JP5782770B2 - Protective layer transfer sheet - Google Patents

Description

  The present invention relates to a protective layer transfer sheet, and more particularly to a protective layer transfer sheet capable of imparting high glossiness and physical durability such as plasticizer resistance and scratch resistance to the surface of a printed material.

  2. Description of the Related Art Conventionally, characters and images are formed on a transfer target using a thermal transfer method, and the thermal transfer method is roughly divided into a thermal sublimation transfer method and a thermal fusion transfer method. The heat-sensitive sublimation transfer method uses a sublimation dye as a colorant and uses a heating device such as a thermal head or laser beam whose heat is controlled according to the image information, and the dye in the sublimation dye layer on the thermal transfer sheet. Is transferred to a transfer target such as a thermal transfer image receiving sheet to form an image. This heat-sensitive sublimation transfer system can control the amount of dye transfer in dot units by heating for a very short time. The image formed in this way is very clear because the coloring material used is a dye and is excellent in transparency, so the resulting image is excellent in halftone reproducibility and gradation, An extremely high-definition image can be obtained. For this reason, a high quality image comparable to a full-color silver salt photograph can be obtained. Because of these advantages, the thermal transfer technology of the heat-sensitive sublimation transfer system is widely used for business photographs, personal computer printers, video printers, and the like.

  However, the above-mentioned thermal sublimation transfer method can control the amount of dye transfer in dot units according to the amount of energy applied, so it is excellent in forming a gradation image, but the formed image is based on ordinary printing ink. In contrast, the coloring material is not a pigment but a relatively low molecular weight dye, and since there is no vehicle, there is a disadvantage that physical durability is inferior. Further, an image formed by the heat-sensitive fusion transfer method has a vehicle, but still has poor durability and particularly wear resistance compared to an image formed with ordinary printing ink.

  Therefore, a protective layer transfer sheet having a transferable protective layer is superimposed on the image obtained by the thermal transfer method, and the transferable protective layer is transferred using a thermal head, a heating roll, or the like, thereby protecting the transferability on the image. Attempts have been made to form layers. Since this transferable protective layer is formed for the purpose of imparting physical durability to the image, it is a layer located on the outermost surface when transferred onto the image among the layers constituting the transferable protective layer. Requires physical durability. In particular, recently, there is a high demand for an image having a high glossiness, and in this case, a layer located on the outermost surface after transfer needs to have a high glossiness. Furthermore, in addition to these functions, the transferable protective layer is required to have functions such as peelability during transfer.

  Under such circumstances, various studies have been made on the transferable protective layer. For example, in Patent Document 1, in addition to solvent resistance, water resistance, and scratch resistance, for the purpose of improving foil breakage during transfer, There has been proposed a protective layer transfer sheet in which a transferable protective layer obtained by laminating a protective layer and an adhesive layer in this order on a substrate is provided, and the main component of the protective layer is an acrylic resin. Patent Document 2 discloses that the improvement of plasticizer resistance is a problem, a transferable protective layer is provided on a substrate, and the transferable protective layer is a layer mainly composed of an acrylic resin from the substrate side, a polyester resin. There has been proposed a protective layer transfer sheet, which is a laminate having a two-layer structure in which layers mainly composed of are laminated in this order. Further, a protective layer transfer sheet has been proposed in which the improvement in glossiness is a problem, and the layer located on the outermost surface after transfer contains a styrene-acrylic copolymer.

JP 2005-262690 A JP 2002-240404 A

  In the protective layer transfer sheet proposed in Patent Documents 1 and 2, the layer located on the outermost surface after transfer is a layer mainly composed of an acrylic resin. However, the layer mainly composed of acrylic resin is excellent in physical durability such as scratch resistance and scratch resistance and plasticizer resistance, but has insufficient glossiness and high glossiness. It cannot be applied to the required fields. On the other hand, according to the layer made of styrene-acrylic copolymer, it has a certain glossiness, so that it can give glossiness to the image, but physical durability such as scratch resistance and scratch resistance. Is insufficient. In other words, there is a trade-off between glossiness and scratch resistance, and the protective layer has a high glossiness and a transferable protective layer with excellent physical durability such as scratch resistance and scratch resistance. Realization of a transfer sheet was considered difficult.

  The present invention has been made in view of such a situation, and can impart physical durability such as plasticizer resistance and scratch resistance while imparting high gloss to the surface of the printed matter. The main object is to provide a protective layer transfer sheet.

