EP0499045B1 - Colour-former preparations - Google Patents
Colour-former preparations Download PDFInfo
- Publication number
- EP0499045B1 EP0499045B1 EP92100814A EP92100814A EP0499045B1 EP 0499045 B1 EP0499045 B1 EP 0499045B1 EP 92100814 A EP92100814 A EP 92100814A EP 92100814 A EP92100814 A EP 92100814A EP 0499045 B1 EP0499045 B1 EP 0499045B1
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- EP
- European Patent Office
- Prior art keywords
- color former
- color
- preparations
- preparation
- 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.)
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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
- B41M5/124—Duplicating or marking methods; Sheet materials for use therein using pressure to make a masked colour visible, e.g. to make a coloured support visible, to create an opaque or transparent pattern, or to form colour by uniting colour-forming components
- B41M5/132—Chemical colour-forming components; Additives or binders therefor
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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
- B41M5/124—Duplicating or marking methods; Sheet materials for use therein using pressure to make a masked colour visible, e.g. to make a coloured support visible, to create an opaque or transparent pattern, or to form colour by uniting colour-forming components
- B41M5/165—Duplicating or marking methods; Sheet materials for use therein using pressure to make a masked colour visible, e.g. to make a coloured support visible, to create an opaque or transparent pattern, or to form colour by uniting colour-forming components characterised by the use of microcapsules; Special solvents for incorporating the ingredients
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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
Definitions
- the invention further relates to aqueous dispersions which contain one or more of these color former formulations and to dispersions which additionally contain one or more electron acceptors as color developers.
- the invention also relates to the use of the color former preparations for the production of heat and pressure-sensitive recording materials and to these recording materials themselves.
- a pressure- or heat-sensitive layer is applied, which contains a colorless or only slightly colored color former, which gives a color reaction in contact with an electron acceptor.
- microcapsules are used for this coating, which contain the color former dissolved in non-volatile or only slightly volatile solvents (core oils) and which are destroyed by applying pressure, with a suitable softening temperature of the wall material, but also by selective heat.
- the color former released in this way then comes into contact with the acidic color developer, which can be dispersed either in the same layer or in a second layer on the same support or, as in the case of so-called reaction carbonless papers, on the opposite side of another sheet of paper.
- non-encapsulated color formers and developers are applied to the carrier in one layer. They are dispersed in the form of disjointed particles in a binder. When the temperature rises, the components melt and thus enable the coloring reaction between color former and developer.
- the wall material has to meet special requirements, since it must soften at a suitable (not too high) temperature.
- the invention was therefore based on the object of finding color former formulations which enable the production of heat and pressure-sensitive recording materials free of background staining in a cost-effective manner.
- aqueous dispersions containing one or more of these color former preparations and those containing one or more of these color former preparations and one or more electron acceptors as developers have been found.
- the color former preparations according to the invention contain a core of solid particles of a color former. Suitable for this are the color formers known to be used in heat- and pressure-sensitive recording media, which are themselves colorless or hardly colored and develop their color in contact with an electron acceptor by donating an electron or taking up a proton.
- the preferred color formers include, for example, the lactones, such as, in particular, crystal violet lactone and the rhodamine and diazarhodamine lactones, the phthalides, the spirodipyrans, in particular the spirodibenzopyrans, and especially the fluoranes.
- color formers are desired which give a black color are e.g. 2-N-Phenylamino-3-methyl-6-dialkyl- or -diarylaminofluorane is particularly preferred.
- color former mixtures which may also contain color formers from several of the compound classes mentioned, can also be used to achieve the desired color, e.g. Black to deliver.
- the first shell surrounding the core of solid color former consists of a water-soluble, non-ionic polymer.
- Polymers which do not contain any free hydroxyl groups in particular, for example, polyalkylene glycol ethers such as polyethylene, polypropylene and polybutylene glycol ether and methyl cellulose with the highest possible proportion of etherified hydroxyl groups, are particularly suitable here.
- Polyvinylpyrrolidone which generally has K values from 10 to 100, preferably from 30 to 90, is very particularly suitable (determination of the K values according to H. Fikentscher, Cellulosechemie, Volume 13, pp. 48-64 and 71-74 ( 1932) in 1% by weight (at K values below 30 in 5% by weight) aqueous solution at 25 ° C).
- the second shell is formed by a cross-linked polymer.
- thermoplastic polymers such as polyamides, polyurethanes, polyisocyanates, polyacrylates, copolymers of acrylates and methacrylates, polybutadiene, polycondensates of urea, melamine, phenol and formaldehyde and gelatin, which have been cured in a known manner and thus have been rendered essentially water-insoluble, are suitable for this.
- Crosslinked melamine-formaldehyde resin which is described, for example, in US Pat. No. 4,406,816, is particularly preferred.
- the color former preparations according to the invention can advantageously be obtained in two process steps.
- the first shell is advantageously made by rubbing the color former with an aqueous dispersion of the water-soluble, nonionic polymer, preferably a polyvinylpyrrolidone dispersion, which generally has a content of 1 to 20% by weight, preferably 5 to 15% by weight.
- Polyvinylpyrrolidone has, applied in an aqueous medium to a particle size of usually 0.1 to 3 microns. Grinding is advantageously carried out in a pearl mill.
- 0.1 to 10 preferably 0.5 to 5% by weight, based on the color former, of polymer is used.
- viscosity-reducing agents such as acrylic acid / styrene copolymers in amounts of generally 1 to 20, preferably 5 to 15,% by weight, based on solid polyvinylpyrrolidone.
- the color former dispersion obtained in the first process step is generally mixed with a protective colloid and an oligomer, which is then added, for example, by adding acid is cured and is deposited on the pretreated color former particles.
- 1 to 20, particularly 5 to 10% by weight, based on the color former, of a mixture of a 20% by weight aqueous solution of polyacrylamidomethylene propanesulfonic acid and a 70% by weight aqueous solution of melamine-formaldehyde solution are preferably used.
