EP0422680B1 - Heat-sensitive recording sheet - Google Patents
Heat-sensitive recording sheet Download PDFInfo
- Publication number
- EP0422680B1 EP0422680B1 EP90119625A EP90119625A EP0422680B1 EP 0422680 B1 EP0422680 B1 EP 0422680B1 EP 90119625 A EP90119625 A EP 90119625A EP 90119625 A EP90119625 A EP 90119625A EP 0422680 B1 EP0422680 B1 EP 0422680B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- recording sheet
- sensitive recording
- colour developing
- heat sensitive
- sheet according
- 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
-
- 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
-
- 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
- B41M5/337—Additives; Binders
- B41M5/3375—Non-macromolecular compounds
Definitions
- the present invention relates to a heat-sensitive recording sheet which is superior in writability when using an oily ink.
- 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 their use in technical recording devices, computer terminal printers, printers for facsimile machines, ticket vending machines, printers for barcode notes, etc. Recently, much higher and more varied requirements have been placed on recording devices, which is why a high quality of the Record sheet required. For example, in the case of rapid recording heat sensitive recording sheet have a clear high density recording image even with little heat input, and it is said to have further superior resistance to the effects of light, climate and oils.
- the heat-sensitive recording sheets have been widely used, so that the description is often made with oily ink.
- the color of the ink on the heat-sensitive recording sheet has changed because the color of the ink mixes with the color developed by the heat-sensitive recording sheet.
- the red of an oily ink used to write a heat-sensitive recording sheet forming a black color mixes with the black of the recording sheet so that the pure red color is not found.
- the present invention is therefore based on the object of providing a heat-sensitive recording sheet with improved writability.
- the color formation layer 4-hydroxy-4'-n-propoxydiphenylsulfone as organic color developing agent and at least one sensitizer from the group 1,2-di (3-methylphenoxy) ethane, di (p-methylbenzyl) oxalate, p- Contains benzylbiphenyl, ⁇ -benzyloxynaphthalene and 4-biphenyl-p-tolyl ether.
- the organic color developing agent is described in EP-A-131631.
- Sensitizers from the above group are described in EP-A-173232.
- the basic colorless or slightly colored chromogenic dyes which are suitable according to the invention are dyes of the triphenylmethane, fluorane, azaphthalide and fluorene series, e.g. of the following type:
- At least one sensitizer from the group consisting of 1,2-di (3-methylphenoxy) ether, di (p-methylbenzyl) oxalate, p-benzylbiphenyl, ⁇ -benzyloxynaphthalene and 4-biphenyl-p-tolyl ether are used according to the invention used.
- This sensitizer is effective for the purpose of the invention.
- the following stabilizers can also be added to the color development layer according to the invention: 4,4′-butylidene (6-t-butyl-3-methylphenol), 2,2′-di-t-butyl-5,5-dimethyl-4,4 ′ sulfonyldiphenol, 1,1,3-tris (2-methyl-4-hydroxy-5-cyclohexylphenyl) butane, 1,1,3-tris (2-methyl-4-hydroxy-5-t-butylphenyl) butane and so on.
- applicable binder include completely saponified polyvinyl alcohol (polymerization degree: 200-1900), partially saponified (polyvinyl alcohol, carboxylated polyvinyl alcohol, amide-modified polyvinyl alcohol, sulfonic acid-polyvinyl alcohol, butyralmod er polyvinyl alcohol, other modified polyvinyl alcohols, hydroxyethylcellulose, methylcellulose, carboxymethylcellulose, styrene-maleic anhydride copolymers, styrene -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 resins, silicone resins, petroleum synthetic resins, terpene resins, ketone resins and coumarone resins dissolved in
- binders can be used in combination depending on the purpose.
- 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 oxide 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 add 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 use, 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 applying a coating composition of the above composition on a support such as paper, synthetic paper, film, plastic, etc.
- a top layer e.g. from a polymer, are applied to the color development layer.
- the above organic color developing agent according to the invention, the colorless basic chromogenic dye and optionally the other additives are ground to a particle size of several microns or smaller by means of a grinding device such as a ball mill, attritor, sand grinder etc. or by means of a suitable emulsifying device.
- a grinding device such as a ball mill, attritor, sand grinder etc. or by means of a suitable emulsifying device.
- Various additives are added to produce the coating composition of the invention.
