JPS62191191A - Cyanic-pigment dative element used for heat-sensitive type die transfer - 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 The present invention relates to a cyan dye donor for thermal dye transfer with good hue and dye stability.

In recent years, thermal transfer systems have been developed for obtaining prints from images produced electronically by color video cameras. According to one method of obtaining this type of print, an electrophotograph is first subjected to color separation using color filters.

Each color-separated image is then converted into an electrical signal. These signals are then manipulated to obtain cyan, magenta and yellow electrical signals. These signals are then transmitted to a thermal printer. To get the print,
A cyan, magenta, or yellow dye-donor element is placed opposite the dye-receiver element.

Both are then inserted between the thermal printhead and the platen roller. Heat is applied from the back side of the dye-donor sheet using a line-type thermal printhead.

Thermal printheads include a number of heating elements that are heated in response to sequential cyan, magenta and yellow signals. This process is then repeated for the other two colors. A color hard copy is thus obtained which corresponds to the current image seen on the screen.

European Patent Application No. 147,747 relates to a dye-receiving element for thermal die transfer printing. The dyes for the dye-donor elements used therewith are also generally indicated. This general description includes a description of iodoaniline dyes prepared by the oxidative coupling reaction of p-phenylenediamine derivatives with phenols or naphthols. Individual naphthol compounds are not shown.

Many of these dyes proposed for thermal dye transfer printing are problematic in that they do not have adequate photostability. Others do not have good hue.

The aim of the present invention is to provide dyes with good photostability and improved hue.

For these and other purposes, the cyan dye is 2-carbamoyl-4-[N-(p-substituted aminoaryl)imino]-
Achieved by the present invention, which comprises a cyan dye-donor element for thermal dye transfer applied from a support carrying a dye layer consisting of a cyan dye dispersed in a high molecular weight binder, characterized in that it consists of 1,4-naphthoquinone. be done.

In a preferred form of the invention, the cyan dye has the following structure.

In this formula, B 1 , B R and R″ are substituted or unsubstituted alkyl groups having 1 to 6 carbon atoms, such as methyl, ethyl, propyl, isopropyl, methyl, pentyl, hexyl, methoxyethyl, benzyl, 2-methanesulfone. Amidoethyl, 2-hydroxyethyl, 2-cyanoethyl, methoxycarbonylmethyl, etc.: substituted or unsubstituted cycloalkyl group with 5 to 7 carbon atoms, cyclohexyl, cyclopentyl, etc.; substituted or unsubstituted with 5 to 10 carbon atoms Aryl groups such as phenyl, pyridyl, naphthyl, p-tolyl, p-chlorophenyl,
a-(N-methylsulfamoyl)phenyl; and Bm and R4 are hydrogen atoms; substituted or unsubstituted alkyl groups of 1 to 6 carbon atoms, such as methyl, ethyl, furoyl, isopropyl, methyl, pentyl, hexyl,
-NHCOR'' or -NH8O,R' Compounds included in include the following:

Compound 10　　　　C, H, C, Hs l　1　　　　C, Hs, H.

12　　　　C, H, C, H.

13 C, Hs Ctf
fs14 C, H, C, Hs l5 C, HsC, H.

16　　　　C, H40HC, Hs l　7　　　　C, H, OHC, H.

18 CH, CM, NIPjO, CH, C, l
l519 C,H, to H8 RI R4R"h-HCHs HHt -C4H.

HH-CH,C,H.

HH-C6H13(ring) 2-CM, 5-Nm0. CH, CH
.

2 CHm HC6Hm2-CH8
H.C.H.

2 CH@HCH2CHtO[N
H2-CM, HCH.

2-CH, CH, NH30, CH, HCH.

A dye barrier layer can be used in the dye-donor elements of the invention to improve the density of the transferred dye.