- Curing is advantageously carried out by adding generally 0.1 to 5, preferably 1 to 3% by weight, based on the color former, of an electrolyte such as an alkali metal or alkaline earth metal salt of an inorganic acid, e.g. Sodium chloride, potassium chloride, disodium hydrogen phosphate and especially sodium dihydrogen phosphate, and an acid such as formic acid, with which a pH value of about 3.5 to 4.5 is set, at a temperature of about 70 ° C.
- an electrolyte such as an alkali metal or alkaline earth metal salt of an inorganic acid, e.g. Sodium chloride, potassium chloride, diso
- the color former preparations according to the invention have the great advantage that they have no visible intrinsic coloration, since a pre-development of the color former during its fine grinding required for the coating of heat- and pressure-sensitive papers is prevented by the addition of the polymers mentioned, in particular polyvinylpyrrolidone.
- aqueous dispersions can be mixed with aqueous developer dispersions without any discoloration.
- a reaction of the color former with any dissolved developer is prevented by the double protective cover of the color former.
- the mixtures are generally stable for more than 24 hours, so that they can be used for other purposes without any problems.
- the color former preparations according to the invention can advantageously be used in heat- and pressure-sensitive recording materials.
- aqueous dispersions of the color former preparations are mixed with about 55% by weight aqueous developer dispersions, depending on the type of color former and developer, in a weight ratio of about 1: 4 to 1:15 and with a Layer thickness of about 4 to 7 g / m 2 is applied to the support, usually paper, the surface of which has generally been smoothed. The paper coated in this way is then dried.
- Phenol-based developers are preferred for the recording materials of the invention. Among them, 4,4'-isopropylidene diphenol (bisphenol A) is particularly preferred.
- the recording materials according to the invention can contain further additives which are usually used in the heat- or pressure-sensitive layer. These are e.g. Lubricants such as zinc stearate, which help smooth the paper surface. Sensitizers can also be used, particularly in heat-sensitive layers. These are special waxes with low melting points, which lower the softening temperature and thus accelerate development.
- Lubricants such as zinc stearate, which help smooth the paper surface.
- Sensitizers can also be used, particularly in heat-sensitive layers. These are special waxes with low melting points, which lower the softening temperature and thus accelerate development.
- the pressure- and heat-sensitive recording materials according to the invention have no visible background stains. Photometric measurements show intensity values well below 1 K / S ⁇ 100. The blackening or coloring in general that is achieved when printing are well above 40 K / S100 (evaluation according to Kubelka-Munk; Kunststoff-Rundschau 17, pp. 282-291 (1970)). The requirements that must be placed on such materials are thus clearly met.
- the recording materials according to the invention also have the great advantage that color formers and developers can be selected in any manner without having to do without particularly reactive color formers and water-soluble developers.
- color formers and developers can be selected in any manner without having to do without particularly reactive color formers and water-soluble developers.
- the color former dispersions obtained under a) were diluted to a color former content of 13% by weight and mixed in a weight ratio of 1: 1 with a 55% by weight aqueous dispersion of bisphenol A.
- the thermal dispersions were applied to coating base paper with a 30 ⁇ m doctor blade in such a way that a layer thickness of approximately 6 g / m 2 resulted.
- the coated paper was dried with warm air at a maximum of 50 ° C.
Description
Die vorliegende Erfindung betrifft neue Farbbildner-Zubereitungen aus
- A) einem Kern aus festen Teilchen eines Farbbildners,
- B) einer ersten Hülle aus einem wasserlöslichen, nicht-ionogenen Polymeren und
- C) einer zweiten Hülle aus einem vernetzten Polymeren.
- A) a core of solid particles of a color former,
- B) a first shell made of a water-soluble, non-ionic polymer and
- C) a second shell made of a cross-linked polymer.
Weiterhin betrifft die Erfindung wäßrige Dispersionen, die eine oder mehrere dieser Farbbildner-Zubereitungen enthalten, sowie solche Dispersionen, die zusätzlich einen oder mehrere Elektronenakzeptoren als Farbentwickler enthalten.The invention further relates to aqueous dispersions which contain one or more of these color former formulations and to dispersions which additionally contain one or more electron acceptors as color developers.
Außerdem betrifft die Erfindung die Verwendung der Farbbildnerzubereitungen zur Herstellung von wärme- und druckempfindlichen Aufzeichnungsmaterialien sowie diese Aufzeichnungsmaterialien selbst.The invention also relates to the use of the color former preparations for the production of heat and pressure-sensitive recording materials and to these recording materials themselves.
Der Aufbau und die Wirkungsweise von druck- und wärmeempfindlichen Aufzeichnungsmaterialien sind wohlbekannt.The structure and operation of pressure and heat sensitive recording materials are well known.
Auf einem Träger, in der Regel Papier, Karton oder Folie, ist eine druck- oder wärmeempfindliche Schicht aufgebracht, die einen farblosen oder nur schwach gefärbten Farbbildner enthält, der in Kontakt mit einem Elektronenakzeptor eine Farbreaktion ergibt.On a carrier, usually paper, cardboard or film, a pressure- or heat-sensitive layer is applied, which contains a colorless or only slightly colored color former, which gives a color reaction in contact with an electron acceptor.
Insbesondere bei druckempfindlichen Systemen werden für diese Beschichtung Mikrokapseln verwendet, die den Farbbildner in nicht oder nur schwer flüchtigen Lösungsmitteln (Kernölen) gelöst enthalten und die durch Druckausübung, bei geeigneter Erweichungstemperatur des Wandmaterials aber auch durch punktuelle Wärmeeinwirkung, zerstört werden. Der auf diese Weise freiwerdene Farbbildner kommt dann in Kontakt mit dem sauren Farbentwickler, der entweder in derselben Schicht oder in einer zweiten Schicht auf demselben Träger oder, wie bei den sog. Reaktionsdurchschreibepapieren, auf der gegenüberliegenden Seite eines weiteren Blattes Papier dispergiert sein kann.In particular in pressure-sensitive systems, microcapsules are used for this coating, which contain the color former dissolved in non-volatile or only slightly volatile solvents (core oils) and which are destroyed by applying pressure, with a suitable softening temperature of the wall material, but also by selective heat. The color former released in this way then comes into contact with the acidic color developer, which can be dispersed either in the same layer or in a second layer on the same support or, as in the case of so-called reaction carbonless papers, on the opposite side of another sheet of paper.
