JP2015091633A - Protective layer transfer sheet and intermediate transfer medium - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a protective layer transfer sheet with a higher interlayer adhesion of a transferable protective layer including a protective layer, the protective layer transfer sheet capable of transferring the transferable protective layer that can impart physical and chemical durability to a printed matter with excellent foil cutting properties, and also to provide an intermediate transfer medium with a higher interlayer adhesion of a transfer layer including a protective layer and a reception layer, the intermediate transfer medium capable of transferring an image having higher physical and chemical durability onto a transfer-target body.SOLUTION: A protective layer transfer sheet 10 includes, on one surface of a substrate 1, a transferable protective layer 20 in a manner peelable from the substrate 1. The transferable protective layer 20 has a laminate constitution including, from the substrate side 1, a first protective layer 3A and a second protective layer 3B directly making contact with the first protective layer formed in this order. The first protective layer 3A includes a curable resin obtained by causing curing reaction to a reactive resin having a functional group that reacts with a curative, by the curative. The second protective layer 3B includes a polyester resin having number average molecular weight (Mn) of 8000 or more and glass-transition temperature (Tg) of 45°C or higher.

Description

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

  Excellent thermal transparency, high reproducibility and gradation of intermediate colors, and easy formation of high-quality images equivalent to conventional full-color photographic images. 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 transfer object and the dye layer of the thermal transfer sheet are overlapped, and the thermal transfer image is transferred onto the transfer object by transferring the dye of the dye layer by applying heat from the back side of the thermal transfer sheet by the thermal head. A formed print can be obtained. 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. A similar attempt has been made for an intermediate transfer medium. 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. It is said that durability can be imparted to the thermal transfer image.

  Patent Document 3 discloses a protective layer transfer in which a thermosetting transparent resin layer composed of an acrylic polyol resin and a curing agent as a transferable resin layer and a thermoadhesive resin layer are sequentially laminated on a base film. A sheet has been proposed.

JP-A-62-238791 JP 2004-351656 A JP 2008-238525 A

  By the way, when a protective layer whose main purpose is to improve durability is used, the protective layer has poor foil cutting properties, 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. In addition, when the releasability of the protective layer from the base material is low, there may be a problem that the protective layer is not partially transferred, and the releasability of the protective layer from the base material may be improved. is important.

  According to the protective layer transfer sheet proposed in Patent Document 3, it is said that both durability and foil cutting property (“cutting property” in Patent Document 3) can be satisfied. However, in general, a protective layer containing a curable resin obtained by curing a predetermined resin with a predetermined curing agent is a layer in direct contact with the protective layer, for example, an adhesive layer provided on the protective layer, Interlayer adhesion with a layer called a primer layer is low, and the protective layer peels off from the image when the transferable protective layer (corresponding to the transferable resin layer in Patent Document 3) transferred onto the image is rubbed. May cause a reduction in scratch resistance. Further, even if the protective layer proposed in Patent Document 3 (corresponding to the thermosetting transparent resin layer in Patent Document 3) is adopted and the foil breakability of the protective layer itself is improved, transferability is improved. When the interlayer adhesion of each layer constituting the protective layer is low, make the good foil breakability of the protective layer follow the layer in contact with the protective layer (corresponding to the thermal adhesive resin layer in Patent Document 3) The foil breakability of the entire transferable protective layer is reduced. That is, in order to improve the foil breakability of the entire transferable protective layer and improve the scratch resistance, it is considered important to improve the interlayer adhesion of each layer included in the transferable protective layer. .

  Furthermore, the thermosetting transparent resin layer composed of an acrylic polyol resin and a curing agent proposed in Patent Document 3 is excellent in physical durability, but has chemical durability such as solvent resistance. However, the property and plasticizer resistance are not sufficient, and there is still room for improvement. The same can be said for an intermediate transfer medium having a transfer layer in which a protective layer and a receiving layer are laminated.

  The present invention has been made in view of such a situation. The transferable protective layer including the protective layer has high interlayer adhesion, and can impart physical and chemical durability to the printed matter. Protective layer transfer sheet capable of transferring a transferable protective layer with good foil cutting properties, and a transfer layer including a protective layer and a receiving layer having high interlayer adhesion, and an image having high physical and chemical durability. It is a main object to provide an intermediate transfer medium that can be transferred onto.

  The present invention for solving the above problems is a protective layer transfer sheet in which a transferable protective layer is provided on one surface of a base material so as to be peelable from the base material. From the base material side, the 1st protective layer and the 2nd protective layer which contact | connects the said 1st protective layer directly are exhibiting the laminated structure provided in this order, The said 1st protective layer reacts with a hardening | curing agent. It contains a curable resin obtained by curing and reacting a reactive resin having a functional group with the curing agent, and the second protective layer has a number average molecular weight (Mn) of 8000 or more and a glass transition temperature ( Tg) contains a polyester resin having a temperature of 45 ° C. or higher.

  The reactive resin having a functional group that reacts with the curing agent may be an acrylic polyol resin having a glass transition temperature (Tg) of 50 ° C. or higher.

  In addition, the curing agent is an epoxy curing agent, the reactive resin is a reactive resin having a functional group that reacts with an epoxy group, and the glass transition temperature (Tg) of the reactive resin is 60 ° C. or higher. There may be. Moreover, 15000 or more and 70000 or less may be sufficient as the weight average molecular weight (Mw) of the reactive resin which has a functional group which reacts with the said epoxy group. The reactive resin having a functional group that reacts with the epoxy group may be an amino-modified acrylic resin.

  Moreover, 30 mass% or more of content of the said polyester resin with respect to solid content total amount of a said 2nd protective layer may be sufficient.

  Further, the present invention for solving the above problems is an intermediate transfer medium in which a transfer layer is provided on one surface of a substrate so as to be peelable from the substrate, and the transfer layer is formed on the substrate side. The first protective layer, the second protective layer in direct contact with the first protective layer, and the receiving layer are laminated in this order, and the first protective layer reacts with the curing agent. The second protective layer has a number average molecular weight (Mn) of 8000 or more, and has a glass transition temperature. (Tg) contains the polyester resin of 45 degreeC or more, It is characterized by the above-mentioned.

  According to the protective layer transfer sheet of the present invention, the interlayer adhesiveness of the transferable protective layer including the protective layer is high, and physical and chemical durability is imparted to the printed matter to which the transferable protective layer is transferred. be able to. In addition, according to the intermediate transfer medium of the present invention, the interlayer adhesion of the transfer layer including the protective layer and the receiving layer is high, and a highly durable print can be obtained by transferring the transfer layer onto the transfer target. Can do. Further, by improving the interlaminar adhesion with the transferable protective layer and the first protective layer and the second protective layer constituting the transfer layer, the transferable protective layer and the transfer layer have good foil breakability.

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 FIG. 1, the protective layer transfer sheet 10 of the present invention is provided with a transferable protective layer 20 on one surface of a base material 1 so as to be peelable from the base material 1. From the base material 1 side, the 1st protective layer 3A and the 2nd protective layer 3B which contact | connects the said 1st protective layer 3A directly are exhibiting the laminated structure provided in this order. The present invention is not limited to the illustrated form. For example, as shown in FIG. 2, an optional release layer 2 may be provided between the substrate 1 and the first protective layer 3 </ b> A. Further, an arbitrary adhesive layer 4 may be provided on the second protective layer 3B. In addition, an optional back layer 5 may be provided on the other surface of the substrate 1. In addition, another protective layer (not shown) different from the first protective layer 3A and the second protective layer 3B is provided between the substrate 1 or the optional release layer 2 and the first protective layer 3A. Alternatively, the other protective layer may be a laminate of two or more layers. In addition, another protective layer (not shown) may be provided on the second protective layer 3B. Similarly to the above, another protective layer is a laminate of two or more layers. Also good. That is, the transferable protective layer 20 includes two or more protective layers, and one of the two or more protective layers is a first protective layer 3A described below, and the two One of the protective layers is a second protective layer 3B described below, and the first protective layer 3A and the second protective layer 3B are in direct contact with each other, and the second protective layer 3B is in contact with the second protective layer 3B. The protective layer 3B only needs to be provided at a position farther from the base material 1 than the first protective layer 3A. Hereinafter, each structure of the protective layer transfer sheet 10 of this invention is demonstrated concretely. Unless otherwise specified, the protective layer 3 refers to a laminate of the first protective layer 3A and the second protective layer 3B.