The present invention for solving the above problems is a protective layer transfer sheet comprising a base material and a transfer layer provided on the base material so as to be peelable, and the transfer layer is a release layer from the base material side. And the protective layer are laminated in this order, and the release layer contains (1) a phenoxy resin and (2) any one of an acrylic resin, a polyester resin, and a polyester urethane resin. ) When the release layer contains the acrylic resin, the content of the acrylic resin when the total amount of the phenoxy resin and the acrylic resin is 100 parts by mass is 10 to 30 parts by mass. And (B) when the release layer contains the polyester resin and / or polyester urethane resin, the polyester resin and / or polyester with respect to 100 parts by mass of the phenoxy resin. The content of the ester urethane resin is characterized in that it is in the range of 3 to 5 parts by weight.
The invention of one embodiment is a protective layer transfer sheet comprising a base material and a transfer layer that is detachably provided on the base material, and the transfer layer protects the release layer from the base material side. The layers are laminated in this order, and the release layer contains a phenoxy resin.

  The release layer may contain any of an acrylic resin, a polyester resin, and a polyester urethane resin. The phenoxy resin may be a copolymer of a phenoxy resin and an acrylic resin, or a copolymer of a phenoxy resin and a polyester resin. An adhesive layer may be provided on the protective layer.

  According to the protective layer transfer sheet of the present invention, physical durability such as plasticizer resistance and scratch resistance can be imparted while imparting high gloss to the surface of the printed material. Furthermore, according to one embodiment of the present invention, the foil breakability of the transfer layer at the time of transfer can be further improved.

It is a schematic sectional drawing of the protective layer transfer sheet of one Embodiment of this invention.

  Embodiments of the present invention will be described with reference to the drawings. FIG. 1 is a schematic cross-sectional view showing a protective layer transfer sheet according to an embodiment of the present invention.

  As shown in FIG. 1, the protective layer transfer sheet 10 of the present invention includes a base material 1 and a transfer layer 20 that is detachably provided on the base material 1. Further, the transfer layer 20 has the release layer 2 and the protective layer 3 in this order from the substrate 1 side so that the release layer 2 is positioned on the outermost surface when the transfer layer 20 is transferred onto the transfer target. It takes a stacked configuration. The protective layer transfer sheet 10 of the present invention is characterized in that the release layer 2 contains a phenoxy resin. Hereinafter, the protective layer transfer sheet 10 of the present invention will be specifically described.

(Base material)
The substrate 1 used in the protective layer transfer sheet 10 of the present invention is not particularly limited as long as it has a certain degree of heat resistance and strength, and a conventionally known material can be appropriately selected and used. . Examples of such a substrate 1 include polyethylene terephthalate film, 1,4-polycyclohexylenedimethylene terephthalate film, polyethylene naphthalate film, polyphenylene sulfide having a thickness of about 0.5 to 50 μm, preferably about 1 to 10 μm. 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. .

(Transfer layer)
As shown in FIG. 1, a transfer layer 20 is provided on the substrate 1. The transfer layer 20 is conventionally known, such as a printer provided with a thermal head for thermal transfer on the side of the substrate 1 on which the transfer layer 20 is not provided, with the protective layer sheet 10 of the present invention and a transfer medium to be described later overlaid. It is a layer that is peeled off from the substrate 1 by being heated by the heating means and transferred onto the transfer target. In the present invention, the transfer layer 20 has a laminated structure in which the peeling layer 2 and the protective layer 3 are laminated in this order from the substrate 1 side, and the peeling layer 2 is transferred onto the transfer target. When the layer 20 is transferred, it is positioned on the outermost surface on the transfer target.

(Peeling layer)
A release layer 2 constituting the transfer layer 20 is provided on the substrate 1. The release layer 2 is an essential component in the protective layer sheet 10 of the present invention and contains a phenoxy resin.

  The phenoxy resin is a polyhydroxy polyether resin produced from the same raw material as the epoxy resin, and is a thermoplastic resin having a molecular weight larger than that of a normal epoxy resin. Typically, it is a resin derived from bisphenol A and epichlorohydrin and having the following general formula (I) as a repeating unit.

  In the present invention, a bisphenol type phenoxy resin produced from a dihydric phenol and epichlorohydrin can be preferably used. Examples of dihydric phenols include 2,2-bis (4-hydroxyphenyl) propane [bisphenol A], bis (4-hydroxyphenyl) methane [bisphenol F], 1,1-bis (4-hydroxyphenyl) ethane, 4,4′-dihydroxybiphenyl and the like can be mentioned. Further, the phenoxy resin may be a resin in which a part of the hydroxyl group is alkylesterified or alkyletherified. Moreover, you may use it in mixture of 2 or more types of phenoxy resin. In addition, what is described in Unexamined-Japanese-Patent No. 2006-104329 can be used for a bisphenol type phenoxy resin.

  Moreover, a commercial item can also be used as a phenoxy resin. Commercially available phenoxy resins (bisphenol A type) include PKHB (manufactured by ICHEM, Mw = 13,700, refractive index = 1.595), PKFE (manufactured by INCHEM, Mw = 36,800, refractive index = 1. 595), YP-50 (manufactured by Tohto Kasei Co., Ltd., Mw = 43,500, refractive index = 1.595), PKCP-80 (manufactured by INCHEM, Mw = 20,100, refractive index = 1.586) and the like. It is done.

