, which are in a trade-off relationship. In addition, even if the acrylic polyol resin in the present invention is an uncured one, its durability is more than that obtained by completely curing an acrylic polyol resin having a glass transition temperature (Tg) of 80 ° C. or less with a curing agent. Therefore, sufficient durability can be imparted to the protective layer 2 without reducing the foil cutting property.

  The protective layer 2 preferably contains a curable acrylic polyol resin obtained by curing the acrylic polyol resin of the present invention with a curing agent, instead of or together with the acrylic polyol resin of the present invention. According to the protective layer 2 containing a curable acrylic polyol resin, further improvement in durability of the protective layer 2 can be expected. Hereinafter, a curable acrylic polyol resin obtained by curing an acrylic polyol resin having a glass transition temperature exceeding 80 ° C. with a curing agent may be simply referred to as a curable acrylic polyol resin in the present invention.

  Whether the protective layer 2 contains the acrylic polyol resin in the present invention or the curable acrylic polyol resin in the present invention can be identified by, for example, infrared absorption (FT-IR) analysis. Specifically, when the protective layer is measured, whether the resin contained in the protective layer 2 is an acrylic resin can be specified by the presence or absence of absorption of acrylic acid ester and methacrylic acid ester. In addition, when an isocyanate curing agent is used as the curing agent, it is a curable acrylic polyol resin depending on whether a urethane bond in which an isocyanate group and a hydroxyl group are reacted or whether or not unreacted residual isocyanate is absorbed. Can be specified. In addition to this, it is possible to specify whether or not the curable acrylic polyol resin is based on whether or not another peak bonded to a hydroxyl group is detected by infrared spectroscopy (IR) measurement. Furthermore, when it is specified by these measurements that the protective layer 2 contains an acrylic polyol resin or a curable acrylic polyol resin, the absorption or peak of the acrylic polyol resin or curable acrylic resin becomes a peak. An acrylic polyol resin contained in the protective layer 2 and cured by measuring the glass transition temperature (Tg) of the separately prepared acrylic polyol resin and the separately prepared acrylic polyol resin and curable acrylic polyol resin The glass transition temperature (Tg) of the type acrylic polyol resin can be specified.

  The molecular weight of the acrylic polyol resin in the present invention is not particularly limited, but when the weight average molecular weight (Mw) of the acrylic polyol resin in the present invention is less than 8000, the durability of the protective layer 2 tends to decrease. is there. On the other hand, when the weight average molecular weight (Mw) of the acrylic polyol resin in the present invention exceeds 70000, the foil breakability when the protective layer 2 is transferred tends to be lowered. Considering this point, the protective layer 2 preferably contains an acrylic polyol resin having a weight average molecular weight (Mw) of 8000 to 70000. This does not limit the molecular weight of the acrylic polyol resin in the present invention. Even if the molecular weight is outside the above preferred range, an acrylic polyol resin having a glass transition temperature (Tg) of 80 ° C. or lower, Compared with the case where a polyol resin other than an acrylic polyol resin having a glass transition temperature (Tg) exceeding 80 ° C. is contained in the protective layer, the durability imparted to the protective layer 2, transferability, foil breakage, etc. The printing suitability is good. Even when the weight average molecular weight (Mw) is lower than the above preferred range, the weight average molecular weight is within the above preferred range by curing the acrylic polyol resin having the weight average molecular weight with a curing agent described later. Durability equivalent to that of acrylic polyol resin can be imparted. In addition, a weight average molecular weight (Mw) means the polystyrene conversion value measured by gel permeation chromatography (GPC).

  The hydroxyl value of the acrylic polyol resin in the present invention is preferably in the range of 10 mgKOH / g to 100 mgKOH / g. By using the acrylic polyol resin in the present invention having a hydroxyl value within this range, the foil breakability can be satisfied regardless of the degree of curing, and the durability can be further improved. . In addition, when the acrylic polyol resin having a hydroxyl value exceeding 100 mgKOH / g is sufficiently cured with a curing agent, the film of the protective layer 2 containing the curable acrylic polyol resin becomes brittle, and the foil breakage is reduced. Tends to decrease. On the other hand, when the hydroxyl value of the acrylic polyol resin in the present invention is less than 10 mgKOH / g, even when the acrylic polyol resin is completely cured, the durability is almost the same as that of the uncured one. Therefore, the durability cannot be further improved.

  In the present specification, the “hydroxyl value” of the acrylic polyol resin means the number of mg of potassium hydroxide required to acetylate the hydroxyl group contained in 1 g of the acrylic polyol resin. The hydroxyl value is determined by making acrylic polyol resin into a pyridine solution containing acetic anhydride, acetylating the hydroxyl group, hydrolyzing the excess acetylating reagent with water, and titrating the produced acetic acid with potassium hydroxide. be able to.

  As the curing agent for obtaining the curable acrylic polyol resin, an isocyanate curing agent, or a metal chelating agent such as a titanium chelating agent, a zirconium chelating agent, or an aluminum chelating agent can be suitably used. The isocyanate curing agent crosslinks an acrylic polyol resin having a hydroxyl group using the hydroxyl group. As the isocyanate curing agent, a polyisocyanate resin can be preferably used. Various polyisocyanate resins are conventionally known, and among them, it is desirable to use an adduct of aromatic isocyanate. As the aromatic polyisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, or a mixture of 2,4-toluene diisocyanate and 2,6-toluene diisocyanate, 1,5-naphthalene diisocyanate, tolidine diisocyanate, Examples include p-phenylene diisocyanate, trans-cyclohexane, 1,4-diisocyanate, xylylene diisocyanate, triphenylmethane triisocyanate, and tris (isocyanatephenyl) thiophosphate, especially 2,4-toluene diisocyanate and 2,6-toluene diisocyanate. Or, a mixture of 2,4-toluene diisocyanate and 2,6-toluene diisocyanate is preferable.

  The isocyanate curing agent is preferably an isocyanate curing agent selected from the group of XDI, HMDI, and IPDI. By using these isocyanate curing agents to cure the acrylic polyol resin, it is possible to prevent the protective layer 2 containing the curable acrylic polyol resin from being yellowed. In addition, when the acrylic polyol resin in the present invention is cured by an isocyanate curing agent other than the isocyanate curing agent selected from these groups, for example, a TDI-based or MDI-based isocyanate curing agent, The protective layer 2 containing the curable acrylic polyol resin may turn yellow, and the appearance of the printed material to which the protective layer 2 has been transferred may deteriorate.

  As explained above, the acrylic polyol resin in the present invention can impart sufficient durability and sufficient foil breakability to the protective layer 2 containing the acrylic polyol resin in an uncured state. In addition, the durability can be further improved by adding the curable acrylic polyol resin in the present invention to the protective layer 2. In particular, the acrylic polyol resin in the present invention can impart extremely high durability to the protective layer 2 even when the degree of curing is low. Depending on the hydroxyl value of the acrylic polyol resin, when the curing of the acrylic polyol resin in the present invention is proceeding, there is a concern that the protective layer 2 becomes brittle and the foil breakage is reduced. When the acrylic polyol resin in the present invention is cured with a curing agent, it is preferable to adjust the degree of curing within a range in which the foil breakability of the protective layer 2 is not deteriorated.

  Specifically, the molar equivalent ratio (—NCO / —OH) between the isocyanate group of the isocyanate curing agent as the curing agent and the hydroxyl group of the acrylic polyol resin in the present invention is 0.2 or more and 3.0 or less. It is preferable that it is hardened within the range. In addition, when a hydroxyl value is a thing within the said preferable range, regardless of the degree of hardening, the foil tearability of the protective layer 2 can be made favorable.

