JPS63319188A - Image-receiving material for thermal transfer recording - Google Patents

Abstract

PURPOSE:To enable transfer recording with high density and enhance preservation stability of a recorded matter, by providing an image-receiving layer comprising as a main constituent a copolymer resin formed by using acrylonitrile and styrene as essential constituents, on the surface of a base. CONSTITUTION:A copolymer resin formed by using acrylonitrile and styrene as essential constituents may be an AS resin, an AAS resin or the like which preferably has a thermal deformation temperature (measured according to the ASTM D-648 method) of 60-120 deg.C. For preventing thermal fusion of a color sheet and an image-receiving material to each other at the time of transfer recording and for enhancing releasability of the two members after transfer, it is desirable that an image-receiving layer comprises a release agent, preferably a silicone compound. A base for the image-receiving material may be one of various papers formed from cellulose fibers, one of various synthetic papers or plastic films prepared from a synthetic resin, or the like.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to an image receptor for thermal transfer recording,
Specifically, the present invention relates to an image receptor for thermal transfer recording using a sublimable dye.

[Conventional technology]

Various methods such as electrophotography, inkjet, and thermal transfer recording are being considered for color recording such as color recording in OA terminals such as facsimile printers and copying machines and color recording of television images, which are rapidly becoming popular in recent years. However, the thermal transfer recording method has advantages such as ease of maintenance of the device, ease of operation,
This method is advantageous compared to other methods in that the equipment and consumables are inexpensive.

In the thermal transfer recording method described above, an image receptor is placed on the ink-coated surface of a color sheet coated with ink containing pigments, binders, etc. on a sheet-like base material, and the back side of the color sheet is printed with a thermal head. Recording is performed by heating and transferring the dye in the color sheet to the image receptor.

Such thermal transfer recording methods include a melt transfer recording method that uses a color sheet coated with heat-melting ink, and a sublimation transfer recording method that uses a color sheet coated with an ink containing a sublimable dye. This method allows you to easily control the amount of dye sublimation transfer by adjusting the energy given to the thermal head, making it easy to express gradation.
It is particularly advantageous for color recording.

Since it is necessary to dye the image receptor in the sublimation type thermal transfer method with the dye sublimated from the color sheet, the surface of the image receptor is mainly composed of a resin that has a high affinity with the dye used. layer (hereinafter simply referred to as the "image-receiving layer").

) and for this purpose it is necessary to have polyvinylhyo IJ )'7 (%IeF[Ef! 7 9
'Kotaza), polyester (Tokkai Showa Or 707e!'
♂r), hi)'.

xyethylcellulose (Japanese Patent Application Laid-Open No. 7-3779/),
Amino alkyd resin (% Kaisho t, r-, zo9r91
! K), PVO (JP-A Sho! 9-2.234t stiffness, styrene-butadiene copolymer (% Kai-Sho, f9-2293 R/), phenolic resin (JP-A Sho! ter/Ilf'g 3)
The use of resins such as 3), polycarbonate (Japanese Patent Application Publication No. 2003-100003), and butyral resin (3) is described in the above-mentioned patents.

By the way, the image receptor not only allows the sublimated dye to flow eastward to obtain a high-density record, but also prevents the color of the resulting transferred record from fading or discoloring, which can lead to counterfeiting and transfer due to bleeding of the dye. It is also necessary that the storage stability of the recorded material is good, such as that the image of the recorded material does not become blurred.

Furthermore, when producing an image receptor, it is necessary to dissolve or disperse the resin that forms the image-receiving layer in a suitable solvent and apply it onto the surface of the substrate. It is necessary to have good solubility or dispersibility in

However, the image receptor using the resin described in the above-mentioned patents does not necessarily satisfy all the requirements for the image receptor described above. [Problem to be solved by the invention] It is an object of the present invention to provide an image receptor for sublimation type thermal transfer recording, which allows easy, high-density transfer recording and has good storage stability of recorded materials.

[Means for solving problems]

The inventors of the present invention have studied resins for forming the image-receiving layer, and have found that by using a copolymer resin containing acrylonitrile and styrene as essential components, manufacturing is easy and high-density transfer recording is possible. Furthermore, we have found that it is possible to obtain an image receptor with good storage stability for recorded materials.

