JP3009930B2 - Sublimation type thermal transfer image receiving medium - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a sublimation type image transfer medium for thermal transfer.

[0002]

2. Description of the Related Art A sublimation type thermal transfer recording system using a thermal transfer recording medium having a transfer layer containing a thermal sublimable dye and an image receiving medium receiving the dye sublimated by thermal printing from the back of the recording medium is excellent. In recent years, it has attracted attention as a medium capable of recording halftones and providing a full-color hard copy close to a color photograph. Conventionally, as an image receiving medium used in this recording method, a dye receiving layer composed of a thermoplastic polyester resin or the like having a strong dyeing property to a thermo-sublimable dye and a release agent is formed on a substrate (synthetic paper or the like). The formed one is used. However, since the polyester resin has low heat resistance, it has a disadvantage that it fuses with a transfer recording medium (color sheet) during recording. Therefore, in order to improve the releasability (releasability) between the dye-receiving layer and the transfer recording medium, a release agent is added to the dye-receiving layer.
Unless a transfer substrate having a very strong adhesive force between the transfer substrate and the dye transfer contributing layer is used, the transfer layer is peeled off to the image receiving medium side after recording. Conversely, to the extent that the peelability between the transfer recording medium / image receiving medium is sufficiently improved.
When the amount of the releasing agent in the dye receiving layer is increased, the adhesive force between the substrate in the image receiving medium and the dye receiving layer is reduced, and the recording layer is peeled off to the transfer recording medium after recording. . In addition, since the release agent used generally has low compatibility with the resin in the dye-receiving layer, increasing the amount of the release agent results in a decrease in the transparency of the dye-receiving layer itself. In a transmission type image receiving medium used as a transmission original such as an overhead projector, it is essential that the transparency of the dye receiving layer is high, but in a reflection type image receiving medium for observing a reflected image, the transparency of the dye receiving layer is also high. The higher the value, the clearer the image.

[0003]

DISCLOSURE OF THE INVENTION The present invention solves the above problems, has good heat resistance, has a high adhesive strength between the substrate and the dye receiving layer, and has an image receiving medium (dye receiving layer) after recording. ) And a transfer recording medium (dye transfer layer), and an image receiving medium having a high image quality and a high transparency of the dye receiving layer.

[0004]