(Base material)
The substrate 1 is an essential component in the protective layer transfer sheet 10 of the present invention, and is optionally formed on the protective layer 3 (an optional release layer 2 in the case shown in FIG. 2) and the other surface of the substrate 1. It is provided to hold the back layer 5 provided on the substrate. The material of the substrate 1 is not particularly limited, but it is desirable that the material has mechanical characteristics that can withstand heat applied when the transferable protective layer 20 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.

(Transferable protective layer)
The transferable protective layer 20 is provided so as to be peelable from the substrate 1, and is a layer that is peeled off from the substrate 1 and transferred onto the transfer target during thermal transfer. As shown in FIG. 1 and FIG. 2, the transferable protective layer 20 includes a first protective layer 3A and a second protective layer 3B in direct contact with the first protective layer 3A in this order from the substrate 1 side. The laminated structure formed by laminating is exhibited. The first protective layer 3 </ b> A and the second protective layer 3 </ b> B are essential layers that constitute the transferable protective layer 20. In FIG. 2, an optional release layer 2 is provided between the substrate 1 and the protective layer 3A, and an optional adhesive layer 4 is provided on the second protective layer 3B. An arbitrary release layer 2 and an arbitrary adhesive layer 4 in FIG. 2 are arbitrary layers constituting the transferable protective layer 20.

  The transferable protective layer including the protective layer includes (1) good foil breakability when the transferable protective layer is transferred onto the transfer target, and (2) wear resistance, It is required to have physical durability such as scratch resistance, and (3) chemical durability such as plasticizer resistance and solvent resistance. However, it is currently difficult to satisfy the requirements (2) and (3) simultaneously with one layer constituting the transferable protective layer. Also, paying attention to one layer constituting the transferable protective layer, even if the foil breakability of the layer is improved, if the interlayer adhesion of each layer constituting the transferable protective layer is low, transferability protection The foil breakability as a whole layer is lowered. In addition, when the interlayer adhesion of each layer constituting the transferable protective layer is low, peeling occurs at the interface between each layer when the surface of the transferable protective layer transferred onto the transfer target is rubbed. The problem that some layers constituting the protective layer may fall off may occur. That is, in order to improve the foil breakability, it is important to improve the interlayer adhesion of each layer constituting the transferable protective layer. Therefore, in the present invention, in order to satisfy the requirements (1) to (3) required for the transferable protective layer 20, the first protective layer 3A and the second protective layer 3B included in the transferable protective layer 20 are provided. It has the characteristics described below.

(First protective layer)
The first protective layer 3A is a protective layer mainly intended to satisfy the requirement (2) in the transferable protective layer 20, and a reactive resin having a functional group that reacts with the curing agent is used as the curing agent. It contains a curable resin that has undergone a curing reaction. Hereinafter, a curable resin obtained by causing a reactive reaction of a reactive resin with a curing agent may be simply referred to as a “curable resin”. According to the transferable protective layer 20 including the first protective layer 3A, due to the presence of the “curable resin” contained in the first protective layer 3A, the transferable protective layer 20 satisfies the requirement (2). Physical durability can be imparted. Further, the “curable resin” contained in the first protective layer 3A serves to reinforce the chemical durability of the transferable protective layer 20, and the transfer effect is obtained by a synergistic effect with the second protective layer 3B described later. The chemical durability of the protective layer 20 can also be improved.

<Reactive resin having a functional group that reacts with the curing agent>
There is no particular limitation on the reactive resin having a functional group that reacts with the curing agent (hereinafter simply referred to as a reactive resin), and it can be appropriately selected depending on the curing agent used. Specific examples include reactive resins having amino groups, isocyanate groups, carboxyl groups, phenolic hydroxyl groups, hydroxyl groups, acid anhydrides, thiol groups, amide groups, and the like.

  Examples of the resin having a hydroxyl group include acrylic polyol resins, polyester polyols, polyether polyols, and polycarbonate polyols. Examples of the resin having a carboxyl group include acrylic resins and polyester resins.

  Among these, the first protective layer 3A containing a curable resin obtained by curing an acrylic polyol resin with a curing agent is more than the first protective layer 3A containing a curable resin obtained by curing another reactive resin with a curing agent. In addition, the physical durability is excellent, and the foil breakability of the first protective layer 3A itself is also good. In the present invention, by improving the interlayer adhesion between the first protective layer 3A and the second protective layer 3B, it is possible to improve the foil breakability of the entire transferable protective layer 20, but the first By improving the foil cutting property of the protective layer 3A itself, the foil cutting property of the entire transferable protective layer 20 can be further improved. From the above points, acrylic polyol resin is suitable as the reactive resin. Hereinafter, an acrylic polyol resin will be mainly described as a preferred form of the reactive resin.

  The acrylic polyol resin means an acrylic resin having a hydroxyl group. For example, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate 1 type or 2 or more types of (meth) acrylic acid alkyl esters such as 2-hydroxyethyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, etc. Acrylic obtained by copolymerizing one or more (meth) acrylic acid ester having a hydroxyl group in the molecule and one or more other polymerizable monomers such as styrene, if necessary. Based polyol resins. 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 acrylic polyol resin that forms the curable resin preferably has a glass transition temperature (Tg) of 50 ° C. or higher. By adding a curable resin obtained by curing an acrylic polyol resin having a glass transition temperature (Tg) of 50 ° C. or higher with a curing agent to the first protective layer 3A, the physical durability of the first protective layer 3A is further increased. Can be improved.

  In the present specification, the glass transition temperature (Tg) of the acrylic polyol resin is a temperature obtained by converting a temperature (Kelvin (K)) obtained based on Fox's theoretical calculation formula into Celsius (° C.). The glass transition temperature (Tg) of other resins such as acrylic resins and polyester resins having a carboxyl group is a temperature determined based on the measurement of the calorimetric change (DSC method) by DSC (differential scanning calorimetry). .

  The molecular weight of the acrylic polyol resin that forms the curable resin is not particularly limited, but includes a first protective layer containing a curable resin obtained by curing an acrylic polyol resin having a weight average molecular weight (Mw) of less than 8000 with a curing agent; In such a case, the physical durability tends to decrease as compared with the first protective layer containing a curable resin obtained by curing an acrylic polyol resin having a weight average molecular weight (Mw) of 8000 or more with a curing agent. It is in. On the other hand, when the first protective layer containing a curable resin obtained by curing an acrylic polyol resin having a weight average molecular weight (Mw) exceeding 70000 with a curing agent, an acrylic having a weight average molecular weight (Mw) of less than 70000 is used. Compared to the first protective layer 3A containing a curable resin obtained by curing a system polyol resin with a curing agent, the foil breakability of the first protective layer 3A tends to decrease. Considering this point, it is preferable that the weight average molecular weight (Mw) of the acrylic polyol resin constituting the curable resin is 8000 or more and 70000 or less. The weight average molecular weight (Mw) and the number average molecular weight (Mn) described later mean polystyrene equivalent values measured by gel permeation chromatography (GPC).

  Moreover, it is preferable that the hydroxyl value of acrylic polyol resin which makes curable resin exists in the range of 10 mgKOH / g or more and 100 mgKOH / g or less. According to the first protective layer containing a curable resin obtained by curing an acrylic polyol resin having a hydroxyl value within this range with a curing agent, the foil breakability and physical durability of the first protective layer 3A can be further improved. Can be improved. When the first protective layer containing a curable resin obtained by curing an acrylic polyol resin having a hydroxyl value exceeding 100 mgKOH / g with a curing agent, an acrylic polyol resin having a hydroxyl value less than 100 mgKOH / g is used. Compared to the first protective layer containing a curable resin cured by a curing agent, the foil breakability tends to decrease. On the other hand, when the first protective layer containing a curable resin obtained by curing an acrylic polyol resin having a hydroxyl value of less than 10 mgKOH / g with a curing agent, an acrylic polyol resin having a hydroxyl value of 10 mgKOH / g or more is used. As compared with the first protective layer containing a curable resin cured by a curing agent, the durability tends to decrease.

  In the present specification, the “hydroxyl value” of the acrylic polyol resin means mg of potassium hydroxide required for acetylating 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.

<Curing agent>
As the curing agent for obtaining the curable resin, an isocyanate curing agent, and a metal chelating agent such as a titanium chelating agent, a zirconium chelating agent, and an aluminum chelating agent are suitable. The isocyanate curing agent crosslinks a resin having a hydroxyl group or a resin having a carboxyl group using the hydroxyl group or the carboxyl 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. It is possible to prevent the first protective layer 3 </ b> A from being yellowed by curing the hydroxyl group-containing resin using these isocyanate curing agents. A curable resin obtained by curing a resin having a hydroxyl group with an isocyanate-based curing agent other than an isocyanate-based curing agent selected from these groups, for example, a TDI-based or MDI-based isocyanate-based curing agent, is used as the first protection. When it is contained in the layer 3A, the first protective layer 3A is yellowed, and the appearance of the printed material to which the transferable protective layer 20 including the first protective layer 3A is transferred may be deteriorated.