That is, the gist of the present invention is an image receptor for thermal transfer recording, characterized in that it has an image receptor layer on the surface of a substrate, the image receptor layer mainly consisting of a copolymer resin formed of acrylonitrile and styrene as essential components.

As the copolymer resin formed from acrylonitrile and styrene as essential components used in the present invention, in addition to copolymers made from acrylonitrile and styrene,
Furthermore, copolymers containing other components such as olefins such as ethylene and propylene, and vinyl compounds such as acrylic esters may also be used. These copolymers include AS
Resin (acrylonitrile-styrene copolymer resin), AA
S resin (acrylo-tolyl-special acrylic rubber-styrene copolymer resin), ABS resin (acrylonitrile-EF
rubber-styrene copolymer resin), AO8 resin (acrylonitrile-chlorinated polyethylene-nutyrene copolymer resin), and the like.

The manufacturing method for these resins is selected from the methods generally adopted when manufacturing this type of copolymer, such as dissolving each resin raw material component in a hydrocarbon bed or an aromatic solvent and polymerizing it. Copolymerization or craft polymerization may be carried out by a solution polymerization method, a suspension polymerization method in which polymerization is carried out in an aqueous dispersion system, an emulsion polymerization method, or the like. Although the properties of the resin change depending on these methods, the copolymer used in the present invention has a heat distortion temperature (as measured by the AST M D-ggz method) of 60.
A resin in the range of ~/20"C is suitable. If a resin with a heat deformation temperature in this range is used, the heat during transfer recording will soften the resin appropriately, and the sublimation-transferred dye will In addition, these resins have good affinity for pigments, so the pigments are firmly attached to them, and the dyed pigments do not migrate under normal conditions and remain on the feet. It is possible to obtain a recorded matter with good gradualness.Furthermore, since the stability of the dye is good in these resins, it is possible to obtain a good recorded matter without fading. can get things.

Specific examples of these resins include the following products that are generally commercially available as molding materials.

Examples of AS resins include Tyril-747.7g and 7? ri, 2?3, style rack-Zθri, 703.7
．． 27 (Product name, Asahi Kasei Corporation aJM)
, Estyrene As-2θ, As-30, As-ri/,
As-j/ (all trade names, manufactured by Nippon Steel Chemical Co., Ltd.), Sepian-N-020, θ, 20F, 020f3F, 0
/ 0, oro, orθF, 0 evening 08F.

N F −/′, 0 and (ysy, NFo/aA (
The above product names are manufactured by Daicel Chemical Industries, Ltd.), Denka A
f3-8. H (all product names, manufactured by Denki Kagaku Kogyo Co., Ltd.)
, Lightac 33θPO5200P01/QQPO.

/20PC (all product names, manufactured by Mitsui Toatsu Chemical Co., Ltd.),
Sunrex 5AN-0, SAN-H, Collimate 5-32! ,E! -3, 20, 8-J'/J- (product names manufactured by Sanen Mon Sando Kasei Co., Ltd.), Kibisan PN-//7, PN-/, 27, PN-/27H (product names Poly Chemical Co., Ltd.) Manufactured by Matsubu Co., Ltd.).

AAS6) If the fat is, for example, Paitakusu Vt.
10OA, V610/AH, V Otsu 10/A.

vtooo, vtooi, V600/A, Vl, 700
, Vt70/, Vt702, M, <#l/AK, Vr0
00゜Vt000, vt, zio, vt/it, vtz
,zo,VaifunenVN,2o/v,VN30/,V'
N30j, VN100'B (The above product names, Hitachi Chemical Co., Ltd. AES resins include, for example, Uniprite@#
7θ/, #≦O/, #-600, $ 00 K.

-#70/, #300. #¥07, #90/ (all product names, manufactured by Sumitomo Naugatuck Co., Ltd.), manufactured by Shikisha.

As AC3B resin, for example, AO8■O8-8=NF-920,HF 9 to O, NF-10&θ, NF
-760 (product name, Showa Denko Co., Ltd.!R).

In the image-receiving layer of the present invention, the above-mentioned resins may be used alone or in the form of a mixture. The image-receiving layer of the present invention mainly contains the above-mentioned resins, but in some cases, it may also contain saturated polyester resins, acrylic resins, methacrylic resins, styrene resins, polycarbonate resins, cellulose acetate, polyvinyl butyral, and vinyl chloride resins. , vinyl chloride, vinyl acetate copolymer resin, polyarylate resin, etc.

