JP3301171B2 - Thermal transfer recording sheet - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermal transfer recording sheet, and more particularly to a sublimation type thermal transfer recording sheet which can use general-purpose plain paper as recording paper.

[0002]

2. Description of the Related Art Heretofore, a heating means such as a thermal head has been used to heat a vaporizable or heat-diffusible coloring material from a coloring material layer, and to use a resin capable of dyeing these coloring materials as a main component. A sublimation type thermal transfer recording system is known in which the image is transferred to a coloring material dyeing layer to obtain an image on the coloring material dyeing layer. Further, in this method, a hot-melt transferable coloring material dyeing layer is provided on a sublimation type thermal transfer recording sheet, this is first transferred to a recording material, and then the color is transferred onto the transferred coloring material dyeing layer. A sublimation type thermal transfer recording sheet is known which is designed so that a general-purpose plain paper can be used as a recording material by transferring a color material from a material layer. For example, see JP-A-63-17
0091 and JP-A-64-87390.

[0003]

When such general-purpose ordinary paper which is generally commercially available is used as a recording material, first, the heat-melt transferable coloring material dyeing layer of the thermal transfer recording sheet and the plain paper are used. It is necessary to superpose and heat the sheet from the opposite side of the base material, and to melt-transfer the hot-melt transferable coloring material dyeing layer from the base material to the plain paper. At this time, it is preferable to employ not only the full-surface transfer method but also a partial transfer method for transferring only a required image portion. In particular, when performing this partial transfer, only the heated portion is transferred, and the non-heated portion is transferred. Is an important factor for obtaining a high-quality image of a desired size.

[0004] However, in the conventional coloring material dyeing layer, the film is strong and the boundary (end) between a portion transferred to plain paper by heating and a non-heated portion to be left on the sheet is present. The cut was bad. Therefore, the coloring material dyed layer transferred by heating is pulled and peeled off, and remains on the sheet, or an unnecessary non-heated portion remains on the recording material together with the heated portion. However, there is a problem that image quality is significantly impaired.
On the other hand, the coloring material dyeing layer peels off under normal handling conditions, or the coloring material dyeing layer fuses with the coloring material layer during image transfer,
You must avoid peeling.

[0005]

That is, an object of the present invention is to provide a thermal transfer recording sheet for easily transferring a high-quality image to an extremely wide variety of general-purpose papers. The end of the coloring material dyeing layer at the time of thermal transfer is good, the adhesion of the transferred coloring material dyeing layer to the recording paper is good, and the coloring material dyeing layer at the time of image transfer is good. An object of the present invention is to provide a thermal transfer recording sheet in which a color material layer is fused and a color material dyeing layer is less peeled.

It is a further object of the present invention to provide a thermal transfer recording sheet which does not cause a problem such as peeling of a dyed portion of a coloring material during normal handling and can perform excellent thermal transfer when heat is applied. Accordingly, an object of the present invention is to provide a base material, a coloring material dyeing layer formed on the base material, which can be transferred onto recording paper by heat, and an adhesive layer formed on the coloring material dyeing layer. The color material dyeing layer in the thermal transfer recording sheet having
Is a white hiding layer containing a resin and fine particles, respectively, and an image receiving layer.
Having a multilayer structure having
It is readily accomplished by a thermal transfer recording sheet, wherein the ratio between fat and fine particles is 50 to 300 parts by weight fine particles relative to 100 parts by weight of the resin.

Hereinafter, the present invention will be described in detail. Examples of the resin used in the coloring material dyeing layer of the present invention include saturated polyester, acrylic resin, methacrylic resin, styrene resin, polycarbonate resin, cellulose acetate, polyvinyl acetal resin, polyvinyl phenyl acetal resin, vinyl chloride resin, vinyl chloride / acetic acid. Resins having a dyeing property to vaporizable or heat-diffusible dyes such as vinyl copolymer resins, polyarylate resins, AS resins, and the above-mentioned crosslinked products are used, and used alone or in combination.