  The content of the acrylic polyol resin in the present invention and / or the curable acrylic polyol resin in the present invention with respect to the total solid content of the protective layer 2 is not particularly limited, and is appropriately determined depending on the content of other optional components and the like. Can be set. When the content of the acrylic polyol resin in the present invention and / or the curable acrylic polyol resin in the present invention is less than 30% by mass with respect to the total solid content of the protective layer 2, the durability is sufficiently satisfied. In some cases, the foil breakability may be reduced depending on other optional components. Considering this point, the acrylic polyol resin in the present invention and / or the curable acrylic polyol resin in the present invention is preferably contained in a proportion of 30% by mass or more based on the total solid content of the protective layer 2. More preferably, it is contained in a proportion of 40% by mass or more. In addition, there is no limitation in particular about an upper limit, and it is 100 mass%.

  The protective layer 2 may contain the acrylic polyol resin in the present invention or the curable acrylic polyol resin in the present invention alone, or may contain both. Further, the protective layer 2 may contain two or more acrylic polyol resins in the present invention having different hydroxyl values and different weight average molecular weights. In this case, it is preferable that the total mass of these acrylic polyol resins is within the range of the preferable content with respect to the total solid content of the protective layer 2.

(Other optional ingredients)
The protective layer 2 may contain other optional components together with the acrylic polyol resin having a glass transition temperature (Tg) exceeding 80 ° C. For example, in the form shown in FIG. 1, the protective layer 2 is required to be peelable from the base material 1 and to adhere to the transfer target. Therefore, in this form, it is preferable that the protective layer 2 contains a component having peelability and a component having adhesiveness. In the form shown in FIG. 1, when the protective layer 2 is transferred using the protective layer transfer sheet 10, the protective layer 2 is positioned on the outermost surface of the transfer target body to which the protective layer is transferred. The protective layer 2 preferably contains a component having scratch resistance (sometimes referred to as slip property). It should be noted that, on the transferred body side, a measure that satisfies the adhesiveness with the protective layer 2 can be taken. For example, an adhesive layer can be provided on the transferred body, and in this case, a material having adhesiveness to the protective layer 2 is provided. It does not necessarily need to be included. Further, as will be described later, the role required for the protective layer 2 in the form shown in FIG. 1 can be supplemented by a separate layer as shown in FIG. For example, a release layer 3 that can satisfy the requirements for peelability and scratch resistance is provided between the base material 1 and the protective layer 2, and the demand for adhesiveness to the transfer target is provided on the protective layer 2. When the adhesive layer 4 that can be filled is provided, the protective layer 2 does not necessarily contain a component having peelability from the substrate, a component having adhesion to the transfer target, and a component having scratch resistance. I don't need it.

  Moreover, it is good also as a structure which provided the adhesive layer 4 on the protective layer 2 instead of the structure shown in FIG. 1, FIG. 2, and contained the component which has peelability and abrasion resistance in the protective layer 2. FIG. In this case, even if the protective layer 2 does not contain an adhesive component, the protective layer 2 can be satisfactorily transferred onto the transfer target. Moreover, it can also be set as the structure which provided the peeling layer 3 between the base material 1 and the protective layer 2, and was made to contain the component which has adhesiveness instead of the structure shown in FIG. 1, FIG. . In this case, even if the protective layer 2 does not contain a component having peelability or scratch resistance, durability and scratch resistance can be imparted to the printed material to which the protective layer 2 has been transferred.

  In addition, it is necessary for the optional component to be contained within a range that does not impair the foil breakability and durability imparted by the acrylic polyol resin in the present invention. Specifically, the optional component contains The amount is preferably 70% by mass or less with respect to the total solid content of the protective layer 2. Hereinafter, arbitrary components will be described.

"Ingredients with scratch resistance"
Examples of the scratch-resistant component include, for example, a methacrylate ester copolymer, a vinyl chloride / vinyl acetate copolymer, a polyester resin, a polycarbonate resin, an acrylic resin, an ultraviolet absorbing resin, an epoxy resin, a polystyrene resin, a polyurethane resin, Examples thereof include acrylic urethane resins, resins obtained by modifying these resins with silicone, mixtures of these resins, ionizing radiation curable resins, ultraviolet absorbing resins, and the like. Of these, the UV-absorbing resin can be suitably used because it is particularly excellent in scratch resistance.

  As the ultraviolet absorbing resin, for example, a resin obtained by reacting and bonding a reactive ultraviolet absorbent to a thermoplastic resin or the above ionizing radiation curable resin can be used. More specifically, addition-polymerizable double-reactive organic UV absorbers such as salicylates, benzophenones, benzotriazoles, substituted acrylonitriles, nickel chelates, hindered amines, etc. Examples thereof include a bond (for example, a vinyl group, an acryloyl group, a methacryloyl group, etc.), an alcoholic hydroxyl group, an amino group, a carboxyl group, an epoxy group, and a reactive group such as an isocyanate group.

"Ingredients with peelability from substrate"
In addition, examples of components having excellent releasability from the substrate 1 include waxes such as polyethylene wax and silicone wax, silicone resins, silicone-modified resins, fluorine resins, fluorine-modified resins, polyvinyl alcohol, acrylic resins, and thermal crosslinkability. Examples include epoxy-amino resins and heat-crosslinkable alkyd-amino resins.

“Ingredients having adhesiveness to the transfer target”
As a component having adhesiveness to the transfer target, for example, acrylic resin, vinyl resin, polyester resin, urethane resin, polyamide resin, epoxy resin, rubber resin, ionomer resin, etc. are the main components. Conventionally known adhesives can be widely used.

"Other optional ingredients"
The protective layer 2 may contain other optional components in addition to the optional components exemplified above. Examples of other optional components include known UV absorbers such as benzophenone, benzotriazole, benzoate, triazine, titanium oxide, and zinc oxide, light stabilizers such as hindered amine and Ni chelate, hindered Phenol-based, sulfur-based, phosphorus-based and lactone-based antioxidants can be exemplified. These optional components may be used alone or in combination of two or more.

  Further, for the purpose of further improving the scratch resistance of the protective layer 2, the protective layer 2 may contain a lubricant. Examples of lubricants include silicones such as modified silicone oils and silicone-modified resins, metal soaps such as zinc stearate, zinc stearyl phosphate, calcium stearate and magnesium stearate, fatty acid amides, polyethylene wax, carbana wax and paraffin. A wax etc. can be mentioned.

  There is no restriction | limiting in particular about the formation method of the protective layer 2, The acrylic polyol resin in this invention and / or the curable acrylic polyol resin in this invention, and the arbitrary components added as needed are melt | dissolved in a suitable solvent. Alternatively, a dispersed protective layer coating solution is prepared, and this protective layer coating solution is applied to the substrate 1 or a layer arbitrarily provided on the substrate 1 by a gravure printing method, a screen printing method, or a gravure. It can be formed by applying and drying using known means such as a reverse roll coating method using a plate. The thickness of the protective layer 2 is not particularly limited, and can be appropriately set within a thickness range that can sufficiently exhibit the durability due to the acrylic polyol resin in the present invention and can make a foil breakage or the like good. Can do. Preferably, it exists in the range of 0.5 micrometer or more and 10 micrometers or less.

  In the above, in the protective layer transfer sheet having the configuration shown in FIG. 1, the description has been made mainly on the configuration in which the protective layer 2 is provided with the peelability from the base material 1 and the adhesion to the transfer target. As shown in FIG. 2, it is good also as a structure which provides these roles to another layer. That is, the protective layer transfer sheet of the present invention may be a single-layered transfer layer in which only the protective layer is transferred onto the transfer target as shown in FIG. 1, and as shown in FIG. A transfer layer having a laminated structure in which an arbitrary layer is transferred onto a transfer medium can also be used. The transfer layer means a layer transferred onto the transfer target, and in the present invention, the protective layer 2 which is an essential layer is included. FIG. 2 is a schematic cross-sectional view showing an example of a protective layer transfer sheet having a configuration in which a release layer 3 is provided between a substrate 1 and a protective layer 2 and an adhesive layer 4 is provided on the protective layer 2. .

