EP0814963A1 - Multi-layer, flexible transfer strip, a process for its production and its use in a hand device - Google Patents

Multi-layer, flexible transfer strip, a process for its production and its use in a hand device

Info

Publication number
EP0814963A1
EP0814963A1 EP96904856A EP96904856A EP0814963A1 EP 0814963 A1 EP0814963 A1 EP 0814963A1 EP 96904856 A EP96904856 A EP 96904856A EP 96904856 A EP96904856 A EP 96904856A EP 0814963 A1 EP0814963 A1 EP 0814963A1
Authority
EP
European Patent Office
Prior art keywords
layer
sensitive adhesive
pressure
adhesive layer
hollow particles
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.)
Granted
Application number
EP96904856A
Other languages
German (de)
French (fr)
Other versions
EP0814963B1 (en
Inventor
Wolfhard Rutz
Wolfgang Giersemehl
Wolfgang Bauersachs
Karl-Heinz Weissmann
Lothar Titze
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Henkel Pritt Produktions GmbH
Original Assignee
Henkel Pritt Produktions GmbH
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Henkel Pritt Produktions GmbH filed Critical Henkel Pritt Produktions GmbH
Publication of EP0814963A1 publication Critical patent/EP0814963A1/en
Application granted granted Critical
Publication of EP0814963B1 publication Critical patent/EP0814963B1/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B44—DECORATIVE ARTS
    • B44C—PRODUCING DECORATIVE EFFECTS; MOSAICS; TARSIA WORK; PAPERHANGING
    • B44C1/00—Processes, not specifically provided for elsewhere, for producing decorative surface effects
    • B44C1/16—Processes, not specifically provided for elsewhere, for producing decorative surface effects for applying transfer pictures or the like
    • B44C1/165—Processes, not specifically provided for elsewhere, for producing decorative surface effects for applying transfer pictures or the like for decalcomanias; sheet material therefor
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41J—TYPEWRITERS; SELECTIVE PRINTING MECHANISMS, i.e. MECHANISMS PRINTING OTHERWISE THAN FROM A FORME; CORRECTION OF TYPOGRAPHICAL ERRORS
    • B41J29/00—Details of, or accessories for, typewriters or selective printing mechanisms not otherwise provided for
    • B41J29/26—Devices, non-fluid media or methods for cancelling, correcting errors, underscoring or ruling
    • B41J29/36—Devices, non-fluid media or methods for cancelling, correcting errors, underscoring or ruling for cancelling or correcting errors by overprinting
    • B41J29/367—Devices, non-fluid media or methods for cancelling, correcting errors, underscoring or ruling for cancelling or correcting errors by overprinting sheet media carrying a pigmented transferable correction layer
    • 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
    • B41M5/10—Duplicating or marking methods; Sheet materials for use therein by using carbon paper or the like
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B44—DECORATIVE ARTS
    • B44C—PRODUCING DECORATIVE EFFECTS; MOSAICS; TARSIA WORK; PAPERHANGING
    • B44C1/00—Processes, not specifically provided for elsewhere, for producing decorative surface effects
    • B44C1/16—Processes, not specifically provided for elsewhere, for producing decorative surface effects for applying transfer pictures or the like
    • B44C1/165—Processes, not specifically provided for elsewhere, for producing decorative surface effects for applying transfer pictures or the like for decalcomanias; sheet material therefor
    • B44C1/17—Dry transfer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B44—DECORATIVE ARTS
    • B44C—PRODUCING DECORATIVE EFFECTS; MOSAICS; TARSIA WORK; PAPERHANGING
    • B44C1/00—Processes, not specifically provided for elsewhere, for producing decorative surface effects
    • B44C1/16—Processes, not specifically provided for elsewhere, for producing decorative surface effects for applying transfer pictures or the like
    • B44C1/165—Processes, not specifically provided for elsewhere, for producing decorative surface effects for applying transfer pictures or the like for decalcomanias; sheet material therefor
    • B44C1/17—Dry transfer
    • B44C1/1733—Decalcomanias applied under pressure only, e.g. provided with a pressure sensitive adhesive
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B44—DECORATIVE ARTS
    • B44C—PRODUCING DECORATIVE EFFECTS; MOSAICS; TARSIA WORK; PAPERHANGING
    • B44C1/00—Processes, not specifically provided for elsewhere, for producing decorative surface effects
    • B44C1/16—Processes, not specifically provided for elsewhere, for producing decorative surface effects for applying transfer pictures or the like
    • B44C1/165—Processes, not specifically provided for elsewhere, for producing decorative surface effects for applying transfer pictures or the like for decalcomanias; sheet material therefor
    • B44C1/175—Transfer using solvent
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/249921—Web or sheet containing structurally defined element or component
    • Y10T428/249953—Composite having voids in a component [e.g., porous, cellular, etc.]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/249921—Web or sheet containing structurally defined element or component
    • Y10T428/249953—Composite having voids in a component [e.g., porous, cellular, etc.]
    • Y10T428/249978—Voids specified as micro
    • Y10T428/24998—Composite has more than two layers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/249921—Web or sheet containing structurally defined element or component
    • Y10T428/249953—Composite having voids in a component [e.g., porous, cellular, etc.]
    • Y10T428/249982—With component specified as adhesive or bonding agent
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/249921—Web or sheet containing structurally defined element or component
    • Y10T428/249953—Composite having voids in a component [e.g., porous, cellular, etc.]
    • Y10T428/249982—With component specified as adhesive or bonding agent
    • Y10T428/249983—As outermost component
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/249921—Web or sheet containing structurally defined element or component
    • Y10T428/249953—Composite having voids in a component [e.g., porous, cellular, etc.]
    • Y10T428/249982—With component specified as adhesive or bonding agent
    • Y10T428/249984—Adhesive or bonding component contains voids
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/249921—Web or sheet containing structurally defined element or component
    • Y10T428/249953—Composite having voids in a component [e.g., porous, cellular, etc.]
    • Y10T428/249982—With component specified as adhesive or bonding agent
    • Y10T428/249985—Composition of adhesive or bonding component specified
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/249921—Web or sheet containing structurally defined element or component
    • Y10T428/249953—Composite having voids in a component [e.g., porous, cellular, etc.]
    • Y10T428/249987—With nonvoid component of specified composition
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/25—Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
    • Y10T428/254—Polymeric or resinous material

Definitions

  • Multi-layer, flexible transmission tape a process for its production and its use in a hand-held device
  • the invention relates to a multilayer, flexible transfer tape with an auxiliary carrier and a pressure-sensitive adhesive layer, a binder-containing transfer layer being present between the auxiliary carrier and the pressure-sensitive adhesive layer, which has stronger adhesion to the pressure-sensitive adhesive layer than to the auxiliary carrier, a method for its production and the use thereof Transfer tape in rolled up form in a handheld device.
  • the binder-containing transfer layer contains 0.5 to 5% by weight of a soluble cellulose derivative as a tear-off aid.
  • the binder-containing transfer layer of this tape can be applied cleanly and with sharp edges to areas or surfaces to be covered (even over a large area). It can be used in a hand-held device in a rolled-up form for simple, quick and uniform application to the respective substrate, with stringing of the pressure-sensitive adhesive layer being largely ruled out when torn off.
  • US Pat. No. 3,413,168 discloses a self-adhesive masking tape which, in the adhesive layer, contains hollow microspheres with a diameter of 40 to 100 ⁇ m protruding therefrom in a statistical distribution.
  • the microspheres allow an exact
  • JP 5814 2944 A describes a fixed cover material containing 20 to 55% hollow microcapsules, which are filled with solvents, resin solutions or liquid resins.
  • the invention was therefore based on the object of developing the known flexible transmission band in such a way that the problems described were remedied or its use properties improved.
  • the binder-containing transfer layer and / or b) the pressure-sensitive adhesive layer contain fine hollow particles and a water-soluble, solid alcohol.
  • a method is particularly suitable for the advantageous production of the transfer belt according to the invention, in which a pigment-containing plastic dispersion is applied to a flexible auxiliary carrier using customary application technologies, the dispersion medium is evaporated, an aqueous dispersion containing a pressure sensitive adhesive is applied to the formed transfer layer using customary application technologies, and then the water is evaporated off, whereby a) the pigment-containing plastic dispersion contains a water-soluble, solid alcohol and fine hollow particles and / or b) the aqueous dispersion containing the pressure sensitive adhesive contains a water-soluble solid alcohol and fine hollow particles.
  • a water-soluble, solid alcohol must be present in at least one of the two layers according to the configurations a) and b). It must be a solid alcohol that is water-soluble at room temperature.
  • This group of alcohols includes, in particular, the tetravalent alcohols, such as erythritol, the pentavalent alcohols, such as arabite, adonite and xylitol, the hexavalent alcohols such as Sortbit, mannitol and dulcitol, but also alcohols with one or more others functional groups which do not interfere with the invention, such as, in particular, glucose and fructose, but also disaccharides, such as sucrose.
  • the binder-containing transfer layer preferably contains about 3 to 25% by weight of water-soluble, solid alcohol, in particular about 5 to 20% by weight.
  • the preferred content of water soluble solid alcohol in the pressure-sensitive adhesive layer is approximately 1 to 40% by weight, in particular approximately 5 to 30% by weight.
  • At least one of the two layers according to variants a) and b) of the transfer belt according to the invention contains fine, in particular flexible, hollow particles in conjunction with the water-soluble, solid alcohol already discussed. This does not rule out that the other layer contains only fine hollow particles or a water-soluble, solid alcohol.
  • the fine hollow particles are preferably spherical.
  • the diameter of the hollow particles, if present in the pressure-sensitive adhesive layer b), is preferably between about 0.25 to 5 ⁇ m, in particular between about 0.3 and 2 ⁇ m. If they are present in the binder-containing transfer layer, the hollow particles preferably have a diameter of approximately 0.3 to 10 ⁇ m, in particular between approximately 0.3 to 5 ⁇ m. Overall, it is preferred if the void volume of the
  • Hollow particles is about 20 to 55%, in particular about 25 to 40%. In order to achieve the advantages explained later with the transfer belt according to the invention, it is very particularly preferred if the fine hollow particles represent flexible, water-containing hollow particles with a porous wall.
  • the fine hollow particles usually consist of an opaque polymer. However, it is also possible to color this opaque polymer, and this coloration should be carried out during production using colorants which are coordinated with the colorant of the transfer layer.
  • hollow spheres are those with a ratio of wall thickness to diameter of less than 0.25, in particular 0, 15 or less.
  • the use of hollow spheres of this type made of opaque polymers in paints is described in Park + Lack, 93rd year, 10/1987. These are air-filled in the dried paint to increase their hiding power.
  • the advantageous use of these hollow spheres in intermediate layers of thermosensitive papers is described in EP 0 341 715 B1. There they make a contribution to thermal insulation and elasticity. There is no relevant technological connection to the present invention. Nevertheless, the hollow spheres described in the literature mentioned can be used without restriction and advantageously in the context of the present invention.
  • their walls consist of stryol resins, acrylic resins or styrene-acrylic copolymer resins.
  • Their manufacture is described, for example, in US Pat. No. 4,427,836 and EP 0 022 633 B1 (patent holder Rohm and Haas Company, USA). They are produced in the context of a special emulsion polymerisation process, which will not be discussed in detail here, since it is not the core of the invention.