The fine particles used in the coloring material dyeing layer of the present invention include, for example, silica, silicone resin, calcium carbonate, alumina white and barium sulfate as inorganic particles, and urea resin as organic particles. Benzoguanamine resin, polystyrene resin, polymethyl methacrylate resin, microcapsules and the like. Examples of the white pigment include titanium oxide, zinc oxide, calcium carbonate, talc, clay and the like, and they can be used alone or in combination.

The particle size of these fine particles is 0.01 μm to 5 μm.
μm is preferred. Particularly preferably, 0.02 μm to 3 μm
It is. In addition, in addition to the dyeable polymer compound and the fine particles, various release agents can be added to the coloring material dyeing layer of the present invention for the purpose of preventing blocking with the color sheet coloring material layer. Further, in order to facilitate the releasability of the dyeing layer of the present invention and the substrate during thermal transfer, a silicone-based, ketone resin-based, polyvinyl acetal resin-based release layer is provided on the substrate surface, and white When a hiding layer is provided, various fluorescent whitening agents can be added for the purpose of supplementing whiteness.

The greater the weight ratio of the fine particles to the colorant dyeing layer resin, the better the cut at the end. on the other hand,
If the weight ratio is too large, when transferring to the material to be transferred,
Adhesion to the transfer material deteriorates. In addition, the coloring material dyeing layer becomes brittle, causing problems such as partial peeling or falling off from the substrate. The results are described in Japanese Patent Application No. 4-26919 by the present inventors. When there is no adhesive layer on the color material transfer portion, the amount of the fine particles is reduced to 100 parts by weight or less based on 100 parts by weight of the resin. It is better to keep it down.

However, the above composition is not the best composition in terms of cutting performance because the amount of fine particles is suppressed in order to maintain adhesiveness. The present inventors have further studied and found that it is possible to increase the amount of fine particles that can be added to the coloring material dyeing layer by providing the adhesive layer on the coloring material dyeing portion. As a result, the present invention was completed by improving the cutting performance.

The resin used for the adhesive layer of the present invention is not particularly limited, but is preferably a resin having good hot adhesion. For example, the same saturated polyester, acrylic resin, methacrylic resin, styrene resin, polycarbonate resin, cellulose acetate, polyvinyl acetal resin, polyvinyl phenyl acetal resin, vinyl chloride resin, vinyl chloride / vinyl acetate Polymeric resin, ethylene / vinyl acetate copolymer resin, polyarylate resin, AS resin or the above crosslinked product, polyvinyl alcohol, polyvinyl butyral, polyvinyl acetate, polyvinyl chloride, etc. can be used alone or in combination. Can be.

Although fine particles may be added to the adhesive layer, it is necessary that the amount does not hinder the adhesion to the recording material. Therefore, it is necessary to appropriately select the amount of the particles according to the resin used. Generally, the amount of the particles is preferably 100 parts by weight or less, more preferably 75 parts by weight or less based on 100 parts by weight of the resin of the adhesive layer. preferable. There is no particular limitation on the type of the fine particles. The thickness of the adhesive layer is suitably 10 μm or less, and more preferably 2 to 6 μm. If the adhesive layer is too thick, the cutability of the adhesive layer itself will affect the overall cuttability, while if too thin, it will not be able to fulfill its role as an adhesive layer.

When the adhesive layer is provided on the coloring material dyeing layer, the amount of the fine particles added to the coloring material adhesive layer can be increased as compared with the case where the adhesive layer is not provided as described above. is there.
Actually, it is possible to add from 50 to 300 parts by weight based on 100 parts by weight of the resin of the coloring material dyeing layer. When the addition amount of the fine particles exceeds 300 parts by weight, the coloring material dyeing layer becomes brittle, and there is a high possibility that blocking occurs with the color sheet during recording after peeling from the base material or transferring to the material to be transferred. Become. On the other hand, if the addition amount of the fine particles is less than 50 parts by weight, the cutting properties may be insufficient. Therefore, the amount of the fine particles added to 100 parts by weight of the resin is 60%.
The amount is preferably from 280 to 280 parts by weight, and more preferably from 150 to 260 parts by weight.

