EP0421278B1 - Heat-sensitive recording sheet - Google Patents
Heat-sensitive recording sheet Download PDFInfo
- Publication number
- EP0421278B1 EP0421278B1 EP90118577A EP90118577A EP0421278B1 EP 0421278 B1 EP0421278 B1 EP 0421278B1 EP 90118577 A EP90118577 A EP 90118577A EP 90118577 A EP90118577 A EP 90118577A EP 0421278 B1 EP0421278 B1 EP 0421278B1
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- EP
- European Patent Office
- Prior art keywords
- colour developing
- recording sheet
- heat sensitive
- sensitive recording
- heat
- Prior art date
- 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.)
- Expired - Lifetime
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Classifications
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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
- B41M5/30—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using chemical colour formers
- B41M5/333—Colour developing components therefor, e.g. acidic compounds
- B41M5/3333—Non-macromolecular compounds
- B41M5/3335—Compounds containing phenolic or carboxylic acid groups or metal salts thereof
- B41M5/3336—Sulfur compounds, e.g. sulfones, sulfides, sulfonamides
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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
- B41M5/30—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using chemical colour formers
- B41M5/323—Organic colour formers, e.g. leuco dyes
- B41M5/327—Organic colour formers, e.g. leuco dyes with a lactone or lactam ring
- B41M5/3275—Fluoran compounds
Definitions
- the present invention relates to a heat-sensitive recording sheet which has superior resistance to the effects of heat, water and oils.
- a heat-sensitive recording sheet is generally prepared by applying to the surface of a support such as paper, synthetic paper, film, plastic, etc., a coating composition which is obtained by finely grinding and dispersing a colorless chromogenic substance and a color developing agent, mixing the dispersions obtained and adding one Binder, filler, sensitizer, lubricant and other auxiliaries. Under the influence of heat from the thermal spring, thermal head, thermal stamp, laser beam, etc., an instantaneous chemical conversion takes place, which leads to the recording.
- heat-sensitive recording sheets include use in technical recording equipment, computer terminal printers, facsimile machine printers, ticket machines, bar code printer printers, etc. Recently, essential higher and more diverse demands are made on recording devices, therefore a high quality of the recording sheet is required. For example, in the case of rapid recording, the heat-sensitive recording sheet is said to have a clear, high-density recording image even with little heat input, and it is also said to have superior resistance to the effects of light, climate and oils.
- dyes with high sensitivity such as 3-N-methyl-N-cyclohexylamino-6-methyl-7-anilinofluoran (in JP-OL 49-109120), 3-dibutylamino-6-methyl -7-anilinofluoran (in JP-OL 59-190891) etc. have been developed as leuco dyes.
- Color development agents are also included superior color formation has been proposed, such as 1,7-bis (4-hydroxyphenylthio) -3,5-dioxaheptane (in JP-OL 59-106456), 1,5-bis (4-hydroxyphenylthio) -3-oxaheptane (in JP-OL 59-116262), 4-hydroxy-4'-isopropoxydiphenylsulfone (in Japanese Patent Publication 63-46067).
- the heat-sensitive recording sheets described above have high sensitivity, but have the disadvantages that they are inferior in heat resistance, i.e. discoloration of the background when stored at high temperature.
- heat-sensitive recording sheets have the disadvantages that, due to the inferior storage stability of the recording image, the image density decreases and the image changes color when water or skin secretions adhere to the recording image, or plasticizers (DOP, DOA etc.) from a packaging film, such as a polyvinyl chloride film, with it come into contact.
- plasticizers DOP, DOA etc.
- the invention has for its object to provide a heat-sensitive recording sheet which has a superior resistance to the effects of heat, water and oils.
- the heat-sensitive recording sheet according to the invention contains both 4-hydroxy-4'-n-propoxydiphenylsulfone, ie a special sulfone diphenol compound described in EP-A-131631, as an organic color developing agent and at least one fluorine-leuco dye in the color development layer the group 3-N-dipentylamino-6-methyl-7-anilinofluoran of the following formula (I), 2- (4-oxa-hexyl) -3-dimethylamino-6-methyl-7-anilinofluoran of the following formula (II) and Contains 2- (4-oxa-hexyl) -3-diethylamino-6-methyl-7-anilinofluoran of the following formula (III) as a basic colorless chromogenic dye.
- 4-hydroxy-4'-n-propoxydiphenylsulfone ie a special sulfone diphenol compound described in EP-A-131631
- fluorine-leuco dye in
- the fluoranleuco dye according to the invention can, in combination with other fluoranleuco dyes, in an amount not impairing the effect according to the invention be used.
- Typical examples of these fluorine leuco dyes are: 3-diethylamino-6-methyl-7-anilinofluoran, 3- (N-ethyl-p-toluidino) -6-methyl-7-anilinofluoran, 3- (N-ethyl-N-isoamylamino) -6-methyl-7-anilinofluoran, 3-diethylamino-6-methyl-7- (o, p-dimethylanilino) fluoran, 3-pyrrolidino-6-methyl-7-anilinofluoran, 3-piperidino-6-methyl-7-anilinofluoran, 3- (N-cyclohexyl-N-methylamino) -6-methyl-7-anilinofluorane, 3-diethylamino-7- (m
- the color developing agent according to the invention can also be used in combination with other color developing agents in an amount which does not impair the effect according to the invention.
- a sensitizer can also be added to the color development layer of the present invention.