  There is no particular limitation on the degree of the curing reaction by the reactive resin and the curing agent, but as the degree of the curing reaction proceeds, the physical durability of the first protective layer 3A is improved, while the first protective layer. The foil breakability of 3A tends to decrease. Therefore, in determining the degree of the curing reaction, it is preferable to set appropriately considering the foil breakability of the first protective layer 3A. Note that this does not limit the degree of the curing reaction between the reactive resin and the curing agent, and even when the curing reaction is sufficiently advanced, the interlayer adhesion with the second protective layer 3B described later. According to the present invention with improved properties, it is possible to satisfy the foil breakability of the transferable protective layer 20 as a whole.

  For example, when an acrylic polyol resin is used as the reactive resin and an isocyanate curing agent is used as the curing agent, the first protective layer 3A includes an isocyanate group that is a hydroxyl group of the acrylic polyol resin and a curing agent. A curable resin cured to have a molar equivalent ratio (—NCO / —OH) with an isocyanate group of the curing agent of 3.0 or less, preferably 2.0 or less, more preferably 0.5 or less. It is preferable to contain. By making the first protective layer 3A containing a curable resin that is cured so that the molar equivalent ratio (—NCO / —OH) is 3.0 or less, the foil breakability is further improved. be able to. In particular, the first protective layer 3A is an acrylic type in that it is possible to further improve the physical durability and chemical durability of the transferable protective layer including the first protective layer 3A as well as improving the foil breakability. The molar equivalent ratio (—NCO / —OH) between the hydroxyl group of the polyol resin and the isocyanate group of the isocyanate curing agent as the curing agent is 0.2 or more and 3.0 or less, preferably 0.2 or more and 2. It is preferable to contain a curable resin that is cured in a range of 0 or less, more preferably 0.2 or more and 0.5 or less.

  Next, a method for specifying whether or not the target protective layer satisfies the invention specific matter of the first protective layer 3A in the present invention will be described. Whether or not the target protective layer contains a curable resin can be identified by, for example, infrared absorption (FT-IR) analysis. Specifically, what kind of reactive resin is contained in the target protective layer by infrared absorption (FT-IR) analysis, and further, whether the reactive resin is cured by a curing agent. You can specify whether or not. For example, when absorption of acrylic acid ester and methacrylic acid ester can be confirmed by infrared absorption (FT-IR) analysis, it can be specified that the target protective layer contains an acrylic resin. Moreover, when the urethane bond which the isocyanate group and the hydroxyl group reacted, and absorption of unreacted residual isocyanate were confirmed, the reactive resin contained in the target protective layer is hardened with the hardening | curing agent. Can be specified. In addition to this, the resin component contained in the target protective layer is a curable resin depending on whether another peak bonded to a hydroxyl group is detected by infrared spectroscopy (IR) measurement. Or not.

  There is no restriction | limiting in particular about content of curable resin with respect to solid content total amount of 3A of 1st protective layers, According to content, such as other arbitrary components, it can set suitably. In addition, when content of curable resin with respect to solid content total amount of 1st protective layer 3A is less than 50 mass%, physical durability and chemical durability may not fully be satisfied. In addition, the foil breakability may be lowered depending on other optional components. Considering this point, the content of the curable resin with respect to the total solid content of the first protective layer 3A is preferably 50% by mass or more, and more preferably 70% by mass or more. In addition, there is no limitation in particular about an upper limit, and it is 100 mass%.

  The first protective layer 3A may contain any component other than the curable resin. For example, in the form shown in FIG. 1, the first protective layer 3 </ b> A is provided directly on the substrate 1. In the form shown in FIG. 1, the first protective layer 3 </ b> A needs to have peelability from the base material 1 in order to make the transferable protective layer 20 peelable from the base material 1. Accordingly, when the first protective layer 3A is directly provided on the substrate 1 in the form shown in FIG. 1, in other words, the first protective layer 3A contains a component having peelability. Is preferred. Further, as shown in FIG. 2, in the form shown in FIG. 1, the peelable role required for the first protective layer 3 </ b> A can be supplemented by a separate layer. For example, as shown in FIG. 2, when a release layer 2 that serves to make the transferable protective layer 20 peelable from the base material 1 is provided between the base material 1 and the first protective layer 3 </ b> A, 1 The protective layer 3A does not need to have peelability. Moreover, in order to satisfy the peelability of the transferable protective layer 20 from the base material 1, a treatment for improving the peelability can be performed on the base material 1 side.

  Examples of the peelable component include waxes such as polyethylene wax and silicone wax, silicone resin, silicone-modified resin, fluorine resin, fluorine-modified resin, polyvinyl alcohol, acrylic resin, heat-crosslinkable epoxy-amino resin, and heat-crosslinking. Alkyd-amino resin and the like.

  In the form shown in FIG. 1, when the transferable protective layer 20 is transferred onto the transfer target, the first protective layer 3A is located on the outermost surface of the transfer target. In the present invention, the first protective layer 3A contains a curable resin, and the physical durability of the first protective layer 3A is good. Therefore, good physical durability can be imparted to the transfer target body to which the transferable protective layer 20 has been transferred without containing other components other than the curable resin in the first protective layer 3A. For the purpose of further improving physical durability, particularly scratch resistance, the first protective layer 3A in the form shown in FIG. 1 must contain a component having excellent scratch resistance. Is preferred.

  Examples of components excellent in scratch resistance include silicones such as modified silicone oil and silicone-modified resin, metal soaps such as zinc stearate, zinc stearyl phosphate, calcium stearate, magnesium stearate, fatty acid amide, polyethylene wax, Mention may be made of lubricants such as carnauba wax and paraffin wax. Further, instead of the lubricant, the first protective layer 3A is coated with a methacrylate ester copolymer, vinyl chloride / vinyl acetate copolymer, polyester resin, polycarbonate resin, acrylic resin, ultraviolet absorbing resin, epoxy resin, polystyrene resin, A polyurethane resin, an acrylic urethane resin, a resin obtained by modifying each of these resins with silicone, a mixture of these resins, an ionizing radiation curable resin, an ultraviolet absorbing resin, or the like may be included.

  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.

  In addition to the optional components exemplified above, the first protective layer 3A includes, for example, light stabilizers such as hindered amines and Ni chelates, oxidations such as hindered phenols, sulfurs, phosphoruss, and lactones. Components such as an inhibitor may be contained. One of these optional components may be used alone, or two or more thereof may be used in combination.

  The first protective layer 3A may contain a filler. By making the first protective layer 3A contain a filler, the shearing property of the first protective layer 3A can be improved, and the improvement of the shearing property can further improve the foil cutting property. Examples of the filler include organic fillers, inorganic fillers, and organic-inorganic hybrid fillers. These fillers may be powder or sol-based. Examples of the organic filler in powder include acrylic particles such as non-crosslinked acrylic particles and crosslinked acrylic particles, polyamide particles, fluorine particles, and polyethylene wax. Examples of the powdery inorganic filler include metal oxide particles such as calcium carbonate particles, silica particles, and titanium oxide. Examples of the organic-inorganic hybrid filler include those obtained by hybridizing silica particles to an acrylic resin. Examples of the sol-based filler include silica sol-based and organosol-based fillers. These fillers may be used alone or in combination of two or more. Although there is no limitation in particular about content of a filler, it is preferable that it is 50 mass% or less with respect to solid content total amount of 3 A of 1st protective layers.

  Although there is no limitation in particular about content of arbitrary components other than curable resin, it is preferable to contain in the range which does not prevent the preferable content of curable resin with respect to solid content total amount of said 1st protective layer 3A.

  The first protective layer 3A has been described mainly with respect to a curable resin obtained by curing an acrylic polyol resin with a curing agent. However, the first protective layer 3A contains two or more curable resins. It may be.

  The method for forming the first protective layer 3A is not particularly limited, but a coating for the first protective layer in which a reactive resin, a curing agent, and any components added as necessary are dispersed or dissolved in an appropriate solvent. It can be formed by preparing a liquid and coating / drying the base material 1 or an arbitrary layer provided on the base material 1. The thickness of the first protective layer 3A is not particularly limited, but is preferably 0.5 μm or more and 5 μm or less.