  • the hollow particles or hollow spheres described contain water during the course of the method, which can escape or evaporate at higher temperatures through the micropores formed in the wall of the hollow particles.
  • Ropaque in particular Ropaque OP-62 (particle diameter approximately 0.4 ⁇ m, wall thickness approximately 0.06 ⁇ m), Ropaque HP-91 (particle diameter approximately 1 ⁇ m, wall thickness approximately 0. 1 ⁇ m) (each sold by the Rohm and Haas Company), and Voncoat, in particular Voncoat PP-1100 (particle diameter approximately 0.55 to 0.5 ⁇ m, wall thickness approximately 0.11 to 0.12 ⁇ m) (distributed by Dainippon Inc., Co., Japan).
  • Ropaque OP-62 particle diameter approximately 0.4 ⁇ m, wall thickness approximately 0.06 ⁇ m
  • Ropaque HP-91 particle diameter approximately 1 ⁇ m, wall thickness approximately 0. 1 ⁇ m
  • Voncoat in particular Voncoat PP-1100 (particle diameter approximately 0.55 to 0.5 ⁇ m, wall thickness approximately 0.11 to 0.12 ⁇ m) (distributed by Dainippon Inc., Co., Japan).
  • the auxiliary carrier of the transfer belt according to the invention preferably consists of a plastic film, as is usually used for the carriers of typewriter ribbons, e.g. made of polyethylene terephthalate, polypropylene, polyethylene, polyvinyl chloride or polycarbonate. Silicone-coated paper has also proven to be suitable as an auxiliary carrier. The silicone coating leads to a reduction in the adhesive tension between the binder-containing transfer layer and the auxiliary carrier. It can be replaced by other non-stick agents, such as polytetrafluoroethylene.
  • the auxiliary carrier preferably has a thickness of approximately 10 to 60 ⁇ m, in particular approximately 15 to 55 ⁇ m, the transfer layer a thickness of approximately 5 to 40 ⁇ m, in particular approximately 15 to 25 ⁇ m, and the pressure-sensitive adhesive layer a thickness of approximately 1 to
  • a ratio of the thickness of the pressure-sensitive adhesive layer to the transfer layer of about 1: 4 to 1:12, in particular about 1: 8 to 1:10, is expediently chosen.
  • the pressure sensitive adhesive layer can consist of commercially available pressure sensitive adhesives. These are elastic and permanently adhesive self-adhesive compositions with large adhesive forces which adhere immediately to the various surfaces even under low pressure at room temperature. They are preferably applied in aqueous dispersion to the transfer layer which is already on the auxiliary carrier, since in this way the binder layer which has already been formed is not redissolved. Among pressure-sensitive adhesives of this type, those based on acrylate are particularly advantageous.
  • the starting materials can be viscous solutions or dis- trade persions based on rubber, polyacrylates, polyvinyl ethers or polyvinyl isobutylene. Commercial materials based on polyacrylates are preferred.
  • the pressure-sensitive adhesive to be applied which is initially present in an aqueous medium, preferably contains wetting agents or surfactants (sold under the trade name Byk W).
  • the dispersions of the pressure-sensitive adhesive for forming the pressure-sensitive adhesive layer are preferably applied to the transfer layer in an amount of about 1 to 5 g / m 2 and very particularly preferably in an amount of about 2 to 4 g / m 2 .
  • Thermoplastic or thermoelastic polymers in aqueous solution or in the form of an aqueous dispersion are preferably used to form the binder-containing transfer layer.
  • the following substances are advantageously used to achieve the object: a) Polyurethanes with a molecular weight of 15,000 to 50,000, e.g. Permutane U 4924 from Stahl-Chemie or Desmolac 2100 from Bayer AG, b) linear saturated polyesters with a molecular weight of 20,000 to 30,000, e.g.
  • polymer dispersions based on vinyl propionate e.g. Propiofan 6D from BASF and g) water-soluble carboxymethyl group-containing polymethacrylate, e.g. Rohagit SD 15 from Roehm GmbH.
  • the type of plasticizer used should also be taken into account when choosing the respective binder for forming the transfer layer. This should be when applying the transfer Do not penetrate the application layer onto the surface to be corrected or to be covered through the normally thin pressure-sensitive adhesive layer and come into contact with the point to be corrected or the colorants located there and in this way bring about an undesired coloring of the transfer layer.
  • Common plasticizers such as silicone, castor and mineral oils, are suitable for this purpose.
  • Plasticizers preferably used in other areas of application, such as phthalic acid esters or oleic alcohol, are not equally suitable.
  • a so-called "lacquering agent” can be incorporated into the binder-containing transfer layer, which possibly migrates colorant or makes it insoluble, so that it does not migrate into the applied transfer layer and this color it again.
  • Suitable varnishing agents are tanin and tannin derivatives. It is generally possible to use varnishing agents which are contained in inks and inks. They should preferably be present in the binder-containing transfer layer in an amount of about 0.5 to 5% by weight, in particular about 1.5 to 3.5% by weight, the range of about 2 to 2.5% by weight .-% is very particularly preferred. It has been shown that the amount of plasticizer can be significantly reduced by the inclusion of water-containing porous hollow particles or can be dispensed with in individual cases.
  • the binder selected in each case is preferably converted into an aqueous solution or dispersion to form the transfer layer.
  • the additives discussed below are added if desired.
  • the choice of solvent or dispersant depends on the type of binder used, but also on the material from which the hollow particles, in particular fine, flexible, water-containing hollow particles, are made. The solvent must therefore neither loosen the wall of the hollow particles nor cause the water contained in the hollow particles to be replaced by them to a considerable extent. Water is therefore preferably used as the dispersant or solvent. In principle, other solvents can also be used, provided that they meet the requirements mentioned above.
  • low to medium-boiling organic solvents from the group of alcohols, such as ethanol, isopropanol and butanol, the ketones, such as acetone and methyl ethyl ketone, the esters, such as methyl and ethyl acetate, the aromatic hydrocarbons such as toluene and the aliphatic hydrocarbons substances such as gasoline in the boiling range of 70 to 140 ° C, alone or in a mixture, but especially water, alone or in a mixture with low-boiling, water-soluble organic solvents.
  • concentration of the binder in the solution or dispersion is not essential to the invention.
  • a rough guideline can be that it is between about 3 and 15% by weight, with the range of about 6 to 12% by weight being preferred.
  • the solution or dispersion is preferably applied to the auxiliary carrier in an amount of about 15 to 25 g / m 2 and very particularly preferably between about 18 and 22 g / m 2 .
  • the binder-containing transfer layer can contain colorants.
  • colorant should be understood as much as possible. It should be the collective name for all coloring substances, so that this includes dyes and pigments, the latter also having a filler character. Dyes are to be understood as meaning those colorants which are soluble in water, organic solvents or binders and which are opposed by the insoluble pigments. The coloring can be present immediately, but only through fluorescence in
  • the binder-containing transfer layer contains in particular white pigments, such as titanium white, fallen chalk, alumina or colloidal silicas. If the transfer layer is to be colored, then inorganic pigments such as Hansa yellow (azo pigment yellow), ocher, iron oxide red, iron oxide black, cobalt blue, ultramarine, Berlin blue, or organic pigments such as alkali blue, phthalocyanines, azo dyes, anthraquinones and metal complex are used as colorants -Pigments, and carbon blacks used. Examples of the fluorescent dyes are: Blaze Orange T 15 der
  • the optimum covering function of the transfer belt according to the invention in particular that of the transfer layer containing the binder, can be controlled by the pigment content.
  • the optimum pigment content depends on various factors, such as the type of binder chosen, the pigment and the additives which are further incorporated. A particularly critical value or critical range cannot be specified.
  • a weight ratio of about 1: 1 to 1:12, in particular about 1: 3 to 1: 8 and very particularly between about 1: 4 to 1: 7 can be given for the binder / pigment relationship.
  • An advantageous component of the binder-containing transfer layer of the transfer belt according to the invention is a "tear-off aid". When the transfer layer is applied to a substrate under tensile stress conditions, this is done by a clean tear-off.
  • Soluble cellulose derivatives can be used as a tear-off aid.
  • Particularly preferred cellulose derivatives are the cellulose ethers which are soluble in organic solvents and / or water, such as methyl, ethyl, hydroxyethyl, ethylhydroxyethyl and carboxymethyl celluloses.
  • Cellulose esters such as cellulose acetobutyrate and propionate.
  • Various other soluble cellulose derivatives which bring about the desired effects are also suitable. It appears that the basic cellulose structure in the soluble cellulose derivative is important, while the groups introduced, such as the ethyl group, etc., result in the derivative formed being soluble in the solvent chosen in each case.
  • the amount of the tear-off aid incorporated in the transfer layer is approximately 0.5 to 5% by weight, in particular approximately 1.5 to 3.5% by weight.
  • the range of about 2 to 2.5% by weight is particularly preferred.
  • This information relates to the dry substance.
  • the quantitative ratio of tear aid to binder could also be used.
  • the ratio of demolition aid to binder can be given as about 1: 2 to 1:20, the range from about 1: 4 to 1:10 being preferred.
  • these further additives can be incorporated.
  • These can be agents for improving the covering power, such as in particular aluminum silicate, tinting agents, such as carbon black, or the above-mentioned lacquering agent, in particular for basic dyes in the form of, for example, gallic acid derivatives, e.g. Printan from Ciba Geigy.
  • the materials of the individual layers of the transfer belt according to the invention described above usually meet the basic requirement that the adhesive tension (defined by the work of adhesion according to the Dupre 'see equation, Lit .: KL Wolf “Physics and Chemistry of Interfaces", Springer Verlag 1957, p 164) between the pressure-sensitive adhesive layer and the transfer layer is larger than that between the auxiliary carrier and the transfer layer. If this is not the case in individual cases, then a suitable non-stick layer would have to be applied to the auxiliary carrier in order to meet this basic requirement. In such cases, a further requirement is regularly met, according to which the excess formed on the substrate support layer is non-adhesive to other materials that come into contact with it.
  • the following adhesive tension ratios can be specified for the successful use of the transfer tape according to the invention, the symbol "S" representing the adhesive tension relationship between the different materials: paper / pressure-sensitive adhesive layer, S 2 transfer layer / pressure-sensitive adhesive layer, S 3 transfer layer / Auxiliary carrier, S 4 transfer layer / paper and S 5 adhesive layer / auxiliary carrier.
  • S the adhesive tension relationship between the different materials: paper / pressure-sensitive adhesive layer, S 2 transfer layer / pressure-sensitive adhesive layer, S 3 transfer layer / Auxiliary carrier, S 4 transfer layer / paper and S 5 adhesive layer / auxiliary carrier.
  • S larger than S 3
  • S 2 larger than S 3
  • S 5 very much smaller than S 2 and S 5 smaller than S 3
  • the free surface of the transfer layer applied to a substrate, in particular paper should not show any adhesive power to the outside, ie S 4 is then zero or tends towards zero.
  • the applied transfer layer should therefore be non-adhesive when touched by hand or with paper.