The dye of the dye-donor element of the present invention may be a polymeric binder, such as a cellulose interferon, such as cellulose acetate phthalate, cellulose acetate, cellulose acetate propionate,
Cellulose acetate butyrate, cellulose triacetate; polycarbonate; poly(styrene-co-acrylonitrile),
HoIJ (sulfone) or poly(phenylene oxide)
dispersed inside. The binder can be used at a coverage of 0.1 to 59/ln''.

The dye layer of the dye-donor element can be coated onto the support or printed onto the support by any printing method such as gravure printing.

Any carrier can be used as the support for the dye-donor element of this invention, provided it is dimensionally stable and can withstand the heat of the thermal print head.

Materials of this type include polyesters, such as poly(ethylene terephthalate); polyamides; polycarbonates;
Includes glassine paper; condenser paper; cellulose ester; fluorine-based polymer; polyether; polyacetal; polyolefin and polyimide. The support generally has a thickness of 2 to 30 microns. This may be coated with an undercoat layer if desired.

A slipping layer may be applied to the backside of the dye-donor element to prevent the printhead from sticking to the dye-donor element. Slipping layers of this type consist of lubricants, such as surfactants, liquid lubricants, solid lubricants or mixtures thereof, with or without eddy molecular weight binders.

The dye-receiving element used with the dye-donor element of the present invention usually consists of a support carrying a dye image-receiving layer. The support can be, for example, a transparent film, such as poly(ethylene terephthalate) or a reflective material, such as baryta-coated paper or white polyester (
It may also be a polyester containing a white pigment.

The dye image-receiving layer may be comprised of, for example, polycarbonate, polyurethane, polyester, polyvinyl chloride, poly(styrene-eo-acrylonitrile), poly(carbrolactone), or mixtures thereof.

As mentioned above, the dye-donor element of the present invention is used to form a dye transfer image. The method consists of imagewise heating the dye-donor element described above and transferring the dye image to the dye-receiving element to form a dye transfer image.

The dye-donor elements of this invention can be used in sheet form or in continuous roll or ribbon form. If a continuous roll or ribbon is used, this may carry only cyan dyes, as described above, or may carry alternating areas of different dyes, such as sublimable magenta and/or yellow and/or black. You may.

In a preferred form of the invention, the dye-donor element comprises a poly(ethylene terephthalate) support coated with alternating regions of magenta, yellow and cyan dyes, each of the processing steps described above being carried out sequentially for each color; A three-color die transfer image is obtained. Of course, if this process is performed only for a single color, a monochrome dye transfer image will be obtained.

Thermal printheads that can be used to transfer dye from the dye-donor elements of this invention are commercially available.

For example, Fujitsu thermal head (FTP-040MC
8001), TDK Thermal Hat F415ffff
7-1089, t or Rohm Thermal Head KE2
00B-1311: Can be used.

A thermal die transfer assembly using the present invention comprises a) a dye-donor element as described above, and b) a dye-receiver element as described above, the dye-receiving element having a dye layer of the donor element in contact with a dye image-receiving layer of the receiver element. In this state, it is in a superimposed relationship with the dye-donor element.

The above assemblage consisting of these two elements can be pre-assembled as an integral unit when obtaining a monochrome image. This is done by temporarily attaching the dyads to each other at their peripheries.

After transfer, the dye-receiving element is stripped away to reveal the dye-transfer image.

For three-color tfJCvw, the assemble page described above is assembled three times during the period in which heat is applied by the thermal print head. After the first dye has been transferred, the element is stripped off. A second dye-donor element (or other area of the donor element containing a different dye area) is then aligned with the dye-receiver element and the process repeated. A third color is obtained in the same manner.

The following examples are presented to illustrate the invention.

Example 1 A) A cyan dye-donor element was prepared by coating the following layers in the following order onto a 6 micron poly(ethylene terephthalate) support.

1) A dye barrier layer of gelatin nitrate (gelatin, cellulose nitrate and salicylic acid, weight ratio of approximately 20:5:2;
Solvents acetone, methanol and water') (0,33
f/n") 2) Cyan color change described later, (0,27ri/-)
Cellulose acetate phthalate hydrate (0,4117m”)
The dye layer contained in the cloth from acetone/2-butanone/cyclohexanone solvent.