(Other preferred forms of the first protective layer 3A)
In the above description, the acrylic polyol resin has been described with a focus on the first protective layer 3A obtained by curing with an isocyanate curing agent. However, the first protective layer 3A in another preferred embodiment is the following (1), ( The condition shown in 2) is satisfied.

Condition 1: containing an epoxy curable resin obtained by curing and reacting a reactive resin having a functional group that reacts with an epoxy group with an epoxy curing agent.
Condition 2: The glass transition temperature (Tg) of the reactive resin having a functional group that reacts with the epoxy group is 60 ° C. or higher.

  The above condition 1 is mainly intended to improve the physical durability of the first protective layer 3A and the foil breakability of the entire transferable protective layer including the first protective layer, and has a functional group that reacts with an epoxy group. An epoxy curable resin obtained by curing a reactive resin with an epoxy curing agent is added to the first protective layer 3A to provide durability, and the foil breakability of the transferable protective layer including the first protective layer 3A. It is good.

  In the above condition 1, as the curing with the epoxy curing agent proceeds, the protective layer containing the epoxy curable resin tends to become brittle, and the degree of curing is set to sufficiently improve the physical durability. If it is increased, it is contrary to the improvement of physical durability, and the foil breakability of the first protective layer 3A decreases. Further, depending on the glass transition temperature (Tg) of the reactive resin that reacts with the epoxy curing agent, the physical durability of the first protective layer 3A containing the epoxy curable resin cannot be sufficiently satisfied.

  Therefore, a glass of reactive resin that reacts with the above epoxy group without reducing the physical durability imparted by curing the reactive resin with an epoxy curing agent, and in order to improve the foil breakability. A transition temperature (Tg) of 60 ° C. or higher is a condition for the first protective layer 3A in another preferred form. In order to sufficiently improve the physical durability, the first protective layer 3A contains an epoxy curable resin obtained by curing a reactive resin having a glass transition temperature (Tg) of 60 ° C. or higher with an epoxy curing agent. Even when the curing of the epoxy curing agent and the reactive resin is sufficiently advanced, the foil breakability of the entire transferable protective layer including the first protective layer 3A can be satisfied. In addition, when the protective layer contains an epoxy curable resin obtained by curing a reactive resin having a glass transition temperature (Tg) of less than 60 ° C. with an epoxy curing agent, the first protective layer 3A becomes brittle and the foil breaks. Sex tends to decline. In addition, physical durability tends to be lower than when a reactive resin having a glass transition temperature (Tg) of 60 ° C. or higher is used.

  Hereinafter, the epoxy curing agent and the reactive resin having a glass transition temperature (Tg) of 60 ° C. or higher will be described.

<Epoxy curing agent>
The term “epoxy curing agent” as used herein means “a curing agent having at least two epoxy groups in one molecule”. Moreover, an epoxy curable resin means "resin obtained by carrying out the hardening reaction of the reactive resin which has a functional group which reacts with an epoxy group with the said epoxy hardening agent." There is no particular limitation on the epoxy curing agent, for example, bisphenol type epoxy resin such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, cresol novolac type epoxy resin, phenol novolac type epoxy resin, cyclic aliphatic epoxy resin, glycidyl ester And epoxy resin, glycidylamine epoxy resin, and heterocyclic epoxy resin.

<Reactive resin having a functional group that reacts with an epoxy group>
The reactive resin having a functional group that reacts with the epoxy group satisfies the condition that the glass transition temperature (Tg) is 60 ° C. or more as described above, and reacts with the epoxy group of the epoxy curing agent. It is a resin having a functional group. The functional group that the reactive resin has is not particularly limited as long as it reacts with the epoxy group of the epoxy curing agent. The first protective layer 3A contains an epoxy curable resin obtained by curing a reactive resin satisfying the above condition 2 with the epoxy curing agent.

  Whether the curable resin contained in the first protective layer 3A is an epoxy curable resin obtained by a curing reaction between an epoxy curing agent and a reactive resin, an epoxy curing agent and an epoxy reactive resin, FT-IR analysis of the structure after the reaction of, for example, the presence or absence of absorption after the reaction such as epoxy group-amino group or epoxy-hydroxyl group, the absorption of residual epoxy group, etc. can be specified. Further, by using an analytical instrument such as NMR or GPC, the cured product can be analyzed in more detail.

  Examples of functional groups that react with epoxy groups include amino groups, isocyanate groups, carboxyl groups, phenolic hydroxyl groups, hydroxyl groups, acid anhydrides, thiol groups, and amide groups.

  Specific examples include an amino-modified acrylic resin, a hydroxyl group-containing resin, a carboxyl group-containing resin and the like that satisfy a glass transition temperature (Tg) of 60 ° C. or higher. Among these, an epoxy curable resin obtained by curing an amino-modified acrylic resin having a glass transition temperature (Tg) of 60 ° C. or higher with an epoxy curing agent is a reactive resin because it is extremely excellent in physical durability and foil breakability. It is suitable as.

  The molecular weight of the reactive resin having a functional group that reacts with the epoxy group is not particularly limited, but when the weight average molecular weight (Mw) of the reactive resin is less than 15000, the transferability including the first protective layer 3A. There exists a tendency for the physical durability as the whole protective layer to fall. On the other hand, when the weight average molecular weight (Mw) of the reactive resin exceeds 70000, the foil breakability when transferring the transferable protective layer including the first protective layer 3A tends to be lowered. In consideration of this point, the first protective layer 3A is formed by curing a reactive resin having a glass transition temperature (Tg) of 60 ° C. or more and a weight average molecular weight (Mw) of 15000 or more and 70000 or less with an epoxy curing agent. It preferably contains a curable epoxy resin. Note that this does not limit the molecular weight of the reactive resin, and even when the molecular weight is outside the above preferred range, a reactive resin having a glass transition temperature (Tg) of less than 60 ° C. is included in the protective layer. Compared to the case, the physical durability and foil breakability imparted to the transferable protective layer including the first protective layer 3A are good. In addition, a weight average molecular weight (Mw) means the polystyrene conversion value measured by gel permeation chromatography (GPC).

  In the other preferred first protective layer 3A, a reactive resin having a glass transition temperature (Tg) of 60 ° C. or lower is cured by an epoxy curing agent, and therefore, the curing is sufficiently advanced. However, the foil cutting property can be satisfied. Depending on the functional group of the reactive resin, the foil breakage may slightly decrease with the progress of the reaction, so the degree of curing is appropriately adjusted according to the selected reactive resin. It is preferable.

  There is no particular limitation on the molar equivalent ratio (-epoxy group / -A) between the functional group of the reactive resin (hereinafter sometimes referred to as functional group A) and the epoxy group of the epoxy curing agent. As the ratio (-epoxy group / -A) exceeds 3.0, the foil breakability of the first protective layer 3A containing the curable resin tends to decrease. On the other hand, when the molar equivalent ratio (-epoxy group / -A) is less than 1.0, the durability of the first protective layer 3A containing the curable resin tends to decrease. Considering this point, the first protective layer 3A has a molar equivalent ratio (-epoxy group / -A) of the functional group of the reactive resin to the epoxy group of the epoxy curing agent of 1.0 or more and 3.0. Hereinafter, it is preferable to contain a curable resin which is preferably cured in the range of 1.0 to 2.0. In particular, when the reactive resin is the amino-modified acrylic resin exemplified above, the amino-modified acrylic resin is cured with an epoxy curing agent so that the equivalent ratio falls within this range, whereby the second described later. A synergistic effect with the protective layer 3B is also added, and the physical durability and foil breakability of the transferable protective layer including the first protective layer 3A can be further improved.

  Another preferred form of the first protective layer 3A is that the acrylic polyol resin described above is a reactive resin having a functional group that reacts with an epoxy group, and various curing agents such as an isocyanate curing agent are epoxy-cured. Except for the fact that it is an agent, the form of the first protective layer 3A described above can be appropriately selected and used, and description other than this difference is omitted.

(Second protective layer)
In the above description, the physical durability of the transferable protective layer 20 can be imparted to the transferable protective layer 20 by the first protective layer 3A. However, the transferable protective layer 20 serves as the first protective layer 3A as a protective layer. In the case where it contains only, it has physical durability, but cannot sufficiently satisfy chemical durability such as plasticizer resistance and solvent resistance. That is, the requirement (3) cannot be satisfied.