In order to solve the above-mentioned problems, the constitution of the present invention comprises a layer containing an isocyanate compound on a substrate, a resin containing an active hydrogen, an isocyanate compound and a polyether-modified silicone as main components. A sublimation type image transfer medium for thermal transfer characterized in that layers are sequentially laminated. That is, the image-receiving medium for sublimation type thermal transfer of the present invention is provided with an intermediate layer containing an isocyanate compound between a substrate, a resin containing active hydrogen, an isocyanate compound and a dye-receiving layer containing polyether-modified silicone as a main component. It is a thing. By doing so, the image receiving medium (dye receiving layer) and the transfer recording medium (dye transfer) are not affected by the release agent in the dye receiving layer, so that the adhesive strength between the substrate and the dye receiving layer is maintained. Layer). Next, 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, a dye receiving layer B and an intermediate layer C. Reference numeral 1 denotes a thermal head, and the sublimation transfer recording medium includes 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 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 and dyes in the dye-dyeable resin forming the dye-receiving layer B. As described above, in the conventional image receiving medium, it is known to include a release agent such as silicone oil in the dye receiving layer B in order to prevent thermal fusion at the time of recording and to enhance releasability after recording. However, when the release agent content is low, the effect of improving the releasability is insufficient, and the dye transfer layer 4 is peeled off to the dye receiving layer B side after recording. However, if the content of the release agent is increased in order to enhance the releasability, the adhesive force between the image receiving substrate A and the dye receiving layer B is weakened, and the dye receiving layer B becomes the dye transfer layer 4 after recording. The phenomenon of being stripped to the side occurs. However, in the image receiving medium of the present invention, since the intermediate layer C containing the isocyanate compound is provided between the image receiving substrate A and the dye receiving layer B, the image receiving substrate A is used as the release agent in the dye receiving layer B. Unaffected, the adhesion between the image receiving substrate A and the dye receiving layer B is kept high, and peeling between the image receiving substrate A and the dye receiving layer B after recording is prevented. In the image receiving medium of the present invention containing an isocyanate compound in the intermediate layer C and the dye receiving layer B, the releasability between the dye receiving layer B and the dye transfer layer 4 after recording is higher than that in the case where no isocyanate compound is contained. And greatly improved. The polyether-modified silicone used in the dye receiving layer B of the image receiving medium of the present invention has high compatibility with the dye-dyeing resin and the isocyanate compound, and suppresses light scattering (intralayer diffusion) inside the receiving layer. Further, the transparency of the dye receiving layer B becomes higher (the haze value becomes lower). Further, the resin containing active hydrogen used in the dye receiving layer B of the image receiving medium of the present invention undergoes a crosslinking reaction with an isocyanate compound, and the heat resistance of the dye receiving layer B is improved. The degree of decrease in the flatness of the surface of the dye receiving layer in the portion is small. Therefore, light scattering (epidermal diffusion) on the surface of the receiving layer is suppressed, and transparency is maintained. From the above, in the image receiving medium of the present invention, the adhesive force between the image receiving substrate A and the dye receiving layer B is high, and the releasability between the dye receiving layer B and the dye transfer layer 4 after recording is good.
In addition, since the transparency of the dye receiving layer B is high, the image quality is excellent. As the isocyanate compound used in the intermediate layer C and the dye receiving layer B of the present invention, tolylene diisocyanate, hexamethylene diisocyanate,
Various isocyanate compounds such as 4,4-diphenylmethane diisocyanate, triphenylmethane triisocyanate, xylylene diisocyanate, meta-xylylene diisocyanate, isophorone diisocyanate, bis isocyanate methyl cyclohexane, etc. are used. be able to. The intermediate layer C of the present invention may be composed of only an isocyanate compound, but may contain other components such as a resin as appropriate. As the resin, for example, vinyl chloride resin,
Vinyl acetate resin, polyamide, polyethylene, polycarbonate, polystyrene, polypropylene, acrylic resin, phenol resin, polyester, polyurethane, epoxy resin, silicone resin, fluororesin, butyral resin, melamine resin, natural rubber, synthetic rubber, polyvinyl alcohol, cellulose resin And the like. These resins can be used alone, but several kinds may be mixed or a copolymer may be used. In addition, as the resin containing active hydrogen used in the dye receiving layer B of the present invention, in addition to polyester resin and polyvinyl chloride resin, polyvinyl butyral, polyvinyl acetal, polyurethane polyol, polyether polyol, polyester polyol, acrylic, acrylic -Polyester copolymers, alkyds, silicone polyesters, and those obtained by opening the epoxy group of an epoxy with an alkanolamine to form an -OH group. Byron RV55 as polyester resin
0, RV300, RV103, RV600, RV200, PCR939,
RV220, RV280, RV290 (Toyobo), Elitel 3600, 3200, 3201, 3210, 3220 (Unitika) and the like. Examples of polyvinyl chloride resins containing active hydrogen include vinyl chloride-vinyl acetate copolymers containing OH groups, C
Examples include a vinyl chloride-vinyl acetate copolymer containing an OOH group, such as VAGH and VR manufactured by Union Carbide.
OH, VMCC, VMCH, Denka Vinyl 1000GKT, 1000GK, 1000GKS, 1000C, 1000CK, 100
0CS and the like. The ratio of the resin containing active hydrogen to the isocyanate is preferably in the range of 0.2 to 5.0 in terms of the molar ratio of NCO / OH when the resin contains OH groups. The polyether-modified silicone used in the present invention includes, for example, a polyether-modified silicone represented by the following structural formula 1 or 2, an epoxy / polyether-modified silicone of formula 3, and an alkylaralkyl polyether of formula 4 Silicone.