Cellulose acetate butyrate (0,33ri/-
) in poly(vinyl stearate) (0,76f/m
”) was applied from a tetrahydro solvent.

B) A second cyan dye-donor element was prepared by coating the layers listed below in the order listed on a 6μ poly(ethylene terephthalate) support.

1) one layer of dye barrier of gelatin nitrate (gelatin and cellulose nitrate, weight ratio of approximately 2:1, in solvents mainly acetone and methanol) (0,20 t/m"),
Applied from acetone and water solvents.

2) Cyan dye (0.37 to 0.38f'/Ying 2) described below
) to cellulose acetate (0.41-0.43 r/m”)
The dye layer contained therein is coated from an acetone/2-butanone/cyclohexanone solvent.

Cellulose acetate butyrate (0.46f/
w”) in poly(vinyl stearate) (0,31f
/m”) was applied from a tetrahydrofuran solvent.

The following cyan dyes were evaluated.

- to non-coco 1 nor r -, - anal dye-receiving element Makrolof 5705CMakrolof in methylene chloride and trichlorethylene solvent mixture
L5705, registered surface) (Bayer) Polycarbonate resin (2,9F/1 solution with ICI Melinex 99
0 (Marinez 990®) on a white polyester support or for density evaluation on a transparent polyester support.
(ethylene terephthalate) film support for spectral absorption evaluation.

The dye side of a 0.75 inch wide dye-donor strip was placed in contact with the dye image-receiving layer of a dye-receiving element of the same width. This assembly plage was secured to the jaws of a stepper motor-driven take-off device. This assembly was carried out using a 0.55 inch (14stm) diameter Co9m roller and a Fujitsu thermal head (FTP-040).
Place it on top of MC8OO1) and attach 3.5 bond (1,6#).
) The dye-donating confectionery side of the Asemplage was pressed against a rubber roller with a spring force of .

With the imaging electronics fully activated, the take-off device pulls the assemblage between the print head and the rollers.
．． It was pulled at 123 inches/second (3.1 dragons/second). At the same time, the resistor of the thermal print head is 0.5 mm! 7
Heating was performed from 0 to 4.5 milliseconds in seconds (ssga) increments to obtain a graded concentration test pattern. The voltage applied to the print head was about 19V, which is about 1.75W7
Represents a dot. Estimated head temperature was 250-400°C.

The dye-donor element was separated from the dye-receiver element and the status thread reflection density of the step image was read. The images were then "HID-regressed": 4 days, 50 kLsz, 5
At 400°, 32°C, indoor temperature about 25%. Astringency loss at concentrations around 1.0 was calculated.

The following dye stability data was obtained.

Table 1 Compound I B-0,07 Compound 2
B-0,07 control IA
-0,27 control 2 A -0,46 control 3 A -0,62 control 4
A-0,22 The use of compounds according to the invention showed superior photostability compared to various reference dyes.

The absorption spectrum from 400 to 7005 m was also determined after the dye areas were transferred to a receiver on a transparent support in the manner described above. Jwtcz and HBW (half-bandwidth=width of the dye absorption envelope in % of maximum dye concentration) i1' were calculated from the computer-normalized 1,0 density curve. The following results were obtained.

Table 2 Dye λ-ag HEW Compound 1 669 137 Compound 2
686 107 control 1 622 12
1 Control 2 641 121 Control 3 653 107 Control 4 597 132 The dyes of the present invention have a good cyan hue and all have a λ 8π in the region exceeding the desired 66 (1% duck). They either have λfiat at a shorter wavelength, or have a clear shoulder on the short wavelength side of the spectral curvature, and therefore tend to be too bluish.

Example 2 A) A cyan dye-donor element was prepared by coating the following layers in the following order onto a 6μ poly(ethylene terephthalate) support.

