JP2014080016A - Intermediate transfer medium - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an intermediate transfer medium and a protective layer transfer sheet, which has a good peel-off property when removing a transfer layer of a predetermined area and from which a highly durable printed material can be obtained.SOLUTION: An intermediate transfer medium 10 includes a protective layer 3 and a reception layer 4 laminated on one surface of a substrate sheet 1. The protective layer 3 includes a kneaded material of two or more binder resins having different number average molecular weight (Mn). The sum total (Σ) of the number average molecular weight (Mn) of each component multiplied by respective content ratio is within a range of 3000-17000.

Description

  The present invention relates to an intermediate transfer medium, and more specifically, it is possible to obtain a printed material having good peel-off property and high durability when a transfer layer including a protective layer and a receiving layer is removed by a peel-off layer of a thermal transfer sheet. The present invention relates to a possible intermediate transfer medium.

  Conventionally, a thermal transfer method has been widely used as a simple printing method. In the thermal transfer method, a thermal transfer sheet provided with a color material layer on one surface of a base sheet and a thermal transfer image receiving sheet provided with an image receiving layer as necessary are superposed, and the thermal transfer sheet is heated by a heating means such as a thermal head. In this method, an image is formed on a thermal transfer image receiving sheet by heating the back surface of the image to an image and selectively transferring the color material contained in the color material layer.

  Thermal transfer methods are classified into a melt transfer method and a sublimation transfer method. The melt transfer method uses a thermal transfer sheet in which a heat melt ink layer in which a color material such as a pigment is dispersed in a binder such as a heat meltable wax or resin is supported on a base sheet such as a PET film, and heats a thermal head or the like. In this image forming method, energy is applied to the means in accordance with image information, and a color material is transferred together with a binder onto a thermal transfer image receiving sheet such as paper or a plastic sheet. An image obtained by the melt transfer method has a high density and excellent sharpness, and is suitable for recording binary images such as characters.

  On the other hand, the sublimation transfer method uses a thermal transfer sheet in which a dye layer in which a dye that transfers heat by sublimation is dissolved or dispersed in a resin binder is supported on a base sheet such as a PET film, and is used as a heating means such as a thermal head. This is an image forming method in which energy corresponding to image information is applied and a dye alone is transferred and transferred onto a base sheet such as paper or plastic (on a thermal transfer image receiving sheet provided with a dye receiving layer as required). . In the sublimation transfer method, the amount of dye transfer can be controlled in accordance with the amount of energy applied, so that it is possible to form a gradation image in which the image density is controlled for each dot of the thermal head. Further, since the color material to be used is a dye, the formed image is transparent, and the reproducibility of intermediate colors when dyes of different colors are superimposed is excellent. Therefore, when using thermal transfer sheets of different colors such as yellow, magenta, cyan, black, etc., and transferring each color dye on the thermal transfer image receiving sheet, high-quality photographic tone full-color images with excellent reproducibility of intermediate colors can be obtained. Formation is possible.

  Due to the development of various hardware and software related to multimedia, this thermal transfer method is a full-color hard copy system for analog images such as digital graphics and video such as still images by computer graphics, satellite communications and CD-ROM. As the market is expanding. The specific application of the thermal transfer image receiving sheet by this thermal transfer method is diverse. Typical examples include printing proofs, image output, CAD / CAM design and design output, various medical analytical instruments such as CT scans and endoscopic cameras, measuring instrument output applications and instant As an alternative to photos, output of ID cards, ID cards, credit cards, other face photos on cards, etc., as well as composite photos and amusement photos at amusement facilities such as amusement parks, game centers, museums, and aquariums Etc.

  With the diversification of uses of the above-mentioned thermal transfer image receiving sheet, there is an increasing demand for forming a thermal transfer image on an arbitrary object. Normally, a dedicated thermal transfer image-receiving sheet provided with a receiving layer on a substrate is used as an object for forming a thermal transfer image. However, in this case, the substrate and the like are restricted. Under such circumstances, as shown in Patent Document 1, an intermediate transfer medium in which a receiving layer is provided on a substrate in a detachable manner has been proposed. According to this intermediate transfer medium, using a thermal transfer sheet having a dye layer, the dye is transferred to the receptor layer to form an image, and then the intermediate transfer medium is heated to place the receptor layer on an arbitrary transfer target. Therefore, it is possible to form a thermal transfer image without being restricted by the transfer target.

  In addition, since the intermediate transfer medium can transfer the receiving layer to an arbitrary transfer target, the color material is difficult to migrate and the transfer target that cannot directly form a high-quality image, or the color material layer during thermal transfer. It is preferably used for a transfer medium that is easily fused. For this reason, the intermediate transfer medium is preferably used for creating an identification card such as a passport or a printed matter such as a credit card / ID card.

  Depending on the type of card, there may be inconvenient areas on the same side of the receiving layer transfer when the IC chip part, magnetic stripe part, transmitting / receiving antenna part, signature part, etc. are covered with the receiving layer from the intermediate transfer medium. Yes.

  Under such circumstances, in the stage before transferring the receiving layer onto the transferred body, the region that is inconvenient if it is covered with the receiving layer and the outer peripheral portion of the receiving layer transferred onto the transferred body are Attempts have been made to remove by a peel-off layer provided on the substrate of the thermal transfer sheet. For example, in Patent Document 2, a peel-off layer is provided in advance on a base material of a thermal transfer sheet, and the peel-off layer and the transfer portion of the intermediate transfer medium are overlapped and heated so that the transfer portion in a predetermined area is intermediate transferred. An image forming method, a thermal transfer sheet, and a printed matter that prevent transfer to a transfer medium by being removed from the medium are described.

  By the way, a thermal transfer image formed using the above-mentioned intermediate transfer medium, in other words, an image is formed on the outermost surface of a printed matter obtained by transferring a receiving layer on which an image is formed on a transfer target. As a result, it has a weak point that lacks durability such as weather resistance, friction resistance and chemical resistance. Therefore, in recent years, as shown in Patent Document 3, an intermediate transfer medium in which a release layer, a protective layer, and a receiving layer / adhesive layer are provided on a substrate has been proposed. According to this intermediate transfer medium, since a protective layer is formed on the surface of the thermal transfer image, durability can be imparted to the thermal transfer image.

JP-A-62-238791 JP 2003-326865 A JP 2004-351656 A

  However, the durability of the protective layer of the intermediate transfer medium proposed in Patent Document 3 has come to satisfy the requirements of fields that require extremely high durability, such as identification cards, ID cards, and credit cards. Not in.

  In addition, when a predetermined area of the transfer layer including the receiving layer and the protective layer on which the image is formed is removed from the intermediate transfer medium using the peel-off layer of the thermal transfer sheet, the peel-off property of the transfer layer is low. The transfer layer cannot be removed according to the shape, and there is a problem that the transfer layer in the area that originally needs to remain on the intermediate transfer medium is removed, or a part of the transfer layer is intermediate in the area to be removed. There may be a problem of remaining on the transfer medium side. Accordingly, the protective layer of the intermediate transfer medium needs to have not only high durability but also good peel-off properties. However, the durability of the protective layer and the peel-off property of the transfer layer including the protective layer are in a trade-off relationship. When an attempt is made to improve the durability of the protective layer, the peel-off property of the transfer layer including the protective layer is descend. From this, it is the present condition that one endurance and peel-off property cannot be satisfied with one protective layer. Furthermore, in addition to the above good peel-off properties, the transfer layer including the protective layer is required to have good transferability when re-transferred onto the transfer target. Even if it is improved, the peel-off property cannot be satisfied.

  The present invention has been made in view of such a situation. The peel-off property when a part of the transfer layer including the protective layer is removed by the peel-off layer is good, and the transfer layer is transferred to the transfer target. It is a main object to provide an intermediate transfer medium that can impart high durability and can re-transfer a transfer layer onto a transfer target without any problem.

  The present invention for solving the above problems is an intermediate transfer medium in which a protective layer and a receiving layer are laminated on one surface of a base sheet, wherein the protective layer has two components having different number average molecular weights (Mn). The total (Σ) including the above-mentioned binder resin kneaded product and adding the number average molecular weights (Mn) of the respective components integrated by the respective content ratios is in the range of 3000 to 17,000. And

  Further, at least one of the two or more binder resins may be a polyester resin.

  The two or more component binder resins include a polyester resin A having a number average molecular weight (Mn) of 2000 or more and 10,000 or less and a polyester resin B having a number average molecular weight (Mn) of more than 10,000 and 25,000 or less. It may be.

  The binder resin having two or more components includes a polyester resin A1 having a number average molecular weight (Mn) of 2000 or more and 4000 or less, a polyester resin A2 having a number average molecular weight of more than 4000 and 10,000 or less, and a number average molecular weight (Mn ) May be greater than 10,000 and less than or equal to 25,000.

