JPH0439088A - Thermal transfer image receiving paper - Google Patents

Abstract

PURPOSE:To eliminate blocking and to obtain high transfer image density and a sharp image by further providing a layer consisting of a specific thermoplastic resin and an addition polymerizable composition on the addition polymerizable composition layer applied to a highly smooth support and crosslinking the same. CONSTITUTION:After an addition polymerizable composition is applied to a highly smooth support, a layer consisting of 40 - 90pts.wt. of a thermoplastic resin having dyeing properties to a disperse dye and 60 - 10pts.wt. of an addition polymerizable composition and cured by the irradiation with ultraviolet rays or electron beam to obtain sublimation type thermal transfer image receiving paper. In this case, as the highly smooth support, art paper, coated paper, a synthetic resin film, synthetic resin laminated paper, synthetic paper or the like are used. As the thermoplastic resin, a polyester resin is pref. for the purpose of enhancing the dyeing properties of a sublimable dye to enhance transfer density. Further, as the addition polymerizable composition, a resin having a reactive group such as an acryloyl group, a methacryloyl group or an epoxy group in its molecular terminal or side chain is used.

Description

DETAILED DESCRIPTION OF THE INVENTION [A] Industrial field of application The present invention can be coated onto a highly smooth support such as coachite paper, laminated paper, or synthetic paper to provide excellent blocking properties, high image quality, and image density. The present invention relates to an image-receiving paper for sublimation type heat-sensitive transfer with high quality.

[B] Prior Art In recent years, sublimation type thermal transfer printers have been used as a means of color hard copying, particularly for reproducing multicolor gradation images. The principle of a sublimation type thermal transfer printer is to convert an image into an electrical signal, and then convert this electrical signal into a thermal signal using a thermal head to print a sheet coated with sublimation ink (ink donor sheet). The heated and sublimated ink is fixed on an image-receiving paper that is in close contact with an ink donor sheet, and the image is reproduced. The surface of such image-receiving paper is generally provided with an image-receiving layer made of a polymer such as saturated copolymer polyester or polyacetate for fixing ink.

(C) Problems to be Solved by the Invention In recent years, there has been a demand for faster print speeds and improved transferred image quality in dye-sublimation thermal transfer printers.

When a porous support such as plain paper base paper is used as a support for image receiving paper for thermal transfer, the smoothness is low and the image quality is poor. There is no choice but to use paper, synthetic resin films such as polyethylene, polypropylene, polyethylene terephthalate, polyamide, etc., or laminated paper or synthetic paper in which these synthetic resins are laminated on one or both sides of paper, and these are heat-resistant. This, combined with its high smoothness, causes shrinkage of the support surface due to heat and blocking with the ink donor sheet, leading to a decrease in image quality. Further, since increasing the printing speed inevitably leads to an increase in the thermal printing temperature, there is a tendency to further worsen the above-mentioned situation. As a means to solve such problems, there is known a sublimation type heat-sensitive transfer image-receiving paper in which an addition-polymerizable oligomer is coated on a substrate and cross-linked by radiation (Japanese Patent Laid-Open No. 62-1
73295). However, there are the following problems in actually using such a sublimation type heat-sensitive transfer image-receiving paper. In other words, it is desirable that the sheet used as the substrate has appropriate cushioning properties in order to promote adhesion with the ink donor sheet during printing, but when an addition polymerizable composition is cured, this cushioning property is In addition, such addition-polymerizable compositions generally have poor dyeability with sublimation dyes (although they are excellent in blocking, they have the disadvantage that it is difficult to obtain high transfer density and high image quality as a result).

Therefore, an object of the present invention is to use a thermoplastic resin with excellent dyeability to sublimation dyes as an image-receiving layer for thermal transfer, and at the same time to create an addition polymerization composition between the thermoplastic resin and the support of an image-receiving paper for thermal transfer. By providing the material layer, it is possible to obtain a high transferred image density and high image quality, and at the same time, to obtain an image receiving paper for thermal transfer without blocking.