  In addition to the phenoxy resins exemplified above, a phenoxy resin modified with a partial hydrolyzate of a polyfunctional silane coupling agent described in JP-A-02-106393, or JP-A-06-155932 It is also possible to use a modified phenoxy resin in which the hydroxyl group of the phenoxy resin described in the publication is blocked with an ester group, an amide group, an ether group or a silyl ether group.

  In the present invention, since the phenoxy resin is contained in the release layer 2, in other words, the layer located on the outermost surface when the transfer layer 20 is transferred onto the transfer target, the transfer layer 20 is transferred after the transfer. High glossiness can be imparted to the image. In addition, the phenoxy resin is excellent in physical durability such as scratch resistance and scratch resistance. Therefore, according to the protective layer transfer sheet 10 of the present invention including the release layer 2 containing a phenoxy resin, it is possible to simultaneously impart high glossiness and physical durability to the printed material after the transfer layer 20 is transferred. . Furthermore, the phenoxy resin is excellent in peelability and plasticizer resistance.

  The phenoxy resin only needs to be contained in the release layer 2 within the range where the above-described effects are exhibited. However, when the content of the phenoxy resin is less than 70% by mass with respect to the total solid content of the release layer 2. , Glossiness tends to decrease. Therefore, considering this point, the content of the phenoxy resin is preferably in the range of 70% by mass to 100% by mass with respect to the total solid content of the release layer 2.

  The phenoxy resin preferably has a weight average molecular weight in the range of 20,000 to 40,000. When the weight average molecular weight is within this range, glossiness and physical durability can be further improved. Here, the weight average molecular weight is a value in terms of polystyrene measured by gel permeation chromatography (GPC).

  Further, the phenoxy resin contained in the release layer 2 is particularly preferably one having a refractive index in the range of 1.55 to 1.60. According to the release layer 2 containing a phenoxy resin having a refractive index within the above range, it is possible to effectively prevent the occurrence of uneven interference with the reflected light in the release layer 2, and the protective layer transfer sheet has an extremely high gloss. Degrees can be granted. This is considered to be due to an increase in reflected light near the surface of the release layer 2 and a decrease in transmitted light by using the release layer 2 containing the phenoxy resin having the refractive index.

  Further, the phenoxy resin may be a copolymer of the phenoxy resin and the acrylic resin described above, or may be a copolymer of the phenoxy resin and the polyester resin described above. By containing a copolymer with these phenoxy resins, it is possible to improve the foil breakability and scratch resistance of the release layer 2 when the transfer layer 20 is transferred.

  The copolymerization ratio is not particularly limited, but when the total copolymer is 100, the copolymerization ratio of the phenoxy resin and the acrylic resin or polyester resin is preferably about 50:50 to 100: 0. .

  From the same viewpoint, the release layer 2 preferably contains either an acrylic resin, a polyester resin, or a polyester urethane resin. In addition, when it contains an acrylic resin, it is preferable that the acrylic resin is contained in the range of 10-30 mass parts, when the total amount of a phenoxy resin and an acrylic resin is 100 mass parts. When the content of the acrylic resin is less than 10 parts by mass, the effect of improving the foil cutting property cannot be exhibited to a desired level, and when the content exceeds 30 parts by mass, the ratio of the phenoxy resin in the release layer 2 decreases. This is because there is a concern that the glossiness is lowered.

  Moreover, when it contains a polyester resin and / or a polyester urethane resin, it is preferable to contain these resins in the range of 3-5 mass parts with respect to 100 mass parts of phenoxy resins. Within the said range, foil cutting property can be improved by containing an acrylic resin, a polyester resin, and a polyester urethane resin. In addition, when the content of the polyester resin and the polyester urethane resin is less than 3 parts by mass, the effect of improving the foil cutting property cannot be exhibited to a desired level, and when the content is 5 parts by mass or more, This is because the function as the release layer 2, that is, the peelability tends to be lowered.

  In addition to the phenoxy resin that is the essential component described above, the optional acrylic resin, polyester resin, and polyester urethane resin, other components may be added to the release layer 2 as necessary. it can. Examples of other components include slip agents and ultraviolet absorbers.

  Although there is no limitation in particular about the thickness of the peeling layer 2, the range of 0.1 micrometer-10 micrometers is preferable, and the inside of the range of 0.5 micrometer-5 micrometers is more preferable. Moreover, there is no restriction | limiting in particular about the formation method of the peeling layer 2, The phenoxy resin demonstrated above in the suitable solvent and other resin as needed are added, this is melt | dissolved or disperse | distributed to a solvent, and coating liquid is used. The coating liquid is prepared and then formed on the substrate 1 by applying and drying the substrate 1 using a known means such as a gravure printing method, a screen printing method, or a reverse roll coating method using a gravure plate. it can.

