JPH0379391A - Image receiving medium for sublimation type thermal transfer - Google Patents

Abstract

PURPOSE:To increase image density, to enhance the bonding strength between a substrate and a dye receiving layer and to improve the releasability of an image receiving medium and a transfer recording medium after recording by laminating a specific intermediate layer and the dye receiving layer to the substrate in this order. CONSTITUTION:An intermediate layer C mainly consisting of a resin having a hydroxyl group and an isocyanate compound and a dye receiving layer B mainly consisting of a thermoplastic polyester resin and silicone oil are laminated to an image receiving substrate A in this order. That is, since the intermediate layer C is provided between the image receiving substrate A and the dye receiving layer B, the image receiving substrate A receives no effect of the silicone oil in the dye receiving layer B and the bonding strength of the image receiving substrate A and the dye receiving layer B is kept high and the release between the image receiving substrate A and the dye receiving layer B after recording is prevented. By this method, image density is increased and the dye receiving layer is not released from a dye transfer layer after recording and the releasability between the dye receiving layer and the dye transfer layer is made excellent.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to an image receiving medium for sublimation type thermal transfer. [Prior Art] Conventionally, as an image receiving medium used in this recording method, a dye-receiving layer made of a thermoplastic polyester resin, etc., which exhibits strong dyeability against heat-sublimable dyes, and a release agent is formed on a substrate. The one that was made is used. However, since polyester resin has low heat resistance, the transfer recording medium (
The disadvantage is that it heat-fuses with the color sheet). Therefore, if the dye-receiving layer contains a large amount of a release agent such as silicone oil in order to improve the releasability (peelability) between the dye-receiving layer and the transfer recording medium, the adhesion between the substrate and the dye-receiving layer (
Adhesion) may deteriorate and the receptor layer may be peeled off toward the transfer recording medium after recording, or the transparency of the dye-receiving layer itself may decrease [i.e., the haze value ( This results in a disadvantage in that the image quality as a transparent document deteriorates (the projected image becomes dark and smudged in OHP). H(%)-Td/Ttxloo...(1)H
: Haze value (haze value) (%) Tt: Total light transmittance (%) Td: Diffuse light transmittance (%) [Issue 1i to be solved by the invention] The present invention solves the above problems, The image density is high, and the adhesion between the substrate and the dye-receiving layer is high (good adhesion), and the image-receiving medium (dye-receiving layer) and transfer recording medium (dye-transfer layer) do not peel off after recording. It is an object of the present invention to provide an image receiving medium having good properties, and furthermore, to provide an image receiving medium having good transparency (low haze value) and high image quality. [Means for Solving the Problems] According to the present invention, an intermediate layer mainly composed of a resin having a hydroxyl group and an isocyanate compound and a dye-receiving layer mainly composed of a thermoplastic polyester resin and a silicone oil are formed on a substrate in that order. An image receiving medium for sublimation type thermal transfer is provided, which is characterized in that it is formed by laminating layers. That is, the image-receiving medium for sublimation thermal transfer of the present invention includes an intermediate layer containing a resin having a hydroxyl group and an isocyanate compound as main components between the substrate and a dye-receiving layer containing a thermoplastic polyester resin and a silicone oil as main components. Because of this structure, the transparent substrate is not affected by the silicone oil in the dye-receiving layer, and therefore the adhesive force between the substrate and the dye-receiving layer is maintained while the image-receiving medium (dye-receiving layer) and transfer recording medium (The dye transfer layer) has good releasability. Next, the present invention will be explained with reference to the drawings.The specific structure and operation of the present invention are as follows. In FIG. 1, the image-receiving medium of the present invention is composed of an image-receiving substrate A, a dye-receiving layer B, and an intermediate layer C. That is, the image-receiving medium of the present invention has a structure in which an intermediate layer C consisting mainly of a resin having a hydroxyl group and an isocyanate compound and a dye-receiving layer B consisting mainly of a thermoplastic polyester resin and silicone oil are laminated on an image-receiving substrate A in that order. ing. Further, ■ indicates a thermal head, and the sublimation transfer recording medium is composed of a heat-resistant layer 2, a transfer substrate 3, and a dye transfer layer 4. Heat from the thermal head 1 causes the heat sublimable dye to sublimate and diffuse from the dye transfer layer 4 of the sublimation transfer recording medium, and the sublimated dye is transferred to the dye receiving layer B of the image receiving medium. The sublimation dye transferred to the image-receiving medium diffuses into the dye-staining resin forming the dye-receiving layer B and dyes the medium. As mentioned above, in conventional image-receiving media, it is known that a release agent such as silicone oil is included in the dye-receiving layer B in order to prevent heat fusion during recording and improve releasability after recording. However, when the release agent content is low,
The peelability improvement effect was insufficient, as shown in Figure 2.