- a back coating layer for example made of a polymer containing the filler, can be applied further under the color development layer
- the color developing agent, the leuco dye and the sensitizer of the heat-sensitive color-developing layer are dissolved in the organic solvent contained in the ink. After volatilization of the solvent, a color developing composition consisting of the color developing agent, the leuco dye and the sensitizer is formed at the description point. For example, when using a red ink, the red color and the color developed by the composition mentioned are mixed, thereby forming a dark descriptive color.
- the heat-sensitive recording sheet of the present invention comprises 4-hydroxy-4'-n-propoxydiphenyl sulfone as a special color developing agent, a leuco dye and a special sensitizer. These materials have very low solubility in the solvent and they form practically no color developing composition upon volatilization of the solvent, so that there is no color change when using an oily ink.
- the color developing agents and the dye used according to the invention have a higher solution diffusion rate and very high solubility in the sensitizer.
- the sensitizer and the leuco dye undergo a physico-chemical reaction in the heat, a color developing composition is rapidly formed, so that a colored image having a high density is obtained.
- the sensitizer according to the invention has the property that when it is dissolved in the organic solvent contained in the oily ink and after the solvent has volatilized, it crystallizes only with difficulty. Therefore, white crystals are not formed in the description with the oily ink.
- Parts by weight means “parts”.
- Solution A color developer dispersion
- 4-hydroxy-4'-n-propoxyphenyl sulfone 6.0 parts 10% aqueous polyvinyl alcohol solution 18.8 parts water 11.2 parts
- Solution B die dispersion
- 3-N-n-dibutylamino-6-methyl-7-anilinofluoran 2.0 parts 10% aqueous polyvinyl alcohol solution 4.6 parts water 2.6 parts
- Solution C sensitizer dispersion
- Table 1 sensitizer 4.0 parts 10% aqueous solution of polyvinyl alcohol 5.0 parts water 3.0 parts
- This coating composition was applied in a coating amount of 6.0 g / m2 on a base paper with a weight of 50 g / m2, dried and supercalendered to achieve a smoothness of 200-600 seconds.
- a black color developing heat-sensitive recording sheet was obtained.
- Solution E color developer dispersion
- Color developing agents in Table 1 6.0 parts 10% aqueous polyvinyl alcohol solution 18.8 parts water 11.2 parts
- Solution B die dispersion
- 3-N-n-dibutylamino-6-methyl-7-anilinofluoran 2.0 parts 10% aqueous polyvinyl alcohol solution 4.6 parts water 2.6 parts
- a heat-sensitive recording sheet was obtained in the same manner as in Example 1.
- Solution A color developer dispersion
- 4-hydroxy-4'-n-propoxyphenyl sulfone 6.0 parts 10% aqueous polyvinyl alcohol solution 18.8 parts water 11.2 parts
- Solution B die dispersion
- 3-N-n-dibutylamino-6-methyl-7-anilinofluoran 2.0 parts 10% aqueous polyvinyl alcohol solution 4.6 parts water 2.6 parts
- Solution F sensitizer dispersion
- Table 1 sensitizer 4.0 parts 10% aqueous polyvinyl alcohol solution 5.0 parts water 3.0 parts
- the solutions of the above compositions were individually grinded to a particle size of 1 micron in a sand grinder.
- the solutions were mixed together in the following ratio; a heat-sensitive coating composition is obtained.
- the heat-sensitive recording sheets obtained according to the examples and comparative examples were tested for their quality, and the test results were summarized in Table 1.
Description
Die Erfindung betrifft ein wärmeempfindliches Aufzeichnungsblatt, das eine überlegene Beschreibbarkeit bei der Verwendung einer öligen Tinte besitzt.The present invention relates to a heat-sensitive recording sheet which is superior in writability when using an oily ink.
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 rascher 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 their use in technical recording devices, computer terminal printers, printers for facsimile machines, ticket vending machines, printers for barcode notes, etc. Recently, much higher and more varied requirements have been placed on recording devices, which is why a high quality of the Record sheet required. For example, in the case of rapid recording heat sensitive recording sheet have a clear high density recording image even with little heat input, and it is said to have further superior resistance to the effects of light, climate and oils.