(Protective layer)
On the release layer 2, a protective layer 3 constituting the transfer layer 20 is provided. The protective layer 3 imparts light resistance and weather resistance to an image or the like of a transfer target covered with the transfer layer 20 after the transfer layer 20 is transferred, and improves adhesion between the transfer layer 20 and the transfer target. It is a layer provided to make it.

  Examples of the material of the protective layer 3 include acrylic resin, vinyl chloride-vinyl acetate copolymer resin, epoxy resin, polyester resin, polycarbonate resin, butyral resin, polyamide resin, and vinyl chloride resin. In the present invention, a polyester resin such as a polyester resin or a polycarbonate resin is particularly preferably used because of its high compatibility with the release layer 2.

  Moreover, it is preferable that the protective layer 3 contains the ultraviolet absorber. According to the protective layer 3 containing an ultraviolet absorber, it is possible to further improve the light resistance, weather resistance, and the like of the image of the transfer object that is covered with the transfer layer 20 after the transfer layer 20 is transferred. Examples of the ultraviolet absorber include salicylate-based, benzophenone-based, benzotriazole-based, triazine-based, substituted acrylonitrile-based, nickel chelate-based, hindered amine-based and the like, which are conventionally known organic ultraviolet absorbers. In addition, for example, polymers having addition polymerizable double bonds such as vinyl groups, acryloyl groups, and methacryloyl groups, or alcoholic hydroxyl groups, amino groups, carboxyl groups, epoxy groups, isocyanate groups, etc., are introduced into these ultraviolet absorbers. The material is a UV-absorbing resin, and the adhesive layer can be constituted from this UV-absorbing resin.

  The method for forming the protective layer 3 is not particularly limited, and the resin described above is added to an appropriate solvent, and this is dissolved or dispersed in an appropriate solvent to prepare a coating solution. The liquid can be formed on the release layer 2 by coating and drying using a known means such as a gravure printing method, a screen printing method, or a reverse roll coating method using a gravure plate. Although there is no limitation in particular about the thickness of the protective layer 3, about 0.5-50 micrometers is preferable.

(Adhesive layer)
Further, an adhesive layer may be provided on the protective layer 3 as necessary. By providing the adhesive layer, the adhesion between the transfer layer 20 and the transfer target can be further improved. The adhesive layer is preferably formed of a material having transparency and adhesiveness. For example, acrylic resin, vinyl resin, polyester resin, urethane resin, polyamide resin, epoxy resin, rubber resin A conventionally known adhesive mainly composed of an ionomer resin or the like can be widely used. Although there is no limitation in particular about the film thickness of an contact bonding layer, it is preferable that it is the range of 0.1-50 micrometers, and 1-10 micrometers is more preferable.

(Heat resistant slipping layer)
Moreover, as shown in FIG. 1, it is good also as providing the heat resistant slipping layer 5 in the surface on the opposite side to the side in which the transfer layer 20 of the base material 1 was provided. The heat-resistant slip layer 5 is an arbitrary layer in the protective layer transfer sheet 10 of the present invention, but by providing the heat-resistant slip layer 5, the thermal head can be improved in slidability and sticking can be prevented.

  The heat-resistant slip layer 5 includes a heat-resistant thermoplastic resin binder and a thermal release agent or a substance that functions as a lubricant as basic constituent components. The thermoplastic resin binder is not particularly limited as long as it is a thermoplastic resin binder having heat resistance. Examples of such a thermoplastic resin binder include acrylic resins, polyester resins, styrene-maleic acid copolymers, polyimide resins, and polyamides. Examples include resins, polyamideimide resins, cellulose acetate propionate, cellulose acetate butyrate, cellulose acetate, vinylidene fluoride resin, nylon, polyvinyl carbazole, chlorinated rubber, cyclized rubber, and polyvinyl alcohol. These resins have a glass transition point of 60 ° C. or higher, or a compound having two or more amino groups or a diisocyanate or triisocyanate added to a thermoplastic resin having an OH group or a COOH group to be slightly crosslinked and cured. What was caused is preferable.

  Thermal release agents or lubricants to be blended with the above thermoplastic resins include waxes such as polyethylene wax and paraffin wax, higher fatty acid amides, esters or salts, higher alcohols and phosphate esters such as lecithin. There are those that melt by heating to act, and those that are useful as solids, such as fluororesin or inorganic powder. In addition to these lubricants or thermal release agents, other release agents such as fluorine-containing resin powder, guanamine resin powder and wood powder can be used in combination. High effect is obtained.