After recording, the dye transfer layer 4 is peeled off to the dye receiving layer B side. However, when the content of the release agent is increased in order to improve the releasability, the adhesive force between the image-receiving substrate A and the dye-receiving layer B becomes weaker, and as shown in FIG. dye. A phenomenon occurs in which the receiving layer B is peeled off toward the dye transfer layer 4 side. However, in the image-receiving medium of the present invention, since the intermediate layer C mainly composed of a resin having a hydroxyl group and an isocyanate compound is provided between the image-receiving substrate A and the dye-receiving layer B, the image-receiving medium A is not affected by the silicone oil in the dye-receiving layer B, the adhesive strength between the image-receiving substrate A and the dye-receiving layer B is maintained high, and peeling between the image-receiving substrate A and the dye-receiving layer B after recording is prevented. is prevented. As shown in the comparative example below, when an intermediate layer containing a resin having a hydroxyl group and not containing an incyanate compound is provided, the adhesion between the image receiving substrate A and the dye receiving layer B is improved, but the dye receiving substrate The peelability between the layer B and the dye transfer layer 4 is lower than in the case where no intermediate layer is provided, and the dye transfer layer 4 is peeled off to the dye receiving layer B side after recording. In the image receiving medium of the present invention having the intermediate layer C mainly composed of a resin having a hydroxyl group and an isocyanate compound, the peelability between the dye receiving layer B and the dye transfer layer 4 after recording is lower than that when no intermediate layer is provided. Since the dye-receiving layer B is significantly improved in comparison, the amount of silicone oil blended in the dye-receiving layer B can be reduced. Therefore, in the image-receiving medium of the present invention, the adhesive strength between the image-receiving substrate A and the dye-receiving layer B is high, and the dye-receiving layer B after recording is
The releasability between the dye transfer layer 4 and the dye transfer layer 4 becomes good. Furthermore, in an image receiving medium for producing a transparent original, it is a matter of course that the substrate has high transparency, but it is also required that the dye-receiving layer has high transparency. The smaller the amount of silicone oil in the dye-receiving layer, the more
The dye-receiving layer becomes more transparent (lower haze value). Examples of the resin having a hydroxyl group used in the intermediate layer C of the present invention include polyester resins, polyvinyl alcohol-modified vinyl chloride/vinyl acetate copolymers, etc. Commercially available products include, for example, Vylon 200,
Byron 600, Byron 290 [both Toyobo ■
manufactured by Union Carbide Co., Ltd., VAGHSVROH etc. manufactured by Union Carbide, Denkabinyl 100OGKT manufactured by Denki Kagaku Kogyo Co., Ltd.
100OGK. Examples include 1000 KGS. In addition, as the isocyanate compound, tolylene diisocyanate, hexamethylene diisocyanate, 4,4
Various isocyanate compounds such as -diphenylmethane diisocyanate and triphenylmethane triisocyanate are used, and adducts of these with hexanetriol and the like can also be used. Note that the ratio of the resin having a hydroxyl group to the isocyanate compound used is preferably in the range of 0.2 to 2.0 in molar ratio of NC010H. The thermoplastic polyester resin used in the dye-receiving layer B of the present invention has a glass transition temperature of 40 to 85°C.
For example, commercially available products include Byron 200, Byron 103, Byron 600, manufactured by Toyobo Co., Ltd.
Byron 290, Byron PCR92B, Byron PC
Examples include R939. As the silicone oil, for example, amino-modified silicone oil, epoxy-modified silicone oil, alkyl-modified silicone oil, polyether-modified silicone oil, etc. are used, and commercially available products include 5P8417, BYlB-828, 5F84 manufactured by Toray Silicone ■.