  Moreover, you may have a peeling layer between the said base material sheet and the said protective layer.

  According to the intermediate transfer medium of the present invention, the peel-off property when a desired region of the transfer layer is removed by the peel-off layer of the thermal transfer sheet is good, and the transfer layer can be re-transferred onto the transfer medium without any problem. it can. Furthermore, high durability can be imparted to the transfer object onto which the transfer layer has been retransferred.

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. It is a schematic plan view which shows embodiment of the thermal transfer sheet used by this invention. FIG. 2 is a schematic diagram for explaining an intermediate transfer medium of the present invention. 1 is a schematic plan view of an intermediate transfer medium of the present invention. FIG. 2 is a schematic diagram for explaining an intermediate transfer medium of the present invention. It is explanatory drawing which shows the measurement position of an obi amount.

<< Intermediate transfer medium >>
Next, an embodiment of the intermediate transfer medium of the present invention will be described in detail. FIG. 1 is a schematic sectional view showing an example of the intermediate transfer medium of the present invention. As shown in FIG. 1, the intermediate transfer medium 10 of the present invention has a configuration in which a base sheet 1 and a transfer layer 2 are provided on one surface of the base sheet 1. The transfer layer 2 has a laminated structure in which the protective layer 3 and the receiving layer 4 are laminated in this order from the base sheet 1 side. The protective layer 3 and the receiving layer 4 are layers that are transferred onto the transfer medium during thermal transfer, and constitute the transfer layer 2.

  FIG. 2 shows another embodiment of the intermediate transfer medium of the present invention. The intermediate transfer medium 10 in the form shown in FIG. 2 has a laminated structure in which a release layer 5, a protective layer 3, and a receiving layer 4 are laminated on one surface of a substrate sheet 1. The release layer 5 is an arbitrary layer that is transferred onto the transfer medium during thermal transfer together with the protective layer 3 and the receiving layer 4, and is a layer that constitutes the transfer layer 2.

  Hereinafter, each layer constituting the intermediate transfer medium of the present invention will be described in detail.

(Substrate sheet)
The base sheet 1 in the intermediate transfer medium has a function of holding the transfer layer 2 and heat is applied at the time of thermal transfer. Therefore, the base sheet 1 has a mechanical strength that does not hinder handling even in a heated state. preferable. The material of such a base sheet is not particularly limited. For example, highly stretched polyester such as polyethylene terephthalate and polyethylene naphthalate, polypropylene, polycarbonate, cellulose acetate, polyethylene derivatives, polyamide, polymethylpentene and the like are stretched. Or an unstretched film is mentioned. Moreover, the composite film which laminated | stacked 2 or more types of these materials can also be used. The thickness of the base sheet 1 can be appropriately selected according to the material so that the strength, heat resistance and the like are appropriate, but usually a thickness of about 1 μm to 100 μm is preferably used.

(Transfer layer)
As shown in FIG. 1, a transfer layer 2 is formed on a base sheet 1 so as to be peelable from the base sheet 1 during thermal transfer. The transfer layer 2 includes at least the protective layer 3 and the receiving layer 4 that are essential components of the intermediate transfer medium 10 of the present invention, and is a layer that is peeled off from the base sheet 1 during thermal transfer and transferred to a transfer target.

(Protective layer)
As shown in FIG. 1, protection between the base sheet 1 and the receiving layer 4 (between the release layer 5 and the receiving layer 4 in FIG. 2) is an essential configuration of the intermediate transfer medium 10 of the present invention. Layer 3 is provided. In the present invention, in order to satisfy both the peel-off property of the transfer layer 2 and the durability of the protective layer 3, the protective layer 3 is made of a kneaded mixture of two or more binder resins having different number average molecular weights (Mn). In addition, the sum (Σ) when the number average molecular weight (Mn) of each component is added by integrating each content ratio (mass basis) is in the range of 3000 to 17000. . According to the transfer layer 2 including the protective layer 3 having this feature, the peel-off property of the transfer layer 2 is good, and any desired peel-off layer of the thermal transfer sheet can be obtained according to the desired shape. This area can be removed by the peel-off layer of the thermal transfer sheet. Moreover, durability of the protective layer 3 can be improved. The peel-off layer of the thermal transfer sheet will be described later. The number average molecular weight (Mn) in the present invention is a number average molecular weight in terms of polystyrene measured by gel permeation chromatography (GPC). Further, the glass transition temperature (Tg) in the present invention is a temperature determined based on measurement of a calorie change (DSC method) by DSC (differential scanning calorimetry).

  As described above, the present invention is provided on the condition that a kneaded product of two or more binder resins is included, and a protective layer containing only one kind of binder resin is excluded from the present invention. . In the case of a protective layer containing only one kind of binder resin, both the peel-off property and durability are obtained even if the number average molecular weight (Mn) of the one kind of binder resin is in the range of 3000 to 17,000. It is because it cannot be satisfied. The sum (Σ) when including the kneaded product of the binder resin of two or more components and adding the number average molecular weight (Mn) of each component integrated with each content ratio (mass basis) is 3000 or more and 17,000 or less. As a result, the detailed mechanism for improving the peel-off property and durability has not been clarified at present, but in the present invention, starting from the above summation (Σ), the summation (Σ), Since a binder resin with a high number average molecular weight (Mn) and a binder resin with a low number average molecular weight (Mn) are included, a balance between peel-off property and durability is achieved by the synergistic effect of the binder resin of two or more components, Thereby, it is assumed that both the peel-off property and the durability can be satisfied. Even if this mechanism is not used, the protective layer of the present invention is superior in both the peel-off property of the transfer layer 2 and the durability of the protective layer 3 as compared with a protective layer containing only one binder resin. This is also apparent from the results of Examples and Comparative Examples described later.

  In the present specification, “peel-off” means that the transfer layer 2 of the intermediate transfer medium 10 used in the present invention and the peel-off layer 11 of the thermal transfer sheet are overlapped with each other as shown in FIG. Is applied, and the peel-off layer 11 removes the transfer layer 2 at a position corresponding to a region to which heat is applied (hereinafter referred to as a transfer region). “Peel-off property” is an index indicating whether only the transfer layer 2 corresponding to the transfer region 9 can be accurately removed from the intermediate transfer medium. On the other hand, the “transferability” of the intermediate transfer medium indicates whether the transfer layer corresponding to the transfer region 9 can be accurately transferred onto the transfer medium when the back side of the intermediate transfer medium is heated. It is an indicator to show. In other words, “peel-off” indicates the characteristics when removing the transfer layer, whereas “transfer” indicates the characteristics when transferring the transfer layer. Is different. The present invention aims to improve this “peel-off property”. In the present invention, improvement of the “peel off property” of the transfer layer 2 is considered as one of the problems. However, in order to improve the “peel off property”, the above “transfer property” of the transfer layer 2 is not sacrificed. . That is, according to the intermediate transfer medium having the protective layer 3 having the above characteristics, the peel-off property of the transfer layer 2 including the protective layer 3 is good, and the transfer layer 2 after peel-off can be placed on the transfer target without problems. Can be re-transferred. Note that “transfer properties” and “peel off properties” are different characteristics, and even if a conventionally known protective layer that is simply excellent in transfer properties is adopted, “peel off properties” cannot be satisfied. .

  When the peel-off property of the intermediate transfer medium is low, of the transfer layer corresponding to the transfer region 9, the transfer located near the boundary between the transfer region 9 and the non-heated region (hereinafter referred to as a non-transfer region). There is a problem that the layer is not accurately removed, and a part of the transfer layer that should be originally removed remains on the intermediate transfer medium side. Or, starting from the boundary between the transfer area 9 and the non-transfer area, a part of the transfer layer corresponding to the non-transfer area is removed by dragging the transfer layer corresponding to the non-transfer area. The transfer layer that should originally remain on the intermediate transfer medium side, that is, the transfer layer corresponding to the non-transfer area, may be removed together with the transfer layer corresponding to the transfer area 9.

  If the total sum (Σ) is less than 3000, the peel-off property is good, but the durability such as mechanical strength cannot be sufficiently satisfied. On the other hand, when the total sum (Σ) exceeds 17000, the durability is satisfactory, but the peel-off property of the transfer layer 2 decreases, and when the desired portion of the transfer layer 2 is removed, the transfer is performed in accordance with the target shape. Layer 2 cannot be removed.

  If the sum (Σ) satisfies the above conditions, both peel-off property and durability can be satisfied. However, in applications where higher durability and peel-off properties are required, the protective layer 3 has a number average. It is preferable to contain a binder resin having a molecular weight (Mn) of 3000 or more and 30000 or less. In applications where even higher durability is required, it is preferable to contain a binder resin having a number average molecular weight (Mn) of 12,000 or more.