Bei wärmeempfindlichen Systemen sind meist nicht verkapselter Farbbildner und Entwickler in einer Schicht auf den Träger aufgebracht. Sie sind dabei in Form unzusammenhängender Teilchen in einem Bindemittel dispergiert. Bei Temperaturerhöhung schmelzen die Komponenten und ermöglichen so die farbgebende Reaktion zwischen Farbbildner und Entwickler.In heat-sensitive systems, mostly non-encapsulated color formers and developers are applied to the carrier in one layer. They are dispersed in the form of disjointed particles in a binder. When the temperature rises, the components melt and thus enable the coloring reaction between color former and developer.
Besonders bei den letztgenannten Systemen besteht das Problem, daß bereits bei ihrer Präparation qualitätsvermindernde Hintergrundanfärbungen auftreten können. Diese entstehen durch Vorabentwicklung des Farbbildners, zum einen bei seiner für die Herstellung einer Dispersion erforderlichen extrem feinen Anreibung in wäßrigem Medium, insbesondere wenn dabei Dispergierhilfsmittel wie Polyvinylalkohol zugesetzt werden, und zum anderen vor allem bei Verwendung kostengünstiger, in geringen Mengen wasserlöslicher Entwickler durch Reaktion von Farbbildner und Entwickler bei Aufstreichen ihrer wäßrigen Dispersionen auf die Papieroberfläche. Dies ist insbesondere der Fall bei schnell reagierenden Systemen mit reaktiven Komponenten, wie sie beispielsweise für das Telefax-Verfahren erwünscht sind.The problem with the latter systems, in particular, is that background stains which reduce quality can occur even during their preparation. These arise from advance development of the color former, on the one hand in the extremely fine grinding in an aqueous medium required for the preparation of a dispersion, in particular if dispersing aids such as polyvinyl alcohol are added, and on the other hand especially when using inexpensive, small amounts of water-soluble developers by reacting Color formers and developers spread their aqueous dispersions on the paper surface. This is particularly the case with fast-reacting systems with reactive components, such as are desired for the fax process, for example.
Auch durch Mikroverkapselung lassen sich Hintergrundfärbungen bei den wärmeempfindlichen Systemen nicht vollständig vermeiden, da immer geringe Mengen an nichtverkapseltem Farbbildner vorliegen. Außerdem sind an das Wandmaterial besondere Anforderungen zu stellen, da es bei geeigneter (nicht zu hoher) Temperatur erweichen muß.Even microencapsulation cannot completely avoid background coloring in the heat-sensitive systems, since there are always small amounts of non-encapsulated color former. In addition, the wall material has to meet special requirements, since it must soften at a suitable (not too high) temperature.
Der Erfindung lag daher die Aufgabe zugrunde, Farbbildner-Zubereitungen zu finden, welche die Herstellung hintergrundanfärbungsfreier wärme- und druckempfindlicher Aufzeichnungsmaterialien auf kostengünstige Weise ermöglichen.The invention was therefore based on the object of finding color former formulations which enable the production of heat and pressure-sensitive recording materials free of background staining in a cost-effective manner.
Demgemäß wurden Farbbildner-Zubereitungen aus
- A) einem Kern aus festen Teilchen eines Farbbildners,
- B) einer ersten Hülle aus einem wasserlöslichen, nicht-ionogenen Polymeren und
- C) einer zweiten Hülle aus einem vernetzten Polymeren
- A) a core of solid particles of a color former,
- B) a first shell made of a water-soluble, non-ionic polymer and
- C) a second shell made of a cross-linked polymer
Weiterhin wurde ein Verfahren zur Herstellung dieser Farbbildner-Zubereitungen durch
- a) Umhüllung von festen Farbbildnerteilchen mit einem wasserlöslichen, nicht-ionogenen Polymeren durch Anreiben des Farbbildners mit dem Polymeren in wäßriger Dispersion und
- b) weitere Umhüllung der in Schritt a) erhaltenen Teilchen mit einem vernetzten Polymeren durch Zugabe einer wäßrigen Dispersion des entsprechenden Oligomeren und dessen Aushärtung zu einer zusammenhängenden, die in Schritt a) erhaltenen Teilchen umhüllenden Schicht
- a) coating solid color former particles with a water-soluble, non-ionic polymer by rubbing the color former with the polymer in aqueous dispersion and
- b) further coating the particles obtained in step a) with a crosslinked polymer by adding an aqueous dispersion of the corresponding oligomer and curing it to form a coherent layer enveloping the particles obtained in step a)
Außerdem wurden wäßrige Dispersionen, enthaltend eine oder mehrere dieser Farbbildner-Zubereitungen, und solche, enthaltend eine oder mehrere dieser Farbbildner-Zubereitungen und einen oder mehrere Elektronenakzeptoren als Entwickler, gefunden.In addition, aqueous dispersions containing one or more of these color former preparations and those containing one or more of these color former preparations and one or more electron acceptors as developers have been found.
Nicht zuletzt wurden die Verwendung dieser Farbbildner-Zubereitungen zur Herstellung von wärme- und druckempfindlichen Aufzeichnungsmaterialien sowie diese Aufzeichnungsmaterialien selbst gefunden.Last but not least, the use of these color former preparations for the production of heat- and pressure-sensitive recording materials and these recording materials themselves were found.