Embedded image However, m and n are integers of 3000 or less, a and b are integers of 50 or less, R is an alkyl group, aryl group, or aralkyl group having 8 or less carbon atoms.

Embedded image However, n is an integer of 3000 or less, a is an integer of 100 or less, R is an alkyl group, an aryl group, or an aralkyl group having 8 or less carbon atoms.

Embedded image However, X is an integer of 3000 or less, Y and Z are integers of 2000 or less, R 'is an alkylene group having 8 or less carbon atoms POA is a polyoxyalkylene group

Embedded image However, W is an integer of 3000 or less, X, Y and Z are integers of 2000 or less, R is an alkyl group having 8 or less carbon atoms, or an aryl group or an aralkyl group, R 'is an alkylene group having 8 or less carbon atoms, POA is a polyoxyalkylene group, and commercial products such as KF351, KF352, KF354,
KF615, X-22-6008, KF-6004 (all manufactured by Shin-Etsu Chemical Co., Ltd.), SH3746, SH3749, SF8410, SF8421, SF
8419 (all made of Torre silicone). The content of polyether silicone in the dye receiving layer is
0.1-20% by weight is preferred. Incidentally, the dye receiving layer B and the intermediate layer C may appropriately contain a surfactant, an ultraviolet absorber, an antioxidant, a colorant, and the like. Further, as the substrate A in the image receiving medium of the present invention, synthetic paper, art paper,
Fine paper, coated paper, gravure paper, baryta paper, cellulose fiber paper, plastic film and the like are preferably used alone or in a laminate thereof. In particular, the substrate A used for the transmission type image receiving medium preferably has a haze value of 5% or less, for example, polyethylene terephthalate,
Films of polyolefin, polyacryl, polyvinyl chloride, polyvinylidene chloride and the like can be mentioned, and among them, a polyethylene terephthalate film is particularly preferable. The thicknesses of the intermediate layer and the dye receiving layer provided on the transparent substrate are each preferably 0.1 to 10 μm, and particularly preferably 0.1 to 5 μm.

[0005]

Next, the present invention will be described in more detail by way of 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 intermediate layer [Solution A] and a coating liquid for receptor layer [Solution B]. [Liquid A] Polyester resin (trade name: Byron 200, manufactured by Toyobo Co., Ltd.) 100 parts Isocyanate (trade name: Vernock DN-950; manufactured by Dainippon Ink and Chemicals, Inc.) 10 parts Toluene 300 parts Methyl ethyl ketone 300 parts [B Liquid] Vinyl chloride / vinyl acetate / vinyl alcohol copolymer (trade name: VAGH; manufactured by Union Carbide Co.) 100 parts Isocyanate (trade name: Coronate L; manufactured by Nippon Polyurethane Industry Co., Ltd.) 50 parts Polyether-modified silicone (trade name: SH3749 Tole Silicone Co., Ltd.) 5 parts Toluene 455 parts Methyl ethyl ketone 455 parts Next, [solution A] and [solution B] were treated with a wire bar using a polyethylene terephthalate film having a thickness of about 100 μm (trade name Lumilar T60; Toray) Co., Ltd.) and drying temperature
After drying at 90 ° C. for 1 minute, an intermediate layer and a receiving layer each having a thickness of about 3 μm were prepared. Thereafter, the obtained image receiving medium was heated at 60 ° C. for 10 hours to produce an image receiving medium of the present invention. On the other hand, as a sublimation transfer recording medium, a coating liquid [C] for an ink layer (that is, a dye transfer layer) of the following formulation is coated on a 6 μm thick PET film provided with a silicone resin film (about 1 μm thick) as a back layer.
Liquid] was applied to a thickness of about 2 μm to obtain a transfer recording medium. [Liquid C] Polyvinyl butyral (trade name BX-1; manufactured by Sekisui Chemical Co., Ltd.) 7 parts Polyethylene oxide (trade name R-400; manufactured by Meisei Kasei Kogyo Co., Ltd.) 3 parts Sublimation disperse dye (trade name Kayaset Blue 714; Nippon Kayaku Co., Ltd.) 15 parts Toluene 95 parts Methyl ethyl ketone 95 parts The obtained thermal transfer recording medium and image receiving medium are overlapped and transferred so that the ink layer of the transfer medium and the dye receiving layer of the image receiving medium face each other. Image recording was performed by changing the heating energy from the back surface of the recording medium with a thermal head. The recording density of the thermal head was 6 dots / mm, and the recording output was 0.42 w / dot.

