JPS61137791A - Thermal transfer recording medium - Google Patents

Abstract

PURPOSE:To obtain transferred coloring matter images with high density to be obtained over a wide range of paper quality and perform favorable printing free of blurring or trailing, by incorporating a specified compound in a heat-fusible color material layer, in a thermal transfer recording medium comprising a heat-fusible color material layer on a base. CONSTITUTION:A compound of general formula (1), wherein each of R1, R2, R3, R4 and R5, which may be the same or different, is hydrogen or 6-30C acyl, and n is an integer of 1-20, is incorporated in a heat-fusible color material layer, in a thermal transfer recording medium comprising a heat-fusible color material layer on a base. The color material layer comprises the compound of general formula (1), a heat-fusible substance (a low melting point substance or allow softening point substance)l, a coloring agent, a softener or the like. The heat-fusible substance may be a substance being solid at normal temperature and capable of dissolving the coloring agent at the time of thermal transfer, and one having a melting or softening point of 40-120 deg.C is preferable. The composition of the color material layer is not limited, but is preferable that the layer comprises 10-80wt% of the heat-fusible substance, 5-20wt% of the coloring agent, 1-20wt% of the softener, 0.5-60wt% of the compound of general formula (1) and 0-10wt% of other components, based on the total amount of solid components of the layer.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a thermal transfer recording medium. More specifically, the present invention relates to a thermal transfer recording medium that provides a good dye transfer image even on plain paper with low surface smoothness.

[Prior Art] Thermal transfer recording media have traditionally been used as recording media for transferring and forming images onto transfer sheets such as plain paper using thermal printers, thermal facsimiles, and the like. This heat-sensitive transfer recording medium has at least one heat-melting coloring material layer on a support, and the coloring material layer contains, for example, a coloring agent made of a pigment and a heat-melting substance. There are known calendars that do this.

[Problems to be Solved by the Invention] These conventional thermal transfer recording media print on various types of paper ranging from paper with low surface smoothness to paper with high surface smoothness.

Paper with a high surface smoothness allows for good L-letter printing, but when printing on paper with a low surface smoothness, the line drawings become blurred and r-tailed, making them very difficult to read. This is a major obstacle to the widespread use of thermal printers, and a solution is urgently needed.

The present invention was developed in view of the above-mentioned circumstances, and it is possible to obtain a high-density dye transfer image on a wide range of paper quality ranging from paper with high surface smoothness to paper with low surface smoothness, and to avoid "fading".
Moreover, it is a technical problem to perform good printing without the "rlt pull" phenomenon.

Means for Solving Problem E] Thermal transfer product 1 of the present invention for solving the above technical problem
1 medium is J! having a heat-melting coloring material layer on the support 1. ! −
The thermal transfer recording medium is characterized in that the TjI heat-melting coloring material layer contains a compound represented by the following general formula (1) (hereinafter referred to as the compound of the present invention).

# Soda General Formula (1) In the formula, R1, R2, R3R4, and R5 are each the same or different (and often represent hydrogen 1fKf- or an acyl group having 6 to 30 carbon atoms, and n is an integer of 1 to 20.

The present invention will be explained in more detail below.

The heat-sensitive transfer recording medium of the present invention has at least a heat-melting coloring material layer on a support, and the heat-melting coloring material layer contains a compound of the present invention, a heat-melting substance Vt<low melting point substance or low softening material. (spot substances), colorants, softeners, etc.

The compound of the present invention is a compound represented by the above general formula (1), in which R1, R2, R3Ra, Rs
represents a hydrogen atom or an acyl group having 6 to 30 carbon atoms,
Preferably represents 8 to 25 acyl groups, while n is 1
It represents an integer of 20 to 20, preferably an integer of 5 to 58.

Particularly preferable examples of the acyl group include those having a long-chain hydrocarbon, such as caproyl group, lauroyl group, myristoyl group, balmitoyl group, stearoyl group, behenoyl group, serotoyl group, montanoyl group, oleoyl group, and lyloyl group. Examples include groups.

The compound of the present invention can also be obtained as a commercial product. For example, "Hexagrin 3SJ, [Hexag I
J 75SJ, r Dekagu U 73SJ.

rDekaglyph 5SJ, rDekaglyph 7SJ, etc. are preferably used.

The compounds of the present invention are not limited to those listed above, but one or more of them can be selectively used, including the commercially available compounds mentioned above.

