JP2925171B2 - Sublimation type thermal transfer image receiving medium - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a sublimation type image transfer medium for thermal transfer.

[Prior Art] A thermal transfer recording medium (color ink sheet) having a transfer layer containing a thermal sublimable dye, and an image receiving medium (image receiving sheet) for receiving the dye sublimated by thermal printing from the back surface of the recording medium. The sublimation type thermal transfer recording system used has attracted attention in recent years as being capable of excellent halftone recording and providing a full-color hard copy close to a color photograph.

However, this sublimation type thermal transfer recording method uses a yellow, magenta, and cyan (black) ink sheet one by one to obtain one full-color image, and performs selective thermal printing for each ink sheet. After that, even if an unused portion remains, it is discarded, so that there is a disadvantage that the running cost is high.

Therefore, in order to remedy this drawback, it has been attempted to replace the image receiving substrate with paper such as gravure paper from the conventional synthetic paper in terms of material, and to reduce the speed of the image receiving sheet from the ink sheet in terms of the printing method. N times (n> 1), an n-times mode method is employed in which printing is repeated while both sheets are running. Note that this n-fold mode method is
Printing is performed a number of times with one ink sheet by a relative speed method in which an overlap between a used portion of the ink layer and a used portion of the ink layer is gradually shifted.

[Problems to be Solved by the Invention] In a conventional image receiving medium, a medium in which a dye receiving layer made of a thermoplastic polyester resin or the like having a strong dyeing property to a sublimation dye is formed on a substrate has been used. However, such an image receiving medium does not have sufficient hardness, friction resistance, and releasability. Particularly, in the n-times mode method, a strong frictional force is applied between the transfer medium and the image receiving medium. Wake up,
It may be damaged. In detail, in the n-times mode method, a large ratio of the moving speed of the moving velocity [V _1] and the image-receiving medium transfer medium changing the ratio of the _{[V 2], n = [} V 2 / [V 1] Thus, the number (n) of prints that can be performed by one transfer medium increases, which is preferable. However, at the time of printing, friction occurs because the speeds of the transfer medium and the image receiving medium are different, and a larger force is applied as n increases, and fusion and breakage are likely to occur. It can be said that the more printable even if n is large, the more preferable image receiving medium.

Accordingly, the present invention provides a peeling method which can be used in an n-times mode method in which an image has high density, high light resistance, and high preservability, and further requires a higher peeling property than a normal sublimation type thermal transfer recording method. It is an object of the present invention to provide a sublimation type image transfer medium for thermal transfer recording having excellent heat resistance.

[Means for Solving the Problems] According to the present invention, (1) a polyvinyl chloride resin containing active hydrogen, a layer mainly containing isocyanate, and a polyvinyl chloride resin containing active hydrogen on a substrate; A sublimation type thermal transfer image receiving medium in which a layer mainly composed of isocyanate and silicone oil is sequentially laminated; and (2) a polyester resin, a layer mainly composed of isocyanate, a polyester resin, isocyanate and silicone oil on a substrate. The present invention provides a sublimation type image transfer medium for thermal transfer, in which layers as components are sequentially laminated.

The present invention will be described with reference to the drawings. The specific configuration and operation of the present invention are as follows.

In FIG. 1, the image receiving medium of the present invention comprises an image receiving substrate A, an intermediate layer B and a dye receiving layer C. That is, the image receiving medium of the present invention is a layer B containing an active hydrogen-containing polyvinyl chloride resin or a polyester resin and an isocyanate as main components on an image receiving substrate A, and an active hydrogen-containing polyvinyl chloride resin or a polyester resin and an isocyanate. By laminating a C layer containing silicone oil as a main component, it has excellent dyeing properties, light resistance, and storage stability, and has extremely high hardness, friction resistance, and peelability suitable for recording by the n-fold mode method. An excellent image without fusing can be obtained.

In FIG. 1, reference numeral 1 denotes a thermal head, and the sublimation thermal transfer recording medium comprises a heat-resistant layer 2, a transfer substrate 3, and a dye transfer layer 4.

By the heating from the thermal head 1, the sublimable dye sublimates and diffuses from the dye transfer layer 4 of the dye of the sublimation thermal transfer recording medium, and the sublimated material is transferred to the dye receiving layer C of the image receiving medium. The sublimation dye transferred to the image receiving medium diffuses and dyes in the dye-dyeable resin forming the dye-receiving layer C.

In the present invention, since the intermediate layer is composed of the dyeable resin and the isocyanate and does not contain the silicone oil, the adhesive force with the substrate is remarkably improved, and the effect of concentrating the silicone oil of the receiving layer near the surface is obtained. The friction resistance is significantly improved.