(Peeling layer)
As shown in FIG. 2, a release layer 3 may be provided between the substrate 1 and the protective layer 2. As the component of the release layer 3, the materials exemplified in the above “component having scratch resistance” and “component having peelability from the substrate” can be appropriately selected and used. In addition, although this peeling layer 3 is a layer transcribe | transferred on a to-be-transferred body normally with the protective layer 2, it is good also as a layer which remain | survives on the base material 1 side. When transferred to the transfer target side, the release layer is positioned on the outermost surface after transfer. In this case, it is preferable that the release layer contains a “component having scratch resistance”. On the other hand, when remaining on the substrate 1 side, the protective layer 2 is positioned on the outermost surface after transfer. In this case, as described above, the protective layer 2 has “scratch resistance”. It is preferable that "component" is contained. When the release layer 3 is transferred onto the transfer medium together with the protective layer 2, the abrasion resistance can be further improved by incorporating the lubricant exemplified above in the release layer 3.

  As a method for forming the release layer 3, a release layer coating solution is prepared by dissolving or dispersing the above “component having scratch resistance” and “component having release property from a substrate” in an appropriate solvent, This release layer coating solution can be formed on the substrate 1 by applying and drying the substrate 1 using a known means such as a gravure printing method, a screen printing method, or a reverse roll coating method using a gravure plate. The thickness of the release layer 3 is generally about 0.5 μm to 5 μm.

(Plasticizer resistant layer)
In order to improve the plasticizer resistance of the printed material to which the protective layer 2 has been transferred, between the base material 1 and the protective layer 2, or when the release layer 3 is provided, between the release layer 3 and the protective layer 4. May be provided with a plasticizer-resistant layer (not shown).

  As the plasticizer-resistant layer, a material that repels the plasticizer component or a material that does not easily reach the image can be preferably used. Examples of the material that repels the plasticizer component include polyvinyl alcohol resin, polyvinyl butyral resin, polyvinyl acetal resin, polyvinyl pyrrolidone resin, and the like. Examples of the material in which the plasticizer component hardly reaches the image include cationic resins such as a cationic urethane emulsion. These materials may be used alone or in combination of two or more.

  In addition, the polyvinyl alcohol resin, polyvinyl butyral resin, and polyvinyl acetal resin exemplified as materials for repelling the plasticizer component preferably have a saponification degree of 30 to 100%, and more preferably 60 to 100%. By including a polyvinyl alcohol resin, polyvinyl butyral resin, or polyvinyl acetal resin having a saponification degree within this range in the plasticizer-resistant layer, the plasticizer resistance of the transfer layer can be further improved. In addition, the saponification degree in this invention means the value which divided the number of moles of the vinyl alcohol structure in a polymer by the number of moles of all the monomers in a polymer. The material that repels the plasticizer component and the material in which the plasticizer component hardly reaches the image is preferably contained within a range of 20% by mass to 100% by mass with respect to the total solid content of the plasticizer-resistant layer.

  In addition, the plasticizer-resistant layer may include, for example, a lubricant, a plasticizer, a filler, an antistatic agent, an antiblocking agent, a crosslinking agent, an antioxidant, an ultraviolet absorber, a light stabilizer, a dye, Colorants such as pigments, fluorescent brighteners, other additives, and the like may be added.

  The plasticizer-resistant layer provided as necessary is a plasticizer-resistant material prepared by dissolving or dispersing one or more of the above-exemplified materials and various materials added as necessary with an appropriate solvent. A layer coating solution can be prepared, and this can be applied and dried on the substrate 1 or the release layer 3 provided as necessary. Although there is no limitation in particular about the thickness of a plasticizer-resistant layer, Usually, it is 0.1 micrometer-50 micrometers in the thickness after drying, Preferably it is about 1 micrometer-20 micrometers.

(Adhesive layer)
As shown in FIG. 2, an adhesive layer 4 may be provided on the protective layer 2. As the component of the adhesive layer 4, the components exemplified in the above “component having adhesiveness to the transfer target” can be appropriately selected and used. Note that the adhesive layer 4 is not necessarily provided when taking a measure to satisfy the adhesiveness with the protective layer 2 on the transfer target side.

  As a method for forming the adhesive layer 4, an adhesive layer coating solution is prepared by dissolving or dispersing the above-mentioned “component having adhesiveness to the transfer object” in an appropriate solvent. On the protective layer 2, it can be formed by applying and drying using a known means such as a gravure printing method, a screen printing method, a reverse roll coating method using a gravure plate. The thickness of the adhesive layer 4 is generally about 0.5 μm to 10 μm.

  In the above description, as an example of a transfer layer having a laminated structure, the transfer layer includes a release layer, a plasticizer-resistant layer, and an adhesive layer as an example. However, the transfer layer is included in any layer constituting the transfer layer. Depending on the components contained, for example, the components contained in the release layer, the plasticizer-resistant layer, and the adhesive layer, the foil breakability of each layer alone may be insufficient. In the present invention, the protective layer 2 that is included in the transfer layer and is an indispensable layer to be transferred onto the transfer medium has excellent foil breakability as described above. Even when the foil breakability of this layer is low, the foil breakability of the entire transfer layer including the protective layer 2 and any layer can be improved.

(Back layer)
In addition, as shown in FIG. 2, a back layer 5 for improving heat resistance and running performance of the thermal head during printing on a surface different from the surface on which the protective layer 2 of the substrate 1 is provided. May be provided. In addition, the back surface layer 5 is an arbitrary structure in the protective layer transfer sheet 10 of the present invention.

  The back layer 5 can be formed by appropriately selecting a conventionally known thermoplastic resin or the like. As such a thermoplastic resin, for example, polyester resins, polyacrylate resins, polyvinyl acetate resins, styrene acrylate resins, polyurethane resins, polyethylene resins, polypropylene resins, and other polyolefin resins, Polystyrene resin, polyvinyl chloride resin, polyether resin, polyamide resin, polyimide resin, polyamideimide resin, polycarbonate resin, polyacrylamide resin, polyvinyl chloride resin, polyvinyl butyral resin, polyvinyl acetoacetal resin, etc. Examples thereof include thermoplastic resins such as polyvinyl acetal resin, and silicone modified products thereof. Among these, from the viewpoint of heat resistance, a polyamideimide resin or a modified silicone product thereof can be preferably used.

  In addition to the above thermoplastic resin, the back layer 5 has a wax, a higher fatty acid amide, a phosphoric ester compound, a metal soap, a silicone oil, a surfactant and other release agents for the purpose of improving slip properties, fluorine It is preferable that various additives such as organic powders such as resin, inorganic particles such as silica, clay, talc, calcium carbonate and the like are contained, and it is particularly preferable that at least one kind of phosphate ester or metal soap is contained. preferable.

For example, the back layer 5 is formed by applying a coating liquid obtained by dispersing or dissolving the above-described thermoplastic resin and various additives added in an appropriate solvent onto the base material 1 on a gravure printing method or a screen printing method. It can be formed by coating and drying by a known means such as a reverse roll coating printing method using a gravure plate. The thickness of the back layer 5, from the viewpoint of improvement of such as heat resistance, 0.1 g / m is preferably ² to 5 g / m ^{2 approximately, 0.3g / m 2 ~2.0g / m} 2 approximately, more preferably.

  The protective layer transfer sheet 10 of the present invention has been described above, but the protective layer transfer sheet of the present invention can take various forms within a range that does not impede the gist of the present invention. For example, a dye layer-integrated protective layer transfer sheet (not shown) in which a dye layer is provided in the same order as the surface on which the protective layer 2 of the substrate 1 is provided can also be used. The dye layer may be a single dye layer. For example, a yellow dye layer, a magenta dye layer, and a cyan dye layer may be provided in this order in a plane order.

<< Intermediate transfer medium >>
Next, the intermediate transfer medium 100 of the present invention will be described with reference to FIGS. The intermediate transfer medium 100 of the present invention has a configuration in which a protective layer 2 and a receiving layer 50 that are peelable from the base material 1 are laminated on one surface of the base material 1. The substrate 1, the protective layer 2, and the receiving layer 50 are essential components in the intermediate transfer medium 100 of the present invention. As shown in FIG. 4, the intermediate transfer medium 100 of the present invention is provided with a release layer 3 between the substrate 1 and the protective layer 2, and a back layer 5 is provided on the other surface of the substrate 1. It may be done. An adhesive layer (not shown) may be provided on the receiving layer 50. Hereinafter, each configuration of the intermediate transfer medium 100 of the present invention will be specifically described.