- Typical examples of such sensitizers are fatty acid amides such as stearic acid amide, palmitic acid amide, etc .; Ethylene bisamide; Montan wax; Polyethylene wax; Terephthalic acid dibenzyl ester; benzyl p-benzyloxybenzoate; Di-p-tolyl carbonate,; p-benzylbiphenyl; Phenyl- ⁇ -naphthyl carbonate; 1,4-diethoxynaphthalene; Phenyl 1-hydroxy-2-naphthoate; 1,2-di- (3-methylphenoxy) ether; Di (p-methylphenoxy) oxalate; ⁇ -benzyloxynaphthalene; 4-biphenyl-p-tolyl ether.
- Binders which can be used according to the invention are, for example, completely saponified polyvinyl alcohol (degree of polymerization: 200-1900), partly saponified polyvinyl alcohol, carboxylated polyvinyl alcohol, amide-modified polyvinyl alcohol, sulfonic acid-modified polyvinyl alcohol, butyral-modified polyvinyl alcohol, other modified polyvinyl alcohols, hydroxyethyl acid carboxymethyl cellulose, methyl cellulose mole cellulose methyl methyl cellulose, methyl cellulose mole cellulose methyl cellulose mole cellulose mole cellulose methyl methyl cellulose mole, Butadiene copolymers, cellulose derivatives such as ethyl cellulose and acetyl cellulose, polyvinyl chloride, polyvinyl acetate, polyacrylamide, polyacrylic acid esters, polyvinyl butyral, polystyrene, copolymers of the above compounds, polyamide resin, silicone resins, petroleum synthetic resins,
- binders can be used after being dissolved in a solvent such as water, alcohol, ketone, ester, hydrocarbon, etc., or emulsified or dispersed in water or solvent. These binders can be used in combination depending on the purpose.
- metal salts of p-nitrobenzoic acid (Ca, Zn salts) or metal salts of phthalic acid monobenzyl ester (Ca, Zn salts) can be used as known stabilizers in an amount which does not impair the effect according to the invention.
- Both inorganic and organic fillers can be used as fillers according to the invention.
- Typical examples of the fillers according to the invention are silicon dioxide, calcium carbonate, kaolin, baked kaolin, diatomaceous earth, talc, titanium dioxide and aluminum hydroxide.
- Release agents such as metal salts of fatty acids, lubricants such as waxes, UV absorbers of the benzophenone and triazone series, water-proofing agents such as glyoxal etc., dispersants, antifoams and the like can also be used.
- the type and the amount of the organic color developing agent according to the invention, the basic colorless dye according to the invention and the other constituents, which are determined depending on the desired effect and suitability for recording purposes, are not particularly limited. It is generally advantageous to use 1-8 parts by weight of the organic color developing agent according to the invention and 1-20 parts by weight of filler, based on 1 part by weight of the basic colorless dye according to the invention, and 10-25 parts by weight of binder, based on the total substance content.
- the heat-sensitive recording sheet of the present invention is produced by coating the coating composition of the above composition on a support such as paper, synthetic paper, film, plastic, etc.
- a top layer e.g. be applied from a polymer to the color development layer.
- the above organic color developing agent of the present invention, the colorless basic chromogenic dye and optionally the other additives by means of a grinding device, such as a ball mill, attritor, sand grinder, etc. or by means of a suitable emulsifying device, to a particle size of several microns or smaller.
- a grinding device such as a ball mill, attritor, sand grinder, etc. or by means of a suitable emulsifying device, to a particle size of several microns or smaller.
- Various additives are added to produce the coating composition of the invention.
- the reason for achieving the effects according to the invention when the special organic color developing agent and the special dye are used in combination is probably as follows:
- the reason for the improved dynamic image density can be attributed to the fact that this dye has a high solution diffusion rate and very high solubility in the color developing agent according to the invention and the recording is thus formed immediately when it is touched with a heated thermal head.
- the reason for the superior resistance to the effects of water and oils is as follows:
- the heat-melt reaction between the basic colorless dye and a color developing agent is a type of acid-base reaction that proceeds with electron donation and uptake, thereby forming a metastable charge-transfer complex, which leads to the colored image.
- Solution A (dye dispersion) Dye (See Table 1.) 2.0 parts 10% aqueous polyvinyl alcohol solution 4.6 parts water 2.5 parts
- Solution B (color developer dispersion) 4-hydroxy-4'-n-propoxydiphenyl sulfone 6.0 parts 10% aqueous polyvinyl alcohol solution 18.8 parts water 11.2 parts
- This coating composition was applied in a coating amount of 5.0 g / m2 on a base paper with a weight of 50 g / m2, dried and supercalendered to achieve a smoothness of 400-500 seconds.
- a black color developing heat-sensitive recording sheet was obtained.
- a heat-sensitive recording sheet was obtained in the same manner as in Example 1, except that the dye shown in Table 1 was used instead of the dye of Solution A.
- Solution C (dye dispersion) Dye (See Table 1.) 2.0 parts 10% aqueous polyvinyl alcohol solution 4.6 parts water 2.5 parts Solution D (color developer dispersion) Color developing agent (See Table 1.) 6.0 parts 10% aqueous polyvinyl alcohol solution 18.8 parts water 11.2 parts
- This coating composition was applied in a coating amount of 5.0 g / m2 on a base paper with a weight of 50 g / m2, dried and supercalendered to give a smoothness of 400-500 seconds adjust. A black color developing heat-sensitive recording sheet was obtained.
Description
Die Erfindung betrifft ein wärmeempfindliches Aufzeichnungsblatt, das eine überlegene Beständigkeit gegenüber den Einwirkungen von Hitze, Wasser und Ölen hat.The present invention relates to a heat-sensitive recording sheet which has superior resistance to the effects of heat, water and oils.