Examples of the polyvinyl chloride resin containing active hydrogen used in the present invention include a vinyl chloride-vinyl acetate copolymer containing an OH group, a vinyl chloride-vinyl acetate copolymer containing a COOH group, and, for example, Union Carbide. VAGH, VRO
H, VMCC, VMCH, Denka Vinyl 1000G manufactured by Denki Kagaku Kogyo
KT, 1000GK, 1000GKS, 1000C, 1000CK, 1000CS and the like.

As the polyester resin used in the present invention, Byron RV550, RV300, RV103, RV600, RV200, PCR939, RV22
0, RV280, RV290 (Toyobo), Elitel 3600, 320
0, 3201, 3210, 3220 (hereinafter Unitika) and the like.

Further, as the isocyanate compound, tolylene diisocyanate, hexamethylene diisocyanate, 4,4-
Various isocyanate compounds such as diphenylmethane diisocyanate and triphenylmethane triisocyanate are used, and adducts thereof with hexanetriol and the like can also be used.

In addition, the use ratio of the above-mentioned dyeing resin and isocyanate is preferably in the range of 0.2 to 2.0 in terms of the molar ratio of NCO / OH when OH groups are contained.

As silicone oil, for example, commercially available KF96,
KF99, KF410, KS707, KM780, KF393, KF857 (Shin-Etsu Chemical), SF8417, SF8411, SH490, SH28PA, SF8427, S
R2101 (toray silicone).

Silicone oil content in the receiving layer is 1 to resin.
20% is preferred.

In addition, a filler can be contained in the intermediate layer and the dye receiving layer. Examples of the filler include silica, titanium oxide, and white pigments such as calcium carbonate. The amount of the filler is 5 to 5% based on the resin amount of the intermediate layer and the receiving layer.
60% by weight is preferred. In addition, the intermediate layer and the dye receiving layer may appropriately contain a surfactant, an ultraviolet absorber, an antioxidant, and the like.

As the substrate A in the image receiving medium of the present invention, synthetic paper, art paper, woodfree paper, coated paper, cellulose fiber paper, plastic film, and the like are preferably used alone or in a laminate thereof.

The coating amount of the intermediate layer and the dye receiving layer on the substrate is preferably 0.1 to 20 g / m ² in terms of solid content.

[Examples] Next, the present invention will be described in more detail with reference to Examples. All percentages and parts shown below are based on weight.

Example 1 A mixture having the following composition was sufficiently mixed and dispersed to prepare a coating liquid for an intermediate layer [Solution A] and a coating liquid for a dye receiving layer [Solution B].

[Solution A] Vinyl chloride / vinyl acetate / vinyl alcohol copolymer (trade name VAGH: manufactured by Union Carbide) 15 parts Isocyanate (trade name Coronate L: manufactured by Nippon Polyurethane Industry) 5 parts Toluene 40 parts Methyl ethyl ketone 40 parts [Solution B] 7 parts of vinyl chloride / vinyl acetate / vinyl alcohol copolymer (trade name VAGH; manufactured by Union Carbide) 7 parts Silicone oil (trade name KF393; manufactured by Union Carbide) ; Shin-Etsu Chemical Co., Ltd. 1 part Isocyanate (trade name: Coronate L; Nippon Polyurethane Industry Co., Ltd.) 1 part Toluene 40 parts Methyl ethyl ketone 40 parts Next, [Liquid A] was about 180 μm thick using a wire bar.
m synthetic paper (Yupo; manufactured by Oji Yuka Synthetic Paper) to form an intermediate layer having a thickness of about 2 μm, and then apply [Liquid B] onto the intermediate layer using a wire bar. An image receiving medium of the present invention was prepared by forming a dye receiving layer having a thickness of about 3 μm.

On the other hand, as the sublimation thermal transfer recording medium, a silicone cured resin film (about 1 μm thick) having a thickness of 6 μm is provided as a back layer.
A coating liquid [liquid C] for an ink layer (ie, a dye transfer layer) having the following formulation was applied to a thickness of about 2 μm on a μm PET film to obtain a transfer medium.