The method of incorporating the compound of the present invention into the heat-melting coloring material layer is arbitrary.For example, heat-melting coloring material N! ! It may be dispersed as it is in the coating solution, or dissolved in an appropriate solvent and added to the coating solution for the heat-melting coloring material layer, and the coating solution may be applied.

By adding the compound of the present invention to the heat-melting coloring material layer,
It is possible to improve the dispersibility of the R coloring agent, such as carbon black, and at the same time increase the mR force between the transfer paper and the ink, thereby increasing the releasability from the support. This means that in a wide paper quality range from high smoothness paper to low smoothness paper,
It is believed that it is possible to obtain a dye transfer image of high density and to perform good printing without "fading" or "tailing" phenomenon.

The heat-melting substance used in the present invention includes a substance that has the ability to dissolve the colorant during thermal transfer and is solid at room temperature, and has a melting point (measured by Yanagimoto MPJ-2 model) or a softening point. 40 to 120 points (measured by ring sparse method)
℃ is preferred, more preferably a solid material with a temperature of 80-120℃. Specific examples include carnauba wax, wood wax, auriculie wax, plant wax exclusively for Esparturo, beeswax, insect wax, animal waxes such as Sera owl and spermaceti wax, paraffin wax, microcrystalline wax, ester wax, and oxidized wax. In addition to waxes such as petroleum waxes such as wax, mineral waxes such as montan wax, osikerite, and ceresin; higher fatty acids such as palmitic acid, stearic acid, margaric acid, and behenic acid; palmityl alcohol, stearyl alcohol, behenyl alcohol, Higher alcohols such as marganyl alcohol, myricyl alcohol, eicosanol; higher fatty acid esters such as cetyl palmitate, myricyl palmitate, cetyl stearate, myricyl stearate; acetamide, propionic acid amide, palmitic acid amide, stearic acid amide, amide Amides such as wax; ester gum, rosin maleic resin, rosin phenol resin, rosin derivatives such as hydrogenated rosin, phenol resin, terpene tree 1M, cyclopentadiene resin, aromatic resin, etc. polymer compounds; stearylamine, hehenyl 7min,
Higher amines such as palmitinamine; polyethylene glycol 4000. Examples include polyethylene oxides such as polyethylene glycol 6000, which may be used in bran or in combination of two or more. Among these, palmitic acid amide, stearic acid amide, oleic acid amide , higher amides such as amide waxes are particularly preferred. Any "vehicle" described may also be used.

It is preferable to use a low-melting point substance as the heat-melting substance in the heat-melting coloring material layer of the present invention, and in this case, a hard wax and a soft wax are used in combination (one type or two or more of each type). Examples of hard waxes (waxes with a penetration rate (according to JIS K 253G) of less than 8 at 25° C. (100 g)) include:

■Ester wax (natural ester wax such as carnauba wax, monothane wax, Hoechst Hoechst wax, etc.)
ahgL flax E, F, KP, KPS, BJ
, OP, ON,
, NFS-11115 PETR0 manufactured by Toyo Petrolite Co., Ltd.
NABA@G, CARDIS 314, etc.), ■Low molecular weight polyethylene wax (especially molecular weight 300-1000)
POLYwAX 50 manufactured by Toyo Petrolite Co., Ltd.
0 Oyobi 855, etc.), Q acid wax (Hoechst Ho
echst Wax S and LP, etc.), and Diakaruna 30 and Diakaruna 30L (Mitsubishi Kasei NI). In addition, soft wax [25℃ (10℃)
Penetration (according to JIS K 2530) at 0 g).

) is 8 or more] Examples of microcrystalline wax (1 stone micro wax 155.18
0 (manufactured by Nippon Oil Co., Ltd.), old-NIC-1080, HI-W
IG-2085, II-AIC-2095, old-WIG
-1070, old-) II (i-1045, Hl-MIG
-2045 (manufactured by E1 Honseirosha), 5YAR11^X
10G, BE 5QIIARE 175,185. V
IC-ORY, υLTRAFLEX (manufactured by Higashi #1000 Petrolite Co., Ltd.), stearic acid, behenic acid, stearyl alcohol, white acetate, 'M wax, dodecyl stearate,
Examples include stearone, sorbitan monostearate, polyoxyethylene monostearate, and the like. Note that when such hard wax and soft wax are used in combination, the lt ratio used is 1:9 to 3:1.
(More preferably 2:8 to B=2).

