EP0482896A1 - Wärmeempfindliches Übertragungsaufzeichnungsverfahren - Google Patents

Wärmeempfindliches Übertragungsaufzeichnungsverfahren Download PDF

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Publication number
EP0482896A1
EP0482896A1 EP91309768A EP91309768A EP0482896A1 EP 0482896 A1 EP0482896 A1 EP 0482896A1 EP 91309768 A EP91309768 A EP 91309768A EP 91309768 A EP91309768 A EP 91309768A EP 0482896 A1 EP0482896 A1 EP 0482896A1
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EP
European Patent Office
Prior art keywords
group
formula
image
heat
transfer recording
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Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Application number
EP91309768A
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English (en)
French (fr)
Inventor
Tawara C/O Konica Corporation Komamura
Katsunori C/O Konica Corporation Katoh
Noritaka c/o Konica Corporation Nakayama
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Konica Minolta Inc
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Konica Minolta Inc
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Publication date
Application filed by Konica Minolta Inc filed Critical Konica Minolta Inc
Publication of EP0482896A1 publication Critical patent/EP0482896A1/de
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
    • B41M5/382—Contact thermal transfer or sublimation processes
    • B41M5/38235—Contact thermal transfer or sublimation processes characterised by transferable colour-forming materials

Definitions

  • This invention relates to a heat-sensitive transfer recording method by use of a heat-sensitive recording material, more particularly to a heat-sensitive transfer recording method which forms an image having sufficient image density and also excellent in color reproducibility.
  • the heat-sensitive transfer system has such advantages as easy operation and maintenance, smaller size of device, possible reduction of cost, and further inexpensive running cost, etc.
  • the heat-sensitive transfer system includes the two kinds, namely the system in which a transfer sheet having a meltable ink layer provided on a support (heat-sensitive transfer recording material) is heated with a heat-sensitive head to have the ink melt transferred onto a transferable sheet (image-receiving material), and the thermal diffusion transfer system (sublimation transfer system) in which a transfer sheet having an ink layer containing a thermally diffusible dye (sublimable dye) on a support is heated with a heat-sensitive head to have the above thermally diffusible dye transferred onto a transferable sheet, but the latter thermally diffusible transfer system is more advantageous for full color recording, because the tone of the image can be controlled by varying the amount of the dye transferred corresponding to the change in thermal energy of the heat-sensitive head.
  • the dye used for the heat-sensitive transfer recording material is important, and those of the prior art had the drawback that stability, namely light resistance and fixability of the image obtained is not good.
  • Japanese Unexamined Patent Publications Nos. 78893/1984, 109394/1984 and 2398/1985 disclose image forming methods which comprises using a chelatable thermally diffusible dye to form an image with a chelated dye on an image receiving material.
  • the cyan dye described in the above published specifications is low in transferability to give no image with sufficient density, or when as the compound to be added for chelation of the dye through the reaction of the dye (hereinafter called metal source), for example, a stearic acid salt, etc. of a transition metal (e.g. nickel, etc.) described in Japanese Unexamined Patent Publication No. 2398/1985 are employed, the reaction efficiency with the dye (hereinafter called chelate formation efficiency) is poor, whereby an image with a dye not chelated is formed on the image and therefore there has been involved such problem as undesirable color reproducibility, etc. Improvement of that point has been deired for a long time.
  • the present invention has been accomplished in order to solve the above problem, and an object of the present invention is to provide a heat-sensitive transfer recording method which can obtain a cyan image preferable in color reproduction having high density and excellent image stability (fixability, light resistance) by use of a dye having good diffusibility and a metal source having a high chelate formation efficiency.
  • a heat-sensitive transfer recording method which comprises superposing a heat-sensitive transfer recording material having on a support at least an ink layer containing a compound represented by the formula (1) on an image-receiving material, giving a heat corresponding to an image information to said heat-sensitive transfer recording material and forming an image with the chelate dye formed by the reaction between the compound represented by the formula (1) and a compound represented by the formula (2) on the image receiving material:
  • X1 represents a group of atoms necessary for formation of an aromatic ring
  • X2 represents a group of atoms necessary for formation of thizaole ring or benzothiazole ring
  • R1 represents an alkyl group
  • M represents a metal ion
  • Q1, Q2 and Q3 each represent a coordination compound coordination bonded with the metal ion represented by M
  • Y is an anion forming an anion pair with the complex
  • 1 represents an integer of 1,2 or 3
  • m represents an integer of 1, 2 or
  • n represents 1 or
  • p represents +, 2+ or 3+
  • q represents 1, 2 or 3].
  • Fig. 1 and Fig. 2 are illustrations showing the heat-sensitive transfer recording method of the present invention.
  • X1 in the above formula (1) represents a group of atoms necessary for formation of an aromatic ring, preferably a group of atoms necessary for formation of benzene ring or naphthalene ring.
  • the aromatic ring may also have a substituent.
  • X2 is a group of atoms necessary for formation of thiazole ring or benzothiazole ring, which may also have a substituent.
  • R1 represents an alkyl group, preferably a straight or branched alkyl group having 1 to 12 carbon atoms, as exemplified by methyl, ethyl, n-propyl, n-butyl, n-hexyl, n-decyl, i-propyl, 2-ethylhexyl groups and the like.
  • the alkyl group may also have a substituent such as alkoxy group (e.g. a methoxy group, an ethoxy group), halogen atoms (e.g. a fluorine atom, a chlorine atom), carboxyl group, aryl groups (e.g a phenyl group), etc.
  • R1 has the same meaning as defined in the formula (1)
  • R2 and R3 each represent a hydrogen atom, an alkyl group (e.g. a methyl group, an ethyl group) or a nitro group
  • R4 represents a hydrogen atom, an alkyl group (e.g. a methyl group, an ethyl group), a halogen atom (e.g. a chlorine atom), an alkoxy group (e.g. a methoxy group, an ethoxy group) or an alkoxycarbonyl group (e.g. an ethoxycarbonyl group)
  • R5 represents a hydrogen atom, a halogen atom (e.g.
  • R2, R3, R4 and R5 respectively represent alkyl groups, they may also have a substituent, and as the substituent, the same substituents as mentioned for R1 may be included.
  • M in the above formula (2) represents a metal ion, including preferably Al2+, Co2+, Cr2+, Cu2+, Fe2+, Mg2+, Mn2+, Mo2+, Ni2+, Sn2+, Ti2+, Zn2+, etc.
  • Q1, Q2 and Q3 each represent a coordination compound, including, for example, the coordination compounds described in Chelate Chemistry (5) (Nankodo), etc., but particularly preferable in the present invention are ethylenediamine and derivatives thereof, glycineamide and derivatives thereof, picolineamide and derivatives thereof, etc.
  • Y represents an anion, including inorganic compound anions such as Cl ⁇ , SO4 ⁇ ClO4 ⁇ , etc. organic compound anions of benzensulfonic acid derivatives, alkylsulfonic acid derivatives, etc., particularly preferably tetraphenylboron anion and its derivatives.
  • l represents an integer of 1, 2 or 3
  • m represents 1, 2 or 0,
  • n represents 1 or 0, and these are determined depending on whether the complex represented by the above formula is tetra-dentate coordination or hexa-dentate coordination or depending on the number of the ligands of Q1, Q2, Q3.
  • the heat-sensitive transfer recording material comprises an ink layer containing the dye represented by the formula (1) (hereinafter sometimes called heat-sensitive layer) provided on a support.
  • the content of the dye in the above heat-sensitive layer may be preferably 0.1 to 20 g per 1 m2 of the support.
  • the above heat-sensitive layer can be formed by preparing a paint for formation of heat-sensitive layer by dissolving one kind or two or more kinds of the above dyes together with a binder in a solvent or dispersing in fine particles into a solvent, and coating said paint on a support, followed by suitable drying.
  • the thickness of the heat-sensitive layer may be preferably 0.1 to 5 ⁇ m as dry film thickness.
  • the above binder may include water-soluble polymers such as cellulose type, polyacrylic acid type, polyvinyl alcohol type, polyvinyl pyrrolidone type, acrylic resin, methacrylic resin, polystyrene, polycarbonate, polysulfone, polyether sulfone, polyvinyl butyral, polyvinyl acetal, nitrocellulose, ethylcellulose, etc.
  • water-soluble polymers such as cellulose type, polyacrylic acid type, polyvinyl alcohol type, polyvinyl pyrrolidone type, acrylic resin, methacrylic resin, polystyrene, polycarbonate, polysulfone, polyether sulfone, polyvinyl butyral, polyvinyl acetal, nitrocellulose, ethylcellulose, etc.
  • binders either one kind or two or more kinds, may be used not only as a solution dissolved in an organic solvent, but also in the form of a latex dispersion.
  • the amount of the binder used may be preferably 0.1 to 50 g per 1 m2 of the support.
  • solvent there may be included water, alcohols (e.g. ethanol, propanol), cellosolves (e.g. methylcellosolve), esters (e.g. ethyl acetate), aromatics (e.g. toluene, xylene, chlorobenzene), ketones (e.g. acetone, methyl ethyl ketone), ethers (e.g. tetrahydrofuran, dioxane), chlorine type solvents (e.g chloroform, trichloroethylene), etc.