  • the procedure according to the invention for the production of the transfer belt is preferably such that flexible, water-containing hollow particles with a porous wall are used as fine hollow particles and the dispersant of the plastic dispersion and the water of the aqueous dispersion are evaporated under such gentle conditions be that the water present within the hollow particles largely remains therein. It should not be attempted here that the water remains entirely in the hollow spheres, but it should be ensured that at least a sufficient amount of water remained in the hollow spheres after completion of the production process.
  • the presence of solid alcohol causes the water exiting through the microporous wall to be retained to a certain extent due to the hygroscopic behavior of the alcohol.
  • This "water reservoir" within the pressure-sensitive adhesive layer is particularly preserved when the pressure-sensitive adhesive tape according to the invention is used rolled up in a hand-held roller. This will be discussed in more detail below.
  • the above-mentioned mechanism when using the transmission belt according to the invention with regard to solid alcohol / porous hollow particles also applies accordingly to the functionality of the transmission layer of the transmission belt according to the invention.
  • water is pressed through the microporous wall of the hollow particles by the application pressure, with the result that the solid alcohol is at least dissolved or dissolved in individual cases.
  • the solid alcohol temporarily softens the binder-containing transfer layer so that it becomes more flexible during the application process and no microcracks occur.
  • the water pressed out of the hollow particles evaporates to a certain extent in spite of the hygroscopic behavior of the solid alcohol, so that it becomes firm again and the temporary softening is eliminated.
  • porous hollow particles in particular in the transfer layer seems to have further advantages: it has been shown that with increasing proportion of hollow particles the "bleeding through" of a corrected lettering is suppressed, probably due to the hydrophobic character of the wall of the hollow particles. This desirable effect is achieved particularly in the optimal weight percentage framework of the hollow particles.
  • the proportion of hollow particles increases the hiding power, which means that the proportion of expensive, for example, white pigment in the form of titanium dioxide can be reduced.
  • the very small and exceptionally regular particle size of the hollow particles mentioned prevents the pigment particles, in particular the titanium dioxide particles, from accumulating, so that there are no inhomogeneities in the transfer layer which often cause the occurrence of microcracks when the transfer belt is used. Therefore, the covering layer is given an improved elasticity, which also counteracts the occurrence of microcracks.
  • the user takes the housing in his hand and uses the application foot to press the outer (removable) tape layer running over its end edge against the substrate to which it is to be transferred (e.g. a printed sheet of paper to make corrections).
  • the user moves the device relative to the substrate and transfers, for example, a covering layer or a fluorescent layer to the substrate, the flexible auxiliary carrier being wound off the supply spool and wound onto the take-up spool.
  • the operation of the hand-held device described above makes it necessary to adhere to the previously mentioned adhesive tension ratios, i.e. the pressure-sensitive adhesive layer has an adhesion to the back of the auxiliary carrier which is less than the adhesion between the binder-containing transfer layer and the pressure-sensitive adhesive layer and less than the adhesion between the binder-containing transfer layer and the auxiliary carrier.
  • the transmission tape according to the invention is particularly distinguished as a correction means in the office, school and household for covering faulty characters, markings and graphic representations and rewriting.
  • Another use of the transfer belt can be the strikingly colored marking of areas, fonts and / or characters.
  • the transmission band carries a transmission layer containing a bun pigment.
  • Another use is to highlight text passages, characters or pictorial representations.
  • the transfer layer is preferably transparent and colored with a colorant that is fluorescent in daylight. In all of the application examples mentioned here, it proves to be particularly advantageous that the application takes place “dry”, ie there is no smudging of liquid spreads and no evaporation of questionable solvents and immediate rewriting is possible.
  • covering for example, Apply layers that contain colorants in particular to substrates. If the transfer layer of the transfer tape according to the invention is transparent, for example does not contain any covering pigments, then it can be used for mere covering without coloring and preserving characters that are otherwise sensitive to the effects of air and the like.
  • the performance characteristics of the transmission tape according to the invention are particularly comprehensively improved.
  • the long-term storage of the pressure-sensitive adhesive layer if it has largely dried out, is at least slightly moistened and the adhesive force is improved in this way if it contains the hollow particles described.
  • they cohesion is reduced and thus the tear behavior is improved. This is done by temporary softening.
  • the inclusion of a larger amount of conventional plasticizers is disadvantageous, as already shown above, since this would permanently soften the cover layer.
  • One of the consequences of this would be that undesired bleeding of the covered lettering or even bleeding would occur. Writing on such a transfer layer with ink would cause it to leak.
  • the use of the fine, flexible, water-containing hollow particles means that, for example when using expensive pigments, in particular, for example, titanium dioxide, the amount of pigment can be reduced.
  • Lactimon ® WS alkyl ammonium salts of polycarboxylic acids
  • Titanium dioxide 35.00 parts by weight ivory black 0.06 parts by weight aqueous dispersion of fine hollow spheres 30.00 parts by weight
  • aqueous hollow sphere dispersion is prepared as follows:
  • the above masking compound is applied with a doctor blade in an amount of 18 g / m 2 onto a siliconized paper carrier. Then the water is evaporated at about 80 ° C by passing warm air over it.
  • aqueous dispersion consisting of the following constituents is then applied with a doctor blade to the surface of the colorant-containing cover layer.
  • Acrylic-based pressure sensitive adhesive 57.3 parts by weight
  • the PSA is applied with a doctor blade in a thickness of 3 g / m. Then the water portion of the PSA is evaporated at about 80 ° C by passing air over it. The water inside the hollow spheres in the transfer layer remains in it.
  • the transfer tape obtained is particularly suitable for covering characters written on paper. It leads to the rapid and uniform application of an immediately rewritable cover strip, the application being carried out using a commercially available hand roller. Newly applied characters are clear and, when viewed microscopically, show no leakage in the edge areas.
  • Lactimon ® WS alkyl ammonium salts of polycarboxylic acids
  • Titanium dioxide 35.00 parts by weight of ivory black 0.06 parts by weight of aqueous dispersion of hollow spheres 30.00 parts by weight
  • This dispersion was used in the same manner as described in Example 1. The same applies to the formation of the pressure sensitive adhesive layer.
  • the pressure-sensitive adhesive layer was formed in accordance with Example 1.
  • Example 4 embdiment of the pressure-sensitive adhesive layer
  • Acrylic-based pressure sensitive adhesive (50%) 57.3 parts by weight
  • the pressure-sensitive adhesive layer was formed in accordance with Example 1.

Landscapes

  • Adhesives Or Adhesive Processes (AREA)
  • Adhesive Tapes (AREA)
  • Laminated Bodies (AREA)
  • Decoration By Transfer Pictures (AREA)
  • Medicinal Preparation (AREA)
  • Belt Conveyors (AREA)
  • Details Of Aerials (AREA)
  • Manufacturing Of Electric Cables (AREA)
  • Auxiliary Devices For And Details Of Packaging Control (AREA)
  • Pens And Brushes (AREA)
  • Materials For Medical Uses (AREA)

Abstract

PCT No. PCT/EP96/00757 Sec. 371 Date Nov. 17, 1997 Sec. 102(e) Date Nov. 17, 1997 PCT Filed Feb. 23, 1996 PCT Pub. No. WO94/28308 PCT Pub. Date Sep. 19, 1996Described is a multi-layer, flexible transfer tape with a backing and an adhesive layer, wherein between the backing and adhesive layer a bonding agent-containing transfer layer is provided, which adheres more strongly to the adhesive layer than to the backing. With this a) the bonding agent-containing transfer layer and/or b) the adhesive layer contains fine hollow particles and a water-soluble, solid alcohol. Furthermore the invention relates to a suitable process for producing such a transfer tape as well as to special application possibilities of same, in particular in rolled-up form in a hand apparatus. In particular, when used it leads to a transferred layer in which fractures, in particular micro-cracks, are excluded, and in an improvement of the initial adhesion when the transfer tape is used again after it has been stored for a long time.

Description

Mehrschichtiges, flexibles Übertragungsband, ein Verfahren zu dessen Herstellung sowie dessen Verwendung in einem Handgerät Multi-layer, flexible transmission tape, a process for its production and its use in a hand-held device
Die Erfindung betrifft ein mehrschichtiges, flexibles Übertragungsband mit einem Hilfsträger und einer Haftkleberschicht, wobei zwischen dem Hilfsträger und der Haftkleberschicht eine bindemittelhaltige Übertragungsschicht, die zur Haftkleber¬ schicht eine stärkere Haftung als zum Hilfsträger aufweist, vorliegt, ein Verfahren zu dessen Herstellung sowie die Verwendung dieses Übertragungsbandes in aufgerollter Form in einem Handgerät.The invention relates to a multilayer, flexible transfer tape with an auxiliary carrier and a pressure-sensitive adhesive layer, a binder-containing transfer layer being present between the auxiliary carrier and the pressure-sensitive adhesive layer, which has stronger adhesion to the pressure-sensitive adhesive layer than to the auxiliary carrier, a method for its production and the use thereof Transfer tape in rolled up form in a handheld device.
Das oben beschriebene Übertragungsband geht aus der EP 0 318 804 hervor. Seine Besonderheit besteht darin, daß die bindemittelhaltige Übertragungsschicht 0,5 bis 5 Gew.-% eines löslichen Cellulosederivats als Abrißhilfsmittel enthält. Die bindemit- telhaltige Übertragungsschicht dieses Bandes kann sauber und randscharf auf zu be¬ deckende Stellen oder Flächen (auch großflächig) aufgebracht werden. Es kann in einem Handgerät in aufgerollter Form zum einfachen, schnellen und gleichmäßigen Auftrag auf das jeweilige Substrat verwendet werden, wobei ein Fadenziehen der Haftkleberschicht beim Abriß weitgehend ausgeschlossen ist. Es hat sich bei diesem Übertragungsband gezeigt, daß, wenn es in der Übertragungsschicht Pigmente enthält, beim Auftrag auf ein Substrat mittels eines Handgeräts in der übertragenen Schicht Mikrorisse auftreten können, die beim Beschreiben der übertragenen Schicht, bei¬ spielsweise mit Tinte oder Tusche, zu einem unscharfen Schriftzug führen. Gelegent¬ lich ist bei längerem Lagern des Übertragungsbandes die Haftkleberschicht mehr oder weniger "ausgetrocknet" und zeigt einen Tackverlust. Dies führt zu einer mangelhaf¬ ten Anfangshaftung beim erneuten Einsatz des Übertragungsbandes.The transmission band described above is evident from EP 0 318 804. Its special feature is that the binder-containing transfer layer contains 0.5 to 5% by weight of a soluble cellulose derivative as a tear-off aid. The binder-containing transfer layer of this tape can be applied cleanly and with sharp edges to areas or surfaces to be covered (even over a large area). It can be used in a hand-held device in a rolled-up form for simple, quick and uniform application to the respective substrate, with stringing of the pressure-sensitive adhesive layer being largely ruled out when torn off. It has been shown in this transfer tape that if it contains pigments in the transfer layer, microcracks can occur in the transferred layer when applied to a substrate by means of a hand-held device, which cracks when writing on the transferred layer, for example with ink or ink with a blurred lettering. Occasionally, if the transfer tape is stored for a long time, the pressure-sensitive adhesive layer is more or less "dried out" and shows a loss of tack. This leads to poor initial liability when the transmission belt is used again.