The composition for forming the heat-resistant slip layer 5 is not limited to obtain, but 10 to 100 parts by mass of the above-mentioned lubricant or thermal release agent acts on 100 parts by mass of the thermoplastic resin binder. It is preferable that they are blended in proportions. Further, the formation of the heat-resistant slip layer 5 is not particularly limited. For example, the heat-resistant slip layer 5 is kneaded with an appropriate solvent to form an ink. It can be carried out by applying and drying the material 1 on the surface opposite to the transfer layer 20. Although there is no particular limitation on the thickness of the heat-resistant lubricating layer 5 is generally about 0.01 to 1.0 g / m ^2, preferably from 0.1 to 0.2 g / m ^2.

(Heat transferable color material layer)
In addition, the protective layer transfer sheet of the present invention can form a transfer layer 20 and a heat transferable color material layer (not shown) on the same base material 1 in the surface order. As a result, the thermal transfer colorant layer and the protective layer can be transferred with one head of the thermal transfer printer, and it is not necessary to provide a plurality of units for supplying and winding the thermal transfer sheet. And the printer transport system is not complicated.

  The heat transferable color material layer may be either a color material layer made of heat-meltable ink or a color material layer containing a sublimable dye. The heat-meltable ink is composed of a colorant and a vehicle, and various additives are added as necessary. As the colorant, among organic or inorganic pigments or dyes, those having a color density required as a recording material and not discolored by light, heat, temperature or the like are preferable. In addition, a substance that develops color when heated or a substance that develops color when in contact with a substance applied to the transfer target can also be used. In addition to cyan, magenta, yellow, black and the like, various colorants can be used as the colorant.

The vehicle is mainly composed of a wax, and in addition, a mixture of a wax and a drying oil, resin, mineral oil, cellulose, rubber derivatives, or the like is used. The heat transferable color material layer made of heat meltable ink may contain a heat conductive material in order to give good heat conductivity and melt transferability. Examples of such a heat conductive material include carbonaceous materials such as carbon black, aluminum, copper, tin oxide, and molybdenum disulfide. Examples of the method for forming the heat transferable color material layer on the base film using the above hot melt ink include known methods such as hot melt coating, hot lacquer coating, gravure coating, gravure reverse coating, and roll coating. It is done. The coating amount of the heat transferable color material layer made of a heat-meltable ink can be appropriately determined in consideration of the required printing density, thermal sensitivity, etc., and usually 0.1 to 30 g / m ² when dried. It is.

  The heat transferable color material layer containing a sublimable dye is obtained by dispersing or dissolving a heat transferable dye in a binder resin. As the binder resin, those having a moderate affinity with the dye, and those in which the dye in the binder resin is sublimated (heat transferred) by heating with a thermal head, and transferred to the transfer target are good. Use resin that does not transfer. Examples of the resin used as such a binder resin include cellulose resins such as ethyl cellulose, hydroxyethyl cellulose, ethyl hydroxyethyl cellulose, hydroxypropyl cellulose, methyl cellulose, cellulose nitrate, cellulose acetate, and acetic acid / butyric acid cellulose, polyvinyl alcohol, and polyacetic acid. Examples thereof include vinyl resins such as vinyl, polyvinyl butyral, polyacrylamide, and polyvinyl pyrrolidone, polyester, and polyamide.

  The proportion of the dye contained in the heat transferable color material layer varies depending on the dye sublimation (melting) temperature, dyeing property, etc., but is preferably 30 parts by mass or more, more preferably 100 parts by mass of the binder resin. Is 30 to 300 parts by weight. When the amount of the dye is less than 30 parts by mass, the printing density and the thermal sensitivity are low, and when it exceeds 300 parts by mass, the storage property and the adhesion of the heat transferable color material layer to the base film are lowered.

  The dye used in the heat transferable color material layer is a dye which melts, diffuses or sublimates by heat and moves to the transfer target, and a disperse dye is particularly preferably used. The dye is selected in consideration of sublimation (melting) property, hue, light resistance, solubility in a binder resin, and the like. Examples of these dyes include methine series such as diarylmethane series, triarylmethane series, thiazole series, and merocyanine, indoaniline, acetophenone azomethine, pyrazoloazomethine, imidazole azomethine, imidazoazomethine, and azomethine series represented by pyridone azomethine. , Xanthene series, oxazine series, dicyanostyrene, cyanomethylene series represented by tricyanostyrene, thiazine series, azine series, acridine series, benzeneazo series, pyridoneazo, thiophenazo, isothiazole azo, pyrrole azo, pyrazole azo, imidazole azo, Azos such as thiadiazole azo, triazole azo, disazo, spiropyran, indolinospiropyran, fluoran, rhodamine lactam, naphthoquinone, anthraquino Systems include the quinophthalone like.