Ein wärmeempfindliches Aufzeichnungsblatt wird im allgemeinen hergestellt, indem man auf die Oberfläche eines Trägers wie Papier, synthetisches Papier, Film, Kunststoff usw. eine Beschichtungsmasse aufbringt, die durch Feinvermahlen und Dispergieren eines farblosen chromogenen Stoffes und eines Farbentwicklungsmittels, Vermischen der erhaltenen Dispersionen und Zugabe eines Bindemittels, Füllstoffs, Sensibilisators, Gleitmittels und anderer Hilfsmittel erhält. Unter der Wärmeeinwirkung von Thermofeder, Thermokopf, Thermostempel, Laserstrahl usw. erfolgt eine augenblickliche chemische Umsetzung, die zur Aufzeichnung führt.A heat-sensitive recording sheet is generally prepared by applying to the surface of a support such as paper, synthetic paper, film, plastic, etc., a coating composition which is obtained by finely grinding and dispersing a colorless chromogenic substance and a color developing agent, mixing the dispersions obtained and adding one Binder, filler, sensitizer, lubricant and other auxiliaries. Under the influence of heat from the thermal spring, thermal head, thermal stamp, laser beam, etc., an instantaneous chemical conversion takes place, which leads to the recording.
Die vielfältigen praktischen Verwendungen dieser wärmeempfindlichen Aufzeichnungsblätter umfassen die Anwendung bei technischen Aufzeichnungsgeräten, Terminaldruckern von Computern, Druckern von Faksimiliermaschinen, Fahrscheinautomaten, Druckern für Strichcode-Zettel usw. In letzter Zeit werden wesentlich höhere und vielfältigere Anforderungen an Aufzeichnungsvorichtungen gestellt, daher ist eine hohe Qualität des Aufzeichnungsblattes erforderlich. Beispielsweise soll bei der raschen Aufzeichnung das wärmeempfindliche Aufzeichnungsblatt ein deutliches Aufzeichnungsbild mit hoher Dichte sogar bei geringer Wärmezufuhr haben, und es soll weiter überlegene Beständigkeit gegenüber den Einwirkungen von Licht, Klima und Ölen haben.The various practical uses of these heat-sensitive recording sheets include use in technical recording equipment, computer terminal printers, facsimile machine printers, ticket machines, bar code printer printers, etc. Recently, essential higher and more diverse demands are made on recording devices, therefore a high quality of the recording sheet is required. For example, in the case of rapid recording, the heat-sensitive recording sheet is said to have a clear, high-density recording image even with little heat input, and it is also said to have superior resistance to the effects of light, climate and oils.
Bekannte wärmeempfindliche Aufzeichnungsblätter sind in den japanischen Patentpublikationen 43-4160 und 45-14039 beschrieben. Solche wärmeempfindlichen Aufzeichnungsblätter haben z.B. die Nachteile, daß sich wegen der nachteiligen thermischen Ansprechbarkeit bei rascher Aufzeichnung keine ausreichende Bilddichte ergibt.Known heat sensitive recording sheets are described in Japanese Patent Publications 43-4160 and 45-14039. Such heat sensitive recording sheets have e.g. the disadvantages that due to the disadvantageous thermal responsiveness with rapid recording, there is no sufficient image density.
Zur Überwindung der Nachteile der obigen wärmeempfindlichen Aufzeichnungsblätter sind Farbstoffe mit hoher Empfindlichkeit, wie 3-N-Methyl-N-cyclohexylamino-6-methyl-7-anilinofluoran (in der JP-OL 49-109120), 3-Dibutylamino-6-methyl-7-anilinofluoran (in der JP-OL 59-190891) usw. als Leukofarbstoffe entwickelt worden. Weiter sind Farbentwicklungsmittel mit überlegener Farbbildung vorgeschlagen worden, wie 1,7-Bis (4-hydroxyphenylthio)-3,5-dioxaheptan (in der JP-OL 59-106456), 1,5-Bis (4-hydroxyphenylthio)-3-oxaheptan (in der JP-OL 59-116262), 4-Hydroxy-4'-isopropoxydiphenylsulfon (in der japanischen Patentpublikation 63-46067).To overcome the disadvantages of the above heat-sensitive recording sheets, dyes with high sensitivity such as 3-N-methyl-N-cyclohexylamino-6-methyl-7-anilinofluoran (in JP-OL 49-109120), 3-dibutylamino-6-methyl -7-anilinofluoran (in JP-OL 59-190891) etc. have been developed as leuco dyes. Color development agents are also included superior color formation has been proposed, such as 1,7-bis (4-hydroxyphenylthio) -3,5-dioxaheptane (in JP-OL 59-106456), 1,5-bis (4-hydroxyphenylthio) -3-oxaheptane (in JP-OL 59-116262), 4-hydroxy-4'-isopropoxydiphenylsulfone (in Japanese Patent Publication 63-46067).
Durch die Verwendung dieser Chemikalien ist die Technologie einer raschen Aufzeichnung mit hoher Empfindlichkeit ermöglicht worden.The use of these chemicals has made rapid recording technology with high sensitivity possible.
Die oben beschriebenen wärmeempfindlichen Aufzeichnungsblätter haben eine hohe Empfindlichkeit, weisen jedoch die Nachteile auf, daß sie eine unterlegene Hitezbeständigkeit, d.h. eine Verfärbung des Hintergrundes bei der Lagerung bei hoher Temperatur, ergeben.The heat-sensitive recording sheets described above have high sensitivity, but have the disadvantages that they are inferior in heat resistance, i.e. discoloration of the background when stored at high temperature.