  Although there is no limitation in particular about content of the binder resin which comprises the protective layer 3, Inclusion of the kneaded material of the 2 or more component binder resin from which total ((SIGMA)) is 3000-17000 with respect to the solid content total amount of the protective layer 3 When the amount is less than 20% by mass, the peel-off property of the transfer layer 2 and the durability of the protective layer 3 tend to decrease. Therefore, in consideration of this point, it is preferable that a kneaded mixture of two or more components of the total amount (Σ) of 3000 or more and 17000 or less with respect to the total solid content of the protective layer 3 is 20% by mass or more. More preferably, the content is 30% by mass or more. There is no particular upper limit on the content of the kneaded product of two or more components of the binder resin having a total (Σ) of 3000 or more and 17000 or less, and the upper limit is 100% by mass.

  The binder resin component constituting the protective layer 3 of the present invention is not particularly limited, and includes a kneaded mixture of two or more binder resins having different number average molecular weights (Mn), and the number average molecular weight (Mn) of each component i is determined. A resin component having a total sum (Σ) of 3000 to 17000, which is obtained by adding up the values accumulated at the respective content ratios r, can be appropriately selected and used. For example, polyester resin, polyester urethane resin, polycarbonate resin, acrylic resin, ultraviolet absorbing resin, epoxy resin, acrylic urethane resin, butyral resin, polyamide resin, vinyl chloride resin, phenoxy resin, bisphenol resin that satisfy the above conditions A resin obtained by modifying the resin with silicone, a mixture of these resins, an ionizing radiation curable resin, an ultraviolet absorbing resin, and the like can be given. Especially, in this invention, it is preferable that at least 1 binder resin is a polyester-type resin, such as a polyester resin and a polyester urethane resin, among 2 or more component binder resins. The polyester resin or polyester urethane resin may be a copolymer with another thermoplastic resin.

  Next, a more preferable form of the protective layer will be described. The protective layer 3 in a preferred form includes a polyester resin A having a number average molecular weight (Mn) of 2000 or more and 10,000 or less, and a polyester resin B having a number average molecular weight (Mn) of more than 10,000 and 25,000 or less. According to the protective layer 3 including the polyester resin A and the polyester resin B, the total sum (Σ) satisfies the above conditions, and the durability and peel-off property of the transfer layer 2 are extremely good. Can do. Specifically, the polyester resin A is a binder resin for the purpose of further improving the peel-off property, and the polyester resin B is a binder resin for the purpose of further improving the durability. For further improvement of durability and peel-off property, it is preferable to use a polyester resin A having a glass transition temperature (Tg) of 35 ° C to 60 ° C. The same applies to preferable glass transition temperatures (Tg) of the polyester resin A1 and the polyester resin A2 described later.

  In addition, when it is set as the protective layer containing the polyester resin whose number average molecular weight (Mn) is less than 2000 and the polyester resin B instead of the polyester resin A, the polyester resin A and the polyester resin B are included. Compared with a protective layer, durability of a protective layer becomes low. That is, when the polyester resin having a number average molecular weight (Mn) of less than 2000 and the protective layer containing the polyester resin B is used, the peel-off property can be sufficiently improved, but the number average molecular weight (Mn) is The durability is lowered by a polyester resin of less than 2000, and it is difficult to sufficiently improve the lowered durability by the polyester resin B.

  Further, in the above embodiment, when the polyester resin B is replaced with the polyester resin A and the polyester resin A, the polyester resin A and the polyester resin A, the number average molecular weight (Mn) is more than 25000. Compared with the protective layer containing resin B, the peel-off property is low. That is, when the protective layer includes the polyester resin A and a polyester resin having a number average molecular weight (Mn) exceeding 25000, the durability can be sufficiently improved, but the number average molecular weight (Mn) is The peel-off property is lowered by the polyester resin exceeding 25000, and it is difficult to sufficiently improve the lowered peel-off property by the polyester resin A.

  The protective layer containing the polyester-based resin A and the polyester-based resin B is a combination of an optimized binder resin that can sufficiently satisfy both the improvement in durability and the improvement in peel-off property. It can be said that this is a form. Further, the protective layer 3 in a preferred form may contain any other binder resin together with the polyester resin A and the polyester resin B, but the total mass of the polyester resin A and the polyester resin B is The total solid content of the protective layer 3 is preferably 20% by mass or more, and particularly preferably 30% by mass or more.

  Further, when the polyester resin A and the polyester resin B are included in the protective layer 3, the content of the polyester resin A is 10% by mass with respect to the total mass of the polyester resin A and the polyester resin B. The content is preferably 70% by mass or less, more preferably more than 30% by mass and 70% by mass or less. When the content of the polyester resin A is less than 10% by mass, the peel-off property tends to decrease. On the other hand, when the content exceeds 70% by mass, the content of the polyester resin B is small accordingly. The durability tends to decrease.

  In addition to the polyester resin B, a polyester resin A1 having a number average molecular weight (Mn) of 2000 or more and 4000 or less and a polyester resin A2 having a number average molecular weight (Mn) of more than 4000 and 10,000 or less are used. The peel-off property can be further improved by appropriately adjusting the contents of A1 and polyester resin A2. In addition, transferability and durability can be sufficiently satisfied. Therefore, it can be said that the protective layer 3 containing at least the three polyester-based resins as the binder resin having two or more components is the most preferable embodiment in the present invention. The preferable content of the polyester resin A1 is 5% by mass or more and 65% by mass or less with respect to the total mass of the polyester resin A1, the polyester resin A2, and the polyester resin B. The preferable content of the polyester resin A2 is 5% by mass or more and 65% by mass or less with respect to the total mass of the polyester resin A1, the polyester resin A2, and the polyester resin B. The total mass of the polyester resin A1 and the polyester resin A2 with respect to the total mass of the polyester resin A1, the polyester resin A2, and the polyester resin B is preferably 10% by mass or more and 70% by mass or less.

  This does not limit the component of the resin contained in the protective layer 3 and the physical property value of each resin. As described above, the sum of the binder resins contained in the protective layer 3 (Σ ) Satisfies the above conditions, the durability of the protective layer 3 and the peel-off property of the transfer layer 2 can be improved as compared with the conventional protective layer.

  Moreover, the sum total which added the thing which kneaded the binder resin of 2 or more components from which number average molecular weight (Mn) differs, and integrated | accumulated the number average molecular weight (Mn) of each component i by each content ratio r (mass basis). An ionizing radiation curable resin in which (Σ) satisfies the above conditions is suitable as a binder resin contained in the protective layer 3 in terms of excellent plasticizer resistance and scratch resistance. The ionizing radiation curable resin is not particularly limited, and can be appropriately selected and used from conventionally known ionizing radiation curable resins. For example, a radical polymerizable polymer or oligomer is crosslinked by irradiation with ionizing radiation, It can be hardened, added with a photopolymerization initiator as necessary, and polymerized and cross-linked with an electron beam or ultraviolet rays.

  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.

  The protective layer 3 is a mixture of two or more binder resins having a total (Σ) of 3000 or more and 17000 or less, as well as various fillers, fluorescent whitening agents, ultraviolet absorbers for improving weather resistance, and the like. The material may be contained.

(Other optional ingredients)
The protective layer 3 may further contain other optional components. For example, in the form shown in FIG. 1, the protective layer 3 is required to be peelable from the base sheet 1. Therefore, in this embodiment, it is preferable that the protective layer 3 contains a peelable component. Further, the role of peelability can be supplemented by a separate layer as shown in FIG. For example, a release layer 5 that can satisfy the peelability may be provided between the base sheet 1 and the protective layer 3. In this case, it is not always necessary that the protective layer 3 contains a component having releasability from the substrate.

"Ingredients with releasability from substrate sheet"
Examples of the component excellent in peelability from the base sheet 1 include cellulose derivatives such as ethyl cellulose, nitrocellulose, and cellulose acetate, acrylic resins such as polymethyl methacrylate, polyethyl methacrylate, and polybutyl acrylate, and polychlorinated salts. Thermosetting of vinyl copolymer thermoplastic resin such as vinyl, vinyl chloride-vinyl acetate copolymer, polyvinyl butyral, saturated or unsaturated polyester resin, polyurethane resin, thermally crosslinkable epoxy-amino resin, amino alkyd resin Examples include mold resins, silicone waxes, silicone resins, silicone-modified resins, fluorine resins, fluorine-modified resins, and polyvinyl alcohol.