[01 Means for Solving the Problems The inventor of the present invention has conducted extensive research into means for solving the above-mentioned problems, and as a result has found the following method. That is, (1) a thermoplastic resin 4 having dyeability with disperse dyes is placed on an addition polymerizable composition layer coated on a highly smooth support.
1. An image-receiving paper for thermal transfer, characterized in that a layer comprising 0 to 90 parts by weight and 60 to 10 parts by weight of an addition polymerizable composition is provided, and the above composition is crosslinked.

(2) The highly smooth support is a coated paper such as art paper or coated paper, or a synthetic resin film such as polyethylene, polypropylene, polyethylene terephthalate, or polyamide;
Alternatively, an image-receiving paper for thermal transfer characterized by being laminated paper or synthetic paper in which these synthetic resins are laminated on one or both sides of paper.

(3) An image-receiving paper for thermal transfer, wherein the addition-polymerizable composition comprises a compound having an acryloyl group, a methacryloyl group, or an epoxy group.

(4) An image-receiving paper for thermal transfer, characterized in that the thermoplastic resin is a polyester resin.

The present invention will be explained in detail below. That is, in the present invention, after coating an addition polymerizable composition on a highly smooth support, 40 to 90 parts by weight of a thermoplastic resin having dyeability to disperse dyes and 60 to 10 parts by weight of an addition polymerizable composition are added. By providing a layer consisting of
An image receiving paper for sublimation type heat-sensitive transfer is obtained by curing with ultraviolet irradiation or electron beam irradiation.

Examples of thermoplastic resins include those having ester bonds such as polyester resins, polyacrylic ester resins, polycarbonate resins, polyvinyl acetate resins, and styrene acrylate resins, and those having urethane bonds such as polyurethane resins and amide bonds. Polyamide resin (nylon) can be used as a material having a urea bond, urea resin can be used as a material having a urea bond, or a copolymer containing one or more of the constituent units of the above resins as a main component, such as vinyl chloride-acetic acid. It can also be used as a vinyl copolymer, styrene-butadiene copolymer, etc. Furthermore, the above resins can be used alone or in a mixture of two or more.

Any of the above thermoplastic resins can be suitably used for the purpose of the present invention, but polyester resins are particularly preferred for the purpose of increasing the dyeability of sublimation dyes and measuring the improvement of transfer density.

The thermoplastic resin represented by the above polyester resin is 40
When it is less than 90 parts by weight, the image transfer density is low (and when it is more than 90 parts by weight, blocking occurs between the ink donor sheet and the image quality deteriorates.

The above resins can be dissolved in an organic solvent and applied onto the substrate, or
It can also be emulsified in an aqueous solution and applied as an emulsion onto a substrate.

Furthermore, if necessary, additives such as dyes, pigments, wetting agents, antifoaming agents, dispersants, antistatic agents, mold release agents, and optical brighteners can also be contained.

In particular, regarding pigments, the purpose of improving blocking can be achieved by incorporating inorganic particles such as silica, calcium carbonate, kaolin clay, barium sulfate, titanium oxide, etc. into the thermoplastic resin layer or addition polymerizable composition layer. I can do it.

In addition, mold release agents can be used for the same purpose, but specifically, solid waxes such as polyethylene wax, amide wax, and Teflon powder, fluorine-based and phosphate-based surfactants, silicon compounds, etc. However, a curable silicone compound is preferably used because it is unlikely to cause bleeding of the transferred dye or a decrease in transfer or image density. Examples of curing silicon compounds include reaction curing types, ionizing radiation curing types, catalyst curing types, etc.
The present invention is characterized in that it is irradiated with ultraviolet rays or electron beams after forming the image-receiving layer, and an ionizing radiation-curable silicon compound is conveniently used.