(Base material)
As the base material 1, the same material as the base material 1 of the protective layer transfer sheet 10 of the present invention can be used, and detailed description thereof is omitted here.

(Protective layer)
On the base material 1, the protective layer 2 which can be peeled from the said base material 1 is provided. The intermediate transfer medium 100 of the present invention is characterized in that the protective layer 2 contains an acrylic polyol resin having a glass transition temperature (Tg) exceeding 80 ° C. According to the present invention having this feature, after the thermal transfer image is formed on the receiving layer 50, the receiving layer 50 and the protective layer 2 of the intermediate transfer medium 100 of the present invention are transferred onto an arbitrary transfer target. Thus, it is possible to obtain a printed matter in which high durability is imparted to the thermal transfer image formed on the receiving layer 50. Moreover, in this invention, it is excellent also in the foil tearing property of the protective layer 2 at the time of transferring the receiving layer 50 and the protective layer 2 on a to-be-transferred body. The acrylic polyol resin may be a curable acrylic polyol resin obtained by curing an acrylic polyol resin having a glass transition temperature exceeding 80 ° C. with a curing agent.

  The above-mentioned effect brought about by the intermediate transfer medium 100 of the present invention is due to the same reason as that of the protective layer 2 of the protective layer transfer sheet 10 of the present invention, and detailed description thereof is omitted here. Therefore, in the intermediate transfer medium 100 of the present invention, the protective layer 2 described in the protective layer transfer sheet 10 of the present invention can be used as it is. In the present invention, since the receiving layer 50 provided on the protective layer 2 is laminated directly on the transfer target or indirectly through an arbitrary layer such as an adhesive layer, the protective layer 2 is adhesive. It is not particularly necessary to have

  Also in the present invention, as shown in FIG. 3, the protective layer 2 includes “a component having peelability from the base material” and serves as the protective layer 2 (peeling layer / protective layer) having the function of the peeling layer. The peelability from the substrate may be ensured by providing a separate layer. For example, as shown in FIG. 4, a release layer 3 may be provided between the substrate 1 and the protective layer 2. Also for the release layer 3, those described in the protective layer transfer sheet 10 of the present invention can be used as they are, and detailed description thereof is omitted here.

(Receptive layer)
As shown in FIGS. 3 and 4, a receiving layer 50 is provided on the protective layer 2. A thermal transfer image is formed on the receiving layer. Then, the receiving layer 50 on which the image is formed is transferred onto the transfer target body together with the protective layer 2, and as a result, a printed matter is formed. As a material for forming the receiving layer 50, a conventionally known resin material that can easily receive a heat transferable color material such as a sublimation dye or a heat-meltable ink can be used. For example, polyolefin resin such as polypropylene, halogenated resin such as polyvinyl chloride or polyvinylidene chloride, polyvinyl acetate, vinyl chloride-vinyl acetate copolymer, ethylene-vinyl acetate copolymer or polyacrylate Vinyl resins, polyester resins such as polyethylene terephthalate or polybutylene terephthalate, polystyrene resins, polyamide resins, copolymers of olefins such as ethylene or propylene and other vinyl polymers, cellulose resins such as ionomers or cellulose diastases Polycarbonate and the like, and vinyl chloride resin, acrylic-styrene resin or polyester resin is particularly preferable.

  When the receiving layer 50 is transferred to the transfer medium via the adhesive layer, the adhesiveness of the receiving layer 50 itself is not necessarily required. However, when the receptor layer 50 is transferred to the transfer medium without an adhesive layer, the receptor layer 50 may be formed using an adhesive resin material such as vinyl chloride-vinyl acetate copolymer. preferable.

The receiving layer 50 is made of a coating for the receiving layer by adding one or more materials selected from the above-mentioned materials and various additives as necessary, and dissolving or dispersing them in an appropriate solvent such as water or an organic solvent. A working solution is prepared, and this can be applied and dried by means of a gravure printing method, a screen printing method or a reverse coating method using a gravure plate. Its thickness is about 1 to 10 g / m ^{2 in} a dry state.

  When the receiving layer 50 does not have adhesiveness, an adhesive layer (not shown) may be provided on the receiving layer 50. The adhesive layer is an arbitrary configuration in the intermediate transfer medium 100 of the present invention, and it is not necessary to provide an adhesive layer when an adhesive treatment or the like is performed on the transfer target side. As the adhesive layer arbitrarily provided on the receiving layer 50, the adhesive layer 4 of the protective layer transfer sheet 10 of the present invention can be used as it is, and detailed description thereof is omitted here.

(Back layer)
Moreover, as shown in FIG. 4, the back surface layer 5 may be provided on the other surface of the base material 1. As the back layer 5, the back layer 5 of the protective layer transfer sheet 10 of the present invention can be used as it is, and detailed description thereof is omitted here.

(Image forming method)
A method for forming an image on the receiving layer 50 using the intermediate transfer medium of the present invention is not particularly limited, and can be performed by a known thermal transfer method.

  Further, as the thermal transfer sheet used in the image formation, for example, a heat transferable color material layer is provided on one surface of a substrate such as a polyester film, and a back layer is provided on the other surface of the substrate. A conventionally known thermal transfer sheet can be used. Hereinafter, the thermal transfer sheet will be described.

(Base material)
As the base material, any material may be used as long as it has a conventionally known heat resistance and strength. For example, polyethylene terephthalate film, 1,4-polycyclohexylenedimethylene terephthalate film, polyethylene naphthalate film, polyphenylene Sulfide film, polystyrene film, polypropylene film, polysulfone film, aramid film, polycarbonate film, polyvinyl alcohol film, cellophane, cellulose derivatives such as cellulose acetate, polyethylene film, polyvinyl chloride film, nylon film, polyimide film, ionomer film, etc. Resin film; paper such as condenser paper, paraffin paper, synthetic paper; non-woven fabric; composite of paper, non-woven fabric and resin, etc.

  Although there is no limitation in particular about the thickness of a base material, it is 0.5-50 micrometers normally, Preferably it is about 1.5-10 micrometers.

  The base material may be surface-treated in order to improve the adhesiveness with an adjacent layer. As the surface treatment, known resin surface modification techniques such as corona discharge treatment, flame treatment, ozone treatment, ultraviolet treatment, radiation treatment, surface roughening treatment, chemical treatment, plasma treatment, grafting treatment, etc. can be applied. it can. Only one type of surface treatment may be performed, or two or more types may be performed. Moreover, the undercoat layer (primer layer) may be provided in the one surface or both surfaces as needed.

(Heat transferable color material layer)
The thermal transfer colorant layer is a layer containing a sublimation dye when the thermal transfer sheet is a sublimation type thermal transfer sheet, and a layer containing a thermal melt composition containing a colorant in the case of a thermal melt type thermal transfer sheet. It becomes. Also, thermal transfer in which a layer region containing a sublimable dye and a layer region containing a heat-meltable ink comprising a heat-melting composition containing a colorant are provided on a single continuous substrate in a surface sequential manner. A sheet can also be used. Hereinafter, although the case where the thermal transfer sheet is a sublimation type thermal transfer sheet will be mainly described, the intermediate transfer medium 100 of the present invention is not limited to being used in combination with a sublimation type thermal transfer sheet.