Comparative Example 1 An image receiving medium of Comparative Example 1 was prepared in the same manner as in Example 1 except that the following [Solution D] was used as the coating liquid for the receiving layer, and no intermediate layer was provided. went. [D Solution] Vinyl chloride / vinyl acetate copolymer resin (trade name VYHH; manufactured by Union Carbide) 100 parts Amino-modified silicone (trade name SF8417; manufactured by Toray Silicone Co., Ltd.) 1 part Toluene 300 parts Methyl ethyl ketone 300 parts

Comparative Example 2 Comparative Example 2 was carried out in the same manner as in Example 1 except that the following [Solution E] was used as the coating solution for the image receiving layer and no intermediate layer was provided.
Was manufactured, and image recording was performed. [Solution E] Vinyl chloride / vinyl acetate copolymer resin (VYHH) 100 parts Amino-modified silicone (SF8417) 5 parts Toluene 300 parts Methyl ethyl ketone 300 parts

Comparative Example 3 The image receiving medium of Comparative Example 3 was prepared in the same manner as in Example 1 except that the above-mentioned [Solution A] was used as the coating solution for the intermediate layer, and the following [Solution F] was used as the coating solution for the receiving layer. Was prepared and an image was recorded. [Solution F] Vinyl chloride / vinyl acetate copolymer resin (trade name: VYHH; manufactured by Union Carbide) 100 parts Polyether-modified silicone (trade name: SH3749; manufactured by Toray Silicone Co., Ltd.) 5 parts Toluene 300 parts Methyl ethyl ketone 300 parts or more Table 1 shows the results of image recording, the haze value of the image receiving medium, and the adhesion between the substrate and the receiving layer.

[Table 1] Note 1) Peeling property between the dye receiving layer and the dye transfer layer after recording. Note 2) Adhesive strength between the substrate and the dye receiving layer (○; sufficient, ×: insufficient). Note 3) Direct reading haze computer HGM-2DP manufactured by Suga Test Instruments. The haze value of the background portion of the image receiving medium according to the type. Note 4) 60 ° / 60 ° gloss of the surface of the receiving layer in the image recording portion (applied energy: 3.46 mJ / dot). , The image quality was high, and the transportability was also good.

Comparative Example 4 Example 1 was used except that the following [Solution G] was used as the coating liquid for the receiving layer, a 6 μm receiving layer was provided, and no intermediate layer was used.
An image receiving medium of Comparative Example 4 was produced in the same manner as in Example 1, and image recording was performed. [G Solution] Vinyl chloride / vinyl alcohol copolymer (trade name: SLECK A; manufactured by Sekisui Chemical Co., Ltd.) 100 parts Isocyanate (trade name: Coronate L; manufactured by Nippon Polyurethane Industry Co., Ltd.) 6 parts Amino-modified silicone (KF-393; manufactured by Shin-Etsu Chemical Co., Ltd.) 2.5 parts Toluene 140 parts Methyl ethyl ketone 240 parts