  In the present invention, since the peel-off property of the transfer layer 2 is good, the thickness of the transfer layer 2 can be made larger than the thickness of the conventional protective layer, and the total (Σ) is 2 or more components of 3000 to 17000. In addition to the durability imparted by the kneaded product of the binder resin, an improvement in durability by increasing the thickness can be expected. Even when the thickness of the protective layer 3 is reduced, the durability of the protective layer 3 can be satisfied by a kneaded mixture of two or more components of the binder resin having a total sum (Σ) of 3000 or more and 17000 or less. The thickness of the protective layer 3 is not particularly limited. However, when the thickness of the protective layer 3 exceeds 30 μm, the peel-off property of the transfer layer 2 including the protective layer 3 tends to decrease, and when the thickness is less than 1 μm, The durability of the protective layer 3 tends to decrease. Therefore, considering this point, the thickness of the protective layer 3 is preferably 1 μm or more and 30 μm or less.

  As a method for forming the protective layer 3, a kneaded mixture of two or more binder resins having a total sum (Σ) of 3000 or more and 17000 or less, other binder resins added as necessary, and various materials are appropriately used. A protective layer-forming coating solution is prepared by dissolving or dispersing in a solvent, and this is applied to the substrate sheet 1 (the peeling layer 5 provided on the substrate sheet 1 as necessary) by a gravure printing method, a screen. It can be formed by applying and drying by means of a printing method or a reverse coating method using a gravure plate.

(Receptive layer)
As shown in FIGS. 1 and 2, a receiving layer 4 is provided on the protective layer 3. On this receiving layer, an image is formed by thermal transfer from a thermal transfer sheet having a color material layer by thermal transfer. Then, the transfer layer 2 of the intermediate transfer medium on which the image has been formed is retransferred onto the transfer target, and as a result, a printed matter in which the transfer layer 2 is provided on the transfer target is formed. For this reason, as a material for forming the receiving layer 4, a resin material that can easily receive a heat-transferable colorant 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.

  In the embodiment shown in FIGS. 1 and 2, since the receiving layer 4 is located on the outermost surface of the intermediate transfer medium, when the transfer layer in the predetermined area is removed by the peel-off layer of the thermal transfer sheet, or the predetermined area is set by the peel-off layer. When the transfer layer from which the toner is removed is retransferred onto the transfer target, the receiving layer 4 comes into direct contact with the peel-off layer or the transfer target. Therefore, when taking this form, it is preferable that the receiving layer 4 itself has adhesiveness. By imparting adhesiveness to the receiving layer 4, the adhesion between the peel-off layer of the thermal transfer sheet and the transfer layer 2 can be improved, and the peel-off property can be further improved. In addition, the transfer layer 2 can be retransferred onto the transfer medium with good adhesion. In addition, when the countermeasure for the adhesiveness with the transfer layer 2 is taken on the transfer target side, it is not always necessary that the receiving layer 4 itself has adhesiveness. Further, instead of imparting adhesiveness to the receiving layer 4 itself, an adhesive layer (not shown) may be provided on the receiving layer 4.

  Materials for the adhesive receiving layer 4 include vinyl chloride-vinyl acetate copolymer, acrylic resin, vinyl resin, polyester resin, urethane resin, polyamide resin, epoxy resin, rubber resin, ionomer. A resin material having adhesiveness such as a resin can be given. The same material can be used for any adhesive layer.

The receiving layer 4 is used for forming a receiving layer by adding one or more materials selected from the above materials and various additives as necessary, and dissolving or dispersing them in an appropriate solvent such as water or an organic solvent. A coating solution can be prepared, and this can be formed by applying and drying by means of a gravure printing method, a screen printing method or a reverse coating method using a gravure plate. Its coating amount is 1g / m ² ~10g / m ² approximately in a dry state.

(Peeling layer)
For the purpose of improving the peelability of the transfer layer 2 from the base sheet 1 and the peel-off property, a release layer 5 may be provided between the base sheet 1 and the protective layer 3 as shown in FIG. The release layer 5 is a layer that is removed together with the protective layer 3 and the receiving layer 4 by the peel-off layer of the thermal transfer sheet. Further, when the transfer layer 2 is transferred onto the transfer target, it is a layer transferred onto the transfer target together with the protective layer 3 and the receiving layer 4, and is an arbitrary layer constituting the transfer layer 2. Providing the release layer 5 is preferable in that the peelability of the transfer layer 2 can be improved and the durability of the printed matter can be further improved by a synergistic effect with the protective layer 3. In addition, the peel-off property can be further improved by the presence of the release layer. The mechanism by which the peel-off property of the transfer layer 2 is improved by the presence of the release layer is not always clear at present, but the peel-off property of the transfer layer 2 is that of the protective layer 3 when the transfer layer 2 is removed by the peel-off layer. It is also related to the peelability from the base sheet 1, and as a result, the peel-off property of the transfer layer 2 is further improved by increasing the peelability of the protective layer 3 at the initial peel-off time by the release layer. It is considered a thing.

  Examples of the material for the release layer 5 include conventionally known materials such as cellulose derivatives such as ethyl cellulose, nitrocellulose, and cellulose acetate, acrylic resins such as polymethyl methacrylate, polyethyl methacrylate, and polybutyl acrylate, and polyvinyl chloride. , Thermoplastic resins of vinyl copolymers such as vinyl chloride-vinyl acetate copolymer and polyvinyl butyral, thermosetting types such as saturated or unsaturated polyester resins, polyurethane resins, thermally crosslinkable epoxy-amino resins, amino alkyd resins Resin, silicone wax, silicone resin, silicone-modified resin, fluorine resin, fluorine-modified resin, polyvinyl alcohol and the like. The release layer 5 preferably contains a filler such as micro silica or polyethylene wax in order to improve the peel-off property. Further, the release layer 5 may be made of one kind of resin, or may be made of two or more kinds of resins. Further, the release layer 5 may be formed using a crosslinking agent such as an isocyanate compound, a catalyst such as a tin catalyst, and an aluminum catalyst in addition to the resin exemplified above.

  The release layer 5 provided as necessary is obtained by dispersing or dissolving the above resin in a solvent and applying it to at least a part of the base sheet 1 by a known coating method such as roll coating, gravure coating, bar coating or the like. It can be formed by drying. The thickness of the release layer 5 is usually about 0.1 μm to 5 μm, preferably about 0.5 μm to 2 μm.

(Plasticizer resistant layer)
In order to improve the plasticizer resistance of the transfer material onto which the transfer layer 2 has been transferred, between the base sheet 1 and the protective layer 3 (if the release layer 5 is provided, the release layer 5 and the protection A plasticizer-resistant layer (not shown) may be provided between the layer 3). 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, a polyvinyl butyral resin, or a polyvinyl acetal resin having a saponification degree within this range in the plasticizer-resistant layer, the plasticizer resistance of the transfer layer 2 can be further improved. In addition, the saponification degree in this invention means the value which divided the number of moles of the vinyl alcohol structure in a polymer by the number of moles of all the monomers in a polymer. The material that repels the plasticizer component and the material in which the plasticizer component hardly reaches the image is preferably contained within a range of 20% by mass to 100% by mass with respect to the total solid content of the plasticizer-resistant layer.

  In addition, the plasticizer-resistant layer may include, for example, a lubricant, a plasticizer, a filler, an antistatic agent, an antiblocking agent, a crosslinking agent, an antioxidant, an ultraviolet absorber, a light stabilizer, a dye, Colorants such as pigments, fluorescent brighteners, other additives, and the like may be added. The plasticizer-resistant layer provided as necessary is a plasticizer-resistant material prepared by dissolving or dispersing one or more of the above-exemplified materials and various materials added as necessary with an appropriate solvent. A layer coating solution can be prepared, and this can be applied and dried on the substrate sheet 1 or the release layer 5 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.

(Back layer)
In addition, a back layer (not shown) is provided on a surface different from the surface on which the protective layer 3 of the base sheet 1 is provided to improve heat resistance and running performance of the thermal head during printing. Also good. The back layer has an arbitrary configuration in the intermediate transfer medium 10 of the present invention.

  The back layer 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 has a wax, a higher fatty acid amide, a phosphoric ester compound, a metal soap, a silicone oil, a surfactant release agent, etc., a fluororesin for the purpose of improving slip properties. It is preferable that various additives such as organic particles such as silica, clay, talc, and calcium carbonate are contained, and it is particularly preferable that at least one of phosphoric acid ester or metal soap is contained. .

For example, the back layer 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 sheet 1 by 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.