11.8413, SH203, 5H374B, 5H37
49 etc. are mentioned. Among these, when amine-modified silicone oil is used alone, the transparency of the dye-receiving layer is particularly high (low haze value), and the releasability of the dye-receiving layer and the dye transfer layer is also excellent. The ratio of silicone oil to thermoplastic polyester resin is:
A range of 0.2 to 20% by weight is preferred. Incidentally, the dye-receiving layer B and the intermediate layer C may also contain a filler. Examples of the filler include white pigments such as silica, titanium oxide, and calcium carbonate, and the amount added is 5 to BO
Weight percent is preferred. In addition, these layers may contain surfactants, ultraviolet absorbers, antioxidants, and the like as appropriate. You can also do that. In addition, as the substrate A in the image receiving medium of the present invention, synthetic paper, art paper, high-quality paper, coated paper, gravure paper 1, baryta paper, cellulose fiber paper, plastic film, etc., alone or in a laminate thereof, are suitable. used for. In addition, particularly when selecting a transparent substrate, a polyethylene phthalate film is most preferably used, but films of polyolefin, acrylic resin, vinyl chloride resin, vinylidene chloride resin, etc. can also be used. The thickness of the intermediate layer and dye-receiving layer provided on the substrate is preferably from 11 to 10 μm, particularly preferably from 0.1 to 5 μm. [Example] Next, the present invention will be explained in more detail with reference to Examples. Note that 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 an intermediate layer coating liquid [
Liquid A] and a coating liquid for the receptor layer [Liquid B] were prepared. [Liquid A] Polyester resin [trade name Pylon 200; manufactured by Toyobo ■] 100 parts Isocyanate (trade name Parnock DN-950; manufactured by Dainippon Ink & Chemicals ■) 10 parts Toluene 300 parts Methyl ethyl ketone 300 parts cB liquid] Polyester resin ( Product name Byron 200) 100 parts Amino-modified silicone oil (Product name 5P8417; manufactured by Toray Silicone ■) 1 part Toluene 280 parts Methyl ethyl ketone 280 parts Next, [Liquid A] was added using a wire bar to a synthetic paper with a thickness of about 150 μI. (trade name: Yupo PGP-150, manufactured by Tamago Yuka Synthetic Paper Co., Ltd.) and dried for 1 minute at a drying temperature of 90°C to form an intermediate layer and a receptor layer each having a weight of about 3 μI. On the other hand, as a sublimation transfer recording medium, a PE film with a thickness of 8 μm was provided with a silicone resin film (about 1 μm thick) as a back layer.
An ink layer (i.e. dye transfer layer) with the following formulation on the T film
The coating liquid [Liquid C] was applied to a thickness of about 2 μm to obtain a transfer recording medium. [Liquid C] 10 parts polyvinyl butyral (trade name BX-1, manufactured by Block Chemical Industry ■) Sublimated disperse dye (trade name Kayaset Blue 14; manufactured by Nippon Kayaku ■) 6 parts toluene
95 parts methyl ethyl ketone 95 parts The obtained transfer recording medium and image receiving medium are placed one on top of the other 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 recording medium using a thermal head. I changed it and recorded an image. The recording density of the thermal head is 6 dots/■
The recording output was 0.42 M/dot. Example 2 An image receiving medium of the present invention was produced in the same manner as in Example 1 except that the following [Liquid D] was used instead of [Liquid A] in Example 1. [Liquid D] Polyester resin (trade name: Vylon 200) 100 parts Isocyanate (trade name: Burnock D-750; manufactured by Dainippon Ink & Chemicals) 10 parts Toluene 300 parts Methyl ethyl ketone 300 parts Subsequently, images were prepared in the same manner as in Example 1. Recorded. Example 3 An image receiving medium of the present invention was produced in the same manner as in Example 1, except that the following [Liquid E] was used instead of [Liquid A] in Example 1. [Liquid E] Vinyl chloride/vinyl acetate/vinyl alcohol copolymer (trade name VAGH; manufactured by Union Carbide) 100 parts Isocyanate [trade name Parnock DN-950; manufactured by Dainippon Ink & Chemicals ■] 50 parts Toluene 390 parts Methyl ethyl ketone 390 copies were then subjected to image recording in the same manner as in Example 1. Comparative Example 1 An image receiving medium of Comparative Example 1 was prepared in the same manner as in Example 1, except that the above-mentioned [Liquid B] was used as the receiving layer coating liquid and no intermediate layer was provided, and an image was recorded. Comparative Example 2 An image receiving medium of Comparative Example 2 was prepared in the same manner as in Example 1, except that the following [Liquid F] was used as the receiving layer coating liquid and no intermediate layer was provided, and an image was recorded. [Liquid F] 100 parts of polyester resin (product name: Vylon 200) amino-modified silicone oil [product name: SFI! 417; Made by Toray Silicone ■ 10
Parts Toluene 280 parts Methyl ethyl ketone 280 parts Comparative Example 3 Comparative Example 3 was carried out in the same manner as in Example 1 except that the following [Liquid G] was used as the intermediate layer coating liquid and the above [Liquid F] was used as the receptor layer coating liquid.