Die US-PS 3 413 168 offenbart ein selbstklebendes Abdeckband, das in der Klebe¬ schicht in statistischer Verteilung daraus hervorstehende hohle Mikrokugeln eines Durchmessers von 40 bis 100 μm enthält. Die Mikrokugeln erlauben ein genauesUS Pat. No. 3,413,168 discloses a self-adhesive masking tape which, in the adhesive layer, contains hollow microspheres with a diameter of 40 to 100 μm protruding therefrom in a statistical distribution. The microspheres allow an exact
Positionieren des Bandes und zerbrechen bei dessen Andrücken. Dadurch wird das Band mit der Unterlage verklebt. Die JP 5814 2944 A beschreibt ein festes Abdeck- material, das 20 bis 55 % hohle Mikrokapseln enthält, die mit Lösungsmitteln, Harzlö¬ sungen oder flüssigen Harzen gefüllt sind.Position the tape and break when pressed. This will glue the tape to the pad. JP 5814 2944 A describes a fixed cover material containing 20 to 55% hollow microcapsules, which are filled with solvents, resin solutions or liquid resins.
Der Erfindung lag daher die Aufgabe zugrunde, das bekannte flexible Übertragungs- band so weiterzubilden, daß die beschriebenen Probleme behoben bzw. dessen Ge¬ brauchseigenschaften verbessert werden.The invention was therefore based on the object of developing the known flexible transmission band in such a way that the problems described were remedied or its use properties improved.
Diese Aufgabe wird erfindungsgemäß dadurch gelöst, daß a) die bindemittelhaltige Übertragungsschicht und/oder b) die Haftkleberschicht feine Hohlteilchen und einen wasserlöslichen, festen Alkohol enthalten.This object is achieved in that a) the binder-containing transfer layer and / or b) the pressure-sensitive adhesive layer contain fine hollow particles and a water-soluble, solid alcohol.
Mit anderen Worten bedeutet das, daß die Ausgestaltung a) und die Ausgestaltung b) jeweils allein verwirklicht werden können. Jedoch ist auch eine Kombination der bei¬ den Ausgestaltungen möglich und bietet, was die nachfolgenden Darstellungen zeigen, Vorteile.In other words, this means that the configuration a) and the configuration b) can each be implemented alone. However, a combination of the two embodiments is also possible and, as the following illustrations show, offers advantages.
Zur vorteilhaften Herstellung des erfindungsgemäßen Übertragungsbandes ist insbe¬ sondere ein Verfahren geeignet, bei dem eine pigmenthaltige Kunststoffdispersion nach üblichen Auftragstechnologien auf einen flexiblen Hilfsträger aufgetragen, das Dispersionsmittel abgedampft, darauf eine einen Haftkleber enthaltende wäßrige Dis¬ persion nach üblichen Auftragstechnologien auf die ausgebildete Übertragungsschicht aufgetragen und danach das Wasser abgedampft wird, wobei a) die pigmenthaltige Kunststoffdispersion einen wasserlöslichen, festen Alkohol und feine Hohlteilchen enthält und/oder b) die den Haftkleber enthaltende wäßrige Dispersion einen wasser- löslichen festen Alkohol und feine Hohlteilchen enthält.A method is particularly suitable for the advantageous production of the transfer belt according to the invention, in which a pigment-containing plastic dispersion is applied to a flexible auxiliary carrier using customary application technologies, the dispersion medium is evaporated, an aqueous dispersion containing a pressure sensitive adhesive is applied to the formed transfer layer using customary application technologies, and then the water is evaporated off, whereby a) the pigment-containing plastic dispersion contains a water-soluble, solid alcohol and fine hollow particles and / or b) the aqueous dispersion containing the pressure sensitive adhesive contains a water-soluble solid alcohol and fine hollow particles.
Nach der Forderung gemäß der vorliegenden Erfindung muß mindestens in einer der beiden Schichten gemäß den Ausgestaltungen a) und b) ein wasserlöslicher, fester Alkohol vorliegen. Es muß sich um einen bei Raumtempertur wasserlöslichen, festen Alkohol handeln. Zu dieser Gruppe von Alkoholen zählen insbesondere die 4- wertigen Alkohole, wie Erythrit, die 5-wertigen Alkohole, wie Arabit, Adonit und Xylit, die 6-wertigen Alkohole, wie Sortbit, Mannit und Dulcit, aber auch Alkohole mit einer oder mehreren weiteren funktioneilen Gruppen, die im Rahmen der Erfin¬ dung nicht stören, wie insbesondere Glucose und Fructose, aber auch Disaccharide, wie Saccharose. Sorbit hat sich aufgrund seiner guten hygroskopischen Eigenschaften als besonders geeignet erwiesen. Vorzugsweise enthält die bindemittelhaltige Übertra¬ gungsschicht etwa 3 bis 25 Gew.-% wasserlöslichen, festen Alkohol, insbesondere etwa 5 bis 20 Gew.- %. Der bevorzugte Gehalt des wasserlöslichen, festen Alkohols in der Haftkleberschicht beträgt etwa 1 bis 40 Gew.-%, insbesondere etwa 5 bis 30 Gew.-%.According to the requirement of the present invention, a water-soluble, solid alcohol must be present in at least one of the two layers according to the configurations a) and b). It must be a solid alcohol that is water-soluble at room temperature. This group of alcohols includes, in particular, the tetravalent alcohols, such as erythritol, the pentavalent alcohols, such as arabite, adonite and xylitol, the hexavalent alcohols such as Sortbit, mannitol and dulcitol, but also alcohols with one or more others functional groups which do not interfere with the invention, such as, in particular, glucose and fructose, but also disaccharides, such as sucrose. Sorbitol has proven to be particularly suitable due to its good hygroscopic properties. The binder-containing transfer layer preferably contains about 3 to 25% by weight of water-soluble, solid alcohol, in particular about 5 to 20% by weight. The preferred content of water soluble solid alcohol in the pressure-sensitive adhesive layer is approximately 1 to 40% by weight, in particular approximately 5 to 30% by weight.
Mindestens eine der beiden Schichten nach den Varianten a) und b) des erfindungs- gemäßen Übertragungsbandes enthält feine, insbesondere flexible Hohlteilchen in Verbindung mit dem bereits erörterten wasserlöslichen, festen Alkohol. Dies schließt nicht aus, daß die andere Schicht lediglich feine Hohlteilchen oder einen wasserlösli¬ chen, festen Alkohol enthält.At least one of the two layers according to variants a) and b) of the transfer belt according to the invention contains fine, in particular flexible, hollow particles in conjunction with the water-soluble, solid alcohol already discussed. This does not rule out that the other layer contains only fine hollow particles or a water-soluble, solid alcohol.
Die feinen Hohlteilchen sind vorzugsweise kugelförmig. Der Durchmesser der Hohl¬ teilchen liegt im Falle des Vorliegens in der Haftkleberschicht b) vorzugsweise zwi¬ schen etwa 0,25 bis 5 μm, insbesondere zwischen etwa 0,3 und 2 μm. Die Hohlteil¬ chen haben im Falle des Vorliegens in der bindemittelhaltigen Übertragungsschicht vorzugsweise einen Durchmesser von etwa 0,3 bis 10 μm, insbesondere zwischen etwa 0,3 bis 5 μm. Insgesamt ist es bevorzugt, wenn das Hohlraumvolumen derThe fine hollow particles are preferably spherical. The diameter of the hollow particles, if present in the pressure-sensitive adhesive layer b), is preferably between about 0.25 to 5 μm, in particular between about 0.3 and 2 μm. If they are present in the binder-containing transfer layer, the hollow particles preferably have a diameter of approximately 0.3 to 10 μm, in particular between approximately 0.3 to 5 μm. Overall, it is preferred if the void volume of the
Hohlteilchen etwa 20 bis 55 % , insbesondere etwa 25 bis 40% , beträgt. Um mit dem erfindungsgemäßen Übertragungsband die noch später erläuterten Vorteile zu erzielen, ist es ganz besonders bevorzugt, wenn die feinen Hohlteilchen flexible, wasserhaltige Hohlteilchen poröser Wandung darstellen.Hollow particles is about 20 to 55%, in particular about 25 to 40%. In order to achieve the advantages explained later with the transfer belt according to the invention, it is very particularly preferred if the fine hollow particles represent flexible, water-containing hollow particles with a porous wall.
Die feinen Hohlteilchen bestehen im Regelfall aus einem opaken Polymer. Allerdings ist auch eine Einfärbung dieses opaken Polymers möglich, wobei diese Einfärbung bei der Herstellung durch solche Farbmittel erfolgen sollte, die mit dem Farbmittel der Übertragungsschicht abgestimmt sind.The fine hollow particles usually consist of an opaque polymer. However, it is also possible to color this opaque polymer, and this coloration should be carried out during production using colorants which are coordinated with the colorant of the transfer layer.
Besonders vorteilhafte Hohlkugeln sind solche eines Verhältnisses Wanddicke: Durchmesser von weniger als 0,25, insbesondere 0, 15 oder weniger. In Farbe + Lack, 93. Jahrgang, 10/1987 wird die Verwendung von Hohlkugeln dieser Art aus opaken Polymeren in Anstrichfarben beschrieben. Diese sind in der getrockneten An- strichfarbe luftgefüllt, um deren Deckvermögen zu erhöhen. Der vorteilhafte Einsatz dieser Hohlkugeln in Zwischenschichten thermosensitiver Papiere wird in der EP 0 341 715 Bl beschrieben. Dort leisten sie einen Beitrag zur Wärmeisolierung und Elastizität. Zu vorliegender Erfindung besteht kein relevanter technologischer Zu¬ sammenhang. Dennoch können die in der angesprochenen Literatur beschriebenen Hohlkugeln uneingeschränkt und mit Vorteil im Rahmen der vorliegenden Erfindung eingesetzt werden. Insbesondere bestehen ihre Wandungen aus Stryol-Harzen, Acryl- harzen oder Styrol-Acryl-Copolymerharzen. Ihre Herstellung wird beispielsweise in der US-A-4 427 836 sowie EP 0 022 633 Bl (Patentinhaberin jeweils Rohm and Haas Company, USA) beschrieben. Sie werden im Rahmen eines speziellen Emulsionspo¬ lymer isationsverfahrens hergestellt, auf das hier nicht eingehend eingegangen werden soll, da es nicht Kern der Erfindung ist. Nach diesem bekannten Verfahren hergestellt enthalten die beschriebenen Hohlteilchen bzw. Hohlkugeln bei Verfahrensablauf Was- ser, das bei höheren Temperaturen durch die in der Wandung der Hohlteilchen aus¬ gebildeten Mikroporen entweichen bzw. abdampfen kann. Im Rahmen der Erfindung besonders geeignete Handelsprodukte werden unter der Bezeichnung Ropaque, insbe¬ sondere Ropaque OP-62 (Teilchendurchmesser etwa 0,4 μm, Wandstärke etwa 0,06 μm), Ropaque HP-91 (Teilchendurchmesser etwa 1 μm, Wandstärke etwa 0, 1 μm) (jeweils vertrieben von der Rohm and Haas Company), sowie Voncoat, insbesondere Voncoat PP-1100 (Teilchendurchmesser etwa 0,55 bis 0,5 μm, Wandstärke etwa 0,11 bis 0, 12 μm) (vertrieben von der Dainippon Inc. , Co. , Japan), verwendet.Particularly advantageous hollow spheres are those with a ratio of wall thickness to diameter of less than 0.25, in particular 0, 15 or less. The use of hollow spheres of this type made of opaque polymers in paints is described in Farbe + Lack, 93rd year, 10/1987. These are air-filled in the dried paint to increase their hiding power. The advantageous use of these hollow spheres in intermediate layers of thermosensitive papers is described in EP 0 341 715 B1. There they make a contribution to thermal insulation and elasticity. There is no relevant technological connection to the present invention. Nevertheless, the hollow spheres described in the literature mentioned can be used without restriction and advantageously in the context of the present invention. In particular, their walls consist of stryol resins, acrylic resins or styrene-acrylic copolymer resins. Their manufacture is described, for example, in US Pat. No. 4,427,836 and EP 0 022 633 B1 (patent holder Rohm and Haas Company, USA). They are produced in the context of a special emulsion polymerisation process, which will not be discussed in detail here, since it is not the core of the invention. Produced by this known method, the hollow particles or hollow spheres described contain water during the course of the method, which can escape or evaporate at higher temperatures through the micropores formed in the wall of the hollow particles. Commercial products which are particularly suitable in the context of the invention are Ropaque, in particular Ropaque OP-62 (particle diameter approximately 0.4 μm, wall thickness approximately 0.06 μm), Ropaque HP-91 (particle diameter approximately 1 μm, wall thickness approximately 0. 1 μm) (each sold by the Rohm and Haas Company), and Voncoat, in particular Voncoat PP-1100 (particle diameter approximately 0.55 to 0.5 μm, wall thickness approximately 0.11 to 0.12 μm) (distributed by Dainippon Inc., Co., Japan).