  • alcohols e.g. ethanol, propanol
  • cellosolves e.g. methylcellosolve
  • esters e.g. ethyl acetate
  • aromatics e.g. toluene, xylene, chlorobenzene
  • ketones e.g. acetone, methyl ethyl ketone
  • ethers e.g
  • the above support is not particularly limited, provided it has good dimensional stability and can stand the heat of the heat-sensitive head during recording, but may include thin papers such as condenser paper, grassine paper, etc., heat-resistant plastic films such as polyethylene terephthalate, polyamide, polycarbonate, etc.
  • the thickness of the support may be preferably 2 to 30 ⁇ m, and the support may be also provided with a subbing layer for the purpose of improving adhesivness with the binder or preventing transfer, dyeing of the dye onto the support side.
  • a slipping layer may be also provided for the purpose of preventing sticking of the heat-sensitive head to the support.
  • the heat-sensitive transfer recording material according to the present invention may also have a heat-meltable layer containing a heat-meltable compound disclosed in Japanese Unexamined Patent Publication No. 106997/1984 provided on the heat-sensitive layer.
  • colorless or white compounds having melting points of 65 to 130 °C may be preferably used, as exemplified by waxes such as carunauba wax, beeswax, canderilla wax, etc.; higher fatty acids such as stearic acid, behenic acid, etc.; alcohols such as xylitol, etc.; amides such as acetamide, benzamide, etc.; ureas such as phenylurea, diethylurea, etc.
  • waxes such as carunauba wax, beeswax, canderilla wax, etc.
  • higher fatty acids such as stearic acid, behenic acid, etc.
  • alcohols such as xylitol, etc.
  • amides such as acetamide, benzamide, etc.
  • ureas such as phenylurea, diethylurea, etc.
  • polymers such as polyvinyl pyrrolidone, polyvinyl butyral, saturated polyesters, etc may be also contained.
  • the heat-sensitive transfer recording material according to the present invention can obtain a cyan image from one kind of dye, but when applied to full color image recording, it should preferably have at least three layers of a cyan heat-sensitive layer containing a cyan dye, a magenta heat-sensitive layer containing a magenta dye and a yellow heat-sensitive layer containing a thermally diffusible yellow dye provided by coating successively repeatedly on the same surface of the support.
  • a heat-sensitive layer containing a black image forming substance may be provided by coating successively repeatedly on the same surface of the support.
  • the compound represented by the formula (2) is used as the metal source, and added into the image-receiving material (preferably the image-receiving layer of the image-receiving material) or the heat-meltable layer as described above.
  • the amount added may be preferably 0.2 to 20 g/m2, more preferably 1 to 10 g/m2, based on the image-receiving material or the heat-meltable layer.
  • the image-receiving material to be used in the present invention generally comprises one kind or two or more kinds of polymer layers such as polyester resin, polyvinyl chloride resin, copolymer resin of vinyl chloride with another monomer (e.g. vinyl acetate, etc.), polyvinyl butyral, polyvinyl pyrrolidone, polycarbonate, etc. formed as the image-receiving layer on a support comprising paper, plastic film or paper-plastic film composite.
  • polymer layers such as polyester resin, polyvinyl chloride resin, copolymer resin of vinyl chloride with another monomer (e.g. vinyl acetate, etc.), polyvinyl butyral, polyvinyl pyrrolidone, polycarbonate, etc.
  • the above support itself may also sometimes made the image-receiving material.
  • the heat-sensitive transfer recording method of the present invention after the heat-sensitive layer of the above heat-sensitive transfer recording material is superposed on the image-receiving material, the heat corresponding to the image information is given to the heat-sensitive transfer recording material, and the image is formed on the image-receiving material with the chelate dye formed through the reaction between the metal source and the dye.
  • the compound (1) is employed as the dye and the compound (2) is employed as the metal source, a cyan image preferable in color reproduction with high density and excellent image stability (fixability, light resistance) can be obtained.
  • Fig. 1 when a metal source is permitted to exist in the image-receiving layer 2 of the image-receiving material 3 comprising the support 1 and the image-receiving layer 2, the dye in the heat-sensitive layer 5 of the heat-sensitive transfer recording material 6 comprising the support 4 and the heat-sensitive layer 5 is diffused and migrated to the image-receiving material 3 with the heat from, for example, the heat-generating resistor 8 of the heat-sensitive head 7, and reacts with the above metal source in the image-receiving layer 2 to form a chelate dye.
  • heating by means of a heat-sensitive head is generally employed, but current passage heating or heating by use of a laser may be also available.