In den letzten Jahren werden die wärmeempfindlichen Aufzeichnungsblätter weitreichend verwendet, so daß die Beschreibung häufig mit öliger Tinte erfolgt. In diesem Fall besteht das Problem, daß die Farbe der Tinte auf dem wärmeempfindlichen Aufzeichnungsblatt sich verändert hat, weil sich die Farbe der Tinte mit der vom wärmeempfindlichen Aufzeichnungsblatt entwickelten Farbe vermischt. Z.B. vermischt sich das Rot einer öligen Tinte, mit der ein eine schwarze Farbe bildendes wärmeempfindliches Aufzeichnungsblatt beschrieben wird, mit dem Schwarz des Aufzeichnungsblattes, so daß die reine rote Farbe nicht gefunden wird. Das gleiche gilt auch für andere Farben.
Der vorliegenden Erfindung liegt daher die Aufgabe zugrunde, ein wärmeempfindliches Aufzeichnungsblatt mit verbesserter Beschreibbarkeit zur Verfügung zu stellen.In recent years, the heat-sensitive recording sheets have been widely used, so that the description is often made with oily ink. In this case, there is a problem that the color of the ink on the heat-sensitive recording sheet has changed because the color of the ink mixes with the color developed by the heat-sensitive recording sheet. For example, the red of an oily ink used to write a heat-sensitive recording sheet forming a black color mixes with the black of the recording sheet so that the pure red color is not found. The same applies to other colors.
The present invention is therefore based on the object of providing a heat-sensitive recording sheet with improved writability.
Diese Aufgabe wird bei dem erfindungsgemäßen wärmeempfindlichen Aufzeichnungsblatt dadurch gelöst, daß die Farbbildungsschicht 4-Hydroxy-4'-n-propoxydiphenylsulfon als organisches Farbentwicklungsmittel und mindestens einen Sensibilisator aus der Gruppe 1,2-Di(3-methylphenoxy)äthan, Di(p-methylbenzyl)oxalat, p-Benzylbiphenyl, β-Benzyloxynaphthalen und 4-Biphenyl-p-tolyläther enthält. Das organische Farbentwicklungsmittel ist in der EP-A-131631 beschrieben. Sensibilisatoren aus der obigen Gruppe sind in der EP-A-173232 beschrieben.This object is achieved with the invention heat-sensitive recording sheet solved in that the color formation layer 4-hydroxy-4'-n-propoxydiphenylsulfone as organic color developing agent and at least one sensitizer from the group 1,2-di (3-methylphenoxy) ethane, di (p-methylbenzyl) oxalate, p- Contains benzylbiphenyl, β-benzyloxynaphthalene and 4-biphenyl-p-tolyl ether. The organic color developing agent is described in EP-A-131631. Sensitizers from the above group are described in EP-A-173232.
Die erfindungsgemäß geeigneten basischen farblosen oder schwachfarbigen chromogenen Farbstoffe (nachfolgend als basischer farbloser Farbstoff bezeichnet) sind Farbstoffe der Triphenylmethan-, Fluoran-, Azaphthalid- und Fluorenreihe, z.B. der folgenden Art:The basic colorless or slightly colored chromogenic dyes (hereinafter referred to as basic colorless dye) which are suitable according to the invention are dyes of the triphenylmethane, fluorane, azaphthalide and fluorene series, e.g. of the following type:
3,3-Bis-(p-dimethylaminophenyl)-6-dimethylaminophthalid (Kristallviolettlacton)3,3-bis (p-dimethylaminophenyl) -6-dimethylaminophthalide (crystal violet lactone)
3-Diäthylamino-6-methyl-7-anilinofluoran,
3-(N-Äthyl-p-toluidino)-6-methyl-7-anilinofluoran,
3-(N-Ähyl-N-isoamyl)amino-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-N-n-Dibutylamino-6-methyl-7-anilinofluoran,