<< Thermal transfer sheet >>
Next, the thermal transfer sheet used when removing the transfer layer of the intermediate transfer medium 10 of the present invention will be described. FIG. 3 is a schematic plan view showing an embodiment of the thermal transfer sheet 20 used in the present invention. As shown in FIG. 3, the thermal transfer sheet used when removing the transfer layer 2 in combination with the intermediate transfer medium 10 of the present invention has yellow (Y), magenta (M), cyan on the same surface of the base material layer. Each dye layer 12 of (C), a molten layer 13 of black (BK), and a peel-off layer 11 are repeatedly formed in the surface order and applied separately. The thermal transfer sheet does not have the yellow (Y), magenta (M), and cyan (C) dye layers 12 and the black (BK) melt layer 13, and only the peel-off layer is provided on the base material layer. The obtained thermal transfer sheet can also be used. A back layer can be provided on the other surface of the base material layer in order to prevent fusion with a heating means such as a thermal head and to improve slidability.

  Hereinafter, each layer constituting the thermal transfer sheet 20 will be described.

(Base material layer)
The base material layer 14 constituting the thermal transfer sheet is not particularly limited. Specific examples of preferred substrate layers include thin paper such as glassine paper, condenser paper or paraffin paper, or heat resistance such as polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, polyphenylene sulfide, polyether ketone or polyether sulfone. And stretched or unstretched films of plastics such as polyester, polypropylene, polycarbonate, cellulose acetate, polyethylene derivatives, polyvinyl chloride, polyvinylidene chloride, polystyrene, polyamide, polyimide, polymethylpentene, or ionomer. Moreover, the composite film which laminated | stacked 2 or more types of these materials can also be used. Although the thickness of a base material layer can be suitably selected according to material so that the intensity | strength, heat resistance, etc. may become appropriate, the thing about 1 micrometer-about 25 micrometers is normally used preferably.

(Back layer)
Examples of the resin used for the back layer 15 include cellulose resins such as ethyl cellulose, hydroxy cellulose, hydroxypropyl cellulose, methyl cellulose, cellulose acetate, cellulose acetate butyrate, nitrocellulose, polyvinyl alcohol, polyvinyl acetate, polyvinyl butyral, polyvinyl acetal, Vinyl resins such as polyvinyl pyrrolidone, acrylic resins such as polymethyl methacrylate, polyethyl acrylate, polyacrylamide, acrylonitrile-styrene copolymers, polyamide resins, polyvinyl toluene resins, coumarone indene resins, polyester resins, polyurethanes A simple substance or a mixture of natural or synthetic resins such as resin, silicone-modified or fluorine-modified urethane is used. In order to further increase the heat resistance of the back layer, among the above resins, a resin having a hydroxyl group reactive group may be used, and a polyisocyanate or the like may be used as a crosslinking agent to form a crosslinked resin layer. preferable.

  Further, in order to impart slidability with the thermal head, a solid or liquid release agent or lubricant may be added to the back surface layer 15 to provide heat-resistant lubricity. Examples of the release agent or lubricant include various waxes such as polyethylene wax and paraffin wax, higher aliphatic alcohols, organopolysiloxanes, anionic surfactants, cationic surfactants, amphoteric surfactants, nonionic surfactants. Activators, fluorosurfactants, organic carboxylic acids and derivatives thereof, fluororesins, silicone resins, fine particles of inorganic compounds such as talc, silica, and the like can be used. The amount of lubricant contained in the back layer is about 5% to 50% by mass, preferably about 10% to 30% by mass.

As described above, the means for forming the back layer 15 is prepared by dissolving or dispersing a release agent, a lubricant, or the like in the resin as necessary in a suitable solvent to prepare a coating solution. It is coated and dried by conventional coating means such as a gravure coater, roll coater, wire bar or the like. The coating amount of the back layer is 0.1g / m ² ~10g / m ² approximately in a dry state.

(Dye layer)
The sublimable dye layer 12 is formed from a coating liquid containing a sublimable dye, a binder resin, and other optional components. As the sublimation dye, the binder resin and the like, conventionally known ones can be used, and are not particularly limited. The dye layer can be formed by preparing a dye layer coating solution, and coating and drying the substrate layer by means of a gravure printing method or the like. The coating amount of the dye layer is 0.2g / m ² ~3g / m ² approximately in a dry state.

(Molten layer)
The molten layer 13 can be formed using the same hot-melt ink as in the prior art, and various additives are added as necessary. Conventionally known materials can be used for these materials and are not particularly limited. The molten layer is formed by applying a hot-melt ink on a base film using a method such as hot melt coating. The thickness of the molten layer to be formed is determined from the relationship between the required concentration and thermal sensitivity, and is usually preferably in the range of about 0.2 μm to 10 μm.

(Peel-off layer)
The peel-off layer 11 is provided on the base material layer and heated so as to be in contact with the transfer layer 2 of the intermediate transfer medium 10 to remove the transfer layer 2 in a predetermined region 9 from the intermediate transfer medium 10. . The peel-off layer can be composed of a conventionally known pressure-sensitive adhesive or heat-sensitive adhesive, but is more preferably formed from a thermoplastic resin having a glass transition temperature (Tg) of 50 ° C. to 120 ° C., for example, a vinyl chloride resin Adhesion during heating, such as vinyl chloride-vinyl acetate copolymer resin, acrylic resin, polyester resin, polyamide resin, styrene acrylic resin, styrene-vinyl chloride-vinyl acetate copolymer, butyral resin, epoxy resin, polyamide resin It is preferable to select a resin having an appropriate glass transition temperature from among the good resins. By removing the transfer layer 2 of the intermediate transfer medium 10 in advance using a peel-off layer, the transfer layer can be reliably prevented from being transferred to a non-transfer area such as an IC chip or a signature field on the transfer target 30. The function of the accessory 31 such as a column is not impaired.

If necessary, apply a coating solution to which an additive such as an inorganic or organic filler is added to the resin constituting the peel-off layer as described above by a known means such as gravure coating, gravure reverse coating, roll coating, etc. and by drying, preferably formed in the coating amount of dry ^{0.1g / m 2 ~5.0g / m 2} . When the coating amount of the peel-off layer is less than 0.1 g / m ² , the adhesiveness for peeling off the transfer layer of the intermediate transfer medium as the peel-off layer is almost lost, and in some cases, the thermal transfer sheet is cut. . On the other hand, if the amount of the peel-off layer applied is too large, the thermal sensitivity is insufficient, the adhesiveness of the intermediate transfer medium to the transfer layer is lowered, and there may be a portion where the transfer layer cannot be peeled off.

(Transfer)
The transfer layer 2 on which the thermal transfer image of the above-described intermediate transfer medium is formed is transferred onto the transfer target 30, and as a result, a printed matter having a thermal transfer image having various durability is obtained. The transfer target 30 to which the intermediate transfer medium of the present invention is applied is not particularly limited. For example, natural fiber paper, coated paper, tracing paper, plastic film that is not deformed by heat during transfer, glass, metal, ceramics, wood, Any material such as cloth may be used.

  Regarding the shape and use of the transferred object 30, stock certificates, securities, certificates, passbooks, boarding tickets, car horse tickets, stamps, stamps, appreciation tickets, admission tickets, tickets, etc., cash cards, credit cards, prepaid cards , Members cards, greeting cards, postcards, business cards, driver's licenses, cards such as IC cards, optical cards, cases such as cartons and containers, bags, forms, envelopes, tags, OHP sheets, slide films, bookmarks , Calendars, posters, brochures, menus, POP equipment, coasters, displays, nameplates, keyboards, cosmetics, watches, lighters and other accessories, stationery, report paper and other stationery, passports, small books, magazines and other booklets, building materials , Panel, emblem, key, cloth, clothing, footwear, radio, TV, calculator Device such as OA equipment, various types of swatches, the album also computer graphics output, medical image output, etc., do not ask type.

  It is preferable that an accessory 31 such as an IC chip, a signature part, a seal part, a holo CI mark part, etc. is provided on the surface of the transferred object 30 to give added value to the transferred object. This accessory is inconvenient if it is covered with the transfer layer 2 from the intermediate transfer medium 10, and if there is a transfer product in the accessory 31, the function of the accessory cannot be exhibited normally.

  FIG. 4 is a schematic view for explaining the intermediate transfer medium 10 of the present invention. As shown in FIG. 4, the other of the intermediate transfer medium 10 provided with the transfer layer 2 provided with a receiving layer, a protective layer, and the like, and the base material layer 14 provided with the back layer 15, which can be peeled on the base sheet 1 The thermal transfer sheet 20 provided with the peel-off layer 11 on the surface is superposed so that the peel-off layer 11 and the transfer layer 2 are in contact with each other and heated by the thermal head 16, so that the transfer layer 2 in a predetermined region 9 is removed from the intermediate transfer medium 10. Can be removed. A sublimation type or melt type thermal transfer image is formed in advance on the transfer layer 2 of the intermediate transfer medium 10.

  FIG. 5 is a schematic plan view of the intermediate transfer medium 10 of the present invention. As shown in FIG. 5, the intermediate transfer medium 10 is obtained by removing a predetermined region 9 of the transfer layer 2 having a receiving layer on which a thermal transfer image is formed.