Die erfindungsgemäßen Farbbildner-Zubereitungen enthalten einen Kern aus festen Teilchen eines Farbbildners. Hierfür geeignet sind die bekanntermaßen in wärme- und druckempfindlichen Aufzeichnungsmedien eingesetzten Farbbildner, die selbst farblos oder kaum gefärbt sind und ihre Farbe in Kontakt mit einem Elektronenakzeptor durch Abgabe eines Elektrons oder Aufnahme eines Protons entwickeln.The color former preparations according to the invention contain a core of solid particles of a color former. Suitable for this are the color formers known to be used in heat- and pressure-sensitive recording media, which are themselves colorless or hardly colored and develop their color in contact with an electron acceptor by donating an electron or taking up a proton.
Als bevorzugte Farbbildner seien beispielsweise die Lactone wie besonders Kristallviolettlacton und die Rhodamin- und Diazarhodaminlactone, die Phthalide, die Spirodipyrane wie besonders die Spirodibenzopyrane und vor allem die Fluorane aufgeführt.The preferred color formers include, for example, the lactones, such as, in particular, crystal violet lactone and the rhodamine and diazarhodamine lactones, the phthalides, the spirodipyrans, in particular the spirodibenzopyrans, and especially the fluoranes.
Da für viele Verwendungszwecke, u.a. für das Telefax-Verfahren, Farbbildner erwünscht sind, die eine schwarze Farbe ergeben, sind z.B. 2-N-Phenylamino-3-methyl-6-dialkyl- oder -diarylaminofluorane besonders bevorzugt.As for many uses, including for the facsimile process, color formers are desired which give a black color are e.g. 2-N-Phenylamino-3-methyl-6-dialkyl- or -diarylaminofluorane is particularly preferred.
Unter diesen zeichnet sich das 2-N-Phenylamino-3-methyl-6-diethylaminofluoran
durch seine hohe Reaktivität ganz besonders aus.Among these is the 2-N-phenylamino-3-methyl-6-diethylaminofluoran
very special due to its high reactivity.
Selbstverständlich können auch Farbbildner-Mischungen, die auch Farbbildner aus mehreren der genannten Verbindungsklassen enthalten können, eingesetzt werden, um die gewünschte Farbe, z.B. Schwarz, zu liefern.Of course, color former mixtures, which may also contain color formers from several of the compound classes mentioned, can also be used to achieve the desired color, e.g. Black to deliver.
Die erste den Kern aus festem Farbbildner umschließende Hülle besteht aus einem wasserlöslichen, nicht-ionogen Polymeren. Dabei kommen vor allem solche Polymere in Frage, die keine freien Hydroxylgruppen enthalten, also beispielsweise Polyalkylenglykolether wie Polyethylen-, Polypropylen- und Polybutylenglykolether und Methylcellulose mit möglichst hohem Anteil an veretherten Hydroxylgruppen. Ganz besonders geeignet ist Polyvinylpyrrolidon, das in der Regel K-Werte von 10 bis 100, bevorzugt von 30 bis 90 aufweist (Bestimmung der K-Werte nach H. Fikentscher, Cellulosechemie, Band 13, S. 48-64 und 71-74 (1932) in 1 gew.-%iger (bei K-Werten unter 30 in 5 gew.-%iger) wäßriger Lösung bei 25°C).The first shell surrounding the core of solid color former consists of a water-soluble, non-ionic polymer. Polymers which do not contain any free hydroxyl groups, in particular, for example, polyalkylene glycol ethers such as polyethylene, polypropylene and polybutylene glycol ether and methyl cellulose with the highest possible proportion of etherified hydroxyl groups, are particularly suitable here. Polyvinylpyrrolidone, which generally has K values from 10 to 100, preferably from 30 to 90, is very particularly suitable (determination of the K values according to H. Fikentscher, Cellulosechemie, Volume 13, pp. 48-64 and 71-74 ( 1932) in 1% by weight (at K values below 30 in 5% by weight) aqueous solution at 25 ° C).
Die zweite Hülle wird von einem vernetzten Polymeren gebildet. Hierfür sind handelsübliche thermoplastische Polymere wie Polyamide, Polyurethane, Polyisocyanate, Polyacrylate, Copolymere aus Acrylaten und Methacrylaten, Polybutadien, Polykondensate aus Harnstoff, Melamin, Phenol und Formaldehyd sowie Gelatine geeignet, die auf bekannte Weise ausgehärtet und damit im wesentlichen wasserunlöslich gemacht worden sind. Besonders bevorzugt ist vernetztes Melamin-Formaldehyd-Harz, das beispielsweise in der US-A-4 406 816 beschrieben ist.The second shell is formed by a cross-linked polymer. Commercially available thermoplastic polymers such as polyamides, polyurethanes, polyisocyanates, polyacrylates, copolymers of acrylates and methacrylates, polybutadiene, polycondensates of urea, melamine, phenol and formaldehyde and gelatin, which have been cured in a known manner and thus have been rendered essentially water-insoluble, are suitable for this. Crosslinked melamine-formaldehyde resin, which is described, for example, in US Pat. No. 4,406,816, is particularly preferred.
Die erfindungsgemäßen Farbbildner-Zubereitungen sind vorteilhaft in zwei Verfahrensschritten zu erhalten.The color former preparations according to the invention can advantageously be obtained in two process steps.