Weiter haben diese wärmeempfindlichen Aufzeichnungsblätter die Nachteile, daß wegen der unterlegenen Lagerbeständigekit des Aufzeichnungsbildes die Bilddichte abnimmt und sich das Bild verfärbt, wenn Wasser oder Hautabsonderungen am Aufzeichnungsbild haften, oder Weichmacher (DOP, DOA usw.) aus einer Verpackungsfolie, wie einer Polyvinyylchloridfolie, damit in Berührung kommen.Furthermore, these heat-sensitive recording sheets have the disadvantages that, due to the inferior storage stability of the recording image, the image density decreases and the image changes color when water or skin secretions adhere to the recording image, or plasticizers (DOP, DOA etc.) from a packaging film, such as a polyvinyl chloride film, with it come into contact.
Der Erfindung liegt die Aufgabe zugrunde, ein wärmeempfindliches Aufzeichnungsblatt zu schaffen, das eine überlegene Beständigkeit gegenüber den Einwirkungen von Hitze, Wasser und Ölen besitzt.The invention has for its object to provide a heat-sensitive recording sheet which has a superior resistance to the effects of heat, water and oils.
Diese Aufgabe wird bei dem erfindungsgemäßen wärmeempfindlichen Aufzeichnungsblatt dadurch gelöst, daß es in der Farbentwicklungsschicht sowohl 4-Hydroxy-4'-n-propoxydiphenylsulfon, d.h. eine besondere in der EP-A-131631 beschriebene Sulfondiphenolverbindung, als organisches Farbentwicklungsmittel wie auch mindestens einen Fluoranleukofarbstoff aus der Gruppe 3-N-Dipentylamino-6-methyl-7-anilinofluoran der folgenden Formel (I), 2-(4-Oxa-hexyl)-3-dimethylamino-6-methyl-7-anilinofluoran der folgenden Formel (II) und 2-(4-Oxa-hexyl)-3-diäthylamino-6-methyl-7-anilinofluoran der folgenden Formel (III) als basischen farblosen chromogenen Farbstoff enthält.
Der erfindungsgemäße Fluoranleukofarbstoff kann in Kombination mit anderen Fluoranleukofarbstoffen in einer den erfindungsgemäßen Effekt nicht beeinträchtigenden Menge verwendet werden. Typische Beispiele für diese Fluoranleukofarbstoffe sind:
3-Diäthylamino-6-methyl-7-anilinofluoran, 3-(N-Äthyl-p-toluidino)-6-methyl-7-anilinofluoran,
3-(N-Äthyl-N-isoamylamino)-6-methyl-7-anilinofluoran,
3-Diäthylamino-6-methyl-7-(o,p-dimethylanilino)fluoran,
3-Pyrrolidino-6-methyl-7-anilinofluoran,
3-Piperidino-6-methyl-7-anilinofluoran,
3-(N-Cyclohexyl-N-methylamino)-6-methyl-7-anilinofluoran,
3-Diäthylamino-7-(m-trifluoromethylanilino)fluoran,
3-Dibutylamino-6-methyl-7-anilinofluoran,
3-Diäthylamino-6-chlor-7-anilinofluoran,
3-Dibutylamino-7-(o-chloranilino)fluoran und
3-Diäthylamino-7-(o-chloranilino)fluoran.This object is achieved with the heat-sensitive recording sheet according to the invention in that it contains both 4-hydroxy-4'-n-propoxydiphenylsulfone, ie a special sulfone diphenol compound described in EP-A-131631, as an organic color developing agent and at least one fluorine-leuco dye in the color development layer the group 3-N-dipentylamino-6-methyl-7-anilinofluoran of the following formula (I), 2- (4-oxa-hexyl) -3-dimethylamino-6-methyl-7-anilinofluoran of the following formula (II) and Contains 2- (4-oxa-hexyl) -3-diethylamino-6-methyl-7-anilinofluoran of the following formula (III) as a basic colorless chromogenic dye.
The fluoranleuco dye according to the invention can, in combination with other fluoranleuco dyes, in an amount not impairing the effect according to the invention be used. Typical examples of these fluorine leuco dyes are:
3-diethylamino-6-methyl-7-anilinofluoran, 3- (N-ethyl-p-toluidino) -6-methyl-7-anilinofluoran,
3- (N-ethyl-N-isoamylamino) -6-methyl-7-anilinofluoran,
3-diethylamino-6-methyl-7- (o, p-dimethylanilino) fluoran,
3-pyrrolidino-6-methyl-7-anilinofluoran,
3-piperidino-6-methyl-7-anilinofluoran,
3- (N-cyclohexyl-N-methylamino) -6-methyl-7-anilinofluorane,
3-diethylamino-7- (m-trifluoromethylanilino) fluoran,
3-dibutylamino-6-methyl-7-anilinofluoran,
3-diethylamino-6-chloro-7-anilinofluoran,
3-dibutylamino-7- (o-chloroanilino) fluoran and
3-diethylamino-7- (o-chloroanilino) fluoran.
Wie beim erfindungsgemäßen Farbstoff,
kann auch das erfindungsgemäße Farbentwicklungsmittel in Kombination mit anderen Farbentwicklungsmitteln in einer den erfindungsgemäßen Effekt nicht beeinträchtigenden Menge verwendet werden.As with the dye according to the invention,
the color developing agent according to the invention can also be used in combination with other color developing agents in an amount which does not impair the effect according to the invention.