As a solvent used for a coating solution prepared using these resins, fine particles, additives and the like, a commonly used organic solvent may be used. Further, in order for the fine particles in the coloring material dyeing layer to sufficiently exert their effect, it is important that the fine particles are sufficiently dispersed in the coloring material dyeing portion. For that purpose, it is necessary to sufficiently disperse the fine particles when preparing a coating solution for forming the coloring material dyeing layer. A well-known dispersion method may be used for the dispersion, for example,
A homogenizer, a paint conditioner, a sand grind mill, or the like may be used. Further, a small amount of an additive can be added for the purpose of improving the storage stability and redispersibility of the coating liquid.

The coloring material dyeing layer does not need to be formed in one layer, but may be formed in two or more layers. For example, as shown in FIG. 1, one of the coloring material dyeing layers provided on the base material has
An image receiving layer mainly for receiving a dye from a color material layer,
One layer may include a white pigment as a white hiding layer for providing a white background of a transferred image, and an adhesive layer may be provided on the coloring material dyeing layer. In the case where the coloring material dyeing layer is composed of multiple layers, each layer contains fine particles in a range of 25 parts by weight or more with respect to 100 parts by weight of the resin. Although it is preferable to obtain a certain transfer image, even if the fine particle content of the specific layer is outside this range,
As long as the content of the fine particles in the entire coloring material dyeing layer is within a predetermined range, an expected effect can be obtained. In this case, the ratio between the resin and the particles is determined as follows. First, for all the layers constituting the coloring material dyeing layer, the thickness of the layer is multiplied by the number of parts by weight of the fine particles with respect to 100 parts by weight of the resin of the layer. Next, the results of the multiplication are totaled, and the total number is divided by the total thickness of the coloring material dyeing layer. Thus, the averaged fine particle addition ratio as the coloring material dyeing layer can be obtained.

The method for forming the coloring material dyeing layer of the present invention on the substrate and the method for forming the adhesive layer on the coloring material dyeing portion can be arbitrarily selected from commonly used methods. For example, a method using a reverse roll coater, a gravure coater, a rod coater, an air doctor coater, a die coater, a gravure printing machine or the like (for details, see Yuji Harazaki, “Coating Method”, published by Maki Shoten 1979) and the like is used. However, coating by a gravure printing method is particularly preferable. When the coloring material dyed portion is formed by a plurality of coatings, the above coating methods may be arbitrarily combined.

The thickness of the coloring material dyeing layer formed on the substrate is usually 1 to 30 μm, preferably 2 to 20 μm, as a dry film thickness.
μm. Known azo, anthraquinone, nitro, styryl, naphthoquinone, quinophthalone as the vaporizable or heat-diffusible dye used in the color material portion for thermal transfer recording used together with the color material dyeing layer of the present invention. Various non-ionic dyes such as a dye, an azomethine, a coumarin, and a condensed polycyclic dye are used.

The thermal transfer recording sheet of the present invention may be formed, for example, as shown in FIG.
A color material dyeing layer (1) is provided thereon, and a color material layer of yellow (2), magenta (3), and cyan (4) is formed adjacent thereto. According to this method, both the color material dyeing layer and the color material layer are integrated with the thermal transfer recording sheet, so that no extra operation is required. It is also preferable to limit the number to only one, since it is extremely simple. However, the present invention is not limited to this, and the entire surface of the coloring material dyeing layer may be transferred, and furthermore, a coloring material layer separate from the sheet coated with only the coloring material dyeing layer provided with the adhesive layer of the present invention. The transfer of the coloring material dyed layer and the transfer of the image can be performed by separate operations using a color sheet having the following. Therefore, the thermal transfer recording sheet of the present invention includes various cases as described above.