In addition, an addition polymerizable composition is one that is mainly composed of ultraviolet polymerizable or electron beam polymerizable resins shown below, and these resins can be used without a solvent or diluted with a solvent.
If necessary, a reaction initiator is mixed and used.

The ultraviolet or electron beam polymerizable resin used in the present invention is a compound having a reactive group such as an acryloyl group, a methacryloyl group, or an epoxy group at the end of the molecule or in a side chain of the molecule, such as an unsaturated polyester or a modified unsaturated polyester. , acrylic polymer, acrylic monomer,
Methacrylic polymers, methacrylic onomers, monomers having vinyl unsaturated bonds, or oligomeric epoxy compounds can be used alone or in combination with other solvents. Typical examples are shown below.

(a) Polyester acrylate, polyester methacrylate, e.g. Aronix M-5300, Aronix M-
5400, Aronix M-5500, Aronix M
-5600, Aronix M-5700, Aronix M-6100, Aronix M-6200, Aronix M-6300, Aronix M-6500, Aronix M-7100, Aronix M-8030, Aronix M-8060, Aronix M-8100 (and above, Toagosei Chemical Industry Co., Ltd. (product name), Viscodoor 00
, Visco) 3700 (all trade names of Osaka Organic Chemical Industry Co., Ltd.), Kayarad HX-220, Kayarad HX
-620 (all trade names of Nippon Kayaku Co., Ltd.) (b) Epoxy acrylate, epoxy methacrylate, e.g. NK ester, EA-800, NK ester,
EPM-800 (product name of Shin-Nakamura Chemical Co., Ltd.), Viscotro 00, Viscoat 540 (product name of Osaka Organic Chemical Industry Co., Ltd.), Photomer 3016, Photomer 3082 (product name of San Nopco Co., Ltd.) (C) Urethane acrylate, urethane methacrylate, e.g. Aronix M-1100, Aronix M-
1200, Aronix M-121,0, Aronix M-1250, Aronix M-1260, Aronix M-1300, Aronix M-1310 (trade names of Toagosei Chemical Industry Co., Ltd.), Viscoat 812, Viscoat 823, Viscoat 823 (The above are product names of Osaka Organic Chemical Industry Co., Ltd.), NK ester, U-108-
A, NK ester, U-48A (trade name of Shin Nakamura Chemical Co., Ltd.) (d) Monofunctional acrylate, monofunctional methacrylate such as methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate,
2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, tetrahydrofurfuryl acrylate, phenoxyethyl acrylate, cyclohexyl acrylate, cyclohexyl methacrylate, benzyl acrylate, glycidyl methacrylate, N,N-dimethylamino Ethyl acrylate, N,N-dimethylaminoethyl methacrylate, N,N-diethylaminoethyl methacrylate, butoxyethyl acrylate, and the like. Ethylene oxide modified phenoxylated phosphoric acid acrylate Ethylene oxide modified butoxylated phosphoric acid acrylate, other product names of Toagosei Chemical Industry Co., Ltd. include Aronix M-101, Aronix M-102, Aronix M
-111, Aronix M-113, Aronix t-
114, Aronix M-117, Aronix M-1
52, Aronix M-1, 54, etc.

(e) Polyfunctional acrylate, polyfunctional methacrylate, such as 1,6-hexanediol diacrylate, 1
．． 6-hexanethiol dimethacrylate, neopentyl glycol diacrylate, diethylene glycol diacrylate, polyethylene glycol diacrylate,
Polyethylene glycol dimethacrylate, polypropylene glycol diacrylate, polypropylene glycol dimethacrylate, pentaerythritol diacrylate, dipentaerythritol hexaacrylate,
Isocyanuric acid diacrylate, pentaerythritol triacrylate, isocyanuric acid triacrylate,
Examples include trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, ethylene oxide-modified pentaerythritol tetraacrylate, propylene oxide-modified pentaerythritol tetraacrylate, propylene oxide-modified dipentaerythritol polyacrylate, and ethylene oxide-modified dipentaerythritol polyacrylate. Aronix M-21 is the product name of Toagosei Chemical Industry Co., Ltd.
0, Aronix M-215, Aronix M-220
, Aronix M-230, Aronix M-233,
Aronix M-240, Aronix M-245, Aronix M-305, Aronix M-309, Aronix M-310, Aronix M-315, Aronix M-320, Aronix M-325, Aronix M-330, Aronix M-400, TO-45
8, To-747, TO-755, THIC, TA2, etc.