An image-receiving medium was created and images were recorded. [Liquid G] Polyester resin (trade name: Vylon 200) 100 parts Toluene 300 parts Methyl ethyl ketone 300 parts Example 4 Example 4 except that [Liquid A] was used as the intermediate layer coating liquid and [Liquid F] was used as the receptor layer solution. An image receiving medium of the present invention was prepared in the same manner as in Example 1, and images were recorded thereon. Example 5 [Liquid A] was used as the intermediate layer coating liquid, and the following [Liquid A] was used as the coating liquid for the receptor layer.
An image receiving medium of the present invention was prepared in the same manner as in Example 1 except that H solution was used, and an image was recorded. [H solution] Polyester resin (trade name: Vylon 200) 100 parts Amino-modified silicone oil (trade name 5P8417; manufactured by Toray Silicone ■) 5 parts Epoxy-modified silicone oil [trade name 5P8411; manufactured by Toray Silicone ■] 5 parts Toluene 280 parts Methyl ethyl ketone 280 copies. Table 1 shows the results of the above image recording and the adhesion between the substrate and the receptor layer. 1st table Peelability Image density Adhesion Image density...Maximum image density measured by Macbeth RD-514 reflection densitometer Adhesion...Adhesion between substrate and dye receiving layer O Good X Insufficient Example 6 Below An example in which a transparent substrate is used is shown below. Thoroughly mix and disperse a mixture with the following composition to prepare an intermediate layer coating liquid [
Liquid A] and receptor layer coating liquid [Liquid B] were prepared. [Liquid A] Polyester resin [trade name Pylon Z00; manufactured by Toyobo ■] 100 parts / Isocyanate [trade name Parnock DN-950; manufactured by Dainippon Ink Chemical Industry Co., Ltd. 110 parts Toluene 300 parts Methyl ethyl ketone 300 parts [Liquid B] Polyester resin (Product name Byron 200) 100 parts Amino-modified silicone oil [Product name 5P8417; ) - Manufactured by Resilicone ■] 1 part Toluene 280 parts Methyl ethyl ketone 280 parts Next, [Liquid A] was mixed with a wire bar to a thickness of about 100μ■ The image receiving medium of the invention It was created. On the other hand, as a sublimation transfer recording medium, PE with a thickness of Bμ and a silicone resin film (approximately 1 μm thick) was used as a back layer.