In order to provide the heat transferable color material layer, which is a dye layer, on the base film, a known method can be used. For example, a dye and binder resin are dissolved or dispersed together with a solvent to prepare an ink composition for a heat transferable color material layer, which is provided on the substrate 1 by a method appropriately selected from known printing methods or coating methods. It ’s fine. The coating amount of the dye layer, 0.2~5.0g / m ² in dry, preferably from the thickness of 0.4 to 2.0 g / m ^2.

  The heat transferable color material layer described above may be provided with one heat transfer type color material layer on the substrate 1, and two or more different color hues of the heat transfer color material layer are sequentially arranged on the substrate 1. It is good also as forming in. In particular, a yellow color material layer, a magenta color material layer, and a cyan color material layer are sequentially formed on the substrate 1 as a heat transferable color material layer containing a sublimation dye, thereby achieving high quality comparable to a full color photographic image. It is preferable to form a clear image in which a thermal transfer image is formed and a deviation in print length is prevented between hues in a full color thermal transfer image. In the case of a black character or pattern thermal transfer image, it is possible to obtain black by overlaying the above three colors of the yellow color material layer, magenta color material layer, and cyan color material layer of the dye layer. It is preferable that a color material layer made of black heat-meltable ink using a black colorant is added to the base sheet. As a result, a clear image having a high black density can be obtained.

(Transfer material)
The transfer target that can be used for the transfer of the protective layer transfer sheet 10 of the present invention is not particularly limited, and examples thereof include a conventionally known base provided with a receiving layer having dye acceptability. it can. Examples of the substrate in the transfer target include plain paper, high-quality paper, tracing paper, plastic film, and the like, and the substrate is not particularly limited. The receiving layer in the transfer target can be formed by a coating method, a forming method using a thermal head, a hot roll, or the like. In addition, as long as the base material itself has dye receptivity, it is not necessary to provide a receiving layer for the transfer target.

(Transfer method)
When the transfer layer 20 (thermal transferable color material layer if necessary) is transferred by a thermal transfer method using the protective layer transfer sheet 10 of the present invention to form an image on a transfer target, the thermal transfer printer is used for sublimation transfer. Alternatively, the transfer conditions may be set separately such as for hot melt transfer and protective layer transfer, or may be performed by appropriately adjusting the printing energy with a common printer. Moreover, it is not specifically limited as a heating means, In addition, it is good also as performing transfer using a hot plate, a hot stamper, a hot roll, a line heater, an iron, etc.

  The protective layer transfer sheet of the present invention has been described in detail above. However, the present invention is not limited to the above embodiments, and various modifications can be made without departing from the spirit of the present invention.

  Next, an Example is given and this invention is demonstrated further more concretely. “Parts” in the text are based on mass unless otherwise noted.

( Reference Example 1)
Using a PET film having a thickness of 5 μm as a base material, a release layer is formed on the base material by applying the release layer coating liquid 1 having the following composition to 1.2 g / m ² when dried. did. Next, a protective layer coating sheet of Reference Example 1 was obtained by coating a protective layer coating solution having the following composition on the release layer so as to be 1.0 g / m ² when dried.

<Peeling layer coating solution 1>
・ Bisphenol type phenoxy resin 16 parts (PKHB Sakai Kogyo Co., Ltd.)
・ Toluene 12 parts ・ Methyl ethyl ketone 72 parts

<Coating liquid for protective layer>
Polyester resin (number average molecular weight: 3000, Tg: 90 ° C.) 23.5 parts (Byron 700 manufactured by Toyobo Co., Ltd.)
・ Ultraviolet absorber 6 parts Tinuvin 900 Ciba Japan Co., Ltd.)
・ Silica filler 0.5 part (Silicia 310P, manufactured by Fuji Silysia)
・ Toluene 35 parts ・ Methyl ethyl ketone 35 parts

(Example 2)
A protective layer transfer sheet of Example 2 was obtained in the same manner as in Reference Example 1 except that the release layer coating solution 2 having the following composition was used instead of the release layer coating solution 1.

<Peeling layer coating solution 2>
・ Bisphenol type phenoxy resin 15.2 parts (PKHB Sakai Kogyo Co., Ltd.)
・ 0.8 parts of polyester resin (RV240 manufactured by Toyobo Co., Ltd.)
・ Toluene 12 parts ・ Methyl ethyl ketone 72 parts

(Example 3)
A protective layer transfer sheet of Example 3 was obtained in the same manner as in Reference Example 1 except that the release layer coating solution 3 having the following composition was used instead of the release layer coating solution 1.

<Peeling layer coating solution 3>
・ Bisphenol type phenoxy resin 15.2 parts (PKHB Sakai Kogyo Co., Ltd.)
・ Polyester urethane resin 0.8 part (UR1700 manufactured by Toyobo Co., Ltd.)
・ Toluene 12 parts ・ Methyl ethyl ketone 72 parts

Example 4
A protective layer transfer sheet of Example 4 was obtained in the same manner as in Reference Example 1 except that the release layer coating solution 4 having the following composition was used instead of the release layer coating solution 1.