  Further, the curable resin obtained by curing the reactive resin with a curing agent has almost no adhesiveness, and the first protective layer 3A described above is directly connected to the first protective layer 3A. Adhesion with other layers in contact with the film becomes low. Therefore, in order to provide the transferable protective layer 20 with chemical durability in addition to physical durability, another protective layer mainly for improving chemical durability is laminated on the first protective layer 3A. In the case of a transferable protective layer (hereinafter, this transferable protective layer is referred to as a comparative transferable protective layer), the first protective layer is formed at the interface between the first protective layer 3A and another protective layer. 3A is easily peeled off, and the physical durability of the entire transferable protective layer cannot be satisfied. More specifically, when the interlayer adhesion between the first protective layer 3A constituting the comparative transferable protective layer and another protective layer is low, when the surface after transfer is rubbed, the first protective layer 3A And the problem of peeling at the interface with another protective layer occurs, and the physical durability of the entire transferable protective layer is significantly lowered. That is, in the case of the comparative transferable protective layer, even if the physical durability of the first protective layer 3A itself is satisfied, the transferable protective layer as a whole is the requirement (2). Physical durability, specifically, scratch resistance cannot be satisfied.

  When the comparative transferable protective layer is used, when transferring the comparative transferable protective layer including the first protective layer 3A, another protective layer provided on the first protective layer 3A is used as the first protective layer. Transfer cannot be performed so as to follow the protective layer 3A. Therefore, even if the first protective layer 3A itself has a good foil cutting property, the foil cutting property of the entire transferable protective layer cannot be satisfied. That is, the structure of the comparative transferable protective layer cannot satisfy the foil cutting property that is the requirement of the above (1).

  Therefore, in the present invention, as shown in FIGS. 1 and 2, the second protective layer is a layer that is in direct contact with the first protective layer 3A and is provided at a position farther from the base material 1 than the first protective layer 3A. The layer 3B is characterized by containing a polyester resin having a number average molecular weight (Mn) of 8000 or more and a glass transition temperature (Tg) of 45 ° C. or more. According to the transferable protective layer 20 including the second protective layer 3B having the above characteristics in addition to the first protective layer 3A, the interlayer adhesion between the first protective layer 3A and the second protective layer 3B can be improved. And the foil breakability of the entire transferable protective layer 20 can be satisfied. That is, the requirement (1) can be satisfied. Further, by improving the interlayer adhesion, it is possible to prevent the problem of peeling at the interface between the first protective layer 3A and the second protective layer 3B constituting the transferable protective layer 20.

  Although the detailed mechanism by which the interlayer adhesion with the first protective layer 3A is good by using the second protective layer 3B having the above characteristics is not always clear at present, the first protective layer 3A is It contains an unreacted curing agent together with a curable resin obtained by curing a reactive resin with a curing agent, and is present in the first protective layer 3A at the interface between the first protective layer 3A and the second protective layer 3B. The functional group of the unreacted curing agent is bonded to the carboxyl group of the polyester resin contained in the second protective layer 3B, so that the interlayer between the first protective layer 3A and the second protective layer 3B It is inferred that the adhesion is improved. Alternatively, the functional group of the unreacted reactive resin contained in the first protective layer 3A, or the functional group of the reactive resin partially reacted with the curing agent, and the second protective layer 3B Interlayer adhesion between the first protective layer 3A and the second protective layer 3B is improved by bonding the carboxyl group of the contained polyester resin via the functional group of the curing agent. Inferred. Even if this mechanism is not used, the first protective layer 3A and the second protective layer 3B described above are in direct contact with each other, thereby improving interlayer adhesion, physical durability, and chemical durability. It is clear from the results of Examples and Comparative Examples that will be described later that durability and foil breakage are improved.

  The polyester resin contained in the second protective layer 3B has a number average molecular weight (Mn) of 8000 or more and a glass transition temperature (Tg) of 45 ° C. or more. Hereinafter, a polyester resin having a number average molecular weight (Mn) of 8000 or more and a glass transition temperature (Tg) of 45 ° C. or more may be referred to as a “specific polyester resin”. According to the second protective layer 3B containing the “specific polyester resin”, chemical durability can be imparted to the second protective layer 3B. Therefore, according to the transferable protective layer 20 including the first protective layer 3A and the second protective layer 3B, it is possible to impart both physical durability and chemical durability to the transferable protective layer 20. it can. In the present invention, since the interlayer adhesion between the first protective layer 3A and the second protective layer 3B is also good, the transferable protective layer 20 without impairing the imparted physical and chemical durability. Overall foil breakability can also be satisfied.

  In addition, when a polyester resin having a glass transition temperature (Tg) of less than 45 ° C. is contained in the second protective layer instead of the “specific polyester resin”, the number average molecular weight (Mn) of the polyester resin is Even if it is 8000 or more, the solvent resistance which is one of the chemical durability cannot be satisfied. The “specific polyester resin” only needs to satisfy the condition that the glass transition temperature (Tg) is 45 ° C. or higher, and the upper limit is not particularly limited. It is preferable that

  In addition, when a polyester resin having a number average molecular weight (Mn) of less than 8000 is contained in the second protective layer instead of the “specific polyester resin”, the glass transition temperature (Tg) of the polyester resin is 45. Even when the temperature is higher than or equal to ° C., the plasticizer resistance, which is one of chemical durability, cannot be satisfied. The “specific polyester resin” only needs to satisfy the condition that the number average molecular weight (Mn) is 8000 or more, and the upper limit value is not particularly limited, but is 30000 or less in view of the foil breakability. It is preferable. In addition, the second protective layer 3B has a number-average molecular weight (Mn) of 12,000 or more “specific” in that the physical durability of the entire transferable protective layer including the second protective layer 3B can be further improved. It preferably contains a “polyester resin”.

  In the present invention, the first protective layer 3A is mainly intended to improve physical durability, and the second protective layer 3B is mainly intended to improve chemical durability, while the first protective layer 3A is It plays an auxiliary role to further improve the chemical durability of the second protective layer 3B. That is, when the chemical durability of the transferable protective layer composed only of the second protective layer 3B and the transferable protective layer 20 formed by laminating the first protective layer 3A and the second protective layer 3B are compared, The transferable protective layer formed by laminating the first protective layer 3A and the second protective layer 3B as much as the layer 3A is contained is more chemically than the transferable protective layer made of only the second protective layer 3B. Excellent durability.

  In addition, the second protective layer 3B plays an auxiliary role to further improve the physical durability of the first protective layer 3A. That is, when the chemical durability of the transferable protective layer made only of the first protective layer 3A and the transferable protective layer 20 formed by laminating the first protective layer 3A and the second protective layer 3B are compared, Since the layer 3B is included, the transferable protective layer in which the first protective layer 3A and the second protective layer 3B are laminated is excellent in physical durability. That is, the present invention is characterized in that the physical and chemical durability is improved by the synergistic effect of the first protective layer 3A and the second protective layer 3B. In the case of the transferable protective layer comprising, it is not possible to sufficiently satisfy physical durability and chemical durability as in the present invention.

  The “specific polyester resin” contained in the second protective layer 3B only needs to have a glass transition temperature (Tg) and a number average molecular weight (Mn) satisfying the above conditions. For example, the glass transition temperature (Tg), Listed are those obtained by ring-opening of cyclic lactones, such as condensates of polyhydric alcohols and polybasic carboxylic acids having a number average molecular weight (Mn) satisfying the above conditions, and the like. Can do.

  In addition, the above-mentioned “specific polyester resin” may be cured with a curing agent, but as the degree of curing progresses, a certain improvement in chemical and physical durability is expected. There is a tendency for the cutting performance to decrease slightly.

  Considering this point, the “specific polyester resin” is contained in the second protective layer 3B in an uncured state, or when an isocyanate curing agent is used as a curing agent, for example, The “specific polyester resin” cured in a molar equivalent ratio (—NCO / —OH) between the hydroxyl group of the “polyester resin” and the isocyanate group of the isocyanate curing agent as the curing agent is 3 or less. 2 It is preferable to be contained in the protective layer 3B.

  An uncured “specific polyester resin” or a “specific polyester resin” cured in the range of the preferred molar equivalent ratio of the curing reaction by the isocyanate curing agent is contained in the second protective layer 3B. Thus, flexibility can be imparted to the second protective layer 3B, and the occurrence of cracks that can occur when the transferable protective layer 20 after transfer is bent can be prevented. Specifically, since the first protective layer 3A contains a curable resin, the first protective layer 3A itself is in a state of being easily cracked by bending, but the first protective layer 3A is flexible with the first protective layer 3A. Even when the second protective layer 3B serves as a cushion and the transferable protective layer 20 after transfer is bent, the second protective layer 3B having Generation of cracks that can occur in the first protective layer 3A can be prevented.