  FIG. 6 is a schematic view for explaining the intermediate transfer medium of the present invention. As shown in FIG. 6, the removed region in the transfer layer 2 of the intermediate transfer medium 10 is a transfer layer from the intermediate transfer medium 10 provided with an accessory 31 such as an IC chip or a signature box in the transfer target 30. The transfer layer 2 is retransferred to the transfer target 30 by the heating means of the heat roll 17 in accordance with a region where inconvenience occurs when 2 is transferred. During the retransfer, the transfer layer 2 is not transferred onto the accessory 31 included in the transfer target 30.

  The thermal transfer image formation and the heating means for the peel-off layer and the transfer layer are not limited to the thermal head, and may be a heating means using a light source or a laser light source. Further, the heating means for retransferring the transfer layer 2 from which the predetermined area has been removed by the peel-off layer to the transfer target is not limited to the heat roll method, and may be a hot stamp method, a thermal head method, or the like.

  Incidentally, there is a problem due to transferability as one of the problems in the conventional image formation. If the transferability of the transfer layer is poor, for example, when the transfer layer of the intermediate transfer medium is retransferred to the transfer object 30 such as a card, a part of the transfer layer to be retransferred remains on the transfer object side. This causes a phenomenon that the product is taken out of the printer as it is, or peeled off inside the printer, resulting in quality degradation.

  In view of this point, as a preferred mode for eliminating the above-described fear, it is possible to employ a step of removing in advance by the peel-off layer 11 a transfer layer at a position that tends to remain on the intermediate transfer medium side during retransfer. preferable. As described above, the intermediate transfer medium 10 of the present invention is improved in the peel-off property of the protective layer 3, and is particularly suitable when this process is employed. In the above description, the intermediate transfer medium of the present invention and the thermal transfer sheet having a peel-off layer are used in combination, and the explanation is focused on an example in which a part of the transfer layer of the intermediate transfer medium is removed by the peel-off layer. The intermediate transfer medium of the present invention is not limited to this application. Specifically, since the intermediate transfer medium of the present invention can retransfer the transfer layer 2 onto the transfer target without problems and has transferability, the peel-off layer does not remove a part of the transfer layer 2. The transfer layer 2 of the intermediate transfer medium can also be used for retransfer onto the transfer target.

  Next, the present invention will be described more specifically with reference to examples. Hereinafter, unless otherwise specified, parts are based on mass.

Example 1
Using a polyethylene terephthalate film having a thickness of 12 μm (Lumirror, manufactured by Toray Industries, Inc.) as the base material sheet, a coating solution for forming a release layer having the following composition is applied on the base material sheet in a dry state of 1.0 g / m ² . A release layer was formed by coating so as to have a work amount. Next, the protective layer-forming coating solution 1 and the protective layer-forming coating solution 2 having the following composition were kneaded on the release layer at the content ratio of each binder resin shown in Table 1, and 4.5 g / m in a dry state. ^A protective layer was formed by coating so that the coating amount was ² . Further, a coating solution for forming a receiving layer having the following composition was applied on the protective layer so as to give a coating amount of 2.0 g / m ^{2 in} a dry state to form a receiving layer. A transfer medium was obtained. The release layer forming coating solution, the protective layer forming coating solution, and the receiving layer forming coating solution were all applied by gravure coating. In addition, the number average molecular weight (Mn1) 23000 of the binder resin of the protective layer forming coating solution 1 is integrated by the content ratio (r1) 0.65, and the number average of the binder resin of the protective layer forming coating solution 2 As a result of adding the values obtained by integrating the molecular weight (Mn2) 3000 with the content (r2) 0.35, the total sum (Σ) was 16000. As a result, the sum (Σ) of the binder resin in the kneaded product of the protective layer-forming coating liquid 1 and the protective layer-forming coating liquid 2 in Example 1 was in the range of 3000 to 17,000.

<Peeling layer forming coating solution>
・ 95 parts acrylic resin (BR-87, manufactured by Mitsubishi Rayon Co., Ltd.)
・ Polyester resin 5 parts (Byron 200, manufactured by Toyobo Co., Ltd.)
・ Toluene 200 parts ・ MEK 200 parts

<Protective layer forming coating solution 1>
20 parts of polyester resin (Byron 270, manufactured by Toyobo Co., Ltd., number average molecular weight 23000, Tg = 67 ° C.)
・ Toluene 40 parts ・ MEK 40 parts

<Protective layer forming coating solution 2>
20 parts of polyester resin (Byron 220, manufactured by Toyobo Co., Ltd., number average molecular weight 3000, Tg = 53 ° C.)
・ Toluene 40 parts ・ MEK 40 parts

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

(Example 2)
An intermediate transfer medium of Example 2 was obtained in the same manner as in Example 1 except that the content ratios of the protective layer forming coating solution 1 and the protective layer forming coating solution 2 were changed to those shown in Table 1. It was. In addition, the number average molecular weight (Mn1) 23000 of the binder resin of the protective layer forming coating liquid 1 is integrated by the content ratio (r1) 0.50, and the number average of the binder resin of the protective layer forming coating liquid 2 As a result of adding the values obtained by integrating the molecular weight (Mn2) 3000 with the content (r2) of 0.50, the total sum (Σ) was 13000. As a result, the sum (Σ) of the binder resin in the kneaded product of the protective layer-forming coating liquid 1 and the protective layer-forming coating liquid 2 in Example 2 was in the range of 3000 to 17,000.

(Example 3)
An intermediate transfer medium of Example 3 was obtained in the same manner as in Example 1 except that the contents of the protective layer forming coating liquid 1 and the protective layer forming coating liquid 2 were changed to the contents shown in Table 1. It was. In addition, the number average molecular weight (Mn1) 23000 of the binder resin of the protective layer forming coating liquid 1 is integrated by the content ratio (r1) 0.35, and the number average of the binder resin of the protective layer forming coating liquid 2 As a result of adding the values obtained by integrating the molecular weight (Mn2) 3000 with the content (r2) 0.65, the total sum (Σ) was 10,000. As a result, the sum (Σ) of the binder resin in the kneaded product of the protective layer-forming coating liquid 1 and the protective layer-forming coating liquid 2 in Example 3 was in the range of 3000 to 17,000.

(Example 4)
An intermediate transfer medium of Example 4 was obtained in the same manner as in Example 1 except that the content ratios of the protective layer forming coating solution 1 and the protective layer forming coating solution 3 were changed to those shown in Table 1. It was. In addition, the number average molecular weight (Mn1) 23000 of the binder resin of the protective layer forming coating solution 1 is integrated by the content ratio (r1) 0.35, and the number average of the binder resin of the protective layer forming coating solution 3 As a result of adding the values obtained by integrating the molecular weight (Mn3) 10,000 with the content (r3) 0.65, the total sum (Σ) was 14550. As a result, the sum (Σ) of the binder resin in the kneaded product of the protective layer-forming coating solution 1 and the protective layer-forming coating solution 3 in Example 4 was in the range of 3000 to 17,000.

<Protective layer forming coating solution 3>
Polyester resin 20 parts (Byron GK-250, manufactured by Toyobo Co., Ltd., number average molecular weight 10,000, Tg = 60 ° C.)
・ Toluene 40 parts ・ MEK 40 parts

(Example 5)
Intermediate transfer of Example 5 in the same manner as in Example 1 except that the contents of the protective layer forming coating liquid 2 and the protective layer forming coating liquid 4 having the following composition were changed to the contents shown in Table 1. A medium was obtained. In addition, the number average molecular weight (Mn2) 3000 of the binder resin of the protective layer forming coating liquid 2 is integrated by the content ratio (r2) 0.20, and the number average of the binder resin of the protective layer forming coating liquid 4 As a result of adding the values obtained by integrating the molecular weight (Mn4) 17000 with the content (r4) 0.80, the total sum (Σ) was 14200. As a result, the sum (Σ) of the binder resin in the kneaded product of the protective layer-forming coating liquid 2 and the protective layer-forming coating liquid 4 in Example 5 was in the range of 3000 to 17,000.

<Protective layer forming coating solution 4>
20 parts of polyester resin (Byron 200, manufactured by Toyobo Co., Ltd., number average molecular weight 17000, Tg = 67 ° C.)
・ Toluene 40 parts ・ MEK 40 parts

(Example 6)
An intermediate transfer medium of Example 6 was obtained in the same manner as in Example 1 except that the content ratios of the protective layer forming coating solution 2 and the protective layer forming coating solution 4 were changed to those shown in Table 1. It was. In addition, the number average molecular weight (Mn2) 3000 of the binder resin of the protective layer forming coating liquid 2 is integrated by the content ratio (r2) 0.80, and the number average of the binder resin of the protective layer forming coating liquid 4 As a result of adding the values obtained by integrating the molecular weight (Mn4) 17000 with the content (r4) 0.20, the total sum (Σ) was 5800. As a result, the total sum (Σ) of the binder resins in the kneaded product of the protective layer-forming coating solution 2 and the protective layer-forming coating solution 4 in Example 6 was in the range of 3000 to 17,000.