(f) Epoxy compounds such as glycidyl methacrylate,! , 3 screws (N, N
-jepoxypropylaminomethyl)cyclohexane,
Examples include 1,3 bis(N,N-jepoxypropylaminomethyl)benzene. The product names of Mitsubishi Gas Chemical Co., Ltd. are GE-51,0, TETRAD-X,
Examples include TETRAD-C.

Photoinitiators used in the present invention include acetophenones such as di- and trichloroacetophenone, benzophenone, Michler's ketone, benzyl, benzoin, benzoin alkyl ether, benzyl dimethyl ketal, tetramethylthiuram monosulfide, thioxanthone, azo compounds, etc. It is selected from the viewpoints of the type of polymerization reaction of the addition polymerizable resin, stability, and compatibility with the irradiation equipment. The amount of photoinitiator used is usually in the range of 1 to 5% based on the addition polymerizable resin. Further, a storage stabilizer such as hydroquinone may be used in combination with the photoinitiator.

Highly smooth supports used in the present invention include art paper,
Coated paper such as coated paper, synthetic resin film such as polyethylene, polypropylene, polyethylene terephthalate, polyamide, etc., or one side of paper with these synthetic resins,
Alternatively, laminated paper laminated on both sides, synthetic paper, etc. are used.

Examples of methods for applying the thermoplastic resin or addition polymerizable composition onto the substrate include blade coating, air doctor coating, squeeze coating, air knife coating,
Methods such as reverse roll coating, gravure roll and transfer roll coating, bar code coating, curtain coating, etc. are used.

If necessary, after coating the addition polymerizable composition on the support, a highly smooth film or the like is laminated and cured by irradiating an electron beam from the film side, and then the film is peeled off and further coated with a thermoplastic resin. A layer of addition polymerizable composition may also be provided.

The amount of addition polymerizable composition applied onto the substrate varies depending on the type of substrate, but is 1 to 20 g/rrf, more preferably 2 to 1 g/rrf.
0g/rT! It is.

Ionizing radiation for curing the addition polymerizable composition generally includes ultraviolet rays, α rays, β rays, γ rays, X rays, and electron beams, but α rays, β rays, γ rays, and X rays are Since there is the issue of danger to the environment, ultraviolet rays and electron beams are effective because they are easy to handle and are widely used industrially.

When using an electron beam, the amount of electron beam irradiated is 0.1~
It is desirable to adjust within a range of about 10 Mrad. 0.
Below IMrad, sufficient irradiation effect cannot be obtained, and 10
If it exceeds M r a d, it is not preferable because it deteriorates the paper or film substrate.

As the electron beam irradiation method, a scanning method, a curtain beam method, etc. are adopted, and an appropriate accelerating voltage for electron beam irradiation is about 100 to 300 KV.

Further, when using ultraviolet rays, it is necessary to incorporate a sensitizer into the addition polymerization composition, and the sensitizers listed above can be used as appropriate.

As the light source, for example, a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, a xenon lamp, a tungsten lamp, etc. are suitably used.

(E) Function The present invention is an image-receiving paper for thermal transfer, which has a hardened addition polymerizable composition layer, a thermoplastic resin, and an addition polymerizable composition layer on a highly smooth support in the production of an image-receiver paper for thermal transfer. ,
Since there is a further hardened addition polymerizable composition layer between the highly smooth support and the ink donor sheet or the thermoplastic resin and the addition polymerization composition layer, thermal shrinkage and blocking of the support are prevented, and the image High transfer density.