  Although there is no limitation in particular about content of "specific polyester resin" with respect to solid content total amount of 2nd protective layer 3B, when it is less than 30 mass%, chemical durability and physical by 1st protective layer 3A There is a tendency for the effect of supplementing mechanical durability to decline. Therefore, the “specific polyester resin” is preferably contained in an amount of 30% by mass or more based on the total solid content of the second protective layer 3B. There is no limitation in particular about an upper limit, and it is 100 mass%. The second protective layer 3B can also contain two or more “specific polyester resins”.

  Similar to the first protective layer 3A, the second protective layer 3B can contain an optional component. For example, in the embodiment shown in FIG. 1, the second protective layer 3B is positioned on the outermost surface of the protective layer transfer sheet 10, and therefore, when the transferable protective layer 20 is transferred onto the transfer target, The layer 3B is a layer in direct contact with the transfer target. Therefore, in the embodiment shown in FIG. 1, the second protective layer 3B needs to have adhesiveness. Since the second protective layer 3B containing the “specific polyester resin” has adhesiveness, even if the second protective layer 3B containing only the “specific polyester resin” is used, the transferred object is transferred. The transferable protective layer can be adhered and transferred onto the body.

  In the form shown in FIG. 1, when the purpose is to further improve the adhesion between the transferable protective layer 20 and the transfer target, the second protective layer 3 </ b> B contains a component having adhesiveness to the transfer target. It is preferable that 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.

  The second protective layer 3B can contain the “component having scratch resistance” described in the first protective layer 3A. Moreover, the filler demonstrated by said 1st protective layer 3A for improving the foil cutting property of 2nd protective layer 3B can also be contained.

  Although there is no limitation in particular about the formation method of 2nd protective layer 3B, coating for 2nd protective layers which disperse | distributed or melt | dissolved "specific polyester resin" and the arbitrary components as needed in a suitable solvent A liquid can be prepared and formed on the first protective layer 3A by coating and drying. In forming the second protective layer 3B, it is preferable to form the second protective layer on the first protective layer before the curing reaction in the first protective layer is completed.

  Although there is no limitation in particular about the thickness of the 2nd protective layer 3B, it is preferable to exist in the range of 0.5 micrometer or more and 10 micrometers or less.

  In the protective layer transfer sheet having the structure shown in FIG. 1, the first protective layer 3A is provided with adhesion to the transfer target in addition to physical durability, and the second protective layer 3B is chemically durable. In addition to the properties, the example of giving the peelability from the substrate 1 has been described. However, as shown in FIG. It is good also as a structure to provide. For example, as shown in FIG. 2, a layer (peeling layer 2) having a peeling property from the base material 1 is provided between the base material 1 and the first protective layer 3A, and the second protective layer 3B is covered You may provide the layer (adhesion layer 4) which has adhesiveness with a transfer body.

(Peeling layer)
As a component of the peeling layer 2, the material illustrated as a component which has peelability in the said 1st protective layer 3A can be selected suitably, and can be used. The release layer 2 is a layer that is transferred onto the transfer target body together with the first protective layer 3A and the second protective layer 3B, but may be a layer that remains on the substrate 1 side.

  As a method for forming the release layer 2, a release layer coating solution prepared by dissolving or dispersing the component having the above-described release property in an appropriate solvent is prepared. 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 release layer 2 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 3 has been transferred, the release layer 2 and the first protective layer 3A are provided between the substrate 1 and the first protective layer 3A or when the release layer 2 is provided. Between them, a plasticizer-resistant layer (not shown) may be provided.

  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 transferable protective layer 20 can be further improved. The material that repels the plasticizer component 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 formed by coating and drying on the substrate 1 or the release layer 2 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 second protective layer 3B. 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 in the case of taking a measure that satisfies the adhesiveness with the second protective layer 3B 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 second protective layer 3B, a known means such as a gravure printing method, a screen printing method, or a reverse roll coating method using a gravure plate may be applied and dried. The thickness of the adhesive layer 4 is generally about 0.5 μm to 10 μm.

  In the above description, the case where the transferable protective layer 20 includes a release layer, a plasticizer-resistant layer, and an adhesive layer is described as an example of the laminated transferable protective layer 20. Depending on the components contained in any layer constituting 20, for example, depending on the components contained in the release layer, the plasticizer-resistant layer, and the adhesive layer, the foil breakability of each layer alone is insufficient. It may become. However, the second protective layer 3B is not only in contact with the first protective layer 3A in contact with one surface of the second protective layer 3B, but also with the layer in contact with the other surface of the second protective layer 3B, for example, adhesion to the adhesive layer 4 Therefore, the interlayer adhesion of each layer constituting the transferable protective layer 20 can be satisfied. In addition, since the arbitrary release layer 2 is usually much thinner than the first protective layer 3A and the second protective layer 3B, the foil breakability of the optional release layer 2 is particularly considered. The foil breakability of the transferable protective layer 20 as a whole can be satisfied.

(Back layer)
Further, as shown in FIG. 2, on the surface different from the surface on which the transferable protective layer 20 of the substrate 1 is provided, the rear surface for improving the heat resistance and the running performance of the thermal head during printing. Layer 5 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 transferable protective layer 20 of the substrate 1 is provided may 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 FIG. FIG. 3 is a schematic sectional view showing an example of the intermediate transfer medium of the present invention. As shown in FIG. 3, the intermediate transfer medium 100 of the present invention has a configuration in which a transfer layer 30 is provided on one surface of a substrate 1 so as to be peelable from the substrate 1. The transfer layer 30 has a laminated structure in which the first protective layer 3A, the second protective layer 3B in direct contact with the first protective layer 3A, and the receiving layer 50 are provided in this order from the base material 1 side. . The present invention is not limited to the form shown in FIG. 3. For example, as shown in FIG. 4, a release layer 2 may be provided between the substrate 1 and the first protective layer 3 </ b> A. Further, the adhesive layer 4 may be provided on the receiving layer 50. Further, the back layer 5 may be provided on the other surface of the substrate 1. Further, another protective layer (not shown) or an optional layer may be provided between the base material 1 or the optional release layer 2 and the first protective layer 3A. Similarly, another protective layer (not shown) or an arbitrary layer may be provided between the second protective layer 3B and the receiving layer 50.

  In the intermediate transfer medium of the present invention, in the protective layer transfer sheet 10 of the present invention described above, a receiving layer provided directly or indirectly on the second protective layer 3B is an essential component. This is different from the protective layer transfer sheet 10 of the present invention. Hereinafter, each configuration of the intermediate transfer medium 100 of the present invention will be described focusing on the receiving layer 50.

(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.

(Transfer layer)
The transfer layer 30 including the protective layer 3 and the receiving layer 50 is provided so as to be peelable from the substrate 1, and is a layer that is peeled off from the substrate and transferred onto the transfer object during thermal transfer. The transfer layer 30 has a laminated structure including the first protective layer 3A, the second protective layer 3B, and the receiving layer 50 as essential components.

(First protective layer)
As the first protective layer 3A constituting the transfer layer 30, the first protective layer 3A described in the protective layer transfer sheet 10 of the present invention can be used as it is, and detailed description thereof is omitted here.

(Second protective layer)
As the second protective layer 3B constituting the transfer layer 30, the second protective layer 3B described in the protective layer transfer sheet 10 of the present invention can be used as it is, and detailed description thereof is omitted here.

  In the intermediate transfer medium 100 of the present invention, the receiving layer 50 provided on the second protective layer 3B is laminated directly on the transfer target or indirectly through an arbitrary layer such as an adhesive layer. Therefore, it is not necessary that the second protective layer 3B itself has adhesiveness.

  Similar to the transferable protective layer 20 of the protective layer transfer sheet 10 of the present invention, the transfer layer 30 in the intermediate transfer medium of the present invention includes a first protective layer 3A and a second protective layer 3B. The first protective layer 3A and the second protective layer 3B are in direct contact with each other. Therefore, by transferring the transfer layer 30 onto the transfer target, a printed matter having excellent physical and chemical durability can be obtained. Further, since the second protective layer 3B has higher adhesiveness with the layer in contact with the second protective layer 3B than the first protective layer 3A, the second protective layer 3B is an interlayer between the second protective layer 3B and the receiving layer 50. Adhesion can be increased. In addition, since the interlayer adhesion between the first protective layer 3A and the second protective layer 3B is also high, the interlayer adhesion of each layer constituting the transfer layer 30 can be enhanced, and the foil breakability of the entire transfer layer 30 is good. Can be.

(Receptive layer)
As shown in FIG. 3, a receiving layer 50 is provided on the second protective layer 3B. The receiving layer 50 is a layer included in the transfer layer 30. 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 first protective layer 3A and the second protective layer 3B, 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.