1) Poly(acrylic acid) applied from water (0,16f
2) a layer of cyan dye (0.77 mmol/m”) shown in Table 3 below and a cellulose acetate (acetyl 40%) binder (1
, 2f/l/dye), coated from a 2-butanone solvent.

A conventional slipping layer was applied to the back side of this device.

A dye-receiving element was manufactured in the same manner as the platform of Example 1.

The dye side of a 1 inch (25 mm) wide dye-donor strip was placed in contact with the dye image-receiving layer of a dye-receiving element of the same width. Stepper-1 with this Assemble Raj!
The motive was fixed to the jaws of the privately operated retrieval device. This assembly plage is attached to a rubber roller with a diameter of 0.55 inches (14I!I) and a TDK thermal head L-133 (4C6
-0242) and was pressed with a spring of 8 pounds 1.6) with the dye-donor surface of the Assemble Plage pressed against the rubber roller.

The imaging electronics are activated and the take-off device pulls the assemblage between the printhead and the rollers.
．． It was pulled at 123 inches/second (3.1 fins/second). Simultaneously, the resistor of the thermal print head was heated in fixed increments from 0 to 8.3 milJ seconds to obtain a graded density test pattern. The voltage applied to the print head was approximately 21
V, which generates about 1.7 W/dot (12 millijoules/dot).

Separate the dye receiving element from the dye donating element and step.

The status thread reflection density of the whelk image was read. The images were then @HID-regressed. 50 k for 7 days.
Lsz, 54000, indoor temperature about 25%.

The % concentration loss at the highest concentration was calculated.

The following dye stability was obtained.

Table 3 Compound 10 8 Compound 11 9 Compound 12
10 Compound 13 B Compound 14
6 Compound 15 5 Compound 16
8 Compound 17 9 Compound 18 8 Compound 19 25 Control 4 14 With the exception of Compound 19, the cyan dyes in the present invention exhibit superior photostability compared to the control compounds.

The absorption spectrum was determined, and λsang and HBWl were determined in the same manner as in Example 1, and the following results were obtained.

Table 3 λ-mat HBW Compound 10 669 137 Compound 11
654 127 compound 12
662 12g Compound 13 655
12g Compound 14 697 13g
Compound Is 705 142 Compound 1
6 687 134 compound P+IIJ17
684 129 compound 18
659 139 Compound 19 680
128 Control 4 597 132 The cyan dyes of the present invention have a good cyan hue, and each
It has a λ≧α2 of more than 50 am. Control dye is 600
It has a λmat of less than %, and therefore tends to have too strong a bluish tinge.

Preparation of compound 1 N-(p-diethylamino)phenyl-2-(N-methyl)carbamoyl-1,4-naphthoquinone ethyl acetate 1
A solution of 2-(N-methylcarbamoyl)-1-naphthol (20,11,0,1 mol) in 000-
N,N-diethyl-p-phinyl diamine hydrochloric acid in 0〇-! (2o, 1r, 0.1 mol).

The two-phase system was rapidly stirred while solid sodium carbonate (
106 t, 1.0 mol) was added little by little. Then 164.5f of potassium ferricyanide in 500ml of distilled water
(0.5 mol) was added dropwise over 30 minutes.

The reaction was stirred at room temperature for 16 hours and then filtered through a pad of diatom.

Part F was transferred to a separatory funnel, the layers were separated and the organic phase was washed three times with distilled water. The organic phase was dried over magnesium sulfate, passed through a short (3 inch diameter x 2 inch height) column of silica gel (Guelm TSC) and evaporated to dryness. The crude product was crystallized from methanol 250 to give a blue solid 28.5f (78.9% of theory). melting point 12
7-128℃.

The present invention provides a dye-donor element containing a cyan dye with good photostability and improved hue.

Claims (1)

[Scope of Claims] Cyan dispersed in a high molecular weight binder, characterized in that the cyan dye consists of 2-carbamoyl-4-[N-(p-substituted aminoaryl)imino]-1,4-naphthoquinone. A cyan dye donor element for thermal dye transfer consisting of a dye.