[F] Examples The present invention will be explained in detail below using examples, but the content of the present invention is not limited to the examples.

Example 1 Photographic support laminated with polyethylene (RC paper)
On top, 98 parts of acrylic monomer M-220 (Toagosei Chemical Industry Co., Ltd.) and benzyl dimethyl ketal (IRGACU) were added.
After applying an addition polymer composition layer consisting of 2 parts of RE951 (Ciba Geigy) to a weight of 5.0 g/d, 50 parts of polyester resin (Vylon 300: Toyobo Co., Ltd.) dissolved in ethyl acetate and acrylic monomer were added using a gravure offset coater. 49 parts of M-220 (Toagosei Chemical Industry)
and benzyl dimethyl ketal (IRGACURE951
A layer of an addition polymer composition consisting of 1 part (Ciba Geigy) was applied so that the dry solid content was 3.0 g/nf, and after drying, it was cured by ultraviolet irradiation (80 W: 3 lines) to obtain an image receiving paper for thermal transfer. Ta.

Example 2 An addition polymerization composition of 50 parts of acrylic oligomer TC-120S (Nippon Kayaku) and 50 parts of acrylic monomer M-210 (Toagosei Kagaku Kogyo) was coated on coated paper at 3°0 g/rrl using a gravure offset coater. After curing by electron beam irradiation (acceleration voltage: 175 KV, irradiation dose IMrad), 40 parts of polyester resin (Vylon 300: Toyobo Co., Ltd.) dissolved in ethyl acetate and acrylic monomer M-210 (Toagosei Co., Ltd.) were applied. 60 parts of the coating was applied so that the total dry solid content was 3.0 g/rrr, and after drying, it was further cured by electron beam irradiation (acceleration voltage: 175 KV, irradiation dose IMrad) to obtain an image-receiving paper for thermal transfer.

Example 3 Synthetic paper (YUBO FPG-110: Tamago Yuka) was coated with a gravure offset coater using 95 parts of acrylic oligomer M-210 (Toagosei Kagaku Kogyo) and 5 parts of Thyroid 162 (Fuji Davison) as an addition polymerization composition layer. Using 2.
5g/rrf and cured by electron beam irradiation (acceleration voltage: 150KV, irradiation dose: 1.5Mrad), 90 parts of polyester resin (Byron 200: Toyobo) and acrylic oligomer M-210 (Toa Synthesis) 10 parts were coated with a gravure offset coater so that the dry solid content was 2.5 g/rrr in total, and after drying, irradiated with an electron beam (acceleration voltage: 150 KV, irradiation dose: 1° 5 Mrad)
) to obtain an image-receiving paper for thermal transfer.

Example 4 An addition polymerization composition layer of 95 parts of acrylic oligomer M-210 (Toagosei Kagaku Kogyo) and 5 parts of Thyroid 162 (Fuji Davison) was applied to art paper using a gravure offset coater (X gives 2.5 g/I). Apply as shown,
Electron beam irradiation (acceleration voltage 150KV, irradiation dose 1.5Mr
ad), 50 parts of polyester resin (Vylon 300, Toyobo Co., Ltd.) and 45 parts of acrylic oligomer M-210 (Toagosei Co., Ltd.) dissolved in ethyl acetate.

Id 162 (Fuji Davison) 5 parts with a total dry solid content of 3. Coated with a gravure offset coater so that the ratio was 0/rd, and after drying, irradiated with an electron beam (acceleration voltage: 150 KV,
It was cured at an irradiation dose of 1.5 Mrad) to obtain an image receiving paper for thermal transfer.