3-N-n-Dibutylamino-7-(o-chloroanilino)fluoran,
3-(N-Ähtyl-N-tetrahydrofurfurylamino)-6-methyl-7-anilinofluoran,
3-Dibutylamino-6-methyl-7-(o,p-dimethylanilino)fluoran,
3-(N-äthyl-N-propylamino)-6-methyl-7-anilinofluoran,
3-Diäthylamino-6-chlor-7-anilinofluoran,
3-Dibutylamino-7-(o-chloranilino)fluoran,
3-Diäthylamino-7-(o-chloranilino)fluoran,
3-Diäthylamino-6-methyl-chlorfluoran,
3-Diäthylamino-6-methyl-fluoran,
3-Cyclohexylamino-6-chlorfluoran,
3-Diäthylamino-benzo(a)-fluoran.3-diethylamino-6-methyl-7-anilinofluoran,
3- (N-ethyl-p-toluidino) -6-methyl-7-anilinofluorane,
3- (N-ethyl-N-isoamyl) amino-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-Nn-dibutylamino-6-methyl-7-anilinofluoran,
3-Nn-dibutylamino-7- (o-chloroanilino) fluoran,
3- (N-ethyl-N-tetrahydrofurfurylamino) -6-methyl-7-anilinofluoran,
3-dibutylamino-6-methyl-7- (o, p-dimethylanilino) fluoran,
3- (N-ethyl-N-propylamino) -6-methyl-7-anilinofluoran,
3-diethylamino-6-chloro-7-anilinofluoran,
3-dibutylamino-7- (o-chloroanilino) fluoran,
3-diethylamino-7- (o-chloroanilino) fluoran,
3-diethylamino-6-methylchlorofluoran,
3-diethylamino-6-methyl-fluoran,
3-cyclohexylamino-6-chlorofluorane,
3-diethylamino-benzo (a) -fluorane.
3-(4-Diäthylamino-2-äthoxyphenyl)-3-(1-äthyl-2-methylindol-3-yl)-4-azaphthalid,
3-(4-Diäthylamino-2-äthoxyphenyl)-3-(1-äthyl-2-methylindol-3-yl)-7-azaphthalid,
3-(4-Diäthylamino-2-äthoxyphenyl)-3-(1-octyl-2-methylindol-3-yl)-4-azaphthalid,
3-(4-Cyclohexyl-N-methylamino-2-methoxyphenyl)-3-(1-äthyl-2-methylindol-3-yl)-4-azaphthalid.3- (4-diethylamino-2-ethoxyphenyl) -3- (1-ethyl-2-methylindol-3-yl) -4-azaphthalide,
3- (4-diethylamino-2-ethoxyphenyl) -3- (1-ethyl-2-methylindol-3-yl) -7-azaphthalide,
3- (4-diethylamino-2-ethoxyphenyl) -3- (1-octyl-2-methylindol-3-yl) -4-azaphthalide,
3- (4-Cyclohexyl-N-methylamino-2-methoxyphenyl) -3- (1-ethyl-2-methylindol-3-yl) -4-azaphthalide.
3,6,6′-Tris(dimethylamino)spiro[fluoren-9,3′-phthalid]
3,6,6′-Tris(diäthylamino)spiro[fluoren-9,3′-phthalid].3,6,6′-tris (dimethylamino) spiro [fluorene-9,3′-phthalide]
3,6,6′-tris (diethylamino) spiro [fluorene-9,3′-phthalide].
Erfindungsgemäß werden außer dem oben angegebenen Farbentwicklungsmittel und Farbstoff wenigstens ein Sensibilisator aus der Gruppe 1,2-Di(3-methylphenoxy)äthan, Di(p-methylbenzyl)oxalat, p-Benzylbiphenyl, β-Benzyloxynaphthalen und 4-Biphenyl-p-tolyläther verwendet. Dieser Sensibilisator ist wirksam für den erfindungsgemäßen Zweck.In addition to the above-mentioned color developing agent and dye, at least one sensitizer from the group consisting of 1,2-di (3-methylphenoxy) ether, di (p-methylbenzyl) oxalate, p-benzylbiphenyl, β-benzyloxynaphthalene and 4-biphenyl-p-tolyl ether are used according to the invention used. This sensitizer is effective for the purpose of the invention.
Weiter können die folgenden Stabilisatoren zur erfindungsgemäßen Farbentwicklungsschicht zugegeben werden: 4,4′-Butyliden(6-t-butyl-3-methylphenol), 2,2′-Di-t-butyl-5,5-dimethyl-4,4′sulfonyldiphenol, 1,1,3-Tris(2-methyl-4-hydroxy-5-cyclohexylphenyl)butan, 1,1,3-Tris-(2-methyl-4-hydroxy-5-t-butylphenyl)butan und so weiter.The following stabilizers can also be added to the color development layer according to the invention: 4,4′-butylidene (6-t-butyl-3-methylphenol), 2,2′-di-t-butyl-5,5-dimethyl-4,4 ′ sulfonyldiphenol, 1,1,3-tris (2-methyl-4-hydroxy-5-cyclohexylphenyl) butane, 1,1,3-tris (2-methyl-4-hydroxy-5-t-butylphenyl) butane and so on.