  Examples of sublimation dyes include diarylmethane dyes; triarylmethane dyes; thiazole dyes; merocyanine dyes; pyrazolone dyes; methine dyes; indoaniline dyes; Azomethine dyes such as azomethine and pyridone azomethine; xanthene dyes; oxazine dyes; cyanostyrene dyes such as dicyanostyrene and tricyanostyrene; thiazine dyes; azine dyes; acridine dyes; benzeneazo dyes; Azo dyes such as azo, isothiazole azo, pyrrole azo, pyrazole azo, imidazole azo, thiadiazole azo, triazole azo, disazo; spiropyran dyes; indolinospiropyran dyes ; Fluoran dyes; rhodamine lactam dyes; naphthoquinone dyes; anthraquinone dyes; quinophthalone dyes; and the like, and more specifically, the compounds exemplified in JP-A-7-149062 and the like. In the heat transferable color material layer, the sublimation dye is 5 to 90% by weight, preferably 10 to 70% by weight, based on the total solid content of the heat transferable color material layer. If the amount of sublimable dye used is less than the above range, the print density may be low, and if it exceeds the above range, the storage stability may be lowered.

  Examples of the binder resin for supporting the dye include cellulose resins such as ethyl cellulose resin, hydroxyethyl cellulose resin, ethyl hydroxy cellulose resin, methyl cellulose resin, nitrocellulose resin, and cellulose acetate resin, polyvinyl alcohol resin, and polyvinyl acetate resin. , Polyvinyl butyral resin, polyvinyl acetal resin, vinyl resins such as polyvinyl pyrrolidone, acrylic resins such as poly (meth) acrylate and poly (meth) acrylamide, polyurethane resins, polyamide resins, polyester resins, phenoxy resins, phenols Examples thereof include resins and epoxy resins. Among these, cellulose-based, vinyl-based, acrylic-based, polyurethane-based, and polyester-based resins are preferable from the viewpoints of heat resistance, dye transferability, and the like.

  The heat transferable color material layer may contain a release agent, inorganic fine particles, organic fine particles and the like. Examples of the mold release agent include silicone oil, polyethylene wax, and phosphate ester. Examples of the silicone oil include straight silicone oil, modified silicone oil, and cured products thereof. The silicone oil may be reactive or non-reactive. Inorganic fine particles include carbon black, aluminum, molybdenum disulfide and the like. The modified silicone oil can be classified into a reactive silicone oil and a non-reactive silicone oil. The reactive silicone oil includes amino modification, epoxy modification, carboxyl modification, hydroxy modification, methacryl modification, mercapto modification, phenol modification, one-terminal reactivity and heterofunctional modification. Non-reactive silicone oils include polyether modification, methylstyryl modification, alkyl modification, higher fatty acid ester modification, hydrophilic special modification, higher alkoxy modification, fluorine modification and the like. The amount of silicone oil added is preferably 0.1 to 15% by mass, more preferably 0.3 to 10% by mass, based on the mass of the binder. Examples of the organic fine particles include polyethylene wax.

  The heat transferable color material layer is, for example, a coating solution for a heat transferable color material layer in which a sublimable dye, a binder resin, and various components optionally added as necessary are dispersed or dissolved in an appropriate solvent. It can be formed on a substrate by coating and drying using a conventionally known coating method. Conventionally known coating methods include a gravure printing method, a reverse roll coating method using a gravure plate, a roll coater, a bar coater and the like. Examples of the solvent include toluene, methyl ethyl ketone, ethanol, isopropyl alcohol, cyclohexanone, dimethylformamide [DMF] and the like.

  There is no limitation in particular about the thickness of a heat transferable color material layer, and it is about 0.2 micrometer-5 micrometers normally.

(Back layer)
In addition, a back layer for improving heat resistance, running performance of the thermal head during printing, and the like may be provided on the other surface of the substrate. As the back layer of the thermal transfer sheet, the back layer 5 of the protective layer transfer sheet 10 of the present invention can be used as it is.

  Next, the present invention will be described more specifically with reference to examples and comparative examples. Hereinafter, unless otherwise specified, parts or% is based on mass. Tg represents a glass transition temperature, Mw represents a weight average molecular weight, and Mn represents a number average molecular weight. The unit of hydroxyl value is mgKOH / g.

Example 1
A polyethylene terephthalate film (Lumirror, manufactured by Toray Industries, Inc.) having a thickness of 12 μm is used as a substrate, and a coating solution for a release layer having the following composition is dried on the substrate to a thickness of 1.0 g / m ² Was applied to form a release layer. Subsequently, the protective layer coating liquid 1 having the following composition was applied on the release layer so as to have a thickness of 2.0 g / m ^{2 in} a dry state to form a protective layer. Further, on the protective layer, a receiving layer coating liquid having the following composition was applied to a thickness of 1.0 g / m ^{2 in} a dry state to form a receiving layer, whereby the intermediate transfer medium of Example 1 was formed. Obtained. The release layer coating solution, the protective layer coating solution 1, and the receiving layer coating solution were all applied by gravure coating.

<Coating liquid for release layer>
・ Acrylic resin 80 parts (BR-87, manufactured by Mitsubishi Rayon Co., Ltd.)
・ Polyester resin 5 parts (Byron 200, manufactured by Toyobo Co., Ltd.)
・ 5 parts of polyethylene wax
・ Ultraviolet absorbing acrylic resin 25 parts (PUVA-50M-40TM, manufactured by Otsuka Chemical Co., Ltd., solid content: 40%)
・ Toluene 192.5 parts ・ MEK 192.5 parts

<Protective layer coating solution 1>
Acrylic polyol resin (solid content: 36.5% Tg: 102 ° C. Mw: 55000 Hydroxyl value: 30.1, —OH: 11) 100 parts (6 KW-700 Taisei Fine Chemical Co., Ltd.)
・ MEK 82.5 parts

<Coating liquid for receiving layer>
・ 95 parts of vinyl chloride-vinyl acetate copolymer (CNL, manufactured by Nissin Chemical Industry Co., Ltd.)
・ Epoxy-modified silicone oil 5 parts (KP-1800U, manufactured by Shin-Etsu Chemical Co., Ltd.)
・ Toluene 200 parts ・ MEK 200 parts

(Example 2)
An intermediate transfer medium of Example 2 was obtained in the same manner as Example 1 except that the protective layer coating solution 1 was changed to the protective layer coating solution 2 having the following composition.

<Protective layer coating solution 2>
Molar equivalent ratio (-NCO / -OH): 0.5
Acrylic polyol resin (solid content: 36.5% Tg: 102 ° C. Mw: 55000 Hydroxyl value: 30.1, —OH: 11) 100 parts (6 KW-700 Taisei Fine Chemical Co., Ltd.)
・ Isocyanate curing agent (solid content: 75% -NCO: 11.5%) 3.6 parts (Takenate D110N (XDI) Mitsui Chemicals, Inc.)
・ 92 parts of MEK

Example 3
An intermediate transfer medium of Example 3 was obtained in the same manner as Example 1 except that the protective layer coating solution 1 was changed to the protective layer coating solution 3 having the following composition.

<Coating liquid 3 for protective layer>
Molar equivalent ratio (—NCO / —OH): 1.0
Acrylic polyol resin (solid content: 36.5% Tg: 102 ° C. Mw: 55000 Hydroxyl value: 30.1, —OH: 11) 100 parts (6 KW-700 Taisei Fine Chemical Co., Ltd.)
・ Isocyanate curing agent (solid content: 75% -NCO: 11.5%) 7.2 parts (Takenate D110N (XDI) Mitsui Chemicals, Inc.)
・ 100 parts of MEK

Example 4
An intermediate transfer medium of Example 4 was obtained in the same manner as in Example 1 except that the protective layer coating solution 1 was changed to the protective layer coating solution 4 having the following composition.

<Coating liquid 4 for protective layer>
Molar equivalent ratio (—NCO / —OH): 2.0
Acrylic polyol resin (solid content: 36.5% Tg: 102 ° C. Mw: 55000 Hydroxyl value: 30.1, —OH: 11) 100 parts (6 KW-700 Taisei Fine Chemical Co., Ltd.)
・ Isocyanate-based curing agent (solid content: 75% -NCO: 11.5%) 14.4 parts (Takenate D110N (XDI system) Mitsui Chemicals, Inc.)
・ 120 parts of MEK

(Example 5)
An intermediate transfer medium of Example 5 was obtained in the same manner as Example 1 except that the protective layer coating solution 1 was changed to the protective layer coating solution 5 having the following composition.