(Thermal transfer sheet 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 ravia 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 of thermal transfer sheet)
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.

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. Next, the protective layer coating solution 1 having the following composition is applied on the release layer so as to have a thickness of 2.0 g / m ^{2 in} a dry state, and dried at 100 ° C. for 2 minutes to thereby form the first protective layer. Formed. Within 1 minute after the formation of the first protective layer, the protective layer coating solution 2 having the following composition was applied to a thickness of 2.0 g / m ^{2 in} a dry state, and at 100 ° C. for 2 minutes. A second protective layer was formed by drying. Next, a receiving layer coating solution having the following composition was applied on the second protective layer to a thickness of 1.0 g / m ^{2 in} a dry state to form a receiving layer, and the intermediate transfer of Example 1 was performed. A medium was obtained. The release layer coating solution, the protective layer coating solution 1, the protective layer coating solution 2, and the receiving layer coating solution were all applied by gravure coating.

<Coating liquid for release layer>
Acrylic resin (Tg: 105 ° C., Mw: 25000) 80 parts (BR-87, Mitsubishi Rayon Co., Ltd.)
・ Polyester resin 5 parts (Byron 200, Toyobo Co., Ltd.)
-Polyethylene wax 5 parts (Polywax 1000, Toyo Adre Co., Ltd.)
・ 25 parts of UV absorbing acrylic resin (PUVA-50M-40TM, Otsuka Chemical Co., Ltd., solid content: 40%)
・ Toluene 192.5 parts ・ Methyl ethyl ketone 192.5 parts

<Protective layer coating solution 1>
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.)
・ Methyl ethyl ketone 170 parts

<Protective layer coating solution 2>
-Polyester resin (Mn: 17000, Tg: 67 ° C) 80 parts (Byron 200 Toyobo Co., Ltd.)
・ Methyl ethyl ketone 20 parts

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

(Example 2)
An intermediate transfer medium of Example 2 was obtained in the same manner as in Example 1 except that the protective layer coating solution 2 was changed to a protective layer coating solution 3 having the following composition to form a second protective layer. .

<Coating liquid 3 for protective layer>
-Polyester resin (Mn: 10000 Tg: 60 ° C) 20 parts (GK-250 Toyobo Co., Ltd.)
・ Methyl ethyl ketone 80 parts

(Example 3)
An intermediate transfer medium of Example 3 was obtained in the same manner as in Example 1 except that the protective layer coating solution 2 was changed to the protective layer coating solution 4 having the following composition to form the second protective layer. .

<Coating liquid 4 for protective layer>
・ Polyester resin (Mn: 16000 Tg: 47 ° C.) 20 parts (Byron 600 Toyobo Co., Ltd.)
・ Methyl ethyl ketone 80 parts

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 2 was changed to the protective layer coating solution 5 having the following composition to form the second protective layer. .

<Coating liquid 5 for protective layer>
Polyester resin (Mn: 17000, Tg: 67 ° C.) 15 parts (Byron 200 Toyobo Co., Ltd.)
・ Polyester resin (Mn: 3000 Tg: 53 ° C.) 5 parts (Byron 220 Toyobo Co., Ltd.)
・ Methyl ethyl ketone 80 parts

(Example 5)
An intermediate transfer medium of Example 5 was obtained in the same manner as in Example 1 except that the protective layer coating solution 2 was changed to the protective layer coating solution 6 having the following composition to form the second protective layer. .

<Coating liquid 6 for protective layer>
Polyester resin (Mn: 17000, Tg: 67 ° C.) 10 parts (Byron 200 Toyobo Co., Ltd.)
Polyester resin (Mn: 3000 Tg: 53 ° C.) 10 parts (Byron 220 Toyobo Co., Ltd.)
・ Methyl ethyl ketone 80 parts

(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 2 was changed to the protective layer coating solution 7 having the following composition to form the second protective layer. .

<Coating liquid 7 for protective layer>
Polyester resin (Mn: 17000, Tg: 67 ° C.) 10 parts (Byron 200 Toyobo Co., Ltd.)
-Polyester resin (Mn: 5000 Tg: 52 ° C) 10 parts (UE-3350 Unitika Ltd.)
・ Methyl ethyl ketone 80 parts

(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 a protective layer coating solution 8 having the following composition to form the first protective layer. It was.

<Protective layer coating solution 8>
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.)
・ Methyl ethyl ketone 170 parts

(Example 8)
The intermediate transfer medium of Example 8 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 to form the first protective layer. It was.

<Coating liquid 9 for protective layer>
Acrylic polyol resin (solid content: 55%, Tg: 53 ° C., Mw: 26600, hydroxyl value (solid): 72.7, —OH: 40) 100 parts (WZU-591, DIC Corporation)
・ Isocyanate curing agent (solid content: 75% -NCO: 11.5%) 26 parts (Takenate D110N (XDI) Mitsui Chemicals, Inc.)
・ Methyl ethyl ketone 170 parts

Example 9
A protective layer transfer sheet of Example 9 was obtained in the same manner as Example 1 except that the release layer and the receiving layer were not formed.

(Example 10)
The 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 10 having the following composition to form the first protective layer. It was.

<Protective layer coating solution 10>
Molar equivalent ratio (-epoxy group / -amino group): 0.5
Amino-modified acrylic resin (solid content 40%, Tg 75 ° C., Mw 53000) 100 parts (LK-730 Toray Fine Chemical Co., Ltd.)
・ Epoxy curing agent 2.1 parts (Denacol EX-612) Nagase ChemteX Corporation)
・ Toluene / isobutanol = 1/1 mixed solvent 100 parts

(Example 11)
The protective layer coating liquid 1 is changed to a protective layer coating liquid 11 having the following composition to form a first protective layer, and the protective layer coating liquid 2 is replaced with the protective layer coating liquid 4 having the above composition. The intermediate transfer medium of Example 11 was obtained in the same manner as Example 1 except that the second protective layer was formed by changing to

<Protective layer coating solution 11>
Molar equivalent ratio (-epoxy group / -amino group): 3.0
Amino-modified acrylic resin (solid content 40%, Tg 75 ° C., Mw 53000) 100 parts (LK-730 Toray Fine Chemical Co., Ltd.)
-Epoxy curing agent 12.75 parts (Denacol EX-612) Nagase ChemteX Corporation)
・ Toluene / isobutanol = 1/1 mixed solvent 100 parts

(Example 12)
The protective layer coating solution 1 is changed to a protective layer coating solution 12 having the following composition to form a first protective layer, and the protective layer coating solution 2 is replaced with the protective layer coating solution 4 having the above composition. The intermediate transfer medium of Example 12 was obtained in the same manner as in Example 1 except that the second protective layer was formed by changing to

<Coating liquid 12 for protective layer>
Molar equivalent ratio (-epoxy group / -amino group): 2.0
Amino-modified acrylic resin (solid content 50%, Tg 62 ° C., Mw 25000) 100 parts (LK-714 Toray Fine Chemical Co., Ltd.)
・ Epoxy curing agent 6.46 parts (Denacol EX-612) Nagase ChemteX Corporation)
・ Toluene / isobutanol = 1/1 mixed solvent 100 parts

(Example 13)
The protective layer coating liquid 1 is changed to the protective layer coating liquid 12 having the above composition to form a first protective layer, and the protective layer coating liquid 2 is converted to the protective layer coating liquid 7 having the above composition. The intermediate transfer medium of Example 13 was obtained in the same manner as in Example 1 except that the second protective layer was formed by changing to

(Example 14)
The 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 to form the first protective layer. It was.

<Protective layer coating solution 13>
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.)
・ Methyl ethyl ketone 240 parts

(Comparative Example 1)
Except that the protective layer coating solution 1 was changed to the protective layer coating solution 2 having the above composition to form the first protective layer and the second protective layer was not formed, all were the same as in Example 1. An intermediate transfer medium of Comparative Example 1 was obtained.

(Comparative Example 2)
Except that the protective layer coating solution 1 was changed to the protective layer coating solution 4 having the above composition to form the first protective layer and the second protective layer was not formed, everything was the same as in Example 1. An intermediate transfer medium of Comparative Example 2 was obtained.

(Comparative Example 3)
The protective layer coating solution 1 was changed to the protective layer coating solution 14 having the following composition to form the first protective layer, and all the same procedures as in Example 1 were performed except that the second protective layer was not formed. An intermediate transfer medium of Comparative Example 3 was obtained.