[Liquid C] Polyvinyl butyral (trade name BX-1; manufactured by Sekisui Chemical Co., Ltd.) 10 parts Sublimation disperse dye for cyan (trade name Kayaset 714; manufactured by Nippon Kayaku Co., Ltd.) 6 parts Polyethylene wax (trade name: 320P manufactured by Mitsui Petrochemical Co., Ltd.) 3 parts Methyl ethyl ketone 45 parts Toluene 45 parts The obtained transfer medium and image receiving medium are overlapped so that the ink layer of the transfer medium and the dye receiving layer of the image receiving medium face each other, and heated from the back of the transfer medium by a thermal head. Image recording was performed by changing the energy, and the presence or absence of heat fusion was observed by changing the speed ratio between the transfer medium and the image receiving medium. The recording density of the thermal head is 6 dots / mm, and the recording output is
It was 0.42 W / dot.

Example 2 An image receiving medium of the present invention was prepared in the same manner as in Example 1 except that [Liquid A] and [Liquid B] were used instead of [Liquid A] and [Liquid E], respectively. Was prepared.

[Solution D] Vinyl chloride / vinyl acetate / maleic acid copolymer (VMC
C) 15 parts Isocyanate (Coronate L) 5 parts Toluene 40 parts Methyl ethyl ketone 40 parts [Solution E] Vinyl chloride / vinyl acetate / vinyl alcohol copolymer (trade name VAGH; manufactured by Union Carbide) 10 parts Isocyanate (trade name Coronate L) ; Nippon Polyurethane Industry Co., Ltd. 1 part Silicone oil (trade name: SF8417; Toray Silicone Co., Ltd.) 0.5 part Silicone oil (trade name: SF8411; Toray Silicone Co., Ltd.) 0.5 part Toluene 40 parts Methyl ethyl ketone 40 parts Subsequently, the same as in Example 1. Then, image recording was performed, and the presence or absence of heat fusion was observed.

Example 3 Instead of the dye receiving layer coating solution [solution B] in Example 1,
An image receiving medium of the present invention was produced in the same manner as in Example 1 except that the following [Solution F] was used.

[Solution F] Vinyl chloride / vinyl acetate / vinyl alcohol copolymer (trade name: VAGH; manufactured by Union Carbide) 10 parts Silicone oil (trade name: SF8411: manufactured by Toray Silicone) 0.5 part Isocyanate (brand name: Coronate L: manufactured by Nippon Polyurethane) 5 parts Toluene 40 parts Methyl ethyl ketone 40 parts Comparative Example 1 The procedure of Example 1 was repeated except that [Solution G] was used instead of [Solution A] and [Solution B].

[Solution G] Vinyl chloride / vinyl acetate copolymer (trade name VYHH; manufactured by Union Carbird) 20 parts Silicone oil (trade name SF8417; manufactured by Toray Silicone) 2 parts Toluene 40 parts Methyl ethyl ketone 40 parts Comparative Example 2 Comparative Example 2 The same procedure as in Example 1 was carried out except that only [Liquid B] was used without using the intermediate layer of [Liquid A].

The results are shown below. The heat-fusibility was evaluated by changing the transfer speed ratio [V ₂ / V ₁ ] = n of the transfer medium and the image receiving medium from 1 to 10, and observing the peeling state between them.

Example 4 Hereinafter, an example in which a polyester resin is used will be described.

The mixture having the following composition was sufficiently mixed and dispersed to prepare a coating liquid [liquid A] for the intermediate layer and a coating liquid [liquid B] for the dye receiving layer.

[Solution A] Polyester resin (Vylon 200; Toyobo) 18 parts Isocyanate (Coronate L; Nippon Polyurethane) 2 parts Toluene 40 parts Methyl ethyl ketone 40 parts [Solution B] Polyester resin (Vylon 200) 7 parts Polyester resin (Vylon 290) 7 parts Silicone oil (trade name KF393; manufactured by Shin-Etsu Chemical Co., Ltd.) 1 part Isocyanate (trade name: Coronate L; manufactured by Nippon Polyurethane Industry Co., Ltd.) 1 part Toluene 40 parts Methyl ethyl ketone 40 parts Next, [Liquid A] was added using a wire bar. 180μ thick
m synthetic paper (Yupo; manufactured by Oji Yuka Synthetic Paper) to form an intermediate layer having a thickness of about 2 μm, and then apply [Liquid B] onto the intermediate layer using a wire bar. An image receiving medium of the present invention was prepared by forming a dye receiving layer having a thickness of about 3 μm.

On the other hand, as a sublimation thermal transfer recording medium, a 6 μm thick silicone cured resin film (about 1 μm thick) was provided as a back layer.
A coating liquid [liquid C] for an ink layer (that is, a dye transfer layer) having the following formulation was applied to a thickness of about 2 μm on a PET film having a thickness of about 2 μm to obtain a transfer medium.