<Peeling layer coating solution 4>
・ Bisphenol-type phenoxy resin 12.8 parts (PKHB Sakai Industrial Co., Ltd.)
-Acrylic resin 3.2 parts (MB7333 manufactured by Mitsubishi Rayon Co., Ltd.)
・ Toluene 12 parts ・ Methyl ethyl ketone 72 parts

(Comparative Example 1)
A protective layer transfer sheet of Comparative Example 1 was obtained in the same manner as in Reference Example 1 except that the release layer coating solution 5 having the following composition was used instead of the release layer coating solution 1.

<Coating solution 5 for release layer>
・ Acrylic resin 15.9 parts (MB7333 manufactured by Mitsubishi Rayon Co., Ltd.)
・ Polyester resin 0.1 part (Byron GK880 manufactured by Toyobo Co., Ltd.)
・ Toluene 12 parts ・ Methyl ethyl ketone 72 parts

(Comparative Example 2)
A protective layer transfer sheet of Comparative Example 2 was obtained in the same manner as in Reference Example 1, except that the release layer coating solution 6 having the following composition was used instead of the release layer coating solution 1.

<Peeling layer coating solution 6>
・ Styrene acrylic resin 15.9 parts (MB7668 manufactured by Mitsubishi Rayon Co., Ltd.)
・ Polyester resin 0.1 part (Byron GK880 manufactured by Toyobo Co., Ltd.)
・ Toluene 12 parts ・ Methyl ethyl ketone 72 parts

(Comparative Example 3)
A protective layer transfer sheet of Comparative Example 3 was obtained in the same manner as in Reference Example 1 except that the release layer coating solution 7 having the following composition was used instead of the release layer coating solution 1.

<Coating liquid 7 for release layer>
・ Cycloolefin resin 15.9 parts (APL6011T made by Mitsui Chemicals, Inc.)
・ Polyester resin 0.1 part (Byron GK880 manufactured by Toyobo Co., Ltd.)
・ Toluene 12 parts ・ Methyl ethyl ketone 72 parts

(Glossiness evaluation)
Using a sublimation type thermal transfer printer (manufactured by ALTECH ADS, model: MEGAPICEL III) and an ink ribbon dedicated to the printer, a solid black image was printed on the thermal transfer image-receiving sheet produced as follows by applying maximum energy. Next, using the protective layer transfer sheets of Reference Example 1, Examples 2 to 4 and Comparative Examples 1 to 3, the transfer layer (peeling layer + protective layer) was transferred onto the above image by the same printer, and Reference Example 1 was carried out. Prints of Examples 2 to 4 and Comparative Examples 1 to 3 were obtained. Glossiness on this black solid image was measured using a gloss meter (Gloss meter VG2000 (manufactured by Nippon Denshoku Co., Ltd.)) (measurement incident angle: 20 °, measurement direction: MD (main scanning direction)) and below The glossiness was evaluated according to the evaluation criteria of Table 1. The evaluation results are shown in Table 1.

(Preparation of thermal transfer image receiving sheet)
An adhesive layer forming coating solution having the following composition was applied to one surface of a 39 μm-thick microvoided film of the fine void layer and dried to form an adhesive layer. Next, according to the formation conditions described later, a support having a back layer provided on one side of the coated paper (186 g / m ² ) and a microvoid film are provided on the side opposite to the side on which the back layer is provided. It bonded together so that an adhesive bond layer might overlap.

<Coating liquid for forming the adhesive layer>
・ Polyfunctional polyol 30.0 parts (Takelac A-969V, manufactured by Mitsui Chemicals, Inc.)
・ Isocyanate 10.0 parts (Takenate A-5, manufactured by Mitsui Chemicals, Inc.)
Ethyl acetate 60.0 parts

Subsequently, on the surface opposite to the surface on which the adhesive layer of the microvoid film is provided, the primer layer forming coating solution having the following composition is coated with a wire bar so that the dry coating amount is 2.0 g / m ^2. Was applied and dried to form a primer layer.

<Primer layer forming coating solution>
・ Polyester polyol 15.0 parts (Adcoat, manufactured by Toyo Morton Co., Ltd.)
・ Methyl ethyl ketone / toluene (mass ratio 2: 1) 85.0 parts

On the formed primer layer, a dye receiving layer forming coating solution having the following composition is applied by wire bar coating so that the dry coating amount is 4.0 g / m ² and dried to form a dye receiving layer. As a result, a thermal transfer image receiving sheet was obtained.