Weiter kann ein Sensibilisator zur erfindungsgemäßen Farbentwicklungsschicht zugegeben werden. Typische Beispiele für solche Sensibilisatoren sind Fettsäureamide wie Stearinsäureamid, Palmitinsäureamid usw.; Äthylenbisamid; Montanwachs; Polyäthylenwachs; Terephthalsäuredibenzylester; p-Benzyloxybenzoesäurebenzylester; Di-p-tolylcarbonat, ;p-Benzylbiphenyl; Phenyl-α-naphthylcarbonat; 1,4-Diäthoxynaphthalin; 1-Hydroxy-2-naphthoesäurephenylester; 1,2-Di-(3-methylphenoxy)äthan; Di(p-methylphenoxy)oxalat; β-Benzyloxynaphthalen; 4-Biphenyl-p-tolylether.A sensitizer can also be added to the color development layer of the present invention. Typical examples of such sensitizers are fatty acid amides such as stearic acid amide, palmitic acid amide, etc .; Ethylene bisamide; Montan wax; Polyethylene wax; Terephthalic acid dibenzyl ester; benzyl p-benzyloxybenzoate; Di-p-tolyl carbonate,; p-benzylbiphenyl; Phenyl-α-naphthyl carbonate; 1,4-diethoxynaphthalene; Phenyl 1-hydroxy-2-naphthoate; 1,2-di- (3-methylphenoxy) ether; Di (p-methylphenoxy) oxalate; β-benzyloxynaphthalene; 4-biphenyl-p-tolyl ether.
Erfindungsgemäß anwendbare Bindemittel sind z.B. vollständig verseifter Polyvinylalkohol (Polymerisationsgrad: 200-1900), teilweise verseifter Polyvinylalkohol, carboxylierter Polyvinylalkohol, amidmodifizierter Polyvinylalkohol, sulfonsäuremodifizierter Polyvinylalkohol, butyralmodifizierter Polyvinylalkohol, andere modifizierte Polyvinylalkohole, Hydroxyäthylcellulose, Methylcellulose, Carboxymethylcellulose, Styrol-Maleinsäureanhydrid-Copolymere, Styrol-Butadien-Copolymere, Cellulosederivate wie Äthylzellulose und Acetylcellulose, Polyvinylchlorid, Polyvinylazetat, Polyacrylamid, Polyacrylsäureester, Polyvinylbutyral, Polystyrol, Copolymere von obigen Verbindungen, Polyamidharz, Siliconharze, Petroleumkunstharze, Terpenharze, Ketonharze und Cumaronharze. Diese hochmolekularen Bindemittel können verwendet werden, nachdem sie in einem Lösungsmittel wie Wasser, Alkohol, Keton, Ester, Kohlenwasserstoff usw. gelöst oder in Wasser oder Lösungsmittel emulgiert oder dispergiert worden sind. Diese Bindemittel können je nach dem Verwendungszweck in Kombination verwendet werden.Binders which can be used according to the invention are, for example, completely saponified polyvinyl alcohol (degree of polymerization: 200-1900), partly saponified polyvinyl alcohol, carboxylated polyvinyl alcohol, amide-modified polyvinyl alcohol, sulfonic acid-modified polyvinyl alcohol, butyral-modified polyvinyl alcohol, other modified polyvinyl alcohols, hydroxyethyl acid carboxymethyl cellulose, methyl cellulose mole cellulose methyl methyl cellulose, methyl cellulose mole cellulose methyl cellulose methyl methyl cellulose mole cellulose methyl methyl cellulose mole, Butadiene copolymers, cellulose derivatives such as ethyl cellulose and acetyl cellulose, polyvinyl chloride, polyvinyl acetate, polyacrylamide, polyacrylic acid esters, polyvinyl butyral, polystyrene, copolymers of the above compounds, polyamide resin, silicone resins, petroleum synthetic resins, Terpene resins, ketone resins and coumarone resins. These high molecular weight binders can be used after being dissolved in a solvent such as water, alcohol, ketone, ester, hydrocarbon, etc., or emulsified or dispersed in water or solvent. These binders can be used in combination depending on the purpose.
Erfindungsgemäß können als bekannte Stabilisatoren Metallsalze von p-Nitrobenzoesäure (Ca-, Zn-Salze) oder Metallsalze von Phthalsäuremonobenzylester (Ca-, Zn-Salze) in einer den erfindungsgemäßen Effekt nicht beeinträchtigenden Menge verwendet werden.According to the invention, metal salts of p-nitrobenzoic acid (Ca, Zn salts) or metal salts of phthalic acid monobenzyl ester (Ca, Zn salts) can be used as known stabilizers in an amount which does not impair the effect according to the invention.
Als erfindungsgemäße Füllstoffe können sowohl anorganische wie organische Füllstoffe verwendet werden. Typische Beispiele für die erfindungsgemäßen Füllstoffe sind Siliciumdioxid, Carciumcarbonat, Kaolin, gebranntes Kaolin, Diatomeenerde, Talk, Titandioxid und Aluminiumhydroxid.Both inorganic and organic fillers can be used as fillers according to the invention. Typical examples of the fillers according to the invention are silicon dioxide, calcium carbonate, kaolin, baked kaolin, diatomaceous earth, talc, titanium dioxide and aluminum hydroxide.
Weiter können Trennmittel wie Metallsalze von Fettsäuren, Gleitmittel wie Wachse, UV-Absorptionsmittel der Benzophenon- und Triazonreihe, wasserfest machende Mittel wie Glyoxal usw., Dispergiermittel, Antischaummittel und dergleichen verwendet werden.Release agents such as metal salts of fatty acids, lubricants such as waxes, UV absorbers of the benzophenone and triazone series, water-proofing agents such as glyoxal etc., dispersants, antifoams and the like can also be used.