Comparative Example 5 A 1 μm intermediate layer was provided using the following [H Solution] as a coating solution for the intermediate layer, and a 6 μm receiving layer was provided using the following [I Solution] as the coating solution for the receiving layer. Except for the above, an image receiving medium of Comparative Example 5 was produced and image recording was performed in the same manner as in Example 1. [H Liquid] Polyester resin (trade name: Byron 200, manufactured by Toyobo Co., Ltd.) 100 parts Isocyanate (trade name: Vernock DN-950; manufactured by Dainippon Ink and Chemicals, Inc.) 7 parts Toluene 800 parts Methyl ethyl ketone 200 parts [I Liquid] Polyester resin (trade name: Byron 290, manufactured by Toyobo Co., Ltd.) 100 parts Amino-modified silicone (trade name: KF-393; Shin-Etsu Chemical Co., Ltd.) 2.5 parts Epoxy-modified silicone (trade name: KF-100T; Shin-Etsu Chemical Industry Co., Ltd.) 2.5 parts Toluene 180 parts Methyl ethyl ketone 180 parts Cyclohexanone 60 parts

Example 2 The image receiving of Example 2 was carried out in the same manner as in Example 1 except that the above-mentioned [Solution A] was used as the coating solution for the intermediate layer, and the following [Solution J] was used as the coating solution for the receiving layer. A medium was prepared, and an image was recorded. [Liquid J] Polyester resin (trade name: Byron 200, manufactured by Toyobo Co., Ltd.) 100 parts Isocyanate (trade name: Coronet L; manufactured by Nippon Polyurethane Industry Co., Ltd.) 15 parts Polyether-modified silicone (trade name: SH3746; Toray) -Silicone Co., Ltd.) 5 parts Toluene 320 parts Methyl ethyl ketone 320 parts The results of the above image recording, the haze value of the image receiving medium, and the adhesion between the substrate and the receiving layer are shown in Table 2.

[Table 2]

[0013]

The image-receiving medium for sublimation-type thermal transfer according to the present invention comprises an intermediate layer containing an isocyanate compound, a resin containing active hydrogen, a dye-receiving layer mainly containing an isocyanate compound and a polyether-modified silicone on a substrate. Due to the configuration in which the layers are laminated in that order, the dye transfer layer is not peeled off to the dye receiving layer side after recording, the dye receiving layer is not peeled off to the dye transfer layer side, and the dye receiving layer and the dye transfer are performed. The peelability between the layers (that is, between the image receiving medium and the transfer recording medium) is good, and the image density is high, and the transparency of the dye receiving layer is high (the haze value is low), so that the image quality is excellent. ing. In addition, since the polyether-modified silicone oil is used, the surface of the receiving layer does not excessively slip and has an antistatic effect, so that the image receiving medium has excellent transportability, and further has a good writing property on the surface of the receiving layer. Are better.

[Brief description of the drawings]

FIG. 1 is a schematic sectional view showing an image receiving mechanism of a sublimation type thermal transfer image receiving medium according to the present invention, and also includes a schematic sectional view of a sublimation transfer recording medium.

[Explanation of symbols]

 A image receiving substrate, B dye receiving layer, C intermediate layer, 1 thermal head, 2 heat resistant layer of transfer recording medium 3 transfer substrate of transfer recording medium, 4 dye transfer layer of transfer recording medium.

──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Masaru Shimada 1-3-6 Nakamagome, Ota-ku, Tokyo Inside Ricoh Co., Ltd. (72) Inventor Chiharu Nogawa 1-3-6 Nakamagome, Ota-ku, Tokyo (72) Inventor Yutaka Ariga 1-3-6 Nakamagome, Ota-ku, Tokyo, Japan (56) References JP-A-1-280585 (JP, A) JP JP-A-61-132387 (JP, A) JP-A-64-34792 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) B41M 5/38-5/40

Claims (1)

(57) [Claims] 1. A sublimation type thermal transfer method comprising: sequentially laminating a layer containing an isocyanate compound, a resin containing an active hydrogen, an isocyanate compound and a polyether-modified silicone on a substrate. Image receiving medium.