Comparative Example I 50 parts of acrylic oligomer TC-12O8 (Nippon Kayaku) and 50 parts of acrylic monomer M-210 (Toagosei Kagaku Kogyo) were prepared as an addition polymerization composition on RC paper using a gravure offset coater. Coat it so that it is Og/g, and irradiate it with electron beam (acceleration voltage: 175KV, irradiation dose IM
After curing with rad), polyester resin (Byron 200: Toyobo Co., Ltd.) dissolved in ethyl acetate was applied so that the total dry solid content was 3.0 g/rrr, and after drying, it was further irradiated with electron beam (acceleration voltage: 175 KV). , an irradiation dose of 1 Mrad) to obtain an image-receiving paper for thermal transfer.

Comparative Example 2 50 parts of acrylic oligomer TC-12O8 (Nippon Kayaku) and 50 parts of acrylic monomer M-210 (Toagosei Kagaku Kogyo) were added as an addition polymerization composition on synthetic paper (YUBO FPG-110: Tamago Yuka). A polyester resin (Vylon 200: Toyobo Co., Ltd.) dissolved in ethyl acetate was coated with a gravure offset coater to a concentration of 3.0 g/nf and cured by electron beam irradiation (acceleration voltage: 175 KV, irradiation dose IMrad). part and acrylic monomer M-2
10 (Toagosei) 80 parts with a total dry solid content of 3°0 g
/rrr, and after drying, it was further cured by electron beam irradiation (acceleration voltage: 175 KV, irradiation dose IMrad) to obtain an image receiving paper for thermal transfer.

Comparative Example 3 Polyester resin emulsion (Pyronal MD-1330: Toyobo P) was coated on coated paper with an air knife coater.
A) and silica with dry solid content of 3゜0g/A and 0.5, respectively.
g/nf, and after drying, 20 parts of polyester resin (Vylon 200: Toyobo Co., Ltd.) dissolved in ethyl acetate and acrylic monomer M-21,0 (Toagosei Co., Ltd.) were added.
80 parts was applied so that the total dry solid content was 3.0 g/rrf, and after drying, it was further irradiated with an electron beam (acceleration voltage: 175 KV).
, irradiation dose IM r a d ) to obtain an image-receiving paper for thermal transfer.

The ink donor sheet was placed on the image receiving paper for thermal transfer thus obtained, facing each other, and heated from the donor sheet side at 180°C for 5 seconds to determine the transfer density and blocking (the state of fusion between the image receiving sheet and the ink film, and the image receiving sheet). heat shrinkage)
was evaluated.

Regarding the transfer density, the value of the cyan image density measured using a Macbeth densitometer is shown. Regarding blocking, all (
A state in which no blocking was observed was evaluated as ◯, and a state in which blocking was completely observed was evaluated as ×, and the results are shown in Table 1.

(Table 1) [G] Effect In the production of an image receiving paper for thermal transfer as in the present invention, a hardened addition polymerizable composition layer on a highly smooth support and 40 to 90 parts of a thermoplastic resin on the layer are used. The addition polymerizable composition is 60 to 1
By providing 0 parts, thermal shrinkage and blocking of the support were prevented, and an image receiving paper for thermal transfer with high image transfer density could be obtained.

Claims (4)

[Claims] (1) On the addition polymerizable composition layer coated on the highly smooth support, 40 to 90 parts by weight of a thermoplastic resin having dyeability to disperse dyes and 60 to 10 parts by weight of the addition polymerizable composition are added. 1. An image-receiving paper for thermal transfer, characterized in that the above-mentioned composition is crosslinked. (2) The image-receiving paper for thermal transfer according to claim 1, wherein the highly smooth support is coated paper, laminated paper, or synthetic paper. (3) The image-receiving paper for thermal transfer according to claim 1 or 2, wherein the addition polymerizable composition comprises a compound having an acryloyl group, a methacryloyl group, or an epoxy group. (4) The image receiving paper for thermal transfer according to claim 1, 2 or 3, wherein the thermoplastic resin is a polyester resin.