Die Art sowie die Menge des erfindungsgemäßen organischen Farbentwicklungsmittels, des erfindungsgemäßen basischen farblosen Farbstoffs und der anderen Bestandteile, die je nach dem gewünschten Effekt und der Eignung für Aufzeichnungszwecke bestimmt werden, sind nicht besonders beschränkt. Es ist im allgemeinen vorteilhaft, 1-8 Gewichtsteile des erfindungsgemäßen organischen Farbentwicklungsmittels und 1-20 Gewichtsteile Füllstoff, bezogen auf 1 Gewichtsteil des erfindungsgemäßen basischen farblosen Farbstoffs, und 10-25 Gewichtsteile Bindemittel, bezogen auf den Gesamtstoffgehalt, zu verwenden.The type and the amount of the organic color developing agent according to the invention, the basic colorless dye according to the invention and the other constituents, which are determined depending on the desired effect and suitability for recording purposes, are not particularly limited. It is generally advantageous to use 1-8 parts by weight of the organic color developing agent according to the invention and 1-20 parts by weight of filler, based on 1 part by weight of the basic colorless dye according to the invention, and 10-25 parts by weight of binder, based on the total substance content.
Das erfindungsgemäße wärmeempfindliche Aufzeichnungsblatt wird hergestellt, indem man die Beschichtungsmasse der obigen Zusammensetzung auf einen Träger wie Papier, synthetisches Papier, Film, Kunststoff usw. aufträgt.The heat-sensitive recording sheet of the present invention is produced by coating the coating composition of the above composition on a support such as paper, synthetic paper, film, plastic, etc.
Zur weiteren Verbesserung der Haltbarkeit kann eine Deckschicht, z.B. aus einem Polymerisat auf der Farbentwicklungsschicht aufgebracht werden.To further improve durability, a top layer, e.g. be applied from a polymer to the color development layer.
Das obige erfindungsgemäße organische Farbentwicklungsmittel, der farblose basische chromogene Farbstoff und gegebenenfalls die anderen Additive werden mittels einer Mahlvorrichtung, wie Kugelmühle, Reibmühle, Sandschleifmaschine usw. oder mittels einer geeigneten Emulgiervorrichtung bis zu einer Teilchengröße von mehreren Mikron oder kleiner zermahlen. Hierzu gibt man verschiedene Additive, um die erfindungsgemäße Beschichtungsmasse herzustellen.The above organic color developing agent of the present invention, the colorless basic chromogenic dye and optionally the other additives by means of a grinding device, such as a ball mill, attritor, sand grinder, etc. or by means of a suitable emulsifying device, to a particle size of several microns or smaller. Various additives are added to produce the coating composition of the invention.
Die Ursache für die Erzielung der erfindungsgemäßen Effekte bei kombinierter Verwendung des besonderen organischen Farbentwicklungsmittels und des besonderen Farbstoffs ist wahrscheinlich folgende:
Die Ursache für die verbesserte dynamische Bilddichte läßt sich darauf zurückzuführen, daß dieser Farbstoff eine große Lösungsdiffusionsgeschwindigkeit und sehr große Löslichkeit in dem erfindungsgemäßen Farbentwicklungsmittel hat und dadurch die Aufzeichnung bei der Berührung mit einem erhitzten Thermokopf augenblicklich gebildet wird.The reason for achieving the effects according to the invention when the special organic color developing agent and the special dye are used in combination is probably as follows:
The reason for the improved dynamic image density can be attributed to the fact that this dye has a high solution diffusion rate and very high solubility in the color developing agent according to the invention and the recording is thus formed immediately when it is touched with a heated thermal head.
Die Ursache für die überlegene Beständigkeit gegenüber den Einwirkungen von Wasser und Ölen ist wie folgt:
Im allgemeinen besteht ein wärmeempfindliches Aufzeichnungsblatt aus einem basischen farblosen Farbstoff als Elektronendonator und einer organischen sauren Substanz, z.B. einer phenolischen Verbindung, aromatischen Carbonsäure, organischen Sulfonsäure usw. als Elektronenakzeptor. Die Hitzeschmelzreaktion zwischen dem basischen farblosen Farbstoff und einem Farbentwicklungsmittel ist eine Art von Säure-Base-Reaktion, die unter Elektronenabgabe und -aufnahme verläuft, wodurch ein metastabiler Charge-Transfer-Komplex gebildet wird, was zum gefärbten Bild führt.The reason for the superior resistance to the effects of water and oils is as follows:
Generally there is a heat sensitive Recording sheet of a basic colorless dye as an electron donor and an organic acidic substance, for example a phenolic compound, aromatic carboxylic acid, organic sulfonic acid, etc. as an electron acceptor. The heat-melt reaction between the basic colorless dye and a color developing agent is a type of acid-base reaction that proceeds with electron donation and uptake, thereby forming a metastable charge-transfer complex, which leads to the colored image.
Bei der Verwendung von 4-Hydroxy-4'-n-propoxydiphenylsulfon als organischem Farbentwicklungsmittel ist die chemische Bindung in der Farbbildungsreaktion zwischen 4-Hydroxy-4'-n-propoxydiphenylsulfon und einem erfindungsgemäßen Fluoranleukofarbstoff als basischem farblosen Farbstoff erheblich stärker als diejenige zwischen einem Fluoranleukofarbstoff und einem anderen Farbentwicklungsmittel (beispielsweise 4-Hydroxybenzoesäurebenzylester, 4-Hydroxy-4'-isopropoxydiphenylsulfon, 1,7-Di(4-hydroxyphenylthio)-3,5-dioxaheptan oder 4,4'-Dihydroxydiphenylsulfon) als dem erfindungsgemäßen Farbentwicklungsmittel. Daher vermutet man, daß die chemische Bindung sogar unter der Einwirkung von Wasser, Ölen usw. lange Zeit nicht gelöst wird, so daß das Aufzeichnungsbild stabil ist.When 4-hydroxy-4'-n-propoxydiphenylsulfone is used as the organic color developing agent, the chemical bond in the color formation reaction between 4-hydroxy-4'-n-propoxydiphenylsulfone and a fluoranleuco dye according to the invention as a basic colorless dye is considerably stronger than that between a fluoranleuko dye and another color developing agent (e.g., benzyl 4-hydroxybenzoate, 4-hydroxy-4'-isopropoxydiphenyl sulfone, 1,7-di (4-hydroxyphenylthio) -3,5-dioxaheptane or 4,4'-dihydroxydiphenyl sulfone) as the color developing agent of the present invention. Therefore, it is believed that the chemical bond even under the Exposure to water, oils, etc. is not released for a long time, so that the recording image is stable.