Der Hilfsträger des erfindungsgemäßen Übertragungsbands besteht vorzugsweise aus einer Kunststoffolie, wie sie bei den Trägern von Schreibmaschinenbändern üblicher¬ weise herangezogen wird, so z.B. aus Polyethylenterephthalat, Polypropylen, Polye- thylen, Polyvinylchlorid oder Polycarbonat. Auch silikonbeschichtetes Papier hat sich als Hilfsträger als geeignet erwiesen. Die Silikonbeschichtung führt zu einer Ver¬ ringerung der Haftspannung zwischen der bindemittelhaltigen Übertragungsschicht und dem Hilfsträger. Sie kann durch andere Antihaftmittel ersetzt werden, wie bei- spielswiese durch Polytetrafluorethylen.The auxiliary carrier of the transfer belt according to the invention preferably consists of a plastic film, as is usually used for the carriers of typewriter ribbons, e.g. made of polyethylene terephthalate, polypropylene, polyethylene, polyvinyl chloride or polycarbonate. Silicone-coated paper has also proven to be suitable as an auxiliary carrier. The silicone coating leads to a reduction in the adhesive tension between the binder-containing transfer layer and the auxiliary carrier. It can be replaced by other non-stick agents, such as polytetrafluoroethylene.
Der Hilfsträger hat vorzugsweise eine Stärke von etwa 10 bis 60 μm , insbesondere von etwa 15 bis 55 μm, die Übertragungsschicht eine Stärke von etwa 5 bis 40 μm, insbesondere etwa 15 bis 25 μm, und die Haftkleberschicht eine Stärke von etwa 1 bisThe auxiliary carrier preferably has a thickness of approximately 10 to 60 μm, in particular approximately 15 to 55 μm, the transfer layer a thickness of approximately 5 to 40 μm, in particular approximately 15 to 25 μm, and the pressure-sensitive adhesive layer a thickness of approximately 1 to
8 μm, insbesondere etwa 2 bis 5 μm. Zur Optimierung des erfindungsgemäßen Über¬ tragungsbandes wählt man zweckmäßigerweise ein Dickenverhältnis der Haft¬ kleberschicht zu der Übertragungsschicht von etwa 1:4 bis 1: 12, insbesondere etwa 1:8 bis 1: 10.8 μm, in particular approximately 2 to 5 μm. To optimize the transfer belt according to the invention, a ratio of the thickness of the pressure-sensitive adhesive layer to the transfer layer of about 1: 4 to 1:12, in particular about 1: 8 to 1:10, is expediently chosen.
Die Haftkleberschicht kann aus handelsüblichen Haftklebstoffen bestehen. Dies sind elastische und dauernd klebfähige Selbstklebemassen mit großen Adhäsionskräften, die bereits unter geringem Druck bei Raumtemperatur auf den verschiedenen Oberflä¬ chen sofort haften. Sie werden vorzugsweise in wäßriger Dispersion auf die sich be- reits auf dem Hilfsträger befindende Übertragungsschicht aufgetragen, da so die be¬ reits ausgebildete bindemittelhaltige Übertragungsschicht nicht wieder aufgelöst wird. Unter Haftklebstoffen dieser Art sind insbesondere solche auf Acrylatbasis vor- teilthaft. Bei den Ausgangsmaterialien kann es sich um viskose Lösungen oder Dis- persionen handeln, die auf Kautschuk, Polyacrylaten, Polyvinylethern bzw. Polyviny- lisobutylen beruhen. Bevorzugt werden handelsübliche Materialien auf der Basis von Polyacrylaten. Geeignete Handelsprodukte sind Ucecryl 913 und Ucecryl PC 80 (vertrieben von der Firma ucb, Dogenbos, Belgien) sowie die Kunststoffdispersion VP 859/6 (vertrieben von der Firma Freihoff). Vorzugsweise enthält der aufzubringende Haftklebstoff, der zunächst in einem wäßrigen Medium vorliegt, Netzmittel bzw. Tenside (vertrieben unter der Handelsbezeichnung Byk W). Die Dispersionen des Haftklebstoffs zur Ausbildung der Haftkleberschicht werden vorzugsweise in einer Menge von etwa 1 bis 5 g/m2 und ganz besonders bevorzugt in einer Menge von etwa 2 bis 4 g/m2 auf die Übertragungsschicht aufgetragen.The pressure sensitive adhesive layer can consist of commercially available pressure sensitive adhesives. These are elastic and permanently adhesive self-adhesive compositions with large adhesive forces which adhere immediately to the various surfaces even under low pressure at room temperature. They are preferably applied in aqueous dispersion to the transfer layer which is already on the auxiliary carrier, since in this way the binder layer which has already been formed is not redissolved. Among pressure-sensitive adhesives of this type, those based on acrylate are particularly advantageous. The starting materials can be viscous solutions or dis- trade persions based on rubber, polyacrylates, polyvinyl ethers or polyvinyl isobutylene. Commercial materials based on polyacrylates are preferred. Suitable commercial products are Ucecryl 913 and Ucecryl PC 80 (sold by ucb, Dogenbos, Belgium) and the plastic dispersion VP 859/6 (sold by Freihoff). The pressure-sensitive adhesive to be applied, which is initially present in an aqueous medium, preferably contains wetting agents or surfactants (sold under the trade name Byk W). The dispersions of the pressure-sensitive adhesive for forming the pressure-sensitive adhesive layer are preferably applied to the transfer layer in an amount of about 1 to 5 g / m 2 and very particularly preferably in an amount of about 2 to 4 g / m 2 .
Zur Ausbildung der bindemittelhaltigen Übertragungsschicht werden vorzugsweise thermoplastische oder thermoelastische Polymere in wäßriger Lösung oder in Form einer wäßrigen Dispersion eingesetzt. Im Rahmen der Erfindung werden zur Lösung der gestellten Aufgabe mit Vorteil folgende Substanzen verwendet: a) Polyurethane eines Molekulargewichtes von 15.000 bis 50.000, z.B. Permutha- ne U 4924 der Firma Stahl-Chemie oder Desmolac 2100 der Firma Bayer AG, b) lineare gesättigte Polyester eines Molekulargewichtes von 20.000 bis 30.000, z.B. Vitel PE 307 der Firma Goodyear Tire + Rubber, Polyflex 46962 der Firma Morton, c) Styrol-Isopren-Styrol-Copolymerisate, z.B. Clariflex TR 1107 der Firma Shell- Chemie, d) Acrylate und Methacrylate, z.B. Plexigum 7 H der Roehm GmbH, e) Polyamide, diphenylsäure-modifiziert, z.B. Scope 30 der Firma Rhone-Poulenc oder Emerez 1533 der Firma Emery Chemicals,Thermoplastic or thermoelastic polymers in aqueous solution or in the form of an aqueous dispersion are preferably used to form the binder-containing transfer layer. In the context of the invention, the following substances are advantageously used to achieve the object: a) Polyurethanes with a molecular weight of 15,000 to 50,000, e.g. Permutane U 4924 from Stahl-Chemie or Desmolac 2100 from Bayer AG, b) linear saturated polyesters with a molecular weight of 20,000 to 30,000, e.g. Vitel PE 307 from Goodyear Tire + Rubber, Polyflex 46962 from Morton, c) styrene-isoprene-styrene copolymers, e.g. Clariflex TR 1107 from Shell-Chemie, d) acrylates and methacrylates, e.g. Plexigum 7 H from Roehm GmbH, e) polyamides, diphenylic acid modified, e.g. Scope 30 from Rhone-Poulenc or Emerez 1533 from Emery Chemicals,
0 Polymerdispersionen auf der Basis von Vinylpropionat, z.B. Propiofan 6D der Firma BASF und g) in Wasser lösliches carboxymethylgruppenhaltiges Polymethacrylat, z.B. Ro- hagit SD 15 der Firma Roehm GmbH.0 polymer dispersions based on vinyl propionate, e.g. Propiofan 6D from BASF and g) water-soluble carboxymethyl group-containing polymethacrylate, e.g. Rohagit SD 15 from Roehm GmbH.
Diese Aufzählung erhebt keinen Anspruch auf Vollständigkeit und bedeutet keine Ein¬ schränkung in ihrer Auswahl. Vielmehr ist es für den Fachmann ohne weiteres er¬ sichtlich, daß auch noch andere Bindemittel in Frage kommen können, zumal in der Art des Bindemittels nicht das Wesen der Erfindung zu sehen ist.This list makes no claim to completeness and does not imply any restriction in its selection. Rather, it is readily apparent to the person skilled in the art that other binders can also be considered, especially since the nature of the binder is not the essence of the invention.