<Protective layer coating solution 14>
・ Acrylic resin (Tg: 105 ° C Mw: 95000) 20 parts (BR-80 Mitsubishi Rayon Co., Ltd.)
・ Methyl ethyl ketone 80 parts

(Comparative Example 4)
The protective layer coating solution 1 was changed to the protective layer coating solution 15 having the following composition, the first protective layer was formed, and the second protective layer was not formed. An intermediate transfer medium of Comparative Example 4 was obtained.

<Coating liquid 15 for protective layer>
・ Acrylic resin (Tg: 105 ° C Mw: 25000) 20 parts (BR-87 Mitsubishi Rayon Co., Ltd.)
・ Methyl ethyl ketone 80 parts

(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 2 was changed to the protective layer coating solution 15 having the above composition to form the second protective layer. .

(Comparative Example 6)
An intermediate transfer medium of Comparative Example 6 was obtained in the same manner as in Example 1 except that the protective layer coating solution 2 was changed to the protective layer coating solution 16 having the following composition to form the second protective layer. .

<Coating liquid 16 for protective layer>
・ Polyester resin (Mn: 11000 Tg: 36 ° C.) 20 parts (GK-780 Toyobo Co., Ltd.)
・ Methyl ethyl ketone 80 parts

(Comparative Example 7)
An intermediate transfer medium of Comparative Example 7 was obtained in the same manner as in Example 1 except that the protective layer coating solution 2 was changed to the protective layer coating solution 17 having the following composition to form the second protective layer. .

<Coating liquid 17 for protective layer>
-Polyester resin (Mn: 5000 Tg: 52 ° C) 20 parts (UE-3350 Unitika Ltd.)
・ Methyl ethyl ketone 80 parts

(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 2 was changed to the protective layer coating solution 18 having the following composition to form the second protective layer. .

<Coating liquid 18 for protective layer>
・ Polyester resin (Mn: 3000 Tg: 53 ° C.) 20 parts (Byron 220 Toyobo Co., Ltd.)
・ Methyl ethyl ketone 80 parts

(Comparative Example 9)
An intermediate transfer medium of Comparative Example 9 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 15 having the above composition to form the first protective layer. .

(Formation of prints)
Using a HDP-600 (HID) printer and a thermal transfer sheet prepared by the following method, a gray solid image was formed on the receiving layers of the intermediate transfer media of the examples and comparative examples under the default conditions. Using the printer, the receiving layer, the protective layer, and the release layer after gray solid image formation were transferred onto a PVC card (manufactured by DNP) under retransfer conditions of 175 ° C. and 2 sec / inch. The prints of Comparative Examples 1 to 9 were obtained.

(Creation of thermal transfer sheet)
Using a polyethylene terephthalate film with a thickness of 4.5 μm as the base material and having been subjected to an easy adhesion treatment, a coating solution for heat-resistant slipping layer having the following composition is applied on the base material to a dry weight of 0.8 g / m ^2. A heat resistant slipping 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 slipping layer>
・ 2.0 parts of polyvinyl butyral resin (S-REC 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 (disperse 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

(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>
A: There is no tailing that can be confirmed.
○: 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).

(Durability evaluation)
A wear wheel CS-10F was used for the prints of each Example and Comparative Example, the surface state after polishing 400 times with a load of 500 gf was visually observed, and an evaluation test was performed according to the following evaluation criteria.
<Evaluation criteria>
A: The image is not scratched.
○: Slight scratches are generated on the image.
(Triangle | delta): Although the image has a crack, it is a level which does not have a problem in use.
X: The image is considerably sharpened, and the image is severely scratched.

(Evaluation of plasticizer resistance)
Using a bending tester, after folding 300 times each on the front and back sides, vertically and horizontally, DOP is applied, and after storage at 40 ° C. for 12 hours, it is visually confirmed whether the image has deteriorated, based on the following evaluation criteria The plasticizer resistance was evaluated.
<Evaluation criteria>
○: Image degradation does not occur.
Δ: Image is slightly degraded.
X: The image is greatly deteriorated.

(Evaluation of alcohol resistance)
After immersing the printed matter of each Example and Comparative Example in ethanol for 24 hours, it was visually confirmed whether the image of the printed matter was deteriorated, and the alcohol resistance was evaluated based on the following evaluation criteria. .
<Evaluation criteria>
○: Image degradation does not occur.
Δ: The image is slightly matted.
X: The image is considerably matted.

DESCRIPTION OF SYMBOLS 10 ... Protective layer transfer sheet 1 ... Base material 2 ... Release layer 3A ... 1st protective layer 3B ... 2nd protective layer 4 ... Adhesive layer 5 ... Back surface layer 20 ... Transferable protective layer 100 ... Intermediate transfer medium 30 ... Transfer layer 50 ... Receptive layer

The present invention for solving the above problems is a protective layer transfer sheet in which a transferable protective layer is provided on one surface of a base material so as to be peelable from the base material. From the base material side, the 1st protective layer and the 2nd protective layer which contact | connects the said 1st protective layer directly are exhibiting the laminated structure provided in this order, The said 1st protective layer reacts with a hardening | curing agent. It contains a curable resin obtained by curing and reacting a reactive resin having a functional group with the curing agent, and the second protective layer has a number average molecular weight (Mn) of 8000 or more and a glass transition temperature ( Tg) contains a polyester resin having a temperature of 45 ° C. or more, the curing agent is an epoxy curing agent, the reactive resin is an amino-modified acrylic resin having a functional group that reacts with an epoxy group, and the amino Glass transition temperature of modified acrylic resin Tg) is characterized in that at 60 ° C. or higher.

In the protective layer transfer sheet of one embodiment, the reactive resin having a functional group that reacts with the curing agent may be an acrylic polyol resin having a glass transition temperature (Tg) of 50 ° C. or higher.

Moreover, 15000 or more and 70000 or less may be sufficient as the weight average molecular weight (Mw) of the said reactive resin.

Further, the present invention for solving the above problems is an intermediate transfer medium in which a transfer layer is provided on one surface of a substrate so as to be peelable from the substrate, and the transfer layer is formed on the substrate side. The first protective layer, the second protective layer in direct contact with the first protective layer, and the receiving layer are laminated in this order, and the first protective layer reacts with the curing agent. The second protective layer has a number average molecular weight (Mn) of 8000 or more, and has a glass transition temperature. (Tg) contains a polyester resin of 45 ° C. or higher , the curing agent is an epoxy curing agent, the reactive resin is an amino-modified acrylic resin having a functional group that reacts with an epoxy group, Glass transition temperature of amino-modified acrylic resin (Tg) of is characterized in that at 60 ° C. or higher.

Claims (7)

A protective layer transfer sheet provided with a transferable protective layer on one surface of the base material so as to be peelable from the base material,
The transferable protective layer has a laminated structure in which a first protective layer and a second protective layer in direct contact with the first protective layer are provided in this order from the base material side,
The first protective layer contains a curable resin in which a reactive resin having a functional group that reacts with a curing agent is cured and reacted with the curing agent,
The protective layer transfer sheet, wherein the second protective layer contains a polyester resin having a number average molecular weight (Mn) of 8000 or more and a glass transition temperature (Tg) of 45 ° C or more.   The protective layer transfer sheet according to claim 1, wherein the reactive resin having a functional group that reacts with the curing agent is an acrylic polyol resin having a glass transition temperature (Tg) of 50 ° C. or more. The curing agent is an epoxy curing agent;
The protection according to claim 1, wherein the reactive resin is a reactive resin having a functional group that reacts with an epoxy group, and the glass transition temperature (Tg) of the reactive resin is 60 ° C or higher. Layer transfer sheet.   4. The protective layer transfer sheet according to claim 3, wherein the reactive resin having a functional group that reacts with the epoxy group has a weight average molecular weight (Mw) of 15000 or more and 70000 or less.   The protective layer transfer sheet according to claim 3 or 4, wherein the reactive resin having a functional group that reacts with the epoxy group is an amino-modified acrylic resin.   The protective layer transfer sheet according to any one of claims 1 to 5, wherein a content of the polyester resin is 30% by mass or more based on a total solid content of the second protective layer. An intermediate transfer medium in which a transfer layer is provided on one surface of a base material so as to be peelable from the base material,
The transfer layer has a laminated structure in which a first protective layer, a second protective layer that is in direct contact with the first protective layer, and a receiving layer are laminated in this order from the base material side,
The first protective layer contains a curable resin in which a reactive resin having a functional group that reacts with a curing agent is cured and reacted with the curing agent,
The intermediate transfer medium, wherein the second protective layer contains a polyester resin having a number average molecular weight (Mn) of 8000 or more and a glass transition temperature (Tg) of 45 ° C or more.

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