<Coating liquid 5 for protective layer>
Molar equivalent ratio (—NCO / —OH): 1.0
Acrylic polyol resin (solid content: 36.5% Tg: 102 ° C. Mw: 55000 Hydroxyl value: 30.1, —OH: 11) 100 parts (6 KW-700 Taisei Fine Chemical Co., Ltd.)
・ Isocyanate-based curing agent (solid content: 75% -NCO: 15.5%) 5.3 parts (Duranate 21S-75E (HDI) Asahi Kasei Corporation)
・ 95 parts of MEK

(Example 6)
An intermediate transfer medium of Example 6 was obtained in the same manner as in Example 1 except that the protective layer coating solution 1 was changed to the protective layer coating solution 6 having the following composition.

<Coating liquid 6 for protective layer>
Molar equivalent ratio (—NCO / —OH): 1.0
Acrylic polyol resin (solid content: 36.5% Tg: 102 ° C. Mw: 55000 Hydroxyl value: 30.1, —OH: 11) 100 parts (6 KW-700 Taisei Fine Chemical Co., Ltd.)
・ Isocyanate curing agent (solid content: 75% -NCO: 10.5%) 7.8 parts (Takenate D140N (IPDI) Mitsui Chemicals, Inc.)
・ 100 parts of MEK

(Example 7)
An intermediate transfer medium of Example 7 was obtained in the same manner as Example 1 except that the protective layer coating solution 1 was changed to the protective layer coating solution 7 having the following composition.

<Coating liquid 7 for protective layer>
Acrylic polyol resin (solid content: 36.5% Tg: 102 ° C. Mw: 55000 Hydroxyl value: 30.1, —OH: 11) 100 parts (6 KW-700 Taisei Fine Chemical Co., Ltd.)
・ Titanium chelating agent (solid content: 65%) 1.1 parts (Orgatechs TC-401 Matsumoto Fine Chemical Co., Ltd.)
・ 85 parts of MEK

(Example 8)
An intermediate transfer medium of Example 8 was obtained in the same manner as in Example 1 except that the protective layer coating solution 1 was changed to the protective layer coating solution 8 having the following composition.

<Protective layer coating solution 8>
Acrylic polyol resin (solid content: 36.5% Tg: 102 ° C. Mw: 55000 Hydroxyl value: 30.1, —OH: 11) 100 parts (6 KW-700 Taisei Fine Chemical Co., Ltd.)
・ Aluminum chelating agent (solid content: 76%) 3 parts (Aluminum chelating D Kawaken Fine Chemical Co., Ltd.)
・ 90 parts of MEK

Example 9
Without forming a release layer between the substrate and the protective layer, the protective layer coating solution 1 is changed to a release layer / protective layer coating solution 1 having the following composition, and the following composition is released on the substrate. Example 1 was carried out in the same manner as Example 1 except that the coating solution for layer / protective layer 1 was applied in a dry state to a thickness of 3.0 g / m ² to form a release layer / protective layer. 9 intermediate transfer media were obtained.

<Coating liquid 1 for peeling layer and protective layer>
Molar equivalent ratio (—NCO / —OH): 1.0
Acrylic polyol resin (solid content: 36.5% Tg: 102 ° C. Mw: 55000 Hydroxyl value: 30.1, —OH: 11) 189 parts (6 KW-700 Taisei Fine Chemical Co., Ltd.)
・ Isocyanate-based curing agent (solid content: 75% -NCO: 11.5%) 14.7 parts (Takenate D110N (XDI system) Mitsui Chemicals, Inc.)
・ Polyester resin 5 parts (Byron 200, Toyobo Co., Ltd.)
-Polyethylene wax 5 parts (Polywax 1000 Toyo Adre Co., Ltd.)
-UV-absorbing acrylic resin 25 parts (PUVA-50M-40TM, Otsuka Chemical Co., Ltd.)
・ Toluene 130 parts ・ MEK 130 parts

(Example 10)
An intermediate transfer medium of Example 10 was obtained in the same manner as Example 1 except that the protective layer coating solution 1 was changed to the protective layer coating solution 9 having the following composition.

<Coating liquid 9 for protective layer>
Molar equivalent ratio (—NCO / —OH): 1.0
Acrylic polyol resin (solid content: 45%, Tg: 97 ° C., Mw: 23000, hydroxyl value (solid): 60, —OH: 27) 100 parts (Q-164 Mitsui Chemicals, Inc.)
・ Isocyanate-based curing agent (solid content: 75% -NCO: 11.5%) 17.6 parts (Takenate D110N (XDI system) Mitsui Chemicals, Inc.)
・ 170 parts of MEK

(Example 11)
An intermediate transfer medium of Example 11 was obtained in the same manner as in Example 1 except that the protective layer coating solution 1 was changed to the protective layer coating solution 10 having the following composition.

<Protective layer coating solution 10>
Molar equivalent ratio (—NCO / —OH): 1.0
Acrylic polyol resin (solid content: 50% Tg: 87 ° C. Mn: 15000 Mw:> 15000 Hydroxyl value (solid): 35, —OH: 17.5) 100 parts (A-814 DIC Corporation)
・ Isocyanate curing agent (solid content: 75% -NCO: 11.5%) 11.4 parts (Takenate D110N (XDI) Mitsui Chemicals, Inc.)
・ MEK 180 parts

(Example 12)
An intermediate transfer medium of Example 12 was obtained in the same manner as Example 1 except that the protective layer coating solution 1 was changed to the protective layer coating solution 11 having the following composition.

<Protective layer coating solution 11>
Molar equivalent ratio (—NCO / —OH): 1.0
Acrylic polyol resin (solid content: 60%, Tg: 85 ° C., Mw: 5000, hydroxyl value (solid): 115, —OH: 69) 100 parts (LH-635 Toray Fine Chemical Co., Ltd.)
・ Isocyanate curing agent (solid content: 75% -NCO: 11.5%) 22 parts (Takenate D110N (XDI) Mitsui Chemicals, Inc.)
・ 260 parts of MEK

(Example 13)
An intermediate transfer medium of Example 13 was obtained in the same manner as Example 1 except that the protective layer coating solution 1 was changed to the protective layer coating solution 12 having the following composition.

<Coating liquid 12 for protective layer>
Molar equivalent ratio (—NCO / —OH): 1.0
Curing acrylic polyol / UV absorbing acrylic resin ≒ 7/3
Acrylic polyol resin (solid content: 36.5% Tg: 102 ° C. Mw: 55000 hydroxyl value (solid): 30.1, —OH: 11) 70 parts (6 KW-700 Taisei Fine Chemical Co., Ltd.)
-Isocyanate-based curing agent (solid content: 75% -NCO: 11.5%) 5.46 parts (Takenate D110N (XDI system) Mitsui Chemicals, Inc.)
・ Ultraviolet absorbing acrylic resin 31.8 parts (PUVA-50M-40TM, manufactured by Otsuka Chemical Co., Ltd., solid content 40%)
・ Toluene 50 parts ・ MEK 50 parts

(Example 14)
An intermediate transfer medium of Example 14 was obtained in the same manner as Example 1 except that the protective layer coating solution 1 was changed to the protective layer coating solution 13 having the following composition.

<Protective layer coating solution 13>
Molar equivalent ratio (—NCO / —OH): 1.0
Curing acrylic polyol / UV absorbing acrylic resin ≒ 4/6
Acrylic polyol resin (solid content: 36.5% Tg: 102 ° C. Mw: 55000 hydroxyl value (solid): 30.1, —OH: 11) 40 parts (6 KW-700 Taisei Fine Chemical Co., Ltd.)
・ Isocyanate curing agent (solid content: 75% -NCO: 11.5%) 3.12 parts (Takenate D110N (XDI) Mitsui Chemicals, Inc.)
・ Ultraviolet absorbing acrylic resin 63.5 parts (PUVA-50M-40TM, manufactured by Otsuka Chemical Co., Ltd., solid content 40%)
・ Toluene 50 parts ・ MEK 50 parts

(Example 15)
An intermediate transfer medium of Example 15 was obtained in the same manner as Example 1 except that the protective layer coating solution 1 was changed to the protective layer coating solution 14 having the following composition.