Die erste Hülle wird zweckmäßigerweise durch Anreiben des Farbbildners mit einer wäßrigen Dispersion des wasserlöslichen, nicht-ionogen Polymeren, vorzugsweise einer Polyvinylpyrrolidon-Dispersion, die in der Regel einen Gehalt von 1 bis 20 Gew.-%, bevorzugt 5 bis 15 Gew.-% Polyvinylpyrrolidon aufweist, in wäßrigem Medium auf eine Teilchengröße von üblicherweise 0,1 bis 3 µm aufgebracht. Die Anreibung erfolgt vorteilhaft in einer Perlmühle. In der Regel werden dabei 0,1 bis 10, bevorzugt 0,5 bis 5 Gew.-%, bezogen auf den Farbbildner, an Polymerem verwendet. Oft ist es von Vorteil, viskositätserniedrigende Mittel wie Acrylsäure/Styrol-Copolymerisate in Mengen von in der Regel 1 bis 20, bevorzugt 5 bis 15 Gew.-%, bezogen auf festes Polyvinylpyrrolidon, zuzusetzen.The first shell is advantageously made by rubbing the color former with an aqueous dispersion of the water-soluble, nonionic polymer, preferably a polyvinylpyrrolidone dispersion, which generally has a content of 1 to 20% by weight, preferably 5 to 15% by weight. Polyvinylpyrrolidone has, applied in an aqueous medium to a particle size of usually 0.1 to 3 microns. Grinding is advantageously carried out in a pearl mill. As a rule, 0.1 to 10, preferably 0.5 to 5% by weight, based on the color former, of polymer is used. It is often advantageous to add viscosity-reducing agents such as acrylic acid / styrene copolymers in amounts of generally 1 to 20, preferably 5 to 15,% by weight, based on solid polyvinylpyrrolidone.
Für die zweite Umhüllung wird die im ersten Verfahrensschritt erhaltene Farbbildner-Dispersion in der Regel mit einem Schutzkolloid und einem Oligomeren versetzt, das anschließend z.B. durch Zugabe von Säure ausgehärtet wird und sich auf den vorbehandelten Farbbildnerteilchen niederschlägt.For the second coating, the color former dispersion obtained in the first process step is generally mixed with a protective colloid and an oligomer, which is then added, for example, by adding acid is cured and is deposited on the pretreated color former particles.
Vorzugsweise werden hierfür 1 bis 20, besonders 5 bis 10 Gew.-%, bezogen auf den Farbbildner, einer Mischung aus einer 20 gew.-%igen wäßrigen Lösung von Polyacrylamidomethylenpropansulfosäure und einer 70 gew.-%igen wäßrigen Lösung von Melamin-Formaldehyd-Harz im Gewichtsverhältnis 1:1 verwendet. Die Aushärtung erfolgt vorteilhaft durch Zugabe von in der Regel 0,1 bis 5, bevorzugt 1 bis 3 Gew.-%, bezogen auf den Farbbildner, eines Elektrolyten wie eines Alkali- oder Erdalkalimetallsalzes einer anorganischen Säure, z.B. Natriumchlorid, Kaliumchlorid, Dinatriumhydrogenphosphat und vor allem Natriumdihydrogenphosphat, und einer Säure wie Ameisensäure, mit der ein pH-Wert von etwa 3,5 bis 4,5 eingestellt wird, bei einer Temperatur von etwa 70°C.For this purpose, 1 to 20, particularly 5 to 10% by weight, based on the color former, of a mixture of a 20% by weight aqueous solution of polyacrylamidomethylene propanesulfonic acid and a 70% by weight aqueous solution of melamine-formaldehyde solution are preferably used. Resin in the weight ratio 1: 1 used. Curing is advantageously carried out by adding generally 0.1 to 5, preferably 1 to 3% by weight, based on the color former, of an electrolyte such as an alkali metal or alkaline earth metal salt of an inorganic acid, e.g. Sodium chloride, potassium chloride, disodium hydrogen phosphate and especially sodium dihydrogen phosphate, and an acid such as formic acid, with which a pH value of about 3.5 to 4.5 is set, at a temperature of about 70 ° C.
Die erfindungsgemäßen Farbbildner-Zubereitungen haben den großen Vorteil, daß sie keine sichtbare Eigenfärbung aufweisen, da eine Vorentwicklung des Farbbildners bei seiner für die Beschichtung von wärme- und druckempfindlichen Papieren erforderlichen feinen Mahlung durch die Zugabe der genannten Polymeren wie besonders Polyvinylpyrrolidon verhindert wird.The color former preparations according to the invention have the great advantage that they have no visible intrinsic coloration, since a pre-development of the color former during its fine grinding required for the coating of heat- and pressure-sensitive papers is prevented by the addition of the polymers mentioned, in particular polyvinylpyrrolidone.
Weiterhin können ihre wäßrigen Dispersionen mit wäßrigen Entwickler-Dispersionen gemischt werden, ohne daß eine Verfärbung eintritt. Eine Reaktion des Farbbildners mit eventuell vorhandenem gelösten Entwickler wird durch die doppelte Schutzhülle des Farbbildners verhindert. Die Mischungen sind in der Regel weit über 24 Stunden stabil, so daß sie problemlos für weitere Zwecke eingesetzt werden können.Furthermore, their aqueous dispersions can be mixed with aqueous developer dispersions without any discoloration. A reaction of the color former with any dissolved developer is prevented by the double protective cover of the color former. The mixtures are generally stable for more than 24 hours, so that they can be used for other purposes without any problems.
Es ist möglich, auch die Oberfläche des Entwicklers mit Polymeren zu belegen. In der Regel ist dies jedoch nicht erforderlich, da die Umhüllung des Farbbildners als Schutz ausreicht.It is also possible to cover the surface of the developer with polymers. As a rule, however, this is not necessary since the wrapping of the color former is sufficient as protection.
Die erfindungsgemäßen Farbbildner-Zubereitungen können vorteilhaft in wärme- und druckempfindlichen Aufzeichnungsmaterialien verwendet werden.The color former preparations according to the invention can advantageously be used in heat- and pressure-sensitive recording materials.
Die Herstellung dieser Materialien erfolgt dabei in üblicher Weise. Etwa 40 gew.-%ige wäßrige Dispersionen der Farbbildner-Zubereitungen werden mit etwa 55 gew.-%igen wäßrigen Entwickler-Dispersionen, je nach Art von Farbbildner und Entwickler, im Gewichtsverhältnis von etwa 1:4 bis 1:15 gemischt und mit einer Schichtstärke von etwa 4 bis 7 g/m2 auf den Träger, meist Papier, dessen Oberfläche in der Regel geglättet worden ist, aufgetragen. Das so beschichtete Papier wird anschließend getrocknet.These materials are produced in the usual way. About 40% by weight aqueous dispersions of the color former preparations are mixed with about 55% by weight aqueous developer dispersions, depending on the type of color former and developer, in a weight ratio of about 1: 4 to 1:15 and with a Layer thickness of about 4 to 7 g / m 2 is applied to the support, usually paper, the surface of which has generally been smoothed. The paper coated in this way is then dried.