Die Erfindung wird durch Beispiele und Vergleichsbeispiele erklärt. Als Abkürzung für "Gewichtsteile" wird "Teile" verwendet.The invention is explained by examples and comparative examples. As an abbreviation for "parts by weight", "parts" is used.
Die Lösungen der obigen Zusammensetzungen wurden in einer Sandschleifmaschine einzeln bis zur Teilchengröße von 1 Mikron vermahlen. Die Lösungen wurden im folgenden Verhältnis miteinander vermischt; man erhält dabei eine wärmeempfindliche Beschichtungsmasse.
Diese Beschichtungsmasse wurde in einer Beschichtungsmenge von 5,0 g/m² auf ein Basispapier mit einem Gewicht von 50 g/m² aufgetragen, getrocknet und superkalandriert, um eine Glätte von 400-500 Sekunden einzustellen. Man erhielt ein eine schwarze Farbe entwickelndes wärmeempfindliches Aufzeichnungsblatt.This coating composition was applied in a coating amount of 5.0 g / m² on a base paper with a weight of 50 g / m², dried and supercalendered to achieve a smoothness of 400-500 seconds. A black color developing heat-sensitive recording sheet was obtained.
Man erhielt in der gleichen Weise wie im Beispiel 1 ein wärmeempfindliches Aufzeichnungsblatt, wobei man jedoch den in der Tabelle 1 angegebenen Farbstoff anstatt des Farbstoffes der Lösung A verwendete.A heat-sensitive recording sheet was obtained in the same manner as in Example 1, except that the dye shown in Table 1 was used instead of the dye of Solution A.
Die Lösungen der obigen Zusammensetzungen wurden in einer Sandschleifmaschine einzeln bis zur Teilchengröße von 1 Mikron vermahlen. Die Lösungen wurden im folgenden Verhältnis miteinander vermischt; man erhält dabei eine wärmeempfindliche Beschichtungsmasse.
Diese Beschichtungsmasse wurde in einer Beschichtungsmenge von 5,0 g/m² auf ein Basispapier mit einem Gewicht von 50 g/m² aufgetragen, getrocknet und superkalandriert, um eine Glätte von 400-500 Sekunden einzustellen. Man erhielt ein eine schwarze Farbe entwickelndes wärmeempfindliches Aufzeichnungsblatt.This coating composition was applied in a coating amount of 5.0 g / m² on a base paper with a weight of 50 g / m², dried and supercalendered to give a smoothness of 400-500 seconds adjust. A black color developing heat-sensitive recording sheet was obtained.
Die wärmeempfindlichen Aufzeichnungsblätter aus dem Beispiel und den Vergleichsbeispielen wurden hinsichtlich ihrer Qualität und ihres Verhaltens geprüft, und die Prüfungsergebnisse wurden in Tabelle 1 zusammengefaßt.The heat-sensitive recording sheets from the example and the comparative examples were tested for their quality and behavior, and the test results were summarized in Table 1.
- (1) Dynamische Bilddichte: Ein wärmeempfindliches Aufzeichnungsblatt wird bei einer angelegten Spannung von 18,03 V und einer Pulsbreite von 3,2 ms unter Verwendung einer thermoempfindlichen Faksimiliermaschine KB-4800 (von TOSHIBA CORPORATION hergestellt) aufgezeichnet und mit einem Macbeth-Dichtemesser (RD-914, Verwendung des Amber-Filters; unten gelten die gleichen Bedingungen) bestimmt.(1) Dynamic Image Density: A heat-sensitive recording sheet is recorded at an applied voltage of 18.03 V and a pulse width of 3.2 ms using a thermosensitive facsimile machine KB-4800 (manufactured by TOSHIBA CORPORATION) and recorded with a Macbeth density meter (RD -914, use of the amber filter; the same conditions apply below).
- (2) Hitzebeständigkeit: Ein wärmeempfindliches Blatt vor der Aufzeichnung wird 24 Stunden bei 60 °C stehengelassen. Danach wird die Bilddichte mit einem Macbeth-Dichtemesser gemessen.(2) Heat resistance: A heat sensitive sheet is left to stand at 60 ° C for 24 hours before recording. The image density is then measured using a Macbeth density meter.
-
(3) Wasserbeständigkeit: Das gemäß obiger Anmerkung (1) behandelte wärmeempfindliche Blatt wird 24 Stunden mit Wasser bei 20 °C durchtränkt. Nach der Trocknung wird der aufgezeichnete Teil mit einem Macbeth-Dichtemesser gemessen. Der Restprozentsatz wird nach folgender Formel berechnet.
-
(4) Ölbeständigkeit: Die gemäß obiger Anmerkung (2) aufgezeichnete Bilddichte wird als Bilddichte vor der Behandlung definiert. Ein Tropfen Salatöl wird auf die Aufzeichnung getröpfelt, nach 10 Sekunden mit einem Filtrierpapier abgewischt und 1 Stunde bei Raumtemperatur stehengelassen. Danach wird die Bilddichte mit einem Macbeth-Dichtemesser gemessen. Der Restprozentsatz wird nach folgender Formel berechnet.