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 Äthylcellulose und Acetylcellulose, Polyvinylchlorid, Polyvinylazetat, Polyacrylamid, Polyacrylsäureester, Polyvinylbutyral, Polystyrol, Copolymere von obigen Verbindungen, Polyamidharze, 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.According to the invention applicable binder include completely saponified polyvinyl alcohol (polymerization degree: 200-1900), partially saponified (polyvinyl alcohol, carboxylated polyvinyl alcohol, amide-modified polyvinyl alcohol, sulfonic acid-polyvinyl alcohol, butyralmodifizierter polyvinyl alcohol, other modified polyvinyl alcohols, hydroxyethylcellulose, methylcellulose, carboxymethylcellulose, styrene-maleic anhydride copolymers, styrene -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 resins, silicone resins, petroleum synthetic resins, terpene resins, ketone resins and coumarone resins dissolved in a solvent such as water, alcohol, ketone, ester, hydrocarbon, etc. or emulsified or dispersed in water or solvent have been.
Diese Bindemittel können je nach dem Verwendungszweck in Kombination verwendet werden.These binders can be used in combination depending on the purpose.
Als erfindungsgemäße Füllstoffe können sowohl anorganische wie organische Füllstoffe verwendet werden. Typische Beispiele für die erfindungsgemäßen Füllstoffe sind Siliciumdioxid, Calciumcarbonat, Kaolin, gebrannter Kaolin, Diatomeenerde, Talk, Titanoxid 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 oxide 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 Fullstoff, bezogen auf 1 Gewichtsteil des erfindungsgemäßen basischen farblosen Farbstoffs zu verwenden, 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 add 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 use, and 10-25 parts by weight of binder, based on the total substance content.
Das erfindungsgemäße wärmeempfindliche Aufzeichnungsblatt wird hergestellt, indem man eine 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 applying a 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. from a polymer, are applied 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, Sandschleifvorrichtung 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 according to the invention, the colorless basic chromogenic dye and optionally the other additives are ground to a particle size of several microns or smaller by means of a grinding device such as a ball mill, attritor, sand grinder etc. or by means of a suitable emulsifying device. Various additives are added to produce the coating composition of the invention.
Zur weiteren Verbesserung der Sensibilität kann eine rückseitige Überzugsschicht, z.B. aus einem den Füllstoff enthaltenden Polymerisat, weiter unter der Farbentwicklungsschicht aufgebracht werdenTo further improve the sensitivity, a back coating layer, for example made of a polymer containing the filler, can be applied further under the color development layer
Der Grund dafür, daß keine Farbänderung bei der Beschreibung des erfindungsgemäßen Aufzeichnungsblattes mit öliger Tinte auftritt, ist vielleicht folgender:The reason why there is no color change in the description of the oily ink recording sheet of the present invention is perhaps as follows:
Bei Beschreibung des Blattes mit der öligen Tinte mittels einer Markierungsfeder werden das Farbentwicklungsmittel, der Leukofarbstoff und der Sensibilisator der wärmeempfindlichen Farbenwicklungsschicht, in dem in der Tinte enthaltenen organischen Lösungsmittel aufgelöst. Nach Verflüchtigung des Lösungsmittels wird eine Farbentwicklungszusammensetzung, die aus dem Farbentwicklungsmittel, dem Leukofarbstoff und dem Sensibilisator besteht, an der Beschreibungsstelle gebildet. Beispielsweise werden bei der Verwendung einer roten Tinte die rote Farbe und die von der erwähnten Zusammensetzung entwickelte Farbe vermischt, wodurch eine dunkle Beschreibungsfarbe gebildet wird.When the sheet with the oily ink is written on by a marker pen, the color developing agent, the leuco dye and the sensitizer of the heat-sensitive color-developing layer are dissolved in the organic solvent contained in the ink. After volatilization of the solvent, a color developing composition consisting of the color developing agent, the leuco dye and the sensitizer is formed at the description point. For example, when using a red ink, the red color and the color developed by the composition mentioned are mixed, thereby forming a dark descriptive color.