  • the starting materials shown below were mixed to obtain a paint of a uniform solution containing the thermally diffusible dye according to the present invention.
  • the above paint was coated and dried by use of a wire bar on a polyethylene terephthalate film with a thickness of 4.5 ⁇ m to a coated amount after drying of 1.0 g/m2 to prepare a heat-sensitive transfer recording material - 1 comprising a heat-sensitive layer formed on the polyethylene terephthalate film.
  • a nitrocellulose layer containing a silicone-modified urethane resin SP-2105, produced by Dainichi Seika.
  • the maximum density ⁇ Dmax> reflective density with red light measured by a densitometer PDA-65 produced by Konica K.K.
  • the hue of image visial observation
  • fixability of the image were evaluated. The results evaluated are shown in Table 1.
  • Heating time of heat-sensitive head heating time was adjusted stepwise between 20 msec. and 0.2 msec.
  • Heat-sensitive transfer recording materials 2 - 8 were prepared in the same manner as in Example 1 except for changing the dye from the compound (1) (Exemplary compound C-1) to the Exemplary compounds C-2, C-16, C-5, C-17, C-19, C-10 or C-13 in Example 1, and image recording was performed under the same recording conditions to obtain images 2 to 8. For the respective images obtained, the same evaluation as in Example 1 was conducted. The results are shown in Table 1.
  • Image receiving materials 2 - 5 were prepared in the same manner as in Example 1 except for changing the metal source from the compound (2) (Exemplary compound MS-1) to MS-2, MS-3, MS-5, MS-7.
  • image recording was performed by use of the same recording conditions as in Example 1 to obtain images 9 - 12.
  • the same evaluation as in Example 1 was conducted. The results are shown in Table 1.
  • Heat-sensitive transfer recording materials 9 - 11 were prepared in the same manner as in Example 1 except for changing the dye to Comparative dyes A, B, C shown below in Example 1, and image recording was performed under the same recording conditions as in Example 1 to obtain images 13 - 15. However, for the image-receiving material, the image-receiving material 1 was employed. For the respective images obtained, the same evaluation as in Example 1 was conducted. The results are shown in Table 1.
  • Image-receiving materials 6, 7 were prepared in the same mannerr as in Example 1 except for changing the metal source added in the image-receiving material in Example 1 to nickel stearate or nickel chloride.
  • image recording was performed under the same recording conditions as in Example 1 to obtain images 16 - 19.
  • the same evaluation as in Example 1 was conducted. The results are shown in Table 1.
  • the images formed according to the method of the present invention had high density because the transferability of the dye and the reactivity between the dye and the metal source are high, whereby it was found that they are excellent in hue and fixability as cyan. Also, no precipitation of the metal source or white ground staining was recognized.
  • Example 1 On the heat-sensitive transfer material 1 of Example 1 was provided by coating as the intermediate layer 100 ml of an aqueous solution containing 5 g of a ball mill dispersed product of P-toluamide, 7 g of a polyvinyl pyrrolidone, 3 g of gelatin and 0.3 g of a film hardener shown below to an attached amount of P-toluamide of 0.5 g/m2.
  • the intermediate layer was provided by hot melt coating a carunauba wax (attached amount 2.0 g/m2) containing the compound (2) (Exemplary compound MS-1) (attached amount 1.0 g/m2) as the metal source, the UV-ray preventive shown below (attached amount 0.1 g/m2), the antioxidant shown below (attached amount 0.1 g/m2) and an ethylene-vinyl acetate copolymer (content of vinyl acetate 20% by weight, attached amount 0.2 g/m2) to obtain a heat-sensitive transfer material 12 having a heat-meltable layer.
  • a carunauba wax attached amount 2.0 g/m2
  • the compound (2) Exemplary compound MS-1
  • the antioxidant shown below
  • an ethylene-vinyl acetate copolymer content of vinyl acetate 20% by weight, attached amount 0.2 g/m2
  • the heat-sensitive transfer material was superposed on an image-receiving material and image recording performed under the same conditions as in Example 1. As the result, a cyan image with Dmax 1.75 could be recorded on the image-receiving material.
  • Example 13 On the heat-sensitive transfer recording material 9 of Comparative example 1 was provided by coating an intermediate layer and a heat-meltable layer in the same manner as in Example 13 to obtain a heat-sensitive transfer recording material 13. Also, a heat-transfer recording material 14 was obtained in the same manner as in Example 13 except for changing the metal source added in the heat-meltable layer of the heat-sensitive transfer recording material 12 in Example 13 to nickel stearate.
  • a heat-sensitive recording method capable of obtaining a cyan image preferable in color reproduction with high density and excellent image stability (fixability, light resistance) could be provided.