Als Entwickler kommen dabei die bekanntermaßen in wärme- und druckempfindlichen Aufzeichnungsmaterialien eingesetzten Elektronenakzeptoren in Frage. Das sind beispielsweise
- solche auf der Basis von Silikaten wie aktiviertem und saurem Ton, Attapulgit, Bentonit, kolloidalem Siliciumdioxid und Aluminium-, Magnesium- und Zink-Silikaten,
- Carbonsäuren wie Oxal-, Malein-, Bernstein-, Wein-, Zitronen-, Stearinsäure, Benzoe- und p-tert.-Butylbenzoesäure, Phthalsäure, Gallussäure und Salicyl- und substituierte Salicylsäure wie 3-Isopropyl-, 3-Cyclohexyl-, 3,5-Di-tert.-butyl- und 3,5-Di(2-methylbenzyl)salicylsäure,
- Phenolderivate wie 4,4'-Isopropyliden-diphenol, -bis(2-chlorphenol), -bis(2,6-dichlorphenol), -bis(2,6-dibromphenol), -bis(2,6-dimethylphenol) und -bis(2-tert.-butylphenol), 2,2'-Methylen-bis(4-chlorphenol) und -bis(4-methyl-6-butylphenol), 4,4'-sec.-Butyliden-diphenol, 4,4'-Cyclohexyliden-diphenol und -bis(2-methylphenol), 2,2'-Dihydroxydiphenyl, 4-tert.-Butyl- und 4-Phenyl-phenol, Phenolharze, α- und β-Naphthol und
- Methyl-4-hydroxy-benzoat sowie
- Salze dieser organischen Akzeptoren.
- those based on silicates such as activated and acid clay, attapulgite, bentonite, colloidal silicon dioxide and aluminum, magnesium and zinc silicates,
- Carboxylic acids such as oxalic, maleic, succinic, tartaric, citric, stearic, benzoic and p-tert-butylbenzoic acid, phthalic, gallic and salicylic and substituted salicylic acid such as 3-isopropyl, 3-cyclohexyl, 3 , 5-di-tert-butyl- and 3,5-di (2-methylbenzyl) salicylic acid,
- Phenol derivatives such as 4,4'-isopropylidene-diphenol, -bis (2-chlorophenol), -bis (2,6-dichlorophenol), -bis (2,6-dibromophenol), -bis (2,6-dimethylphenol) and - bis (2-tert-butylphenol), 2,2'-methylene-bis (4-chlorophenol) and -bis (4-methyl-6-butylphenol), 4,4'-sec.-butylidene diphenol, 4, 4'-cyclohexylidene diphenol and bis (2-methylphenol), 2,2'-dihydroxydiphenyl, 4-tert-butyl and 4-phenylphenol, phenolic resins, α- and β-naphthol and
- Methyl 4-hydroxy benzoate and
- Salts of these organic acceptors.
Entwickler auf der Basis von Phenol sind für die erfindungsgemäßen Aufzeichnungsmaterialien bevorzugt. Darunter ist 4,4'-Isopropyliden-diphenol (Bisphenol A) besonders bevorzugt.Phenol-based developers are preferred for the recording materials of the invention. Among them, 4,4'-isopropylidene diphenol (bisphenol A) is particularly preferred.
Die erfindungsgemäßen Aufzeichnungsmaterialien können weitere üblicherweise verwendete Zusätze in der wärme- oder druckempfindlichen Schicht enthalten. Das sind z.B. Gleitmittel wie Zinkstearat, die zur Glättung der Papieroberfläche beitragen. Insbesondere in wärmeempfindlichen Schichten können auch Sensitizer eingesetzt werden. Das sind spezielle Wachse mit niedrigen Schmelzpunkten, die eine Erniedrigung der Erweichungstemperatur bewirken und damit die Entwicklung beschleunigen.The recording materials according to the invention can contain further additives which are usually used in the heat- or pressure-sensitive layer. These are e.g. Lubricants such as zinc stearate, which help smooth the paper surface. Sensitizers can also be used, particularly in heat-sensitive layers. These are special waxes with low melting points, which lower the softening temperature and thus accelerate development.
Die erfindungsgemäßen druck- und wärmeempfindlichen Aufzeichnungsmaterialien weisen keine sichtbaren Hintergrundanfärbungen auf. Photometrische Messungen ergeben Intensitätswerte deutlich unter 1 K/S·100. Die Schwärzungen bzw. die Färbungen allgemein, die beim Drucken erzielt werden, liegen deutlich über 40 K/S·100 (Auswertung nach Kubelka-Munk; Kunststoff-Rundschau 17, S. 282 - 291 (1970)). Die Anforderungen, die an derartige Materialien zu stellen sind, sind damit klar erfüllt.The pressure- and heat-sensitive recording materials according to the invention have no visible background stains. Photometric measurements show intensity values well below 1 K / S · 100. The blackening or coloring in general that is achieved when printing are well above 40 K / S100 (evaluation according to Kubelka-Munk; Kunststoff-Rundschau 17, pp. 282-291 (1970)). The requirements that must be placed on such materials are thus clearly met.
