JPH0439089A - Thermal transfer image receiving paper - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION ['A) Industrial Field of Application The present invention is applicable to coating on a highly smooth support such as coated paper, laminated paper, synthetic paper, etc., to produce images with excellent blocking properties and high image quality. The present invention relates to a high-density sublimation type thermal transfer image receiving paper.

[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. It is necessary to use paper, synthetic resin films such as polyethylene, polypropylene, polyethylene terephthalate, polyamide, etc., or laminated paper, synthetic paper, etc. in which these synthetic resins are laminated on one or both sides of paper, etc., 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, and although they are excellent in blocking, they have the disadvantage that it is difficult to obtain high transfer density and high image quality.

Therefore, an object of the present invention is to use a thermoplastic resin having excellent dyeability to sublimation dyes as an image-receiving layer for thermal transfer, and at the same time to create an addition-polymerizable bond between the thermoplastic resin and the support of an image-receiving paper for thermal transfer. By providing an intermediate layer consisting of a composition and a polyolefin resin, 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.

CD) 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. Namely, (1) an image-receiving paper for thermal transfer characterized by having an intermediate layer mainly composed of an addition polymerizable composition and a polyolefin resin, and a thermoplastic resin layer on a highly smooth support.

(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 forming an intermediate layer by coating an addition polymerizable composition and a polyolefin resin on a highly smooth support, a thermoplastic resin layer is coated, and curing by ultraviolet irradiation or electron beam irradiation is performed to form an intermediate layer. Immediately after coating or after coating the thermoplastic resin layer, an image receiving paper for sublimation type heat-sensitive transfer is obtained.

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 resins. Polyamide resin (nylon) can be used as a material having a 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- It can also be used as a vinyl acetate copolymer, a styrene-butadiene copolymer, etc. Furthermore, the above resins can be used alone or in combination 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 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.

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. Aloex M-5300, Aloex M-
5400, Aloex M-5500, Aloex M
-5600, Aloex M-5700, Aloex M-6100, Aloex M-6200, Aloex M-6300, Aloex M-6500, Aloex M-7100, Aloex M-8030, Aloex M-8060 , Aroex M-8100 (trade name of Toagosei Chemical Industry Co., Ltd.), Viscodoor 00
, Viscoat 3700 (all trade names of Osaka Organic Chemical Industry Co., Ltd.), Kayarad HX-220, Kayarad HX
-620 (the above is a trade name of Nippon Kayaku Co., Ltd.) (b) Epoxy acrylate, epoxy methacrylate, e.g. NK ester, EA, -800, NK ester, EPM-800 (the above is a trade name of Shin Nakamura Chemical Co., Ltd.) ,
Viscotro 00, Viscoat 540 (trade names of Osaka Organic Chemical Industry Co., Ltd.), Photomer 3016, Photomer 3082 (trade names of San Nopco Co., Ltd.) (C) Urethane acrylate, urethane methacrylate For example, Aroex M- 1100, Aloex M-
1200, Aloex M-1210゜Aloex M
-1250, Aloex M-1260, Aloex M-1300, Aloex M-1,310 (Toagosei Chemical Co., Ltd. brand names), Viscoat 812, Viscoat 823, Viscoat 823 (Osaka Organic Chemical Industry Co., Ltd.) Kogyo Co., Ltd. product name), NK ester, U-108-
ASNK ester, U-4HA (Shin Nakamura Chemical (
(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-1-, benzyl acrylate, glycidyl methacrylate, N5N-dimethylaminoethyl acrylate , NXN-diethylaminoethyl methacrylate, NXN-diethylaminoethyl methacrylate, butoxyethyl acrylate, and the like. Ethylene oxide-modified phenoxylated phosphoric acid acrylate, ethylene oxide-modified butoxylated phosphoric acid acrylate, and other product names of Toagosei Kagaku Kogyo Co., Ltd., such as Aroex M
-101, Aloex M-102, Aloex M-
111, Aloex M-113, Aloex M-1
1,4, Aloex pH1,7, Aloex M-1
, 52, Aloex M-154, and the like.

(e) Polyfunctional acrylate, polyfunctional methacrylate, such as 1,6-hexanediol diacrylate, 1
．． 6-hexanediol dimethacrylate, neopentyl glycol diacrylate, diethylene glycol diacrylate, polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, polypropylene glycol diacrylate, polypropylene glycol dimethacrylate, pentaerythritol diacrylate, dipentaerythritol hexa Acrylate, isocyanuric acid diacrylate, pentaerythritol triacrylate, isocyanuric acid triacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, ethylene oxide modified pentaerythritol tetraacrylate, propylene oxide modified pentaerythritol tetraacrylate, propylene oxide modified dipentaerythritol Examples include polyacrylate, ethylene oxide-modified dipentaerythritol polyacrylate, and the like. The product name of Toagosei Chemical Industry Co., Ltd. is Aronix M-2.
10, Aronix M-215, Aronix M-22
0, 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 M325, Aronix M-330, Aronix M-400, To-45
8, To-747, T.