[Liquid C] Polyvinyl butyral (trade name: BX-1; manufactured by Sekisui Chemical Co., Ltd.) 10 parts Sublimation disperse dye for cyan (trade name: Kayaset 714; manufactured by Nippon Kayaku Co., Ltd.) 6 parts Polyethylene wax (320P; manufactured by Mitsui Petrochemical) Part Methyl ethyl ketone 45 parts Toluene 45 parts The obtained transfer medium and image receiving medium are overlapped so that the ink layer of the transfer medium and the dye receiving layer of the image receiving medium face each other, and heating energy is applied from the back side of the transfer medium by a thermal head. Image recording was performed while changing the speed ratio of the transfer medium and the image receiving medium, and the presence or absence of heat fusion was observed. The recording density of the thermal head is 6 dots / mm, and the recording output is
It was 0.42 W / dot.

Example 5 Example 4 was repeated except that the following [Solution D] and [Solution E] were used instead of [Solution A] and [Solution B], respectively.
In the same manner as in the above, an image receiving medium of the present invention was produced.

[Solution D] Polyester resin (Vylon 300) 18 parts Isocyanate (Coronate L) 2 parts Toluene 40 parts Methyl ethyl ketone 40 parts [Solution E] Vinyl chloride / vinyl acetate copolymer (VYNS; manufactured by Union Carbide) 10 parts Polyester Resin (Vylon 200, manufactured by Toyobo) 10 parts Isocyanate (brand name: Coronate L; manufactured by Nippon Polyurethane Industry Co., Ltd.) 1 part Silicone oil (brand name: SF8417; manufactured by Toray Silicone) 0.5 part Silicone oil (brand name: SF8411; manufactured by Toray Silicone Co., Ltd.) 0.5 part Toluene 40 parts Methyl ethyl ketone 40 parts Subsequently, an image was recorded in the same manner as in Example 4, and the presence or absence of heat fusion was observed.

Example 6 Instead of the dye receiving layer coating solution [Solution B] in Example 4,
An image receiving medium of the present invention was produced in the same manner as in Example 4 except that the following [F solution] was used.

[Solution F] Polyester resin (Vylon 200) 15 parts Isocyanate (Coronate L) 4 parts Silicone oil (SF8411) 0.5 part Toluene 40 parts Methyl ethyl ketone 40 parts Comparative Example 3 Instead of [Solution A] and [Solution B] of Example 4 The same operation as in Example 4 was performed except that [G solution] was used.

[Solution G] Vinyl chloride / vinyl acetate copolymer (trade name: VYHH; manufactured by Union Carbide) 20 parts Silicone oil (trade name: SF8417; manufactured by Toray Silicone) 2 parts Toluene 40 parts Methyl ethyl ketone 40 parts Comparative Example 4 Comparative Example 4 [Example 4] The same procedure as in Example 4 was carried out except that only the [solution B] was used without using the intermediate layer formed by the [solution A].

 The results are shown below.

In addition, the heat fusing property was evaluated by changing the moving speed ratio [V ₂ / V ₁ ] = n of the transfer medium and the image receiving medium from 1 to 10, and observing the peeling state between them.

[Effects of the Invention] As described above, the image receiving substrate according to the configuration of the present invention is suitable for recording by the n-times mode method, and is excellent without causing fusion to a transfer medium during recording. It shows releasability.

[Brief description of the drawings]

FIG. 1 is a diagram showing the layer structure of a transfer medium for sublimation type thermal transfer recording and an image receiving medium and their relationship. DESCRIPTION OF SYMBOLS 1 ... Thermal head, 2 ... Heat resistant layer, 3 ... Transfer base, 4 ... Dye transfer layer, A ... Image receiving base, B ... Intermediate layer, C ... Dye receiving layer.

──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Naoya Moroboshi 1-3-6 Nakamagome, Ota-ku, Tokyo Inside Ricoh Co., Ltd. (56) References JP-A-3-47793 (JP, A) (58) Field surveyed (Int.Cl. ⁶ , DB name) B41M 5/38-5/40

Claims (2)

(57) [Claims] An active hydrogen-containing polyvinyl chloride resin and a layer mainly composed of isocyanate and a layer mainly composed of an active hydrogen-containing polyvinyl chloride resin, isocyanate and silicone oil are sequentially formed on a substrate. An image receiving medium for sublimation type thermal transfer characterized by being laminated. 2. An image receiving medium for sublimation type thermal transfer, comprising: a layer mainly composed of a polyester resin and an isocyanate; and a layer mainly composed of a polyester resin, an isocyanate and a silicone oil.