Um die Erfindung weitergehend zu optimieren, sollte bei der Wahl des jeweiligen Bindemittels zur Ausbildung der Übertragungsschicht auch die Art des dabei herange¬ zogenen Weichmachers bedacht werden. Dieser sollte beim Aufbringen der Übertra- gungsschicht auf die zu korrigierende bzw. zu bedeckende Fläche nicht durch die normalerweise dünn ausgebildete Haftkleberschicht dringen und mit der zu korrigie¬ renden Stelle bzw. den sich dort befindenden Farbmitteln in Kontakt treten und auf diese Weise eine unerwünschte Einfärbung der Übertragungsschicht bewirken. Für diesen Zweck sind gängige Weichmacher, wie Silikon-, Rizinus- und Mineralöle ge¬ eignet. In anderen Anwendungsbereichen bevorzugt eingesetzte Weichmacher, wie beispielsweise Phthalsäureester oder Oleinalkohol, sind nicht gleichermaßen gut ge¬ eignet. Um dem angesprochenen nachteiligen Effekt von Weichmachern in Grenzfäl¬ len entgegenzuwirken, kann der bindemittelhaltigen Übertragungsschicht ein soge- nanntes "Verlackungsmittel" einverleibt werden, das eventuell migrierende Farbmittel ausfällt bzw. unlöslich macht, so daß diese nicht in die aufgebrachte Übertragungs¬ schicht migrieren und diese wieder einfärben. Geeignete Verlackungsmittel sind Tan¬ nin und Tanninderivate. Es lassen sich im allgemeinen Verlackungsmittel heranziehen, die in Tinten und Tuschen enthalten sind. Sie sollten vorzugsweise in einer Menge von etwa 0,5 bis 5 Gew.- %, insbesondere etwa 1,5 bis 3,5 Gew.-% in der bindemit¬ telhaltigen Übertragungsschicht vorliegen, wobei der Bereich von etwa 2 bis 2,5 Gew.-% ganz besonders bevorzugt ist. Es hat sich gezeigt, daß die Menge an Weich¬ macher durch die Einbeziehung wasserhaltiger poröser Hohlteilchen deutlich herabge¬ setzt werden bzw. in Einzelfällen darauf verzichtet werden kann.In order to further optimize the invention, the type of plasticizer used should also be taken into account when choosing the respective binder for forming the transfer layer. This should be when applying the transfer Do not penetrate the application layer onto the surface to be corrected or to be covered through the normally thin pressure-sensitive adhesive layer and come into contact with the point to be corrected or the colorants located there and in this way bring about an undesired coloring of the transfer layer. Common plasticizers, such as silicone, castor and mineral oils, are suitable for this purpose. Plasticizers preferably used in other areas of application, such as phthalic acid esters or oleic alcohol, are not equally suitable. In order to counteract the above-mentioned disadvantageous effect of plasticizers in borderline cases, a so-called "lacquering agent" can be incorporated into the binder-containing transfer layer, which possibly migrates colorant or makes it insoluble, so that it does not migrate into the applied transfer layer and this color it again. Suitable varnishing agents are tanin and tannin derivatives. It is generally possible to use varnishing agents which are contained in inks and inks. They should preferably be present in the binder-containing transfer layer in an amount of about 0.5 to 5% by weight, in particular about 1.5 to 3.5% by weight, the range of about 2 to 2.5% by weight .-% is very particularly preferred. It has been shown that the amount of plasticizer can be significantly reduced by the inclusion of water-containing porous hollow particles or can be dispensed with in individual cases.
Bei der Herstellung des erfindungsgemäßen Übertragungssbandes wird das jeweils gewählte Bindemittel zur Ausbildung der Übertragungsschicht vorzugsweise in eine wäßrige Lösung oder Dispersion überführt. Zusätzlich werden die nachfolgend erör¬ terten Additive, wenn gewünscht, zugegeben. Die Wahl des Lösemittels bzw. Dis- persionsmittels hängt von der Art des herangezogenen Bindemittels ab, jedoch auch von dem Material, aus dem die Hohlteilchen, insbesondere feinen flexiblen, wasser¬ haltigen Hohlteilchen bestehen. Das Lösemittel darf demzufolge weder die Wandung der Hohlteilchen lösen noch dazu führen, daß das in den Hohlteilchen enthaltene Was¬ ser durch dieses in erheblichem Maße ausgetauscht wird. Vorzugsweise wird daher Wasser als D ispers ionsmittel bzw. Lösemittel eingesetzt. Grundsätzlich können auch andere Lösemittel herangezogen werden, sofern sie die oben angesprochenen Anfor¬ derungen erfüllen. Hierzu zählen insbesondere niedrig- bis mittelsiedende organische Lösemittel aus der Gruppe der Alkohole, wie Ethanol, Isopropanol und Butanol, der Ketone, wie Aceton und Methylethylketon, der Ester, wie Methyl- und Ethylacetat, der aromatischen Kohlenwasserstoffe, wie Toluol, der aliphatischen Kohlenwasser¬ stoffe, wie Benzin des Siedebereichs von 70 bis 140°C, allein oder im Gemisch, aber insbesondere Wasser, allein oder im Gemisch mit niedrig-siedenden, wasserlöslichen organischen Lösemitteln. Die Konzentration des Bindemittels in der Lösung bzw. Dispersion ist nicht erfin¬ dungswesentlich. Als grobe Richtlinie kann gelten, daß sie zwischen etwa 3 und 15 Gew.-% liegt, wobei der Bereich von etwa 6 bis 12 Gew.-% bevorzugt ist. Die Lö- sung bzw. Dispersion wird zur Ausbildung der Übertragungsschicht vorzugsweise in einer Menge von etwa 15 bis 25 g/m2 und ganz besonders bevorzugt zwischen etwa 18 und 22 g/m2 auf den Hilfsträger aufgetragen.In the production of the transfer belt according to the invention, the binder selected in each case is preferably converted into an aqueous solution or dispersion to form the transfer layer. In addition, the additives discussed below are added if desired. The choice of solvent or dispersant depends on the type of binder used, but also on the material from which the hollow particles, in particular fine, flexible, water-containing hollow particles, are made. The solvent must therefore neither loosen the wall of the hollow particles nor cause the water contained in the hollow particles to be replaced by them to a considerable extent. Water is therefore preferably used as the dispersant or solvent. In principle, other solvents can also be used, provided that they meet the requirements mentioned above. These include in particular low to medium-boiling organic solvents from the group of alcohols, such as ethanol, isopropanol and butanol, the ketones, such as acetone and methyl ethyl ketone, the esters, such as methyl and ethyl acetate, the aromatic hydrocarbons such as toluene and the aliphatic hydrocarbons substances such as gasoline in the boiling range of 70 to 140 ° C, alone or in a mixture, but especially water, alone or in a mixture with low-boiling, water-soluble organic solvents. The concentration of the binder in the solution or dispersion is not essential to the invention. A rough guideline can be that it is between about 3 and 15% by weight, with the range of about 6 to 12% by weight being preferred. To form the transfer layer, the solution or dispersion is preferably applied to the auxiliary carrier in an amount of about 15 to 25 g / m 2 and very particularly preferably between about 18 and 22 g / m 2 .
Die bindemittelhaltige Übertragungsschicht kann Farbmittel enthalten. Hierbei soll der Begriff "Farbmittel" weitestgehend verstanden werden. Es soll sich um die Sammel¬ bezeichnung für alle farbgebenden Stoffe handeln, so daß darunter Farbstoffe und Pigmente, letztere auch mit Füllstoffcharakter, fallen. Dabei sollen unter Farbstoffen diejenigen Farbmittel verstanden werden, die in Wasser, organischen Lösungsmitteln oder Bindemitteln löslich sind und denen die unlöslichen Pigmente gegenüberstehen. Die Farbgebung kann unmittelbar vorhanden sein, aber auch erst durch Fluoreszenz inThe binder-containing transfer layer can contain colorants. Here, the term "colorant" should be understood as much as possible. It should be the collective name for all coloring substances, so that this includes dyes and pigments, the latter also having a filler character. Dyes are to be understood as meaning those colorants which are soluble in water, organic solvents or binders and which are opposed by the insoluble pigments. The coloring can be present immediately, but only through fluorescence in
Erscheinung treten. Letzteres gilt beispielsweise für fluoreszierende Tagesleuchtfar¬ ben. Wenn das erfindungsgemäße Übertragungsband zur Korrektur von Schriftzeichen und bildlichen Darstellungen und dergleichen herangezogen wird, enthält die binde¬ mittelhaltige Übertragungsschicht insbesondere Weißpigmente, wie Titanweiß, gefall- te Kreide, Tonerde oder kolloidale Kieselsäuren. Soll die Übertragungsschicht farbig sein, dann werden als Farbmittel anorganische Pigmente, wie Hansagelb (Azopigmentgelb), Ocker, Eisenoxid-Rot, Eisenoxidschwarz, Kobaltblau, Ultramarin, Berliner Blau, oder organische Pigmente, wie Alkaliblau, Phthalocyanine, Azo- Farbstoffe, Anthrachinone und Metallkomplex-Pigmente, sowie Ruße verwendet. Von den fluoreszierenden Farbstoffen seien beispielhaft genannt: Blaze Orange T 15 derAppearance. The latter applies, for example, to fluorescent daylight colors. If the transfer belt according to the invention is used to correct characters and pictorial representations and the like, the binder-containing transfer layer contains in particular white pigments, such as titanium white, fallen chalk, alumina or colloidal silicas. If the transfer layer is to be colored, then inorganic pigments such as Hansa yellow (azo pigment yellow), ocher, iron oxide red, iron oxide black, cobalt blue, ultramarine, Berlin blue, or organic pigments such as alkali blue, phthalocyanines, azo dyes, anthraquinones and metal complex are used as colorants -Pigments, and carbon blacks used. Examples of the fluorescent dyes are: Blaze Orange T 15 der
Firma Dayglo, Maxilonbrillantflavin 10 GFF der Firma Ciba Geigy, Pyranin der Firma Bayer AG und Basonyl-Rot 540 der Firma BASF.Dayglo, Maxilonbrillantflavin 10 GFF from Ciba Geigy, pyranine from Bayer AG and Basonyl-Rot 540 from BASF.
Die Steuerung der optimalen Abdeckfunktion des erfindungsgemäßen Übertragungs- bandes, insbesondere derjenigen der bindemittelhaltigen Übertragungsschicht, kann durch den Pigmentgehalt erfolgen. Der optimale Pigmentgehalt hängt von verschiede¬ nen Faktoren ab, so von der Art des gewählten Bindemittels, des Pigments und der weiter einverleibten Additive. Ein besonders kritischer Wert bzw. kritischer Bereich kann nicht angegeben werden. Als grobe Richtlinie kann für die Beziehung Bindemit- tel/Pigment ein Gewichtsverhältnis von etwa 1: 1 bis 1: 12, insbesondere etwa 1:3 bis 1 :8 und ganz besonders zwischen etwa 1:4 bis 1:7 angegeben werden. Ein vorteilhafter Bestandteil der bindemittelhaltigen Übertragungsschicht des erfin¬ dungsgemäßen Übertragungsbandes ist ein "Abrißhilfsmittel" . Beim Aufbringen der Übertragungsschicht auf ein Substrat unter Zugspannungsbedingungen erfolgt hier¬ durch ein sauberer Abriß. Als Abrißhilfsmittel kommen lösliche Zellulosederivate in Frage. Besonders bevorzugte Zellulosederivate sind die in organischen Lösemitteln und/oder Wasser löslichen Zelluloseether, wie Methyl-, Ethyl-, Hydroxyethyl-, Ethylhydroxyethyl- und Carboxymethylzellulosen. Zelluloseester, wie Zelluloseaceto- butyrat und -propionat. Es sind auch vielfältige andere lösliche Zellulosederivate ge¬ eignet, die die gewünschten Effekte bewirken. Scheinbar ist das Zellulosegrundgerüst in dem löslichen Zellulosederivat wichtig, während die eingeführten Gruppen, wie die Ethylgruppe etc., dazu führen, daß das gebildete Derivat in dem jeweils gewählten Lösungsmittel löslich ist.The optimum covering function of the transfer belt according to the invention, in particular that of the transfer layer containing the binder, can be controlled by the pigment content. The optimum pigment content depends on various factors, such as the type of binder chosen, the pigment and the additives which are further incorporated. A particularly critical value or critical range cannot be specified. As a rough guideline, a weight ratio of about 1: 1 to 1:12, in particular about 1: 3 to 1: 8 and very particularly between about 1: 4 to 1: 7 can be given for the binder / pigment relationship. An advantageous component of the binder-containing transfer layer of the transfer belt according to the invention is a "tear-off aid". When the transfer layer is applied to a substrate under tensile stress conditions, this is done by a clean tear-off. Soluble cellulose derivatives can be used as a tear-off aid. Particularly preferred cellulose derivatives are the cellulose ethers which are soluble in organic solvents and / or water, such as methyl, ethyl, hydroxyethyl, ethylhydroxyethyl and carboxymethyl celluloses. Cellulose esters such as cellulose acetobutyrate and propionate. Various other soluble cellulose derivatives which bring about the desired effects are also suitable. It appears that the basic cellulose structure in the soluble cellulose derivative is important, while the groups introduced, such as the ethyl group, etc., result in the derivative formed being soluble in the solvent chosen in each case.