Das erfindungsgemäße wärmeempfindliche Aufzeichnungsblatt umfaßt 4-Hydroxy-4′-n-propoxydiphenylsulfon als ein besonderes Farbentwicklungsmittel, einen Leukofarbstoff und einen besonderen Sensibilisator. Diese Materialien haben eine sehr geringe Löslichkeit im Lösungsmittel, und sie bilden bei der Verflüchtigung des Lösungsmittels praktisch keine Farbentwicklungszusammensetzung, so daß keine Farbänderung bei der Verwendung einer öligen Tinte erfolgt.The heat-sensitive recording sheet of the present invention comprises 4-hydroxy-4'-n-propoxydiphenyl sulfone as a special color developing agent, a leuco dye and a special sensitizer. These materials have very low solubility in the solvent and they form practically no color developing composition upon volatilization of the solvent, so that there is no color change when using an oily ink.
Die erfindungsgemäß verwendeten Farbentwicklungsmittel und der Farbstoff haben eine größere Lösungsdiffusionsgeschwindigkeit und sehr große Löslichkeit im Sensibilisator. Bei einer physiko-chemischen Reaktion des organischen Lösungsmittels, des Sensibilisators und des Leukofarbstoffs in der Hitze erfolgt eine rasche Bildung einer Farbentwicklungszusammensetzung, so daß ein gefärbtes Bild mit einer hohen Dichte erhalten wird.The color developing agents and the dye used according to the invention have a higher solution diffusion rate and very high solubility in the sensitizer. When the organic solvent, the sensitizer and the leuco dye undergo a physico-chemical reaction in the heat, a color developing composition is rapidly formed, so that a colored image having a high density is obtained.
Weiter hat der erfindungsgemäße Sensibilisator die Eigenschaft, daß er bei seiner Auflösung in dem in der öligen Tinte enthaltenen organischen Lösungsmittel und nach Verflüchtigung des Lösungsmittels nur schwer kristallisiert. Daher werden bei der Beschreibung mit der öligen Tinte keine weißen Kristalle gebildet.Furthermore, the sensitizer according to the invention has the property that when it is dissolved in the organic solvent contained in the oily ink and after the solvent has volatilized, it crystallizes only with difficulty. Therefore, white crystals are not formed in the description with the oily ink.
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" means "parts".
Die Lösungen der obigen Zusammensetzungen wurden in einer Sandschleifvorrichtung einzeln bis zur Teilchengröße von 1 Mikron vermahlen. Die Lösungen wurden im folgenden Verhaltnis miteinander vermischt; man erhält dabei eine wärmeempfindliche Beschichtungsmasse.
Diese Beschichtungsmasse wurde in einer Beschichtungsmenge von 6,0 g/m² auf ein Basispapier mit einem Gewicht von 50 g/m² aufgetragen, getrocknet und superkalandriert, um eine Glätte von 200-600 Sekunden einzustellen. Man erhielt ein eine schwarze Farbe entwickelndes wärmeempfindliches Aufzeichnungsblatt.This coating composition was applied in a coating amount of 6.0 g / m² on a base paper with a weight of 50 g / m², dried and supercalendered to achieve a smoothness of 200-600 seconds. A black color developing heat-sensitive recording sheet was obtained.
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 erhalt dabei eine wärmeempfindliche Beschichtungsmasse.
Man erhielt in der gleichen Weise wie im Beispiel 1 ein wärmeempfindliches Aufzeichnungsblatt.A heat-sensitive recording sheet was obtained in the same manner as in Example 1.
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 erhalt dabei eine wärmeempfindliche Beschichtungsmasse.
Die gemäß den Beispielen und Vergleichsbeispielen erhaltenen wärmeempfindlichen Aufzeichnungsblätter wurden hinsichtlich ihrer Qualität geprüft und die Prüfungsergebnisse wurden in der Tabelle 1 zusammengefaßt.
The heat-sensitive recording sheets obtained according to the examples and comparative examples were tested for their quality, and the test results were summarized in Table 1.
- (1) Statische Bilddichte: Ein wärmeempfindliches Aufzeichnungsblatt wird 5 Sekunden unter einem Druck von 10 g/cm² gegen eine auf 105 °C erhitzte Platte gepreßt. Die statische Bilddichte wird mit einem MacBeth-Dichtemesser (RD-914, Verwendung des Amber-Filters; unten gelten die gleichen Bedingungen) bestimmt.