The image-receiving layer desirably contains a release agent in order to prevent heat-induced fusion between the color sheet and the receiver during transfer recording and to improve the releasability of both after transfer. Although silicone-based compounds are particularly preferably used, various other waxes, fluorine-based compounds, fine particles, etc. can also be effectively used. Further, in order to improve releasability, a layer containing these mold release agents may be formed on the image-receiving layer.

In addition, ultraviolet absorbers, light stabilizers, antioxidants, fluorescent brighteners, antistatic agents, etc. are added to the image-receiving layer or the mold-releasing agent-containing layer formed on the image-receiving layer. Also good.

Examples of the substrate of the image receptor include various papers made from cellulose fibers, various synthetic papers made from synthetic resins, and plastic films.

The method for forming the image-receiving layer of the present invention is to dissolve the copolymer resin containing acrylonitrile and styrene as essential components in an appropriate solvent, add an appropriate release agent, and add other resins as necessary. and the various additives mentioned above, prepare a coating solution, apply it on the substrate, and dry it.The solvent for preparing the coating solution contains acrylonitrile and styrene used in the present invention as essential components. The resin has good solubility in organic solvents, so it can be used with various organic solvents, but aromatic solvents such as toluene and xylene, ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone, ethyl acetate, Ester solvents such as butyl acetate, halogen solvents such as methylene chloride, trichlorethylene, and chlorobenzene, ether solvents such as tetrahydrofuran and dioxane, and amide solvents such as dimethylformamide and N-methylpyrrolidone are used.

The coating method can be arbitrarily selected from commonly used methods, such as methods using a reverse roll coater, gravure coater, rod coater, air doctor coater, etc. ”, published by Maki Shoten in 7977), etc. are used. The thickness of the image-receiving layer formed on the substrate is usually 0 as a dry film.
．． The thickness is 7 to 20 μm, preferably 7 to 10 μm.

The sublimable dyes used in the color sheet for heat-sensitive transfer recording used with the image receptor of the present invention include azo-based, anthraquinone thread, nidro-based, styryl-based, naphthoquinone-based, quinophthalone-based, azomethine-based, coumarin thread,
A variety of nonionic sublimable dyes such as fused polycyclic systems are used.

〔Example〕

EXAMPLES The present invention will be specifically explained below with reference to Examples, but these Examples do not limit the present invention in any way.

Examples/(a) Preparation of image receptor 70 parts by weight of A8 resin (trade name: Sunrex BAN-0: manufactured by Mitsubishi Monsanto Chemical Co., Ltd., heat distortion temperature 97°C) was added to methyl ethyl ketone/! Part by weight, toluene/! 0.0 parts by weight of amine-modified silicone KFj-3 (trade name: manufactured by Shin-Etsu Chemical Co., Ltd.) is dissolved in the solution. ! The image-receiving layer coating solution prepared by adding parts by weight /! Apply to Oμm thick polypropylene synthetic paper with a wire bar, dry, and the dry film thickness is approx. An image receptor was prepared by forming an image receptor layer with a thickness of μm.

(b) Preparation of color sheet 5 parts by weight of a magenta sublimable dye represented by the following structural formula (1) was added to a biaxially stretched polyethylene terephthalate film (μm thick) whose back surface on which the ink was applied was heat-resistant treated with polyimide resin, 70 parts by weight of polycarbonate resin,
toluene/! An ink consisting of parts by weight was applied and dried to form a coloring material layer having a dry film thickness of about 1 μm to produce a color sheet.

0L)H.

(C) Transfer recording test and storage stability test of recorded material 0) Transfer recording test Is the ink coated surface of the color sheet above overlapped with the image receiving layer surface of the image receptor prepared in (a) above? Recording was carried out under the following conditions using a thin film type line thermal head having a heating resistor density of 71M dots to obtain recorded matter having the color coagulation shown in Table 1 below.

Recording line density? Line/ho Thermal head applied power o, 3W/dot Thermal head applied pulse width 6 milliseconds (1) Storage stability test of recorded matter The recorded matter described above was exposed to light for 20 hours using a xenon fade meter. The degree of discoloration and fading was measured using a color difference meter, and the results are shown in Table 1 below.