The coloring agent to be contained in the color material layer of the present invention may be appropriately selected from various dyes and pigments. Examples of the dye include direct dyes, acid dyes, basic dyes, 1 disperse dye, and oil-soluble dyes (oil-soluble metal (including complex salt dyes), and these dyes may also be ballasting dyes.
On the other hand, as the pigment, in addition to organic pigments such as phthalocyanine pigments, inorganic pigments such as carbon black can be used.

The coloring agent to be contained in the coloring material layer of the present invention is preferably a pigment, and carbon black is particularly preferable.On the other hand, when a dye is used, it is preferably a non-sublimable dye. In this case, any non-sublimable dye that can be transferred to a recording sheet such as plain paper together with a heat-fusible material and has one color is sufficient. Non-sublimable dyes preferably used in the present invention include mordant dyes, etc. These are pigments that exclude sublimable dyes (including those that vaporize with melting or dissolution) used in

Basic dyes preferably used as the colorant in the present invention include, for example, crystal violet (C).

1,42555), malachite green (C,1,4
2000), methyl violet (C, 1,42535
), Victoria Blue (G,!, 44045)
, triphenylmethane dyes such as Mazienta (C, 1, 42510), auramine (c, i.

Diphenylmethane dyes such as 655), Astrafuroxin FF (C, 1, 48070), Eisenkathylon Yellow 3GL) (product of Hodogaya Chemical Co., Ltd., C,
1,48055).

Cramps head a7L/? Doro BH (C, 1, 48020
) Astrathon Golden Yellow GL (Bayer product.

Methine and azamethine dyes such as C, 1, 48054), Rhodaminoro (0, 1, 45170), Roguemi 7
Xanthine dyes such as 8G (G:, 1.45180), ? Strazon Blue GL (C, [, 1I052)
, Astrazonle, ,)”F3BL(fl:,r,
+1055), thi7zole azo dyes and triazole azo dyes, Eisenryoku Chiron Blue-50H (C,1,1
1085), Methylene Blue CC, 1,52015
) and other +/imine dyes, Eisenriki Chiron Red G
TLH (C,l 11085), Cevron Yellow 3R
L (manufactured by Teyupon, G, [, 11087), Astrazone Blue FGL edge-type 7zo dye, and anthraquinone dye.

Oil-soluble metal S11 salt dyes include 5 examples: symmetric l:2 type azo metal complex dyes, asymmetric l:2 type azo metal complex dyes, 1:1 type aso metal complex dyes, asomethine metal complex dyes, formazan. Examples include metal complex dyes, metal phthalocyanine dyes, and organic base salts of these dyes. Specifically, Eisens Viron Yellow 3RH
(Product from Hodogaya Chemical Co., Ltd.)

C, 1, Solvent Yellow 25), Dipon Fast Izo-R (BASF product, C, f, 188 fl
O), Huizensviron Orange 2RH (C, 1, Solvent Orange 40), Zapon Fast Blue Lett B (G, 1.12783), Huisenspiron Red GEM (C, 1, Solvent 1-7 de 84), Zapon Fast Red BE (C, r, 12715), Zapon Fast Violet 5E (G, 1I21116),
Cyaninbu/l/-88 (Sumitomo Chemical product, C, 1,
74180), Varifast Black Minato 3804 (manufactured by Orient Chemical Co., Ltd., C, 1, 121115), Eisen Spiroso Yellow 3RH Special (C, I, Zurghent Yellow 25:1), Eisen Spiroso Orange 21H Special cc, r , Solvent Orange 40:
l), Eisenspiron Blue-28Nll (C, I
, Solvent Blue 117), Zapon Fast Blue 1
(FL (C, 1, 74350), Eisens Viron Black BH Special (C:, I, Tsurubento Black 22:1), etc.

Examples of acidic dyes are G, 1. acid yellow 13
, C, t, Acid Red 37, C0! , Ash 1 Do Blue 62, G, [, 7 C/F O L/ 7 Di 10.
G, 1.7 Sea/Do Blue 83. G.1. Direct dyes such as Ashi and Doblack 01 are C,1, Direct Yellow 44. C.I.

Direct Yellow 142.0.1. Direct Yellow 12. G.1. Direct Blue 15, C, 1,
Direct Blue 25. (:, 1. Direct Blue 249, G, 1. Direct Red 81, C, 1, Direct Red 8, G, 1. Direct Red 31. G
, 1. Direct black +54. (:,!, Direct Black 177 is an example.