(Example 7)
An intermediate transfer medium of Example 7 was obtained in the same manner as in Example 1 except that the content ratios of the protective layer forming coating solution 3 and the protective layer forming coating solution 4 were changed to those shown in Table 1. It was. The number average molecular weight (Mn3) 10000 of the binder resin in the protective layer forming coating solution 3 was integrated by the content ratio (r3) 0.30, and the number average of the binder resin in the protective layer forming coating solution 4. As a result of adding the values obtained by integrating the molecular weight (Mn4) 17000 with the content (r4) 0.70, the sum (Σ) was 14900. As a result, the total sum (Σ) of the binder resins in the kneaded product of the protective layer forming coating solution 3 and the protective layer forming coating solution 4 of Example 7 was in the range of 3000 to 17,000.

(Example 8)
An intermediate transfer medium of Example 8 was obtained in the same manner as in Example 1 except that the content ratios of the protective layer forming coating solution 3 and the protective layer forming coating solution 4 were changed to those shown in Table 1. It was. The number average molecular weight (Mn3) 10000 of the binder resin in the protective layer forming coating solution 3 was integrated by the content ratio (r3) 0.50, and the number average of the binder resin in the protective layer forming coating solution 4. As a result of adding the values obtained by integrating the molecular weight (Mn4) 17000 with the content (r4) 0.50, the total sum (Σ) was 13500. As a result, the total sum (Σ) of the binder resins in the kneaded product of the protective layer forming coating solution 3 and the protective layer forming coating solution 4 in Example 8 was in the range of 3000 to 17,000.

Example 9
An intermediate transfer medium of Example 9 was obtained in the same manner as in Example 1 except that the content ratios of the protective layer forming coating solution 3 and the protective layer forming coating solution 4 were changed to those shown in Table 1. It was. The number average molecular weight (Mn3) 10000 of the binder resin in the protective layer forming coating solution 3 was integrated at a content ratio (r3) of 0.70, and the number average of the binder resin in the protective layer forming coating solution 4. As a result of adding the values obtained by integrating the molecular weight (Mn4) 17000 with the content (r4) 0.30, the total sum (Σ) was 12100. As a result, the total sum (Σ) of the binder resins in the kneaded product of the protective layer forming coating solution 3 and the protective layer forming coating solution 4 of Example 9 was in the range of 3000 to 17,000.

(Example 10)
An intermediate transfer medium of Example 10 was obtained in the same manner as in Example 1 except that the content ratios of the protective layer forming coating solution 3 and the protective layer forming coating solution 4 were changed to those shown in Table 1. It was. The number average molecular weight (Mn3) 10000 of the binder resin in the protective layer forming coating solution 3 was integrated by the content ratio (r3) 0.65, and the number average of the binder resin in the protective layer forming coating solution 4. As a result of adding the values obtained by integrating the molecular weight (Mn4) 17000 with the content (r4) 0.35, the total sum (Σ) was 12450. As a result, the sum (Σ) of the binder resin in the kneaded product of the protective layer forming coating solution 3 and the protective layer forming coating solution 4 of Example 10 was in the range of 3000 to 17000.

(Example 11)
The intermediate transfer of Example 11 was carried out in the same manner as Example 1 except that the contents of the protective layer-forming coating liquid 3 and the protective layer-forming coating liquid 5 having the following composition were changed to the contents shown in Table 1. A medium was obtained. The number average molecular weight (Mn3) 10000 of the binder resin in the protective layer forming coating solution 3 was integrated by the content ratio (r3) 0.5, and the number average of the binder resin in the protective layer forming coating solution 5. As a result of adding the value obtained by integrating the molecular weight (Mn5) 16000 with the content (r5) 0.5, the total sum (Σ) was 13000. As a result, the total sum (Σ) of the binder resins in the kneaded product of the protective layer forming coating solution 3 and the protective layer forming coating solution 5 of Example 11 was in the range of 3000 to 17,000.

<Protective layer forming coating solution 5>
-Polyester resin 20 parts (Byron 600, manufactured by Toyobo Co., Ltd., number average molecular weight 16000, Tg = 47 ° C.)
・ Toluene 40 parts ・ MEK 40 parts

(Example 12)
Except for changing the content rates of the protective layer forming coating solution 2, the protective layer forming coating solution 3, and the protective layer forming coating solution 4 to those shown in Table 1, all the same procedures as in Example 1 were performed. An intermediate transfer medium of Example 12 was obtained. In addition, the number average molecular weight (Mn2) 3000 of the binder resin of the protective layer forming coating solution 2 is integrated by the content ratio (r2) 0.1, and the number average of the binder resin of the protective layer forming coating solution 3 The value obtained by integrating the molecular weight (Mn3) 10,000 with the content ratio (r3) 0.4, and the number average molecular weight (Mn4) 17000 of the binder resin of the protective layer forming coating solution 4 with the content (r4) 0.5 As a result of adding the integrated values, the total sum (Σ) was 12800. As a result, the total sum (Σ) of the binder resins in the kneaded product of the protective layer forming coating liquid 2, the protective layer forming coating liquid 3, and the protective layer forming coating liquid 4 of Example 12 is 3000 to 17000. It was within the range.

(Example 13)
Except for changing the content rates of the protective layer forming coating solution 2, the protective layer forming coating solution 3, and the protective layer forming coating solution 4 to those shown in Table 1, all the same procedures as in Example 1 were performed. An intermediate transfer medium of Example 13 was obtained. In addition, the number average molecular weight (Mn2) 3000 of the binder resin of the protective layer forming coating solution 2 is integrated by the content ratio (r2) 0.25, and the number average of the binder resin of the protective layer forming coating solution 3 The value obtained by integrating the molecular weight (Mn3) 10,000 with the content ratio (r3) 0.25 and the number average molecular weight (Mn4) 17000 of the binder resin of the protective layer forming coating solution 4 with the content (r4) 0.5 As a result of adding the integrated values, the total sum (Σ) was 11750. As a result, the total sum (Σ) of the binder resins in the kneaded product of the protective layer forming coating liquid 2, the protective layer forming coating liquid 3, and the protective layer forming coating liquid 4 of Example 13 is 3000 or more and 17000 or less. It was in the range.

(Example 14)
Except for changing the content rates of the protective layer forming coating solution 2, the protective layer forming coating solution 3, and the protective layer forming coating solution 4 to those shown in Table 1, all the same procedures as in Example 1 were performed. An intermediate transfer medium of Example 14 was obtained. In addition, the number average molecular weight (Mn2) 3000 of the binder resin of the protective layer forming coating solution 2 is integrated by the content ratio (r2) 0.25, and the number average of the binder resin of the protective layer forming coating solution 3 The value obtained by integrating the molecular weight (Mn3) 10,000 at the content ratio (r3) 0.375, and the number average molecular weight (Mn4) 17000 of the binder resin of the protective layer forming coating solution 4 are the content (r4) 0.375. As a result of adding the integrated values, the total sum (Σ) was 10875. As a result, the total sum (Σ) of the binder resins in the kneaded product of the protective layer forming coating solution 2, the protective layer forming coating solution 3, and the protective layer forming coating solution 4 of Example 14 was 3000 or more and 17000 or less. It was in the range.

(Comparative Example 1)
An intermediate transfer medium of Comparative Example 1 was obtained in the same manner as in Example 1 except that the protective layer forming coating solution containing only the protective layer forming coating solution 1 was used. In addition, the value ((SIGMA)) which integrated | accumulated the number average molecular weight (Mn1) 23000 of binder resin of the coating liquid 1 for protective layer formation by the content ratio (r1) 1.00 was 23000, and it was the range exceeding 17000.

(Comparative Example 2)
An intermediate transfer medium of Comparative Example 2 was obtained in the same manner as in Example 1 except that the protective layer forming coating solution containing only the protective layer forming coating solution 2 was used. In addition, the value ((SIGMA)) which integrated | accumulated the number average molecular weight (Mn2) 3000 of binder resin of the coating liquid 2 for protective layer formation by the content ratio (r2) 1.00 was 3000.

(Comparative Example 3)
An intermediate transfer medium of Comparative Example 3 was obtained in the same manner as in Example 1 except that the protective layer forming coating solution containing only the protective layer forming coating solution 4 was used. In addition, the value ((SIGMA)) which integrated | accumulated the number average molecular weight (Mn4) 17000 of the binder resin of the coating liquid 4 for protective layer formation by the content ratio (r4) 1.00 was 17000.