[0020]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples and Comparative Examples as long as the gist is not exceeded.

Comparative Example 1 (a) Preparation of Dyeing Layer for Colorant Vinyl chloride / vinyl acetate copolymer resin (trade name: UCAR)
-VYHD, manufactured by Union Carbide) 100 parts by weight,
60 parts by weight of silicone resin fine particles (trade name: Tospearl 120, average particle size 2 μm, manufactured by Toshiba Silicone Co., Ltd.), 200 parts by weight of toluene, 200 parts of methyl ethyl ketone, and amino-modified silicone as a release agent (trade name: KF-
393, manufactured by Shin-Etsu Chemical Co., Ltd.) A biaxially stretched polyethylene terephthalate film (4.5 μm) in which the back surface of the ink-coated surface was heat-resistant lubricated with a gravure printing machine, Thick) and dry film thickness of 5μ
m color material dyeing layer was produced. The fine particles are 60 parts by weight based on 100 parts by weight of the resin in the coloring material dyeing layer.

(B) Preparation of adhesive layer Acrylic resin liquid (trade name: LR-158, solid content 50%)
Product, manufactured by Mitsubishi Rayon Co., Ltd.), 100 parts by weight of an ethylene / vinyl acetate copolymer resin (trade name: Elvaloy 741, manufactured by Mitsui Dupont Polychemicals), and 800 parts by weight of toluene. Using a gravure printing machine, an adhesive layer was formed on the coloring material dyeing layer prepared in (a) so that the dry film thickness was 2 μm. (C) Preparation of Coloring Material Layer Part On the base material adjacent to the coating part of the coloring material dyeing layer, as shown in FIG. 2, a yellow coloring material layer coating solution: represented by the following structural formula (A) 5 parts by weight of a yellow dye (PTY52, manufactured by Mitsubishi Kasei Corporation)
10 parts by weight of a phenoxy resin (trade name: PKHJ, manufactured by Union Carbide), 90 parts by weight of methyl ethyl ketone,
Coating solution consisting of 10 parts by weight of isopropanol.

[0023]

Embedded image

Magenta color material layer coating solution: Structural formula (B) below
A coating solution comprising 5 parts by weight of a magenta dye (PTR-63, manufactured by Mitsubishi Kasei Co., Ltd.), 10 parts by weight of a phenoxy resin, 90 parts by weight of methyl ethyl ketone, and 10 parts by weight of isopropanol.

[0025]

Embedded image

Cyan color material layer coating liquid: 5 parts by weight of a cyan dye represented by the following structural formula (C) (PBK, manufactured by Mitsubishi Kasei Co., Ltd.), 10 parts by weight of phenoxy resin, 9 methyl ethyl ketone
A coating liquid comprising 0 parts by weight and 10 parts by weight of isopropanol.

[0027]

Embedded image

Each of the three color coating solutions is applied and dried.
A test thermal transfer sheet having a color material layer having a dry film thickness of about 1 μm was prepared. (C) Transfer Recording Test The ink-coated surface of the above-described sublimation type thermal transfer recording sheet is superimposed on a high-quality paper (manufactured by Kanzaki Paper) having a basis weight of 200 g, and a partial grace type line having a heating resistor density of 5.4 dots / mm. Using a thermal head, recording was performed under the following conditions, and the transfer state was observed. The results are shown in Table 2 below.

[0029]

[Table 1] Recording line density 5.4 lines / mm Power applied to thermal head 0.20 W Pulse width applied to thermal head At the time of colorant dyeing part transfer: 14.5 ms At the time of image transfer: 0 to 14.5 ms Second evaluation item Cut of portion: After the transfer, the cut at the boundary between the heated portion and the non-heated portion of the coloring material dyed layer was visually observed and evaluated. Adhesion state: Evaluation was made by visually observing whether the coloring material dyed layer was uniformly transferred to the recording material. Fusing: The color material dyed layer and the color material layer were visually observed and evaluated for fusing after image transfer. Peeling: After image transfer, coloring material dyeing layer becomes coloring material layer,
Evaluation was made by visually observing whether or not the adhesive remained.