Disperse dyes are C, 1, Disboose Yellow 5, C,
l, Disbo's Yellow 51.0.1. Disbors Yellow f14.0.1. Disbors Left 43, C
, +, Disbo's Red 54. C, 1, De(Spose Red 135, C, [, Dispose Blue 517.
Examples include C,1, Disbo's Bluff 3, C,1, Disbo's 91, and the like. .

The palasted dyes used in the present invention are colors such as azo dyes, azomethine dyes, anthraquinone dyes, naphthoquinone dyes, sterine dyes, quinophthalo dyes, and phthalocyanine dyes; dyes having at least one pallast group in the g at nucleus. . Palast group is a group that is highly soluble in heat-fusible substances, such as an alkyl group, a cycloalkyl group, an aralkyl group, an alkoxy group, an alkylsulfonylamine 7 group, an alkylsulfonyl group, a hydroxylalkyl group, a cyanoalkyl group, and an alkoxycarbonylalkyl group. .

It is a group having an alkyl group having 6 or more carbon atoms, such as an alkoxyalkyl group or a furkylthio group, or an alkyref group. Particularly preferred is a palaste group having at least one alkyl group having carbon a6 or more in the molecule. Examples of the structure of the ballasted dye preferably used in the present invention include Japanese Patent Application No. 59-8
Examples include those described in No. 1688, but the present invention is not limited thereto.

It is preferable that the heat-melting color material layer of the present invention contains a softener. The softener used in the present invention preferably has a softening point (measured by the ring and ball method) of 40 to 200°C, and is natural or synthetic. Both wood-loving polymers and hydrophobic polymers can be used.

Examples of wood-philic polymers include gelatin, gelatin/derivatives, cellulose derivatives, proteins such as casein, natural products and natural product derivatives of polysaccharides such as starch, water-soluble nylon, polyvinyl alcohol, polyvinylpyrrolidone, and acrylamide polymers. Synthetic water-soluble polymers such as water-soluble polyvinyl compounds such as synthetic polymers, and polyurethane-based and polyurethane-based polymer latexes can be mentioned. Examples of the aqueous polymer include synthetic polymers described in U.S. Pat. No. 3,142,586, U.S. Pat.

Preferred polymers include polyvinyl butytail, polyvinyl formal, polyethylene, polypropylene, polyamide, ethyl cellulose, cellulose derivatives such as cellulose acetate, polystyrene, polyvinyl acetate, polyvinyl chloride, polyvinylidene chloride, ethylene-ethyl acrylate, ethylene-acetic acid. Vinyl, vinyl chloride-vinyl acetate copolymer, vinyl chloride-vinyl acetate-maleic acid-terpolybutyl, acrylic resins such as polymethyl methacrylate, polyisobutylene, rosin derivatives such as ester gum 1 petroleum resin, coumaron indene resin, cyclic rubber , chlorinated rubber, etc. The present invention is not limited to the above-mentioned softeners, but from among these, 1
It can be used in one species or in combination of two or more.

It is preferable to add various types of dispersion aids to the heat-melting coloring material layer of wood powder 1.As the dispersion aids, one or more kinds may be selected and used from commercially available ones. Examples of the products include Tsuru Sparse 17000, Tsuru Sparse 22000 (101 companies 9!11), Nirasan Polyster, Nissan Phyllanol, Nissan Bremmer (manufactured by NOF Corporation), and the like.

Although the composition ratio of the heat-melting coloring material layer of the present invention is not limited,
The solid content weight of the coloring material layer is 100% and 41%.

(the same applies hereinafter), the heat-melting substance is 10-80% (more preferably 20-70%), the colorant is 5-20%, and the softener is 1-20% (more preferably 2-15%). The compound of the present invention is 0.5 to 60% (more preferably 1 to 40%)
, and other additives are preferably 0 to 10%.

The effect of the compound of the present invention is that it can improve the dispersibility of the colorant, increase the adhesive force between the transfer paper or sheet and the colorant, and increase the releasability from the support. This is clearly different from the technology of simply using it as a dispersant.

In addition to the above-mentioned components, the coloring material layer of the present invention may contain various additives. For example, vegetable oils such as castor oil, linseed oil, and olive oil, animal oils such as whale oil, and mineral oils may be suitably used.

The support used in the thermal transfer recording medium of the present invention preferably has heat-resistant strength, dimensional stability, and surface smoothness. Examples of materials include 1, for example, plain paper, condenser paper, and laminated paper. Papers such as coated paper, resin films such as polyethylene, polyethylene terephthalate, polystyrene, polypropylene, polyimide, and resin film composites, metal sheets such as aluminum foil, etc. are all suitably used. The thickness of the support is preferably about 80 mm or less in order to obtain good thermal conductivity.
More preferably 2 to 20 spiders.