-755, THIC9TA2, and the like.

(f) Epoxy compounds such as glycidyl methacrylate, 1.3 bis(N,
N-jepoxypropylaminomethyl)cyclohexane, l,3bis(N,N-jepoxypropylaminomethyl)benzene, and the like. Mitsubishi Gas Chemical Co., Ltd.
In terms of product names, GE-510, TETRAD-XS
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.

As the polyolefin resin, low density polyethylene (density about 0.91 to about 0.925), high density polyethylene (density about 0.925 to about 0.965), polypropylene, etc. can be used alone or in combination. .

The purpose of using a mixture of an addition polymerizable composition and a polyolefin resin in the thermal transfer image-receiving layer as in the present invention is to maintain high image transfer density and good image quality, and to maintain high blocking resistance while maintaining high cost. The objective is to replace the addition polymerizable composition with an inexpensive polyolefin resin to obtain a thermal transfer image-receiving paper at an effective cost for industrial use. However, if the polyolefin resin exceeds 45 parts by weight, although it is useful in terms of cost, blocking may occur. This occurs and causes a decline in image quality. Furthermore, if the amount of polyolefin resin is less than 5 parts by weight, there is no substantial cost advantage.

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. In other words, either the addition polymerizable composition and the polyolefin resin are both dissolved in an organic solvent and applied.
Alternatively, a water-soluble addition polymerizable composition and a water-dispersible polyolefin emulsion may be mixed and applied. Both can be cured and crosslinked after removing the solvent in a drying section.

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, a mold release agent can be used for the same purpose, and specific examples include solid waxes such as amide wax and Teflon powder, fluorine-based and phosphate-based surfactants, and silicone compounds. 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., but the present invention is characterized in that it is irradiated with ultraviolet rays or electron beams after forming the image-receiving layer. , ionizing radiation-curable silicon compounds are advantageously used.

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,
Or laminated paper, synthetic paper, etc. with laminated paper on both sides 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.

The amount of the addition polymerizable composition applied onto the substrate varies depending on the type of substrate, but is 1 to 20 g/n (more preferably 2 to 10 g/n).
g/rr? 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. O,
], below Mrad, 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 directed to the production of image-receiving paper for thermal transfer, which has a hardened addition polymerizable composition on a highly smooth support, an intermediate layer mainly composed of a polyolefin resin, and a thermoplastic resin layer. It is an image-receiving paper, and since there is an addition polymerizable composition layer between the highly smooth support and the ink donor sheet or thermoplastic resin layer, thermal shrinkage and blocking of the support are prevented, and the image transfer density is improved. expensive.

(F) Examples Hereinafter, the present invention will be explained in detail with reference to Examples, but the content of the present invention is not limited to the Examples.

Example 1 A mixture of 55 parts of acrylic oligomer M-210 (Toagosei Kagaku Kogyo) and 45 parts of polyethylene resin dissolved in ethyl acetate was coated on coated paper, and after drying, the dry solid content was 5.
．． After coating to 0 g/rrr, electron beam irradiation (acceleration voltage: i, 75 KV, irradiation dose 2.0 Mrad)
After that, 90 parts of polyester resin emulsion (Pyronal MD-1330 + Toyobo) and 10 parts of silica were coated with a water solvent, dried, and the dry solid content was 4.
A thermal transfer image-receiving paper was obtained by applying 0 g/i.

Example 2 Kayalad PE as acrylic oligomer on coated paper
60 parts of G400DA (Nippon Kayaku) and Polyron 393 (
Polyethylene emulsion: Chukyo Yushi: concentration 30%) 1
00 parts (solid content 30 parts) and Shitsuka 10 parts were coated with water solvent so that the dry solid content was 5.0 g/n (dry solid content), and after drying, electron beam irradiation (acceleration voltage: 1.75 KV, irradiation dose 1. 5
After curing with Mr a d), polyester resin emulsion (Pyronal MD) was cured with an air knife coater.
-1330 Nitoyobo) and 30 parts of silica were applied so that each had a dry solid content of 4.5 g/rd, and after drying, an image receiving paper for thermal transfer was obtained.