Die erfindinngsgemäßen Aufzeichnungsmaterialien haben weiterhin den großen vorteil, daß Farbbildner und Entwickler in beliebiger Weise ausgewählt werden können, ohne auf besonders reaktive Farbbildner und wasserlösliche Entwickler verzichten zu müssen. Damit können auch die zugleich besonders kostengünstigen Komponenten 2-N-Phenylamino-3-methyl-6-diethylaminofluoran und Bisphenol A eingesetzt werden, so daß schnell reagierende Systeme, die tiefe Schwärzungen ergeben, herstellbar sind.The recording materials according to the invention also have the great advantage that color formers and developers can be selected in any manner without having to do without particularly reactive color formers and water-soluble developers. This means that the components 2-N-phenylamino-3-methyl-6-diethylaminofluorane and bisphenol A, which are particularly inexpensive, can also be used, so that rapidly reacting systems which produce deep blackening can be produced.
10 g des Farbbildners 2-N-Phenylamino-3-methyl-6-diethylaminofluoran wurden unter Zugabe von 15 g Wasser mit 1 g einer 10 gew.-%igen wäßrigen Dispersion von Polyvinylpyrrolidon (K 30) in einer Perlmühle angerieben, bis eine mittlere Teilchengröße von 1 µm erreicht war.10 g of the color former 2-N-phenylamino-3-methyl-6-diethylaminofluoran were ground in a bead mill with the addition of 15 g water with 1 g of a 10% by weight aqueous dispersion of polyvinylpyrrolidone (K 30) until a medium one Particle size of 1 micron was reached.
Anschließend wurde die auf diese Weise vorbehandelte Farbbildner-Dispersion unter Rühren zunächst mit 1,9 g einer Mischung aus einer 70 gew.-%igen wäßrigen Lösung von Melamin-Formaldehyd-Harz (Molverhältnis Melamin:Formaldehyd = 1:5,6 bis 1:6,2) und einer 20 gew.-%igen wäßrigen Lösung von Polyacrylamidomethylenpropansulfosäure im Gewichtsverhälnis 1:1 und dann mit 0,22 g Natriumdihydrogenphosphat versetzt. Danach wurde mit Ameisensäure ein pH-Wert von 4,2 eingestellt. Nach einstündigem Rühren bei Raumtemperatur unter Zugabe von 2,5 g Wasser wurde das Gemisch zur vollständigen Aushärtung weitere 2 h bei 70°C gerührt.Subsequently, the color former dispersion pretreated in this way was first stirred with 1.9 g of a mixture of a 70% strength by weight aqueous solution of melamine-formaldehyde resin (molar ratio of melamine: formaldehyde = 1: 5.6 to 1: 6.2) and a 20% by weight aqueous solution of polyacrylamidomethylene propanesulfonic acid in a weight ratio of 1: 1 and then mixed with 0.22 g of sodium dihydrogen phosphate. Then a pH of 4.2 was set with formic acid. After stirring for one hour at room temperature with the addition of 2.5 g of water, the mixture was stirred at 70 ° C. for a further 2 h to complete curing.
Es wurde eine etwa 35 gew.-%ige wäßrige Dispersion von 2-N-Phenylamino-3-methyl-6-diethylaminofluoran erhalten, die keine sichtbare Verfärbung aufwies. Die photometrische Messung ergab einen Intensitätswert von 0,1 K/S·100.An approximately 35% by weight aqueous dispersion of 2-N-phenylamino-3-methyl-6-diethylaminofluoran was obtained which had no visible discoloration. The photometric measurement showed an intensity value of 0.1 K / S · 100.
Diese in der nachfolgenden Tabelle genannten Farbbildner-Zubereitungen wurden auf analoge Weise zu Beispiel 1 hergestellt und wiesen vergleichbare Eigenfärbungen im Bereich von 0,1 bis 0,6 K/S·100 auf.These color former preparations mentioned in the table below were produced in an analogous manner to Example 1 and had comparable intrinsic colors in the range from 0.1 to 0.6 K / S · 100.
Die unter a) erhaltenen Farbbildner-Dispersionen wurden auf einen Farbbildner-Gehalt von 13 Gew.-% verdünnt und im Gewichtsverhältnis 1:1 mit einer 55 gew.-%igen wäßrigen Dispersion von Bisphenol A gemischt.The color former dispersions obtained under a) were diluted to a color former content of 13% by weight and mixed in a weight ratio of 1: 1 with a 55% by weight aqueous dispersion of bisphenol A.
Zur Beurteilung der Färbung dieser Thermodispersionen wurden photometrische Messungen mit dem Zeiss Photometer Elrepho® durchgeführt und nach Kubelka-Munk in K/S·100 ausgewertet. Die Ergebnisse nach Stehzeiten von 5, 60 und 180 Minuten sind in der unten folgenden Tabelle aufgeführt.To assess the color of these thermal dispersions, photometric measurements were carried out with the Zeiss Elrepho® photometer and evaluated according to Kubelka-Munk in K / S · 100. The results after standing times of 5, 60 and 180 minutes are shown in the table below.
Zur Herstellung der wärmeempfindlichen Aufzeichnungsmaterialien wurden die Thermodispersionen mit einer 30 µm-Rakel so auf Streichrohpapier aufgetragen, daß sich eine Schichtstärke von ca. 6 g/m2 ergab. Das beschichtete Papier wurde mit Warmluft von maximal 50°C getrocknet.To produce the heat-sensitive recording materials, the thermal dispersions were applied to coating base paper with a 30 μm doctor blade in such a way that a layer thickness of approximately 6 g / m 2 resulted. The coated paper was dried with warm air at a maximum of 50 ° C.
Die Entwicklung dieser wärmeempfindlichen Schichten wurde jeweils in dem F+O Electronic Systems Thermodrucker der Neckarsteinach GmbH vom Typ 180/300 TES 9024 B mit Wärmeimpulsen von 7 ms durchgeführt. Die erzielten Schwärzungen (bzw. die Blaufärbung in Beispiel 4) wurden nach Kubelka-Munk in K/S·100 ausgewertet. Die Ergebnisse sind in der folgenden Tabelle zusammengefaßt.
Claims (9)
- A color former preparation comprisingA) a core of solid particles of a color former,B) a first envelope of a water-soluble nonionic polymer, andC) a second envelope of a crosslinked polymer.