- (2) Dynamische Bilddichte: Ein wärmeempfindliches Aufzeichnungsblatt wird bei einer angelegten Energie von 0,58 mj/Dor und einer Pulsbreite von 0,97 ms unter Verwendung einer Faksimiliermaschine UF-1000 (von Matsushita Graphic Communication Systems, Inc.) aufgezeichnet und mit einem MacBeth-Dichtemesser bestimmt.
- (3) Farbänderung durch ölige Tinte: Ein wärmeempfindliches Aufzeichnungsblatt wird mit der öligen Markierungstinte Nr. 500 (von Teranishi Kagaku Co.) beschrieben. Der Farbänderungsgrad wird visuell im Vergleich mit der originalen Rotfarbe bestimmt.
- O :
- fast keine Farbänderung
- Δ :
- deutliche Farbänderung
- X :
- erhebliche Farbänderung
- (4) Bildung weißer Kristalle: Ein wärmeempfindliches Aufzeichnungsblatt wird in der gleichen Weise wie bei der obigen Anmerkung (3) beschrieben. Nach 15 Minuten wird die Bildung weißer Kristalle visuell bestimmt.
- O :
- keine Bildung weißer Kristalle
- X :
- Bildung weißer Kristalle
Die Erfindung weist folgende Vorteile auf:
- 1) Überlegene Beschreibbarkeit mit öliger Tinte bei Verwendung einer Markierungsfeder, weil weder Farbänderung noch Bildung weißer Kristalle erfolgt.
- 2) Bessere thermische Ansprechbarkeit.
- (1) Static image density: A heat-sensitive recording sheet is pressed against a plate heated to 105 ° C for 5 seconds under a pressure of 10 g / cm². The static image density is determined using a MacBeth density meter (RD-914, use of the amber filter; the same conditions apply below).
- (2) Dynamic image density: A heat sensitive recording sheet is recorded at an applied energy of 0.58 mj / Dor and a pulse width of 0.97 ms using a UF-1000 facsimile machine (from Matsushita Graphic Communication Systems, Inc.) and recorded with a MacBeth density meter determined.
- (3) Color change by oily ink: A heat-sensitive recording sheet is written with the oily marking ink No. 500 (from Teranishi Kagaku Co.). The degree of color change is determined visually in comparison with the original red color.
- O:
- almost no color change
- Δ:
- significant color change
- X:
- significant color change
- (4) White crystal formation: A heat-sensitive recording sheet is described in the same manner as in the above note (3). After 15 minutes, the formation of white crystals is determined visually.
- O:
- no formation of white crystals
- X:
- Formation of white crystals
The invention has the following advantages:
- 1) Superior writability with oily ink when using a marker pen because there is no color change or formation of white crystals.
- 2) Better thermal responsiveness.
Claims (8)
- Heat sensitive recording sheet with a heat sensitive colour developing layer on a carrier, wherein the 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 4-hydroxy-4'-n-propoxydiphenylsulphone as organic colour developing agent and at least one sensitiser from the group 1,2-di(3-methylphenoxy)ethane, di(p-methylbenzyl) oxalate, p-benzylbiphenyl, β-benzyloxynaphthalene and 4-biphenyl-p-tolyl ether.
- 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 one 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 or 2, characterised in that the basic colourless or weakly coloured chromogenic dyestuff is at least one from the group of dyestuffs of the triphenylmethane, fluorane, azaphthalide and fluorene series.
- Heat sensitive recording sheet according to Claim 1, characterized in that the colour developing layer further contains a stabiliser.
- Heat sensitive recording sheet according to Claim 1, characterized in that the stabilizer is at least one compound from the group 4,4'-butylidene-(6-t-butyl-3-methylphenol), 2,2'-di-t-butyl-5,5'-dimethyl-4,4'-sulphonyldiphenol, 1,1,3-tris-(2-methyl-4-hydroxy-5-cyclohexyl)butane and 1,1,3-tris(2-methyl-4-hydroxy-5-t-butylphenyl)butane.
- 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.