[0030] Example - 1 as follows instead of the colorant dyeing layer used in Comparative Example 1, tested in the same manner as in Comparative Example 1 but using to create the colorant dyeing layer And the results are shown in Table 2 below.
It was shown to. (A) Preparation of coloring material dyeing layer Vinyl chloride / vinyl acetate copolymer resin (trade name: UCAR)
-VYHD, manufactured by Union Carbide) 100 parts by weight,
25 parts by weight of silicone resin fine particles (trade name: Tospearl 120, average particle size 2 μm, manufactured by Toshiba Silicone Co., Ltd.), 200 parts by weight of toluene, 200 parts of methyl ethyl ketone, and amino-modified silicone as a release agent (trade name: KF-
393, Shin-Etsu Chemical Co., Ltd.) 5 parts by weight of an image receiving layer coating solution and a vinyl chloride / vinyl acetate copolymer resin (trade name: UCAR-VROH, manufactured by Union Carbide) 1
00 parts by weight, titanium oxide fine particles (trade name: CR-60,
Biaxially oriented polyethylene coated with a white concealing layer coating liquid consisting of 200 parts by weight of an average particle size of 0.3 μm and Ishihara Sangyo Co., Ltd. First, an image receiving layer is formed on a terephthalate film (4.5 μm thick) so as to have a dry thickness of 3 μm, and a white opaque layer is applied thereon so as to have a dry thickness of 7 μm. Is 10 μm
Was prepared. Resin 1 in coloring material dyeing layer
The fine particles per 100 parts by weight were 25 parts by weight in the image receiving layer, 200 parts by weight in the white hiding layer, and 148 in total.
Parts by weight.

Example 2 Example 1 was repeated except that an image-receiving layer coating solution having the following composition was used in place of the image-receiving layer coating solution of the coloring material dyeing portion used in Example 1.
A test was conducted in the same manner as in Example 1 and the results were obtained as shown in Table 1 below.
It was shown in 2). Vinyl chloride / vinyl acetate copolymer resin (trade name: UCAR-VYHD, manufactured by Union Carbide)
100 parts by weight, benzoguanamine resin fine particles (trade name:
Eposter S type, average particle diameter 0.3 μm, 15 parts by weight of Nippon Shokubai Chemical Co., Ltd.), 200 parts by weight of toluene, 200 parts of methyl ethyl ketone, and amino-modified silicone as a release agent (trade name: KF-393, Shin-Etsu Chemical Co., Ltd.) Coating solution of 5 parts by weight for image receiving layer. The fine particles with respect to 100 parts by weight of the resin in the coloring material dyeing layer were 15% in the image receiving layer.
Parts by weight, 200 parts by weight in the white hiding layer, 145 parts by weight in total.

Example 3 An adhesive layer coating liquid having the following composition was used instead of the adhesive layer coating liquid and the coating film thickness used in Example 1 , and the coating film thickness was 6
A test was performed in the same manner as in Example 1 except that μ was used.
The results are shown in Table 2 below. Acrylic resin liquid (trade name: LR-158, solid content 50%, manufactured by Mitsubishi Rayon Co., Ltd.) 200 parts by weight, ethylene / vinyl acetate copolymer resin (trade name: Elvaloy 741, manufactured by Mitsui Dupont Polychemical Co., Ltd.) 100 parts by weight , Microcapsules (trade name:
Matsumoto Microsphere F-30 VSD, manufactured by Matsumoto Yushi-Seiyaku Co., Ltd.) 100 parts by weight and 800 parts by weight of toluene. The fine particles are 50 parts by weight based on 100 parts by weight of the resin in the adhesive layer.