Die Menge des der Übertragungsschicht einverleibten Abrißhilfsmittels beträgt etwa 0,5 bis 5 Gew.-% , insbesondere etwa 1 ,5 bis 3,5 Gew.- % . Der Bereich von etwa 2 bis 2,5 Gew.-% ist besonders bevorzugt. Diese Angaben beziehen sich auf die Trok- kensubstanz. Zur optimalen Ausbildung der Übertragungsschicht könnte auch das Mengenverhältnis von Abrißhilfsmittel zu Bindemittel zugrunde gelegt werden. Als grobe Richtlinie kann hier das Verhältnis von Abrißhilfsmittel zu Bindemittel mit etwa 1:2 bis 1 :20 angegeben werden, wobei der Bereich von etwa 1 :4 bis 1 : 10 bevorzugt wird.The amount of the tear-off aid incorporated in the transfer layer is approximately 0.5 to 5% by weight, in particular approximately 1.5 to 3.5% by weight. The range of about 2 to 2.5% by weight is particularly preferred. This information relates to the dry substance. For the optimal formation of the transfer layer, the quantitative ratio of tear aid to binder could also be used. As a rough guideline, the ratio of demolition aid to binder can be given as about 1: 2 to 1:20, the range from about 1: 4 to 1:10 being preferred.
Zur Steuerung des Auftragvorgangs, aber auch der Eigenschaften der auf ein Substrat aufgebrachten Übertragungsschicht können dieser weitere Additive einverleibt wer- den. Hierbei kann es sich um Mittel zur Verbesserung der Deckkraft, wie insbesonde¬ re Aluminiumsilikat, Abtönmittel, wie beispielsweise Ruß, oder um das bereits er¬ wähnte Verlackungsmittel, insbesondere für basische Farbstoffe in Form von bei¬ spielsweise Gallussäurederivate, z.B. Printan der Firma Ciba Geigy, handeln.To control the application process, but also the properties of the transfer layer applied to a substrate, these further additives can be incorporated. These can be agents for improving the covering power, such as in particular aluminum silicate, tinting agents, such as carbon black, or the above-mentioned lacquering agent, in particular for basic dyes in the form of, for example, gallic acid derivatives, e.g. Printan from Ciba Geigy.
Die oben beschriebenen Materialien der einzelnen Schichten des erfindungsgemäßen Übertragungsbandes genügen in der Regel der Grundforderung, daß die Haftspannung (definiert über die Adhäsionsarbeit entsprechend der Dupre' sehen Gleichung, Lit.: K.L. Wolf "Physik und Chemie der Grenzflächen" , Springer Verlag 1957, S. 164) zwischen der Haftkleberschicht und der Übertragungsschicht größer als die zwischen dem Hilfsträger und der Übertragungsschicht ist. Sollte das im Einzelfall nicht zutref¬ fen, dann müßte eine geeignete Antihaftschicht auf den Hilfsträger aufgebracht wer¬ den, um diese Grundforderung zu erfüllen. In solchen Fällen wird regelmäßig eine weitere Forderung eingehalten, wonach die auf dem Substrat ausgebildete Über- tragungsschicht gegenüber anderen damit in Kontakt gelangenden Materialien nicht- haftend ist. Somit lassen sich im Ergebnis folgende Haftspannungsverhältnisse zur erfolgreichen Verwendung des erfindungsgemäßen Übertragungsbandes angeben, wo¬ bei das Symbol "S" das Haftspannungsverhältnis zwischen den unterschiedlichen Ma- terialien wiedergibt: Sι Papier/Haftklebeschicht, S2 Übertragungsschicht/Haft¬ klebeschicht, S3 Übertragungsschicht/Hilfsträger, S4 Übertragungsschicht/Papier und S5 Haftklebeschicht/Hilfsträger. Hierbei sind möglichst folgende Beziehungen einzu¬ halten: S, größer als S3, S2 größer als S3, S5 sehr viel kleiner als S2 und S5 kleiner als S3. Ferner sollte die freie Oberfläche der auf ein Substrat, insbesondere auf Papier, aufgetragenen Übertragungsschicht nach außen möglichst keinerlei Haftvermögen zei¬ gen, d.h. S4 ist dann Null bzw. strebt gegen Null. Die aufgetragene Übertragungs¬ schicht soll daher bei Berühren mit Hand oder mit Papier nicht-haftend sein.The materials of the individual layers of the transfer belt according to the invention described above usually meet the basic requirement that the adhesive tension (defined by the work of adhesion according to the Dupre 'see equation, Lit .: KL Wolf "Physics and Chemistry of Interfaces", Springer Verlag 1957, p 164) between the pressure-sensitive adhesive layer and the transfer layer is larger than that between the auxiliary carrier and the transfer layer. If this is not the case in individual cases, then a suitable non-stick layer would have to be applied to the auxiliary carrier in order to meet this basic requirement. In such cases, a further requirement is regularly met, according to which the excess formed on the substrate support layer is non-adhesive to other materials that come into contact with it. As a result, the following adhesive tension ratios can be specified for the successful use of the transfer tape according to the invention, the symbol "S" representing the adhesive tension relationship between the different materials: paper / pressure-sensitive adhesive layer, S 2 transfer layer / pressure-sensitive adhesive layer, S 3 transfer layer / Auxiliary carrier, S 4 transfer layer / paper and S 5 adhesive layer / auxiliary carrier. The following relationships are to be maintained here if possible: S, larger than S 3 , S 2 larger than S 3 , S 5 very much smaller than S 2 and S 5 smaller than S 3 . Furthermore, the free surface of the transfer layer applied to a substrate, in particular paper, should not show any adhesive power to the outside, ie S 4 is then zero or tends towards zero. The applied transfer layer should therefore be non-adhesive when touched by hand or with paper.
Um die gewünschten Effekte zu erzielen, werden auch bevorzugte quantitative Rah- menbedingungen für die Hohlteilchen in den beiden Schichten a) und b) eingehalten.In order to achieve the desired effects, preferred quantitative framework conditions for the hollow particles in the two layers a) and b) are also observed.
Dabei ist es bevorzugt, wenn etwa 1 bis 25 Gew.-% Hohlteilchen, insbesondere etwa 5 bis 20 Gew.-% in der bindemittelhaltigen Übertragungsschicht sowie etwa 1 bis 25 Gew.-% insbesondere etwa 5 bis 20 Gew.-% Hohlteilchen vorliegen. Bei dieser ge¬ wichtsprozentualen Angabe ist ein eventueller Wassergehalt nicht berücksichtigt.It is preferred if about 1 to 25% by weight of hollow particles, in particular about 5 to 20% by weight, are present in the binder-containing transfer layer and about 1 to 25% by weight, in particular about 5 to 20% by weight, of hollow particles. A possible water content is not taken into account in this weight percentage.
Die vorliegende Erfindung läßt sich im Hinblick auf die vorstehend geschilderten Merkmale und die damit verbundenen Effekte wie folgt technologisch erläutern:The present invention can be explained technologically with regard to the features described above and the associated effects as follows:
Werden die erörterten Hohlteilchen, insbesondere die wasserhaltigen porösen Hohlku- geln, der Haftkleberschicht einverleibt, dann führt das dazu, daß bei der erneuten Be¬ nutzung des Übertragungsbandes die durch "Austrocknen" herabgesetzte Anfangshaf¬ tung der Haftkleberschicht in Verbindung mit dem gleichfalls einverleibten festen, wasserlöslichen Alkohol erhöht wird, indem durch die Druckeinwirkung eine kleine, jedoch ausreichende Menge durch die mikroporöse Wandung der Hohlkugeln aus die- sen austritt und eine Anfeuchtung des festen Alkohols mit der Folge bewirkt, daß ein sonst möglicherweise vorliegender Tackverlust behoben wird. Um diesen Vorteil zu erzielen, wird bei der Herstellung des erfindungsmäßen Übertragungsbandes vorzugs¬ weise so vorgegangen werden, daß als feine Hohlteilchen flexible, wasserhaltige Hohlteilchen poröser Wandung eingesetzt werden und das Dispersionsmittel der Kunststoffdispersion und das Wasser der wässrigen Dispersion unter solchen schonen¬ den Bedingungen abgedampft werden, daß das innerhalb der Hohlteilchen vorliegende Wasser darin weitgehend verbleibt. Hierbei muß es nicht angestebt werden, daß das Wasser gänzlich in den Hohlkugeln verbleibt, sondern es sollte gewährleistet sein, daß nach Abschluß des Herstellungsverfahrens zumindest eine ausreichende Menge Was¬ ser in den Hohlkugeln verblieben ist. Der anwesende feste Alkohol bewirkt, daß das durch die mikroporöse Wandung austretende Wasser aufgrund des hygroskopischen Verhalten des Alkohols in einem gewissen Umfang zurückgehalten wird. Dieses "Wasserreservoir" innerhalb der Haftklebschicht wird dann besonders bewahrt, wenn das erfindungsgemäße Haftklebeband aufgerollt in einem Handkleberoller eingesetzt wird. Hierauf wird nachfolgend noch näher eingegangen.If the hollow particles discussed, in particular the water-containing porous hollow spheres, are incorporated into the pressure-sensitive adhesive layer, this leads to the fact that when the transfer tape is used again, the initial adhesion of the pressure-sensitive adhesive layer reduced by "drying out" in conjunction with the likewise incorporated solid, water-soluble alcohol is increased by a small but sufficient amount of pressure escaping through the microporous wall of the hollow spheres due to the action of pressure and a moistening of the solid alcohol with the result that an otherwise possible loss of tack is eliminated. In order to achieve this advantage, the procedure according to the invention for the production of the transfer belt is preferably such that flexible, water-containing hollow particles with a porous wall are used as fine hollow particles and the dispersant of the plastic dispersion and the water of the aqueous dispersion are evaporated under such gentle conditions be that the water present within the hollow particles largely remains therein. It should not be attempted here that the water remains entirely in the hollow spheres, but it should be ensured that at least a sufficient amount of water remained in the hollow spheres after completion of the production process. The presence of solid alcohol causes the water exiting through the microporous wall to be retained to a certain extent due to the hygroscopic behavior of the alcohol. This "water reservoir" within the pressure-sensitive adhesive layer is particularly preserved when the pressure-sensitive adhesive tape according to the invention is used rolled up in a hand-held roller. This will be discussed in more detail below.