- A color former preparation as claimed in claim 1, obtainable bya) enveloping solid color former particles with a water-soluble nonionic polymer by milling the color former with the polymer in aqueous dispersion, andb) further enveloping the particles obtained in step a) with a crosslinked polymer by adding an aqueous dispersion of the corresponding oligomer and curing it to form a continuous layer which envelops the particles obtained in step a).
- A color former preparation as claimed in claim 1 or 2, including a colorless or barely colored color former which in contact with an electron acceptor gives a color reaction.
- A color former preparation as claimed in claim 1 or 2 or 3, including a color former from the group of the fluorans, the lactones, the phthalides or the spirodipyrans.
- A process for preparing a color former preparation by the process steps of claim 2.
- An aqueous dispersion comprising one or more color former preparations as claimed in claim 1 or 2 or 3 or 4.
- An aqueous dispersion comprising one or more color former preparations as claimed in claim 1 or 2 or 3 or 4 and one or more electron acceptors as developer.
- The use of a color former preparation as claimed in claim 1 or 2 or 3 or 4 for preparing heat- or pressure-sensitive recording materials.
- A heat- or pressure-sensitive recording material comprising one or more color former preparations as claimed in claim 1 or 2 or 3 or 4.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4103966A DE4103966A1 (en) | 1991-02-09 | 1991-02-09 | COLOR IMAGE PREPARATIONS |
| DE4103966 | 1991-02-09 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0499045A1 EP0499045A1 (en) | 1992-08-19 |
| EP0499045B1 true EP0499045B1 (en) | 1996-07-31 |
Family
ID=6424725
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP92100814A Expired - Lifetime EP0499045B1 (en) | 1991-02-09 | 1992-01-20 | Colour-former preparations |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US5346931A (en) |
| EP (1) | EP0499045B1 (en) |
| JP (1) | JPH04310787A (en) |
| BR (1) | BR9200419A (en) |
| DE (2) | DE4103966A1 (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE60305358T2 (en) * | 2002-02-20 | 2007-03-29 | Dai Nippon Printing Co., Ltd. | Thermal transfer sheet |
| US20040002275A1 (en) * | 2002-06-28 | 2004-01-01 | Niranjan Thakore | Fabric reinforced rubber product |
| EP1574534A1 (en) * | 2004-03-11 | 2005-09-14 | Rohm And Haas Company | Polymer carriers and process |
| US20050203215A1 (en) * | 2004-03-11 | 2005-09-15 | Ugazio Stephen P.J. | Polymer carriers and process |
Family Cites Families (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3429827A (en) * | 1962-11-23 | 1969-02-25 | Moore Business Forms Inc | Method of encapsulation |
| US3891572A (en) * | 1965-06-10 | 1975-06-24 | Ici Ltd | Production of stable dispersion of solid particles encapsulated in synthetic polymer |
| US3551346A (en) * | 1966-11-23 | 1970-12-29 | Ncr Co | Method of making dual wall capsules |
| US3578605A (en) * | 1968-08-02 | 1971-05-11 | Moore Business Forms Inc | Process for making dual walled microcapsules |
| BE793246A (en) * | 1971-12-30 | 1973-06-22 | Xerox Corp | ENCAPSULATION PROCESS |
| CA1104881A (en) * | 1977-06-24 | 1981-07-14 | Yu-Sun Lee | Process for producing microcapsules having secondary capsule walls and microcapsules produced thereby |
| DE2940786A1 (en) * | 1979-10-08 | 1981-04-16 | Basf Ag, 6700 Ludwigshafen | METHOD FOR PRODUCING MICROCAPSULES |
| DE3044113A1 (en) * | 1980-11-24 | 1982-07-15 | Basf Ag, 6700 Ludwigshafen | GROCES CONTAINING MICROCAPSULES |
| US4517141A (en) * | 1982-06-30 | 1985-05-14 | Bayer Aktiengesellschaft | Production of microcapsules having walls of polyaddition products of water-insoluble polyamines with water-soluble polyisocyanate adducts |
| US4576891A (en) * | 1984-06-15 | 1986-03-18 | The Mead Corporation | Photosensitive microcapsules useful in polychromatic imaging having radiation absorber |
| US4594370A (en) * | 1985-03-29 | 1986-06-10 | The Mead Corporation | Amine-formaldehyde microencapsulation process |
| JPS6297638A (en) * | 1985-10-25 | 1987-05-07 | Kanzaki Paper Mfg Co Ltd | Preparation of microcapsule |
| JPS62132673A (en) * | 1985-12-05 | 1987-06-15 | Sharp Corp | Recorder |
| US4727011A (en) * | 1986-10-16 | 1988-02-23 | Xerox Corporation | Processes for encapsulated toner compositions with interfacial/free-radical polymerization |
| US4977060A (en) * | 1989-12-07 | 1990-12-11 | The Mead Corporation | Method for producing microcapsules and photosensitive microcapsules produced thereby |
-
1991
- 1991-02-09 DE DE4103966A patent/DE4103966A1/en not_active Withdrawn
-
1992
- 1992-01-20 DE DE59206829T patent/DE59206829D1/en not_active Expired - Lifetime
- 1992-01-20 EP EP92100814A patent/EP0499045B1/en not_active Expired - Lifetime
- 1992-01-24 US US07/825,374 patent/US5346931A/en not_active Expired - Fee Related
- 1992-02-04 JP JP4018835A patent/JPH04310787A/en not_active Withdrawn
- 1992-02-07 BR BR929200419A patent/BR9200419A/en not_active Application Discontinuation
Also Published As
| Publication number | Publication date |
|---|---|
| US5346931A (en) | 1994-09-13 |
| DE59206829D1 (en) | 1996-09-05 |
| DE4103966A1 (en) | 1992-08-13 |
| BR9200419A (en) | 1992-10-13 |
| JPH04310787A (en) | 1992-11-02 |
| EP0499045A1 (en) | 1992-08-19 |
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