(Comparative Example 4)
Comparative Example in the same manner as in Example 1 except that the content ratios of the protective layer forming coating solution 1 and the protective layer forming coating solution 2 were changed to 0.90: 0.10 in Table 1. 4 intermediate transfer media were obtained. In addition, the number average molecular weight (Mn1) 23000 of the binder resin of the protective layer forming coating liquid 1 is integrated by the content ratio (r1) 0.90, and the number average of the binder resin of the protective layer forming coating liquid 2 As a result of adding the values obtained by integrating the molecular weight (Mn2) 3000 with the content (r2) 0.10, the total sum (Σ) was 21,000. As a result, the total sum (Σ) of the binder resins in the kneaded product of the protective layer forming coating solution 1 and the protective layer forming coating solution 2 of Comparative Example 4 was in a range exceeding 17,000.

(Comparative Example 5)
Comparative Example in the same manner as in Example 1 except that the content ratios of the protective layer forming coating solution 1 and the protective layer forming coating solution 3 were changed to 0.70: 0.30. 5 intermediate transfer media were obtained. In addition, the number average molecular weight (Mn1) 23000 of the binder resin of the protective layer forming coating liquid 1 is integrated by the content ratio (r1) 0.70, and the number average of the binder resin of the protective layer forming coating liquid 3 As a result of adding the values obtained by integrating the molecular weight (Mn3) 10,000 with the content (r3) 0.30, the total sum (Σ) was 19100. As a result, the total sum (Σ) of the binder resins in the kneaded product of the protective layer-forming coating liquid 1 and the protective layer-forming coating liquid 3 in Comparative Example 5 was in a range exceeding 17,000.

(Creation of thermal transfer sheet)
As a base sheet, a polyethylene terephthalate film having a thickness of 4.5 μm is used. On one surface of the base sheet, a yellow dye layer coating liquid, a magenta dye layer coating liquid, and a cyan dye layer having the following composition are provided. As shown in FIG. 3, yellow, magenta, and cyan dye layers and a peel-off layer were repeatedly formed in the surface order using the coating liquid for coating and the coating liquid for peel-off layer. Next, on the other surface of the substrate sheet, a coating solution for the back layer having the following composition was applied at a thickness of 0.8 g / m ² when dried to obtain a thermal transfer sheet by forming a back layer. . The coating amount of the yellow dye layer coating liquid, the magenta dye layer coating liquid, the cyan dye layer coating liquid, and the peel-off layer coating liquid is 0.6 g / m ² in terms of thickness when dried. is there.

<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 (Disperthread 60) 1.5 parts ・ Disperse dye (Disperse violet 26) 2.0 parts ・ Polyvinyl acetal resin 4.5 parts (S-REC KS-5, Sekisui Chemical Co., Ltd.)
・ Polyethylene wax 0.1 part ・ Methyl ethyl ketone 45.0 parts ・ Toluene 45.0 parts

<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

(Peel-off layer coating solution)
・ Acrylic resin (Mitsubishi Rayon Co., Ltd., BR-87) 5 parts ・ Methyl ethyl ketone 47.5 parts ・ Toluene 47.5 parts

<Back layer coating liquid>
・ 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

(Printed matter)
Using the HDP-600 printer (manufactured by HID) mounted with the thermal transfer sheet obtained above and a commercially available thermal head on the receiving layers of the intermediate transfer media of Examples 1 to 14 and Comparative Examples 1 to 5, sublimation was performed. A transfer photographic image was formed. Next, the thermal transfer sheets were superposed so that the receiving layers of the intermediate transfer media of the examples and comparative examples on which the thermal transfer images were formed and the peel-off layer of the thermal transfer sheet prepared above were in contact with each other. By heating the back side of the transfer layer, a predetermined region (a region corresponding to the outside of the card edge (see reference A in FIG. 7)) and a region corresponding to the IC chip are formed of the release layer / protective layer / receiving layer. (See symbol B in FIG. 7)) was removed from the intermediate transfer medium. Next, using a heat roll, the printed matter of Examples 1 to 14 and Comparative Examples 1 to 5 was formed by retransferring the transfer layer from which the predetermined area was removed onto the vinyl chloride card as the subject. . In the intermediate transfer medium of each example, it was confirmed that the transfer layer could be retransferred without any problem on a vinyl chloride card as a transfer target.

<Durability (Taber test)>
For the prints of Examples 1 to 14 and Comparative Examples 1 to 5 obtained above, a wear wheel CS-10F was used with a Taber abrasion tester, and the wear wheel was polished every 250 times with a load of 500 gf, for a total of 750 times. did. After polishing, the surface condition was visually observed and evaluated according to the following evaluation criteria. The evaluation results are shown in Table 1.

<Evaluation criteria>
4 ... The image is not cut at all.
3 ... The image is almost not scraped.
2 ... The image is cut to some extent, but there is no problem in use.
1 ... The image is considerably shaved.

<Peel-off property (Obiki) test>
The peel-off properties of the prints of Examples 1 to 14 and Comparative Examples 1 to 5 obtained above were confirmed visually, and evaluated according to the following evaluation criteria. The evaluation results are also shown in Table 1. Note that the amount of crease in the following evaluation criteria indicates that the transfer layer that should originally remain on the intermediate transfer medium side, that is, the transfer layer corresponding to the non-transfer area is the transfer area (transfer areas corresponding to symbols A and B shown in FIG. 7). ) Means the length removed together with the transfer layer corresponding to (2), and the shorter the length of the removed transfer layer in the non-transfer region, that is, the smaller the amount of odor, the better the peel-off property. In the evaluation of the peel-off property, as shown in FIG. 7, the amount of crease was measured in the region of A (peripheral edge of the transferred image) and the region of B (scheduled IC chip placement region) where ubiquity is likely to occur. .

<Evaluation criteria for area A (periphery edge of transferred image)>
4 ... The amount of creaking is less than 0.5 mm.
3 ... The amount of creaking is 0.5 mm or more and less than 1 mm.
2: The amount of crease is not less than 1 mm and less than 2 mm, but this is not a practically problematic level.
1: The amount of ubiquity is 2 mm or more, which is a practically problematic level.
<Evaluation criteria for B (IC chip placement area)>
4 ... The amount of creaking is less than 0.1 mm.
3 ... The amount of creaking is 0.1 mm or more and less than 0.3 mm.
2: The amount of crease is not less than 0.3 and less than 1 mm, but this is not a problem level for practical use.
1: The amount of ubiquity is 1 mm or more, which is a practically problematic level.

  As is clear from Table 1, it was confirmed that the intermediate transfer medium provided with the protective layer satisfying all the matters specific to the invention of the present invention gave good results in both peel-off property and durability. On the other hand, the intermediate transfer medium having a protective layer that does not satisfy the specific matters of the present invention cannot satisfy both the peel-off property and the durability, and the superiority of the present invention is apparent from this. is there.

DESCRIPTION OF SYMBOLS 1 Base material sheet 2 Transfer layer 3 Protective layer 4 Receptive layer 5 Release layer 9 Predetermined area 10 Intermediate transfer medium 11 Peel-off layer 12 Dye layer 13 Molten layer 14 Base material layer 15 Back layer 16 Thermal head 17 Heat roll 20 Thermal transfer sheet 30 Transfer object 31 Accessories A Peripheral edge of transferred image B IC chip placement area

Also, least one binder resins of said two or more components of the binder resin may be a polyester resin.

Claims (5)

An intermediate transfer medium in which a protective layer and a receiving layer are laminated on one side of a base sheet,
The protective layer includes a kneaded mixture of two or more components having different number average molecular weights (Mn), and the sum total of the sums of the number average molecular weights (Mn) of the respective components integrated with each content ratio ( An intermediate transfer medium, wherein Σ) is in the range of 3000 to 17000.   The intermediate transfer medium according to claim 1, wherein at least one binder resin of the two or more component binder resins is a polyester-based resin.   The binder resin having two or more components includes a polyester resin A having a number average molecular weight (Mn) of 2000 or more and 10,000 or less, and a polyester resin B having a number average molecular weight (Mn) of more than 10,000 and 25,000 or less. The intermediate transfer medium according to claim 1 or 2, characterized in that   The binder resin having two or more components includes a polyester resin A1 having a number average molecular weight (Mn) of 2000 or more and 4000 or less, a polyester resin A2 having a number average molecular weight of more than 4000 and 10,000 or less, and a number average molecular weight (Mn). The intermediate transfer medium according to any one of claims 1 to 3, wherein a polyester resin B greater than 10,000 and less than or equal to 25,000 is included.   The intermediate transfer medium according to any one of claims 1 to 4, further comprising a release layer between the base sheet and the protective layer.

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