Es ist ersichtlich, daß das erfindungsgemäße Aufzeichnungsblatt folgende Vorteile besitzt:
- 1) Ein intensives, klares Bild hoher Dichte bei rascher Aufzeichnung aufgrund der vorteilhaften thermischen Ansprechbarkeit.
- 2) Fast keine Entfärbung der Aufzeichnung bei Kontakt mit Weichmacher.
- 3) Fast keine Entfärbung der Aufzeichnung bei Kontakt mit Wasser.
- 4) Stabiler Weißgrad unter Bedingungen bei hoher Temperatur.
- 1) An intense, clear, high-density image with rapid recording due to the beneficial thermal responsiveness.
- 2) Almost no discoloration of the record upon contact with plasticizer.
- 3) Almost no discoloration of the record upon contact with water.
- 4) Stable whiteness under high temperature conditions.
Claims (7)
- Heat sensitive recording sheet with a heat sensitive colour developing layer on a carrier, wherein the heat sensitive colour developing layer contains a basic colourless or weakly coloured chromogenic dyestuff and an organic colour developing agent, characterised in that the heat sensitive colour developing layer contains as organic colour developing agent 4-hydroxy-4'-n-propoxydiphenylsulphone and as basic colourless chromogenic dyestuff at least one of the fluorane leuco dyestuffs of the general formulae (I), (II) and (III):
- Heat sensitive recording sheet according to Claim 1, characterised in that the colour developing layer contains 1-8 parts by weight of the organic colour developing agent and 1-20 parts by weight filler taken on 1 part by weight of the basic colourless dyestuff, and 10-25 parts by weight binding agent taken on the total solids content.
- Heat sensitive recording sheet according to Claim 1, characterised in that the colour developing layer further contains at least one stabiliser from the group of metal salts of p-nitrobenzoic acid and metal salts of phthalic acid monobenzylester.
- Heat sensitive recording sheet according to Claim 1, characterised in that the colour developing layer further contains a sensitiser.
- Heat sensitive recording sheet according to Claim 1, characterised in that the colour developing layer contains at least one other dyestuff which is different from the dyestuffs of Formulae (I), (II) and (III).
- Heat sensitive recording sheet according to Claim 1, characterised in that the carrier is a paper, synthetic paper, film or plastics.
- Heat sensitive recording sheet according to Claim 1, characterised in that a cover layer of a polymer is applied to the colour developing layer.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP255386/89 | 1989-09-30 | ||
| JP1255386A JPH0712751B2 (en) | 1989-09-30 | 1989-09-30 | Thermal recording sheet |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| EP0421278A2 EP0421278A2 (en) | 1991-04-10 |
| EP0421278A3 EP0421278A3 (en) | 1991-06-05 |
| EP0421278B1 true EP0421278B1 (en) | 1994-06-01 |
Family
ID=17278039
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP90118577A Expired - Lifetime EP0421278B1 (en) | 1989-09-30 | 1990-09-27 | Heat-sensitive recording sheet |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US5066634A (en) |
| EP (1) | EP0421278B1 (en) |
| JP (1) | JPH0712751B2 (en) |
| CA (1) | CA2023593C (en) |
| DE (1) | DE59005917D1 (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5984363A (en) * | 1993-05-03 | 1999-11-16 | The Standard Register Company | Business record having a thermally imagable surface |
| DE60030818T2 (en) * | 1999-03-05 | 2007-09-13 | Nippon Paper Industries Co. Ltd. | HEAT-SENSITIVE RECORDING MATERIAL |
| JP4745281B2 (en) * | 2006-11-30 | 2011-08-10 | リズム時計工業株式会社 | Emergency alert receiver |
| US9034790B2 (en) * | 2013-03-14 | 2015-05-19 | Appvion, Inc. | Thermally-responsive record material |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0131631B1 (en) * | 1983-01-17 | 1988-11-02 | Yoshitomi Pharmaceutical Industries, Ltd. | Heat-sensitive recording paper |
| JPS6013852A (en) * | 1983-07-04 | 1985-01-24 | Shin Nisso Kako Co Ltd | Diphenylsulfone derivative and color-developing recording material containing the same |
| JPS6114980A (en) * | 1984-07-02 | 1986-01-23 | Fuji Photo Film Co Ltd | Recording material |
| JPS61108582A (en) * | 1984-11-01 | 1986-05-27 | Kanzaki Paper Mfg Co Ltd | Thermal recording body |
| US4814320A (en) * | 1986-04-15 | 1989-03-21 | Yamada Chemical Co., Ltd. | Heat-sensitive recording material |
-
1989
- 1989-09-30 JP JP1255386A patent/JPH0712751B2/en not_active Expired - Lifetime
-
1990
- 1990-08-20 CA CA002023593A patent/CA2023593C/en not_active Expired - Lifetime
- 1990-09-27 DE DE59005917T patent/DE59005917D1/en not_active Expired - Lifetime
- 1990-09-27 EP EP90118577A patent/EP0421278B1/en not_active Expired - Lifetime
- 1990-09-27 US US07/588,834 patent/US5066634A/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| DE59005917D1 (en) | 1994-07-07 |
| CA2023593C (en) | 2001-04-10 |
| EP0421278A2 (en) | 1991-04-10 |
| EP0421278A3 (en) | 1991-06-05 |
| JPH03118188A (en) | 1991-05-20 |
| US5066634A (en) | 1991-11-19 |
| JPH0712751B2 (en) | 1995-02-15 |
| CA2023593A1 (en) | 1991-03-31 |
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