A coating liquid for an ink layer (ie, dye transfer layer) [liquid 2] having the following formulation was coated on the T film to a thickness of about 2 μm to obtain a transfer recording medium. [Liquid I] Polyvinyl butyral (trade name BX-1, manufactured by Block Chemical Industry ■) 7 parts polyethylene oxide [trade name R-400, manufactured by Meisei Chemical Industry ■] 3 parts sublimation disperse dye (trade name Kayaset Blue 14; Japan) 115 parts manufactured by Kayaji Co., Ltd. Toluene 95 parts Methyl ethyl ketone 95 parts The obtained transfer recording medium and image receiving medium are placed one on top of the other so that the ink layer of the transfer medium and the dye receiving layer of the image receiving medium face each other, and from the back side of the transfer recording medium Images were recorded by changing the heating energy with a thermal head.The recording density of the thermal head was 6
dot/ltrm, and the recording output was 0.42 V/dot. Example 7 An image receiving medium of the present invention was produced in the same manner as in Example 6 except that the following [Liquid D] was used instead of [Liquid A] in Example 6. [Liquid D] 100 parts of polyester resin (trade name: Vylon 200) 10 parts of isocyanate (trade name: Burnock D-750; manufactured by Dainippon Ink & Chemicals) 10 parts of toluene 300 parts of methyl ethyl ketone 300 parts Subsequently, images were prepared in the same manner as in Example 6. Recorded. Example 8 An image receiving medium of the present invention was produced in the same manner as in Example 6, except that the following [Liquid E] was used instead of [Liquid A] in Example 6. [Liquid E] Vinyl chloride/vinyl acetate/vinyl alcohol copolymer (trade name VAGH; manufactured by Union Carbide) 100 parts Isocyanate [trade name Parnock DN-950, manufactured by Dainippon Ink & Chemicals ■] 50 parts Toluene 390 parts Methyl ethyl ketone 390 copies were then subjected to image recording in the same manner as in Example 6. Comparative Example 4 An image receiving medium of Comparative Example 4 was prepared in the same manner as in Example 6, except that the above-mentioned [Liquid B] was used as the receiving layer coating liquid and no intermediate layer was provided, and an image was recorded. Comparative Example 5 An image receiving medium of Comparative Example 5 was prepared in the same manner as in Example 6, except that the following [Liquid F] was used as the receiving layer coating liquid and no intermediate layer was provided, and image recording was performed. [Liquid F] 100 parts of polyester resin (trade name: Vylon 200) Amino-modified silicone oil [trade name: 5P8417; manufactured by Resilicone ■] 10 parts Toluene 280 parts Methyl ethyl ketone 280 parts Comparative Example 6 The following [Liquid G] was used as the intermediate layer coating liquid. ], Comparative Example 6 was prepared in the same manner as in Example 6 except that the above [Liquid F] was used as the receptor layer coating liquid.
An image-receiving medium was created and images were recorded. [Liquid G] Polyester resin (trade name: Vylon 200) 100 parts Toluene 300 parts Methyl ethyl ketone 300 parts or more The results of image recording, the haze value of the image receiving medium, and the adhesive strength between the substrate and the receiving layer are shown in Table 2. 2nd Omote Town) Peelability between dye receiving layer and dye transfer layer after recording 112
) Maximum image density measured by Macbeth TO-504 type transmission densitometer Machi) Background portion of image receiving medium measured by direct reading Heis computer 10M-2DP type [Effects of the Invention] As explained above, the image receiving medium for sublimation thermal transfer of the present invention The medium consists of an intermediate layer mainly composed of a resin containing a hydroxyl group and an isocyanate compound on a substrate, and a dye-receiving layer mainly composed of a thermoplastic polyester resin and silicone oil that exhibit strong dyeing properties for heat-sublimable dyes, in that order. Because of the laminated structure, the image density is high, and the dye-receiving layer is not peeled off to the dye-transfer layer side after recording. Excellent releasability (between). In addition, image receiving media using transparent substrates have high transparency (low haze value).
, the image quality will also be even better.

[Brief explanation of drawings]

FIG. 1 is a diagram showing the structure of each layer of an image receiving medium for sublimation type thermal transfer and a transfer recording medium according to the present invention, and the relationship between them. FIG. 2 is a diagram illustrating failure of peeling from a recording medium during recording in a conventional image receiving medium. FIG. 3 is a diagram illustrating poor adhesion between the substrate and the dye-receiving layer during recording on the same image-receiving medium. A... Image receiving substrate, B... Dye receiving layer, C... Intermediate layer, ■... Thermal head, 2... Heat resistant layer, 3...
- Transfer substrate, 4... dye transfer layer.

Claims (2)

[Claims] (1) It is characterized by being formed by laminating, in this order, an intermediate layer mainly made of a resin having a hydroxyl group and an isocyanate compound, and a dye-receiving layer mainly made of a thermoplastic polyester resin and silicone oil, on a substrate. Image receiving medium for sublimation type thermal transfer. (2) The image receiving medium for sublimation thermal transfer according to claim (1), wherein the substrate is a transparent substrate.