Example 3 NK ester A-600 (Shin Nakamura Chemical) as an acrylic oligomer on synthetic paper (YUBO FPG-110 Tamago Yuka)
95 parts and Polyron E-10 (polyethylene emulsion, Middle East fat: concentration 26%) 19 parts (solid content 5 parts) were applied so that the dry solid content was 4.5 g/H, and after drying, electron beam irradiation (accelerated voltage +150KV, irradiation dose 1.OMra
After curing by step d), 80 parts of polyester resin emulsion (Pyronal MD-1200, Toyobo Co., Ltd.) and 20 parts of Thyroid 162 (Fuji Davison) were applied with a water solvent so that the dry solid content was 5.0 g/rd, and dried. An image receiving paper for thermal transfer was obtained.

Example 4 NK ester A as acrylic oligomer on coated paper
-600 (Shin Nakamura Chemical) 65 parts and Polylon E-1,0 (
Polyethylene emulsion: Chukyo Yushi: Concentration 26%) 1
35 parts (solid content 35 parts) with a dry solid content of 4.5 g/r&
After coating and drying, electron beam irradiation (acceleration voltage 1
80, V, irradiation dose 1.5 Mrad), polyester resin emulsion (Pyronal MD
-1200: Toyobo) and 20 parts of Thyroid 162 (Fuji Davison) were coated with a water solvent so that the dry solid content was 5.0 g/d, and dried to obtain an image receiving paper for thermal transfer.

Comparative Example 1 30% of acrylic oligomer M-21,0 on coated paper
(Toagosei Kagaku Kogyo) and 70 parts of polyethylene resin was dissolved in ethyl acetate and applied, and after drying, the mixture was coated so that the dry solid content was 5.0 g/rrf, and then irradiated with an electron beam (acceleration voltage: 175 KV). , irradiation ff12.OMrad
), then 90 parts of polyester resin emulsion (Pyronal MD-1330, Toyobo Co., Ltd.) and 10 parts of silica were coated with a water solvent, dried, and the dry solid content was 4.
．． A thermal transfer image-receiving paper was obtained by applying 0 g/i.

Comparative Example 2 Kayalad PE as acrylic oligomer on coated paper
G400DA (Nippon Kayaku) 20 parts and Polylon 393 (
Polyethylene emulsion: Chukyo Yushi: Concentration 30%) 2
67 parts (solid content 80 parts) with dry solid content of 5.0 g/rI
After coating with an aqueous solvent so that f is obtained, drying and curing by electron beam irradiation (acceleration voltage: 175 KV, irradiation dose 1.5 Mrad), polyester resin emulsion (Pyronal MD-1330: Toyobo) 70 and 30 parts of silica with a dry solid content of 4.5 g each.
/rd, and after drying, an image receiving paper for thermal transfer was obtained.

Comparative Example 3 25 parts of NK Ester A-600 (Shin Nakamura Chemical) and 288 parts of Polylon E-10 (polyethylene emulsion: Middle East oil and fat: concentration 26%) as acrylic oligomers on synthetic paper (Yubo FPG-110, Tamago Yuka) parts (solid content 75 parts)
The dry solid content is 4.5g/rr? After coating, drying, and curing by electron beam irradiation (acceleration voltage: 150 KV, irradiation dose: 1.OMrad), 80 parts of polyester resin emulsion (Pyronal MD-1200: Toyobo Co., Ltd.) and Thyroid 162 (Fuji Davison) were added. 20
A portion was coated with a water solvent so that the dry solid content was 5.0 g/rd, and dried to obtain an image receiving paper for thermal transfer.

The ink donor sheet was stacked on the image receiving paper for thermal transfer thus obtained, facing each other, and heated from the donor sheet side at 175°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). Thermal shrinkage) was evaluated.

Regarding the transfer density, the value of the cyan image density measured using a Macbeth densitometer is shown. Regarding blocking, 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 [G] Effects In the production of image receiving paper for thermal transfer as in the present invention, an intermediate layer and a thermoplastic resin layer mainly composed of a hardened addition polymerizable composition and a polyolefin resin are provided on a highly smooth support. As a result, it was possible to obtain an image-receiving paper for thermal transfer that prevented thermal shrinkage and blocking of the support and had a high image transfer density.

Claims (4)

[Claims] (1) Addition polymerizable composition 55 to 95 on a highly smooth support
1. An image-receiving paper for thermal transfer, comprising an intermediate layer and a thermoplastic resin layer, the main components of which are 45 to 5 parts by weight of a polyolefin resin. (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.