<Protective layer coating solution 14>
Molar equivalent ratio (—NCO / —OH): 1.0
Curing acrylic polyol / UV absorbing acrylic resin ≒ 85/15
Acrylic polyol resin (solid content: 36.5% Tg: 102 ° C. Mw: 55000 Hydroxyl value: 30.1, —OH: 11) 85 parts (6 KW-700 Taisei Fine Chemical Co., Ltd.)
-Isocyanate-based curing agent (solid content: 75% -NCO: 11.5%) 6.63 parts (Takenate D110N (XDI system) Mitsui Chemicals, Inc.)
UV-absorbing acrylic resin 16.4 parts (PUVA-50M-40TM, manufactured by Otsuka Chemical Co., Ltd., solid content 40%)
・ Toluene 50 parts ・ MEK 50 parts

(Comparative Example 1)
An intermediate transfer medium of Comparative Example 1 was obtained in the same manner as Example 1 except that the protective layer coating solution 1 was changed to the protective layer coating solution A having the following composition.

<Coating liquid A for protective layer>
Molar equivalent ratio (—NCO / —OH): 1.0
Acrylic polyol resin (solid content: 50%, Tg: 48 ° C., Mw: 40000, hydroxyl value (Solid): 100, —OH: 50) 100 parts (A-801-P DIC Corporation)
・ Isocyanate curing agent (solid content: 75% -NCO: 11.5%) 32.5 parts (Takenate D110N (XDI) Mitsui Chemicals, Inc.)
・ 240 parts of MEK

(Comparative Example 2)
An intermediate transfer medium of Comparative Example 2 was obtained in the same manner as in Example 1 except that the protective layer coating solution 1 was changed to the protective layer coating solution B having the following composition.

<Coating liquid B for protective layer>
Molar equivalent ratio (-NCO / -OH): 0.5
Acrylic polyol resin (solid content: 50%, Tg: 48 ° C., Mw: 40000, hydroxyl value (Solid): 100, —OH: 50) 100 parts (A-801-P DIC Corporation)
・ Isocyanate-based curing agent (solid content: 75% -NCO: 11.5%) 16.3 parts (Takenate D110N (XDI system) Mitsui Chemicals, Inc.)
・ 190 parts of MEK

(Comparative Example 3)
An intermediate transfer medium of Comparative Example 3 was obtained in the same manner as Comparative Example 1 except that no release layer was formed between the substrate and the protective layer.

(Comparative Example 4)
An intermediate transfer medium of Comparative Example 4 was obtained in the same manner as Example 1 except that the protective layer coating solution 1 was changed to the protective layer coating solution C having the following composition.

<Coating liquid C for protective layer>
Molar equivalent ratio (—NCO / —OH): 1.0
UV-absorbing group and Hals group-containing acrylic polyol resin (solid content: 40% Tg: 70 ° C. hydroxyl value (Solid): 52.5, —OH: 21) 100 parts (UV-G137 Nippon Shokubai Co., Ltd.)
・ Isocyanate curing agent (solid content: 75% -NCO: 11.5%) 13.7 parts (Takenate D110N (XDI) Mitsui Chemicals, Inc.)
・ 140 parts of MEK

(Comparative Example 5)
An intermediate transfer medium of Comparative Example 5 was obtained in the same manner as in Example 1 except that the protective layer coating solution 1 was changed to the protective layer coating solution D having the following composition.

<Coating liquid D for protective layer>
Molar equivalent ratio (—NCO / —OH): 1.0
Acrylic polyol resin (solid content: 46%, Tg: 75 ° C., Mw: 29000, hydroxyl value (solid): 61, —OH: 28.06) 100 parts (LH-613 Toray Fine Chemical Co., Ltd.)
・ Isocyanate-based curing agent (solid content: 75% -NCO: 11.5%) 18.3 parts (Takenate D110N (XDI system) Mitsui Chemicals, Inc.)
・ MEK 180 parts

(Comparative Example 6)
An intermediate transfer medium of Comparative Example 6 was obtained in the same manner as Comparative Example 5 except that no release layer was formed between the substrate and the protective layer.

(Comparative Example 7)
An intermediate transfer medium of Comparative Example 7 was obtained in the same manner as Example 1 except that the protective layer coating solution 1 was changed to the protective layer coating solution E having the following composition.

<Coating liquid E for protective layer>
Molar equivalent ratio (—NCO / —OH): 1.0
Acrylic polyol resin (solid content: 50%, Tg: 63 ° C., Mw: 31000, hydroxyl value (solid): 103.6, —OH: 51.8) 100 parts (LK-723 Toray Fine Chemical Co., Ltd.)
・ Isocyanate-based curing agent (solid content: 75% -NCO: 11.5%) 18.3 parts (Takenate D110N (XDI system) Mitsui Chemicals, Inc.)
・ 200 copies of MEK

(Comparative Example 8)
An intermediate transfer medium of Comparative Example 8 was obtained in the same manner as in Example 1 except that the protective layer coating solution 1 was changed to the protective layer coating solution F having the following composition.

<Coating fluid F for protective layer>
Molar equivalent ratio (—NCO / —OH): 1.0
Acrylic polyol resin (solid content: 40%, Tg: 75 ° C., Mw: 53000, hydroxyl value (solid): 80.6, —OH: 32.24) 100 parts (LK-730 Toray Fine Chemical Co., Ltd.)
・ Isocyanate-based curing agent (solid content: 75% -NCO: 11.5%) 21 parts (Takenate D110N (XDI system) Mitsui Chemicals, Inc.)
・ 160 parts of MEK

(Comparative Example 9)
An intermediate transfer medium of Comparative Example 9 was obtained in the same manner as Example 1 except that the protective layer coating solution 1 was changed to the protective layer coating solution G having the following composition.

<Coating liquid G for protective layer>
・ Polyester resin (solid content: 100%) 20 parts (Byron 200 Toyobo Co., Ltd.)
・ MEK 80 parts

(Comparative Example 10)
An intermediate transfer medium of Comparative Example 10 was obtained in the same manner as in Example 1 except that the protective layer coating solution 1 was changed to the protective layer coating solution H having the following composition.

<Coating liquid H for protective layer>
・ Acrylic resin (solid content: 100% Mw: 95000) 20 parts (Vaironal BR-80 Mitsubishi Rayon Co., Ltd.)
・ MEK 80 parts

(Comparative Example 11)
An intermediate transfer medium of Comparative Example 11 was obtained in the same manner as in Example 1 except that the protective layer coating solution 1 was changed to the protective layer coating solution I having the following composition.

<Coating liquid I for protective layer>
・ Acrylic resin (solid content: 100% Mw: 25000) 20 parts (Vaironal BR-87 Mitsubishi Rayon Co., Ltd.)
・ MEK 80 parts

(Formation of prints)
Using a HDP-600 (HID) printer and a thermal transfer sheet prepared by the following method, a solid black image was formed on the receiving layer of the intermediate transfer medium of each example and comparative example under default conditions. Example using a printer on a PVC card (DNP) under a re-transfer condition of 175 ° C. and 2 sec / inch, a receiving layer, a protective layer, and a release layer (no release layer) after black solid image formation 9 and Comparative Examples 3 and 6) were transferred to obtain prints of Examples 1 to 15 and Comparative Examples 1 to 11.