- Heat sensitive recording sheet according to Claim 1, characterised in that a rearside overcoat layer of a polymer containing a filler is further applied below the colour developing layer.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP267590/89 | 1989-10-13 | ||
| JP1267590A JPH0745266B2 (en) | 1989-10-13 | 1989-10-13 | Thermal recording sheet |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| EP0422680A2 EP0422680A2 (en) | 1991-04-17 |
| EP0422680A3 EP0422680A3 (en) | 1991-06-05 |
| EP0422680B1 true EP0422680B1 (en) | 1994-06-01 |
Family
ID=17446870
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP90119625A Expired - Lifetime EP0422680B1 (en) | 1989-10-13 | 1990-10-12 | Heat-sensitive recording sheet |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US5118656A (en) |
| EP (1) | EP0422680B1 (en) |
| JP (1) | JPH0745266B2 (en) |
| CA (1) | CA2027362C (en) |
| DE (1) | DE59005918D1 (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2970825B2 (en) * | 1992-01-23 | 1999-11-02 | 日本製紙株式会社 | Thermal recording sheet |
| JP2727849B2 (en) * | 1992-03-18 | 1998-03-18 | 日本製紙株式会社 | Thermal recording sheet |
| EP0585127B1 (en) * | 1992-08-28 | 1997-12-29 | Nippon Paper Industries Co., Ltd. | Thermal Recording sheet |
| US5821196A (en) * | 1997-04-10 | 1998-10-13 | Appleton Papers Inc. | Thermally-responsive record material |
| US8440370B2 (en) * | 2007-06-28 | 2013-05-14 | Dublin Institute Of Technology | Method of making a reflection hologram and a reflection hologram |
Family Cites Families (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5887094A (en) * | 1981-11-18 | 1983-05-24 | Fuji Photo Film Co Ltd | Heat-sensitive recording material |
| JPS59101392A (en) * | 1982-11-30 | 1984-06-11 | Kanzaki Paper Mfg Co Ltd | Heat-sensitive recording medium |
| DE3378361D1 (en) * | 1983-01-17 | 1988-12-08 | Yoshitomi Pharmaceutical | Heat-sensitive recording paper |
| JPS6082382A (en) * | 1983-10-14 | 1985-05-10 | Nippon Steel Chem Co Ltd | Thermal recording material |
| JPS6153084A (en) * | 1984-08-23 | 1986-03-15 | Jujo Paper Co Ltd | Thermal recording paper |
| JPS61233586A (en) * | 1985-04-09 | 1986-10-17 | Mitsubishi Paper Mills Ltd | Thermal recording material |
| JPS6248587A (en) * | 1985-08-27 | 1987-03-03 | Kanzaki Paper Mfg Co Ltd | Thermal recording material |
| JPS62119095A (en) * | 1985-11-20 | 1987-05-30 | Tomoegawa Paper Co Ltd | Thermal recording material |
| JPS62130878A (en) * | 1985-12-03 | 1987-06-13 | Shin Nisso Kako Co Ltd | Thermal color forming recording material |
| US4814320A (en) * | 1986-04-15 | 1989-03-21 | Yamada Chemical Co., Ltd. | Heat-sensitive recording material |
| JPS63272582A (en) * | 1987-04-30 | 1988-11-10 | Jujo Paper Co Ltd | Thermal recording paper |
| JPS6414076A (en) * | 1987-07-08 | 1989-01-18 | Ricoh Kk | Thermal recording material |
-
1989
- 1989-10-13 JP JP1267590A patent/JPH0745266B2/en not_active Expired - Lifetime
-
1990
- 1990-10-01 US US07/590,807 patent/US5118656A/en not_active Expired - Lifetime
- 1990-10-11 CA CA002027362A patent/CA2027362C/en not_active Expired - Lifetime
- 1990-10-12 DE DE59005918T patent/DE59005918D1/en not_active Expired - Lifetime
- 1990-10-12 EP EP90119625A patent/EP0422680B1/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| CA2027362A1 (en) | 1991-04-14 |
| JPH0745266B2 (en) | 1995-05-17 |
| US5118656A (en) | 1992-06-02 |
| JPH03128285A (en) | 1991-05-31 |
| EP0422680A2 (en) | 1991-04-17 |
| CA2027362C (en) | 2001-09-04 |
| DE59005918D1 (en) | 1994-07-07 |
| EP0422680A3 (en) | 1991-06-05 |
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