In addition, the above recorded material was maintained under the conditions of 60"CX 40% R, HO for ! days, and the degree of color bleeding of the recorded material was observed using a microscope. The results are shown in Table 1.

In place of the dye incorporated in Example/(b), the following structural formula (I[
) An image receptor and a color sheet were prepared in the same manner as in Example 1, except that the color sheet was prepared using a yellow dye represented by .

Example 3 The following structural formula (In
) An image receptor and a color sheet were prepared and tested in the same manner as in Example 1, except that the color sheet was prepared using a cyan dye represented by . The results are in the table/
It was shown to.

Examples y-g Instead of the As resin used in Examples/--3, image receptors were created using AASA resin product name Nivitax ■≦700 (manufactured by Hitachi Chemical Co., Ltd., heat distortion temperature 9J-'C) An image receptor and a color sheet were prepared in the same manner as in Examples 1 to 3, except that the test was carried out, and the results are shown in Table 7 below.

15-Example? -2 Instead of the As resin used in Examples/~3, an image receptor was created using A'ns resin (product name: Unibly) UV-1θO: manufactured by Sumitomo Naugatac Co., Ltd., heat distortion temperature: 90°C) Except for the above, image receptors and color sheets were prepared and tested in the same manner as in Examples/--3, and the results are shown in Table 7 below.

An image receptor was made using AO resin (product name: NF-920: manufactured by Showa Denko K.K., heat distortion temperature: 2°C) instead of the As resin used in Examples 10 to 3. .

An image receptor and a color sheet were prepared and tested by the same method as in Examples 1 to 3 and P1, except that the results were shown in Table 1 below.

Comparative Examples 7 to 3 10 parts by weight of polyvinyl chloride (degree of polymerization: 10θ, manufactured by Wako Tsumugi Kogyo Co., Ltd.) was dissolved in 700 parts by weight of tetrahydrofuran, and 0% of amine-modified silicone KF3 was added to the solution.
, 6 parts by weight of the coating liquid prepared by adding /! Apply to θμm thick polypropylene synthetic paper with a wire bar and dry to a dry film thickness of approx. An image receptor was prepared by forming an image receptor layer with a thickness of μm.

The color sheets were prepared in the same manner as in Examples/--3, and tested using the above image receptors in the same manner as in Examples/, Example 3, and Example 3. The results shown are obtained.

Comparative Example 4t-6 Polyester resin (trade name Nibyron, 200 Nitoyobo Co., Ltd. 2) was used instead of the As resin used in Examples/~3.
) An image receptor and a color sheet were prepared in the same manner as in Examples 1 to 3, except that the image receptor was prepared using the following method.

[Effects of the Invention] The image receptor for thermal transfer recording of the present invention is easy to manufacture;
When the image receptor of the present invention is used as an image receptor for sublimation type heat-sensitive transfer recording, it is possible to record with high accuracy and to obtain a recorded material with good storage stability such as light fastness and fixing property.

Therefore, it can be advantageously used for color recording in office automation terminals such as facsimiles, printers, and copying machines, which have become rapidly popular in recent years, and for color recording of television images.

Patent applicant: Mitsubishi Chemical Industries, Ltd. Representative Patent Attorney Hase - (7 others)

Claims (7)

[Claims] (1) An image receptor for thermal transfer recording, characterized in that it has an image-receiving layer on the surface of a substrate, the image-receiving layer being mainly composed of a copolymer resin formed of acrylonitrile and styrene as essential components. (2) The image receptor for thermal transfer recording according to claim 1, wherein the copolymer resin is an acrylonitrile-styrene copolymer resin. (3) The image receptor for thermal transfer recording according to claim 1, wherein the copolymer resin is an acrylonitrile-special acrylic rubber-styrene copolymer resin. (4) The image receptor for thermal transfer recording according to claim 1, wherein the copolymer resin is an acrylonitrile-EP rubber-styrene copolymer resin. (5) The image receptor for thermal transfer recording according to claim 1, wherein the copolymer resin is an acrylonitrile-chlorinated polyethylene-styrene copolymer resin. (6) The image receptor for thermal transfer recording according to any one of claims 1 to 5, wherein the image receiving layer further contains a release agent. (7) The image receptor for thermal transfer recording according to any one of claims 1 to 5, which has a layer containing a release agent on the image-receiving layer.