(Creation of thermal transfer sheet)
Using an easily adhesive-treated polyethylene terephthalate film having a thickness of 4.5 μm as a base material, a coating solution for a heat-resistant active layer having the following composition was applied on the base material to a dry weight of 0.8 g / m ² , A heat resistant active layer was formed. Next, on the other side of the substrate, the yellow dye layer coating liquid, the magenta dye layer coating liquid, and the cyan dye layer coating liquid each have a dry coating amount of 0.6 g / m ^2. In this manner, coating was carried out in the surface order to form a dye layer to obtain a thermal transfer sheet.

<Coating fluid for heat-resistant active layer>
・ 2.0 parts of polyvinyl butyral resin (SREC BX-1 Sekisui Chemical Co., Ltd.)
・ 9.2 parts of polyisocyanate (Bernock D750 Dainippon Ink & Chemicals, Inc.)
・ Phosphate surfactant 1.3 parts (Pricesurf A208N Daiichi Kogyo Seiyaku Co., Ltd.)
・ Talc 0.3 part (Microace P-3 Nippon Talc Industry Co., Ltd.)
・ Toluene 43.6 parts ・ Methyl ethyl ketone 43.6 parts

<Coating solution for yellow dye layer>
-Dye represented by the following formula: 4.0 parts-Polyvinyl acetal resin: 3.5 parts (ESREC KS-5 Sekisui Chemical Co., Ltd.)
・ Polyethylene wax 0.1 part ・ Methyl ethyl ketone 45.0 parts ・ Toluene 45.0 parts

<Coating liquid for magenta dye layer>
・ Disperse dye (Disper thread 60) 1.5 parts ・ Disperse dye (Dispers violet 26) 2.0 parts ・ Polyvinyl acetal resin 4.5 parts (ESREC KS-5 Sekisui Chemical Co., Ltd.)
・ Polyethylene wax 0.1 part ・ Methyl ethyl ketone 45.0 parts ・ Toluene 45.0 parts

<Cyan dye layer coating solution>
-Disperse dye (Solvent Blue 63) 4.0 parts-Polyvinyl acetal resin 3.5 parts (S-REC KS-5 Sekisui Chemical Co., Ltd.)
・ Polyethylene wax 0.1 part ・ Methyl ethyl ketone 45.0 parts ・ Toluene 45.0 parts

(Transferability evaluation)
In the formation of the printed matter of each example and comparative example, it is visually confirmed whether or not the receiving layer and the protective layer can be transferred onto the PVC card (manufactured by DNP), and based on the following evaluation criteria. Transferability was evaluated. The evaluation results are shown in Table 1.
<Evaluation criteria>
○: The receiving layer and the protective layer were transferred without any problem.
(Triangle | delta): The small untransferred part which may become a problem on use has arisen in the receiving layer and the protective layer.
X: The large untransferred part which becomes a problem in use has arisen in the receiving layer and the protective layer.

(Foil tearing evaluation)
As an evaluation of the foil breakability of each example and comparative example, the tailing of the printed material was visually confirmed and evaluated according to the following evaluation criteria. The evaluation results are shown in Table 1. The tailing means the length of the transfer layer that starts from the boundary between the transfer region and the non-transfer region of the transfer layer and protrudes from the boundary to the non-transfer region side.
<Evaluation criteria>
○: The tailing is 0.3 mm or less.
(Triangle | delta): Although slight tailing has arisen, there is no problem in use (0.3 mm-1.0 mm).
X: Tail is considerably generated (1.0 mm or more).

(Abrasion resistance evaluation)
The printed matter of each Example and Comparative Example was worn 250 times with a load of 500 g using a wear wheel CS-10F, the surface condition after wear was visually observed, and an evaluation test was performed according to the following evaluation criteria. The evaluation test results are shown in Table 1.
<Evaluation criteria>
(Double-circle): The printed material is not damaged at all.
○: Slightly scratched prints, but at a level where there is no problem in use.
Δ: Scratches are generated in the printed material, which is a level that causes a problem in use.
X: The printed matter has a large scratch.

  As is apparent from Table 1, a curable type obtained by curing an acrylic polyol resin having a glass transition temperature (Tg) exceeding 80 ° C. or an acrylic polyol resin having a glass transition temperature (Tg) exceeding 80 ° C. with a curing agent. According to the intermediate transfer medium of the example provided with a protective layer containing an acrylic polyol resin, both the foil breakability during transfer and the durability can be sufficiently satisfied. On the other hand, in the intermediate transfer medium of the comparative example not satisfying the invention specific matters of the present invention, the foil breakability of the protective layer and the durability, or both of the requirements cannot be satisfied. The superiority of the present invention is clear from the results.

  Next, in order to evaluate the superiority of the curable acrylic polyol resin of the present invention and optimization of the weight average molecular weight (Mw) of the acrylic polyol resin of the present invention, the following plasticizer resistance evaluation and solvent resistance Sex evaluation was performed.

(Evaluation of plasticizer resistance)
After the plasticizer (DOP) was added on the prints of each Example and Comparative Example, the PET film was covered and the surface condition of the prints after 8 hours at 40 ° C. was visually observed. An evaluation test was conducted. The evaluation test results are shown in Table 2.
<Evaluation criteria>
A: No damage is seen in the image.
○: Slight damage is seen in the image, but there is no problem in use.
(Triangle | delta): It is a level which damage is seen in an image and it becomes a problem on use.
X: Damage to the image causing a problem in use is observed.

(Solvent resistance evaluation)
The prints of each Example and Comparative Example were visually checked for the state of the image after 30 reciprocations with a cotton swab dipped in methyl ethyl ketone (MEK), and the solvent resistance was evaluated based on the following evaluation criteria. It was. The evaluation results are shown in Table 2.
<Evaluation criteria>
A: No damage is seen in the image.
○: Slight damage is seen in the image, but there is no problem in use.
(Triangle | delta): It is a level which damage is seen in an image and it becomes a problem on use.
X: Damage to the image causing a problem in use is observed.

  As is clear from Table 2, the glass transition temperature (Tg) exceeds 80 ° C. and contains a curable acrylic polyol resin obtained by curing an acrylic polyol resin having a weight average molecular weight of 8000 to 70000 with a curing agent. According to the intermediate transfer media of Examples 2 to 11 including the protective layer to be used, in addition to the foil breakability and durability of the protective layer, the plasticizer resistance and the solvent resistance were excellent. In addition, the content of the acrylic polyol resin having a weight average molecular weight of 8000 to 70000 or a curable acrylic polyol resin obtained by curing the acrylic polyol resin with a curing agent with respect to the total solid content of the protective layer is 80 mass. It became clear that the plasticizer resistance and the solvent resistance tend to decrease as the ratio drops below 1%.

DESCRIPTION OF SYMBOLS 1 ... Base material 2 ... Protective layer 3 ... Release layer 4 ... Adhesive layer 5 ... Back surface layer 10 ... Protective layer transfer sheet 50 ... Receiving layer 100 ... Intermediate transfer medium

Claims (5)

A protective layer transfer sheet provided on one surface of the base material with a protective layer that can be peeled off from the base material,
The protective layer transfer sheet, wherein the protective layer contains an acrylic polyol resin having a glass transition temperature (Tg) of more than 80 ° C and a hydroxyl value of 10 mgKOH / g or more and 100 mgKOH / g or less .   2. The protective layer transfer sheet according to claim 1, wherein a weight average molecular weight (Mw) of the acrylic polyol resin is in a range of 8000 to 70000. 3.   3. The acrylic polyol resin according to claim 1, wherein the acrylic polyol resin is a curable acrylic polyol resin obtained by curing an acrylic polyol resin having a glass transition temperature (Tg) exceeding 80 ° C. with a curing agent. Protective layer transfer sheet.   The protective layer transfer sheet according to claim 3, wherein the curing agent is an isocyanate curing agent selected from the group of XDI, HMDI, and IPDI.   An intermediate transfer medium in which a protective layer peelable from the base material and a receiving layer are laminated on one surface of the base material,
  The intermediate transfer medium, wherein the protective layer contains an acrylic polyol resin having a glass transition temperature (Tg) of more than 80 ° C. and a hydroxyl value of 10 mgKOH / g to 100 mgKOH / g.

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