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  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Thermal Transfer Or Thermal Recording In General (AREA)
EP91309768A 1990-10-23 1991-10-22 Wärmeempfindliches Übertragungsaufzeichnungsverfahren Withdrawn EP0482896A1 (de)

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Application Number Priority Date Filing Date Title
JP2284776A JPH04158092A (ja) 1990-10-23 1990-10-23 感熱転写記録方法
JP284776/90 1990-10-23

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EP0482896A1 true EP0482896A1 (de) 1992-04-29

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6827770B2 (en) * 2001-06-19 2004-12-07 Mitsubishi Chemical Corporation Metal chelated dyestuff for inkjet recording, aqueous inkjet recording liquid comprising same and inkjet recording method using same
CN1309791C (zh) * 2002-07-27 2007-04-11 富士胶片映像着色有限公司 方法、组合物和化合物

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08224966A (ja) * 1995-02-22 1996-09-03 Konica Corp 色素受容材料及びそれを用いる画像形成方法

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3602437A1 (de) * 1985-01-30 1986-07-31 Sharp K.K., Osaka Thermosensitives aufzeichnungsmaterial

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3602437A1 (de) * 1985-01-30 1986-07-31 Sharp K.K., Osaka Thermosensitives aufzeichnungsmaterial

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
PATENT ABSTRACTS OF JAPAN vol. 9, no. 25 (M-355)(1748) 2 February 1985 & JP-A-59 171 687 ( KONISHIROKU K.K. ) 28 September 1984 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6827770B2 (en) * 2001-06-19 2004-12-07 Mitsubishi Chemical Corporation Metal chelated dyestuff for inkjet recording, aqueous inkjet recording liquid comprising same and inkjet recording method using same
CN1309791C (zh) * 2002-07-27 2007-04-11 富士胶片映像着色有限公司 方法、组合物和化合物

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