The thermal transfer recording medium of the present invention is the above! ! It may also have other constituent layers such as a protective coating layer or an undercoat layer (for example, a peeling layer to help peel off the heat-melting coloring material layer), especially for rough surfaces with lower surface smoothness. When printing on paper etc.
It is preferable to provide a release layer. Furthermore, in the thermal transfer recording medium of the present invention, the structure on the back side of the support may be arbitrary, and a puffing layer such as a sticking prevention layer may be provided.

In the thermal transfer recording medium of the present invention, techniques suitable for applying the fast-melting colorant layer to the thick support are known in the art, and these known techniques can also be applied to the present invention. 8. The meltable coloring material layer is hot-melt coated on the @* object or the! (ii) It can be formed by coating with a coating solution prepared by dissolving or dispersing the substance in an appropriate solvent. As a method for applying the heat-fusible coloring material layer, any technique such as a roller coater method, an extrusion coater method, a gravure coater method, a wire bar coating method, etc. can be adopted. As long as the thickness of the heat-melting coloring material layer is necessary to obtain a dye transfer image just once, the thinner the better. It is to be done.

The thermal transfer recording medium of the present invention has higher thermal conductivity than the softener in its constituent layers (for example, thermal conductivity 1i, OX 1
0-' ~25. OX 1G-'cal/sec a
ass "0) and a high melting point, many metals such as aluminum and copper can be used, and oxides such as tin oxide, aluminum oxide, and magnesium oxide, and nitrides such as titanium nitride can also be used. LIr ability.

The fine powder having such an Igi thermal conductivity preferably has a particle size of 3 or less, more preferably 14 or less.

[Operations and Effects of the Invention] According to the present invention, as is clear from the examples described below, it is possible to record (print) on transfer paper or sheets such as plain paper by the same method as known thermal transfer recording media, and Good printing can be performed even on paper with low surface smoothness.

[Example] Examples will be given below, but the embodiments of the present invention are not limited thereto. Note that "parts" used below indicate "parts by fL amount".

Example 1 A heat-melting coloring material layer coating solution having the following composition was applied onto a polyethylene terephthalate film having a final thickness of 5.3 using a wire eight.

Coloring material layer coating liquid Carbon Brass 12 parts Carnauba wax 30 parts Paraffin wax 35 parts Ethylene-vinyl acetate copolymer 8 parts Polyester resin (Truspers 17000 manufactured by rcI) 5
After coating 10 parts of Hexagrin 5S (manufactured by Nikko Chemical Co., Ltd.), it was dried at 40°C to obtain a thermal transfer recording medium sample (2) of the present invention. The dry film thickness was approximately 4 lu.Using this thermal transfer recording medium sample (■), a thermal printer (9, a prototype machine using a thin-film line thermal head with a thermal element density of 8 dots/m* and N5) was constructed. using 0.4
Recording was performed with applied energy of mj/dat.

Copy paper with a Beck smoothness of 30 seconds was used as the transfer paper. As a result, clear, high-density printing with no "fading" or "tailing" in the line drawings was obtained. Even when high-speed printing was performed, good printing was obtained.

Comparative Example 1 In Example 1, a heat-melting coloring material layer coating solution having the same composition as the sample was used except that Hexagrin 5S was not added.

The film thickness after drying at 40°C was about 4 layers. Printing was carried out in the same manner as in Example 1 using this comparative thermal transfer recording medium sample (■), but "fading" and "tailing" occurred in the line drawing area.
Only very hard to read prints were obtained.

Comparative Example 2 In Example 1, a heat-melting coloring material layer coating liquid having the same composition as Sample 1 was used except that sodium dodecylbenzenesulfonate was added in place of Hequinagrin 5S. The film thickness after drying at 40° C. was about 4 cm. When printing was carried out in the same manner as in Example 1 using this comparison thermal transfer recording medium sample (■), the printing was of high density with no "fading" in the line drawing area, but when high-speed printing was performed, one trail appeared. ” phenomenon occurred.

Claims (1)

[Scope of Claims] A heat-sensitive transfer recording medium having a heat-melting coloring material layer on a support, characterized in that the heat-melting coloring material layer contains a compound represented by the following general formula (1). Thermal transfer recording medium, general formula (1) ▲Mathematical formulas, chemical formulas, tables, etc.
represents an acyl group, and n is an integer of 1 to 20. ]