<Dye-receiving layer forming coating solution>
-Vinyl chloride-vinyl acetate copolymer resin (vinyl chloride / vinyl acetate = 87/13, number average molecular weight 31,000, glass transition temperature 70 ° C.) 20.0 parts (Solvine C, manufactured by Nissin Chemical Industry Co., Ltd.) )
-Carboxyl-modified silicone 1.0 part (X-22-3701E, manufactured by Shin-Etsu Chemical Co., Ltd.)
・ Methyl ethyl ketone / toluene (mass ratio 1: 1) 79.0 parts

<Evaluation criteria>
○: The glossiness of the black solid part is 70 or more.
Δ: The glossiness of the black solid part is 60 or more and less than 70.
X: The glossiness of the black solid part is less than 60.

(Abrasion resistance evaluation)
In the same manner as in the above glossiness evaluation, a solid black image was formed on the transfer object, and the protective layer transfer sheets of Reference Example 1, Examples 2 to 4, and Comparative Examples 1 to 3 were used on the black solid image. The transfer layer (release layer + protective layer) was transferred to form a printed product. The printed material was cut out to a width of 2 cm, and a surface condition when a 300 g weight was placed on the printed material through a test cloth (Kanakin No. 3) and reciprocated 10 times was visually confirmed, and the following evaluation criteria were used. Scratch resistance was evaluated. The evaluation results are also shown in Table 1.

<Evaluation criteria>
○: Almost no effect on printed matter.
Δ: An effect is seen on the printed matter.
X: Prints have obvious scratches.

(Evaluation of plasticizer resistance)
In the same manner as in the above evaluation of scratch resistance, a black solid image was formed on the transfer target, and the protective layer transfer sheets of Reference Example 1, Examples 2 to 4, and Comparative Examples 1 to 3 were used on the black solid image. The transfer layer (release layer + protective layer) was transferred to form a printed product. Next, the printed materials of Reference Example 1, Examples 2 to 4 and Comparative Examples 1 to 3 cut out to 5 cm × 5 cm and a vinyl chloride sheet (Mitsubishi Chemical Corporation, Altron # 480, thickness 400 μm) are superimposed. , Store for 48 hours in an environment of 50 ° C. under a load of 1000 g, and after storage, peel off the vinyl chloride sheet from the printed material, and visually check whether the image of the printed material has been transferred to the vinyl chloride sheet. The plasticizer resistance was evaluated according to the evaluation criteria. The evaluation results are also shown in Table 1.

<Evaluation criteria>
○: No image transfer to the vinyl chloride sheet is observed.
Δ: Partial transfer of the image to the vinyl chloride sheet was observed.
X: Image transfer to a vinyl chloride sheet was observed throughout.

(Foil tearing evaluation)
In the same manner as in the above evaluation of scratch resistance, a solid black image was formed on the transfer target, and the transfer layer (peeling layer + protection layer) was formed on the image using the protective layer transfer sheet of Reference Example 1 and Examples 2 to 4. Layer) was transferred, the remaining state of the release layer was visually confirmed, and the foil breakage was evaluated according to the following evaluation criteria. The evaluation results are shown in Table 2.

<Evaluation criteria>
○: Trailing hardly occurs (2 mm or less).
Δ: Some tailing occurs (about 5 mm).
X: A considerable amount of tailing occurs (10 mm or more).

  As is apparent from the above results, according to the protective layer transfer sheet of the example in which the release layer contains a phenoxy resin, the gloss, scratch resistance, and plasticizer excellent in the printed matter after transfer of the protective layer. It was possible to impart sex. On the other hand, the comparative protective layer transfer sheet containing no phenoxy resin in the release layer could not give gloss to the printed material after the protective layer transfer. Furthermore, according to the protective layer transfer sheet of Examples 2 to 4 containing either a phenoxy resin or an acrylic resin, a polyester resin, or a polyester urethane resin in the release layer, the foil breakability during transfer is extremely excellent. It was confirmed that the occurrence of tailing can be effectively prevented.

DESCRIPTION OF SYMBOLS 10 Protective layer transfer sheet 1 Base material 2 Release layer 3 Protective layer 5 Heat resistant slipping layer 20 Transfer layer

Claims (2)

A protective layer transfer sheet comprising a base material and a transfer layer that is detachably provided on the base material,
The transfer layer is formed by laminating a release layer and a protective layer in this order from the substrate side,
The release layer contains (1) a phenoxy resin and (2) any one of an acrylic resin, a polyester resin, and a polyester urethane resin ,
(A) When the said peeling layer contains the said acrylic resin, content of the said acrylic resin when the total amount of the said phenoxy resin and the said acrylic resin is 100 mass parts is 10-30 masses Within the scope of
(B) When the said peeling layer contains the said polyester resin and / or polyester urethane resin, content of the said polyester resin and / or polyester urethane resin with respect to 100 mass parts of phenoxy resins is 3-5 mass parts. protective layer transfer sheet, wherein a range in der Rukoto of.   The protective layer transfer sheet according to claim 1, wherein an adhesive layer is provided on the protective layer.

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