Example 4 Same as Example 3 except that a white opaque layer coating solution having the following composition was used instead of the white opaque layer coating solution for the colorant dyeing layer used in Example 3. And the results are shown in (Table 2) below. 100 parts by weight of vinyl chloride / vinyl acetate copolymer resin (trade name: UCAR-VROH, manufactured by Union Carbide Co.), titanium oxide fine particles (trade name: C
R-60, average particle size 0.3 μm, manufactured by Ishihara Sangyo) 300
A coating solution for a white hiding layer consisting of 500 parts by weight of methyl ethyl ketone. The fine particles with respect to 100 parts by weight of the resin in the coloring material dyeing layer were 15 parts by weight in the image receiving layer, 300 parts by weight in the white hiding layer, and 215 parts by weight as a whole.

[0034] Comparative Example - In 2 colorant dyeing layer used in Comparative Example 1, except not using the silicone resin particles was tested in the same manner as in Comparative Example 1, the results below (Table -2).
No fine particles are contained in the coloring material dyeing layer.

Comparative Example- 3 In the coloring material dyeing layer used in Example- 1 , the addition amount of the silicone resin fine particles in the image receiving layer coating liquid was 10 parts by weight, and the addition of titanium oxide fine particles in the white hiding layer coating liquid was added. A test was conducted in the same manner as in Example 1 , except that the amount was changed to 10 parts by weight.
The results are shown in Table 2 below. The fine particles are 10 parts by weight based on 100 parts by weight of the resin in the coloring material dyeing layer.

Comparative Example- 4 Example- 1 except that the adhesive layer was not used in Example- 1.
The test was conducted in the same manner as in
It was shown in 2). The fine particles were 148 parts by weight based on 100 parts by weight of the resin in the coloring material dyeing layer.

[0037]

[Table 2]

[0038]

The sublimation-type thermal transfer recording sheet of the present invention comprises:
The end of the colored material dyed part at the time of transfer is good, the adhesion state with the recording paper is good, the color material dyed layer and the color material layer are fused at the time of image transfer, the color material dyed layer Since there is no peeling or the like, a high-quality transfer image can be transferred to a wide range of general-purpose paper.

[Brief description of the drawings]

FIG. 1 is a schematic view showing an example of the configuration of a thermal transfer recording sheet according to the present invention.

FIG. 2 is a schematic diagram showing a configuration of a portion of a thermal transfer recording sheet used in Examples 1 to 3 and Comparative Example 3 where a coloring material dyeing layer having an adhesive layer is formed.

────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-5-139056 (JP, A) JP-A-1-160682 (JP, A) JP-A-4-2211692 (JP, A) (58) Field (Int.Cl. ⁷ , DB name) B41M 5/38-5/40

Claims (5)

(57) [Claims] 1. A thermal transfer recording method comprising: a base material; a coloring material-dyeing layer formed on the base material and capable of being transferred onto a recording paper by heat; and an adhesive layer formed on the coloring material-dyeing layer. In the sheet, the coloring material dyeing layer contains a resin and fine particles, respectively.
It has a multilayer structure having a concealing layer and an image receiving layer, and
Transfer recording sheet characterized by the ratio between the resin and the fine particles of the colorant dyeing layer is 50 to 300 parts by weight fine particles relative to 100 parts by weight of the resin. 2. The thermal transfer recording sheet according to claim 1 , wherein the thickness of the adhesive layer is 10 μm or less . 3. An image receiving layer comprising 15 parts by weight per 100 parts by weight of resin.
Characterized by containing up to 25 parts by weight of fine particles
The thermal transfer recording sheet according to claim 1. 4. The method according to claim 1 , wherein the ratio between the resin and the fine particles in the coloring material dyeing layer is a resin.
60 to 280 parts by weight of fine particles per 100 parts by weight of fat
The method according to any one of claims 1 to 3, wherein
Thermal transfer recording sheet. 5. A claims 1, characterized in that it is provided at least one color material layer in addition to the color Zaisome adhesive layer on a substrate
5. The thermal transfer recording sheet according to any one of 3 .