Der oben angesprochene Mechanismus beim Einsatz des erfindungsgemäßen Übertra- gungsbandes im Hinblick auf festen Alkohol/poröse Hohlteilchen gilt entsprechend auch für die Funktionalität der Übertragungsschicht des erfindungsgemäßen Übertra¬ gungsbandes. Auch hier wird durch den Auftragsdruck Wasser durch die mikroporöse Wandung der Hohlteilchen mit der Folge gedrückt, daß der feste Alkohol zumindest angelöst oder in Einzelfällen gelöst wird. Hier bewirkt der feste Alkohol in diesem Zustand eine temporäre Weichmachung der bindemittelhaltigen Übertragungsschicht, so daß diese während des Auftragsvorgangs flexibler wird und sich keine Mikrorisse einstellen. Durch Zurücknahme des Auftragdrucks verflüchtigt sich das aus den Hohlteilchen gedrückte Wasser trotz des hygroskopischen Verhaltens des festen Alko¬ hols in einem gewissen Umfang, so daß dieser wieder fest und die temporäre Weich- machung behoben wird.The above-mentioned mechanism when using the transmission belt according to the invention with regard to solid alcohol / porous hollow particles also applies accordingly to the functionality of the transmission layer of the transmission belt according to the invention. Here, too, water is pressed through the microporous wall of the hollow particles by the application pressure, with the result that the solid alcohol is at least dissolved or dissolved in individual cases. In this state, the solid alcohol temporarily softens the binder-containing transfer layer so that it becomes more flexible during the application process and no microcracks occur. By reducing the application pressure, the water pressed out of the hollow particles evaporates to a certain extent in spite of the hygroscopic behavior of the solid alcohol, so that it becomes firm again and the temporary softening is eliminated.
Auf den Einsatz der insbesondere porösen Hohlteilchen in der Übertragungsschicht scheinen weitere Vorteile zurückzugehen: So hat es sich gezeigt, daß mit ansteigen¬ dem Anteil an Hohlteilchen das "Durchbluten" eines korrigierten Schriftzugs, wohl aufgrund des hydrophoben Charakters der Wandung der Hohlteilchen, zurückgedrängt wird. Dieser wünschenwerte Effekt wird besonders in dem angesprochenen optimalen gewichtsprozentualen Rahmen der Hohlteilchen erzielt. Darüber hinaus steigert der Hohlteilchenanteil mit der Folge das Deckvermögen, daß der Anteil an teurem bei¬ spielsweise Weißpigment in Form von Titandioxid gesenkt werden kann. Die sehr kleine und außergewöhnlich regelmäßige Teilchengröße der angesprochenen Hohlteil¬ chen verhindert die Zusammenlagerung der Pigmentteilchen, insbesondere der Titan¬ dioxidteilchen, so daß keine Inhomogenitäten in der Übertragungsschicht auftreten, die beim Einsatz des Übertragungsbandes oft Ursache für das Auftreten von Mikroris- sen bedeuten. Daher wird der Abdeckschicht eine verbesserte Elastizität vermittelt, die ebenfalls dem Auftreten von Mikrorissen entgegenwirkt.The use of the porous hollow particles in particular in the transfer layer seems to have further advantages: it has been shown that with increasing proportion of hollow particles the "bleeding through" of a corrected lettering is suppressed, probably due to the hydrophobic character of the wall of the hollow particles. This desirable effect is achieved particularly in the optimal weight percentage framework of the hollow particles. In addition, the proportion of hollow particles increases the hiding power, which means that the proportion of expensive, for example, white pigment in the form of titanium dioxide can be reduced. The very small and exceptionally regular particle size of the hollow particles mentioned prevents the pigment particles, in particular the titanium dioxide particles, from accumulating, so that there are no inhomogeneities in the transfer layer which often cause the occurrence of microcracks when the transfer belt is used. Therefore, the covering layer is given an improved elasticity, which also counteracts the occurrence of microcracks.
Bei der Verwendung des erfindungsgemäßen Übertragungsbandes bedient man sich vorteilhafterweise Auftragsgeräte, die ein Abrollen der mit dem Haftkleber versehe- nen Übertragungsschicht bei gleichzeitigem Einzug des Hilfsträgers ermöglichen. Dies führt zu einer besonders leichten Handhabung des erfindungsgemäßen Übertragungs¬ bandes. Dies können handelsübliche Handgeräte sein. Als ein hierfür besonders ge¬ eignetes Handgerät kann ein sogenannter "Handroller" eingesetzt werden, bei dem innerhalb eines griffgünstig gestalteten Gehäuses eine Vorratsspule mit dem Übertra¬ gungsband vorgesehen ist, von der aus es über einen aus dem Gehäuse vorstehenden Auftragsfuß geführt und von diesem wieder auf eine Aufwickelspule in das Gehäuse zurückgeleitet wird. Durch ein geeignetes Getriebe zwischen beiden Spulen im Ge¬ häuse wird sichergestellt, daß das Übertragungsband stets ausreichend gespannt ge- führt wird. Der Benutzer nimmt zum Einsatz des Übertragungsbandes das Gehäuse in seine Hand und drückt mittels des Auftragsfußes die über dessen Endkante laufende äußere (ablösbare) Bandschicht gegen das Substrat, auf das sie übertragen werden soll (z.B. ein bedrucktes Blatt Papier, um Korrekturen vorzunehmen). Während des An- drückens bewegt der Benutzer das Gerät relativ zum Substrat und überträgt dabei z.B. eine deckende Schicht oder eine fluoreszierende Schicht auf das Substrat, wobei der flexible Hilfsträger von der Vorratsspule ab- und auf die Aufwickelspule aufgewickelt wird.When using the transfer belt according to the invention, use is advantageously made of applicators which unroll the pressure-sensitive adhesive. Enable a transmission layer while the subcarrier is being pulled in. This leads to particularly easy handling of the transmission belt according to the invention. These can be standard handheld devices. A so-called "hand roller" can be used as a hand-held device that is particularly suitable for this purpose, in which a supply spool with the transfer belt is provided within a housing that is designed to be easy to grip, from which it is guided via an application foot protruding from the housing and from it again is fed back into the housing on a take-up spool. A suitable gear between the two coils in the housing ensures that the transfer belt is always guided with sufficient tension. To use the transfer tape, the user takes the housing in his hand and uses the application foot to press the outer (removable) tape layer running over its end edge against the substrate to which it is to be transferred (e.g. a printed sheet of paper to make corrections). During pressing, the user moves the device relative to the substrate and transfers, for example, a covering layer or a fluorescent layer to the substrate, the flexible auxiliary carrier being wound off the supply spool and wound onto the take-up spool.
Es ist ohne weiteres ersichtlich, daß die Funktionsweise des oben beschriebenen Handgeräts es erforderlich macht, daß die bereits angesprochene Haftspannungsver¬ hältnisse eingehalten werden, d.h. die Haftkleberschicht zur Rückseite des Hilfsträgers eine Haftung aufweist, die kleiner als die Haftung zwischen der bindemittelhaltigen Übertragungsschicht und Haftkleberschicht und kleiner als die Haftung zwischen bin- demittelhaltiger Übertragungsschicht und Hilfsträger ist.It is readily apparent that the operation of the hand-held device described above makes it necessary to adhere to the previously mentioned adhesive tension ratios, i.e. the pressure-sensitive adhesive layer has an adhesion to the back of the auxiliary carrier which is less than the adhesion between the binder-containing transfer layer and the pressure-sensitive adhesive layer and less than the adhesion between the binder-containing transfer layer and the auxiliary carrier.
Das erfindungsgemäße Übertragungsband zeichnet sich in besonderer Weise als Kor¬ rekturmittel in Büro, Schule und Haushalt zum Abdecken fehlerhafter Schriftzeichen, von Markierungen und zeichnerischen Darstellungen und Wiederbeschriften aus. Eine andere Verwendung des Übertragungsbandes kann die auffallend farbige Markierung von Flächen, Schriften und/oder Zeichen sein. Dazu trägt das Übertragungsband eine ein Bunφigment enthaltende Übertragungsschicht. Eine weitere Verwendung besteht in dem Hervorheben von Textstellen, Zeichen oder bildlichen Darstellungen. Dazu ist die Übertragungsschicht vorzugsweise transparent und mit einem in Tageslicht fluo¬ reszierenden Farbmittel eingefärbt. In allen hier genannten Anwendungsbeispielen erweist es sich als besonders vorteilhaft, daß die Anwendung "trocken" erfolgt, d.h. kein Verwischen flüssiger Aufstriche und kein Verdunsten bedenklicher Lösemittel erfolgt und eine sofortige Wiederbeschriftung möglich ist. Mit dem erfindungsgemä¬ ßen Übertragungsband lassen sich also leicht, schnell und gleichmäßig z.B. Deck- schichten, die insbesondere Farbmittel enthalten, auf Substrate auftragen. Wenn die Übertragungsschicht des erfindungsgemäßen Übertragungsbandes transparent ist, also beispielsweise keine deckenden Pigmente enthält, dann kann sie zur bloßen Abdek- kung ohne Farbwirkung und Konservierung von sonst gegenüber Lufteinwirkungen und dergleichen empfindlichen Schriftzeichen herangezogen werden.The transmission tape according to the invention is particularly distinguished as a correction means in the office, school and household for covering faulty characters, markings and graphic representations and rewriting. Another use of the transfer belt can be the strikingly colored marking of areas, fonts and / or characters. For this purpose, the transmission band carries a transmission layer containing a bun pigment. Another use is to highlight text passages, characters or pictorial representations. For this purpose, the transfer layer is preferably transparent and colored with a colorant that is fluorescent in daylight. In all of the application examples mentioned here, it proves to be particularly advantageous that the application takes place “dry”, ie there is no smudging of liquid spreads and no evaporation of questionable solvents and immediate rewriting is possible. With the transfer belt according to the invention, for example, covering, for example, Apply layers that contain colorants in particular to substrates. If the transfer layer of the transfer tape according to the invention is transparent, for example does not contain any covering pigments, then it can be used for mere covering without coloring and preserving characters that are otherwise sensitive to the effects of air and the like.
Die Gebrauchseigenschaften des erfindungsgemäßen Übertragungssbandes sind insbe¬ sondere umfassend verbessert. So wird die Haftkleberschicht bei längerer Lagerung, wenn sie weitgehend ausgetrocknet ist, zumindest geringfügig befeuchtet und auf die- se Weise die Klebekraft verbessert, wenn sie die beschriebenen Hohlteilchen enthält. Durch deren Einbeziehung zusammen mit einem festen Alkohhol in die Übertragungs¬ schicht wird deren Kohäsion herabgesetzt und damit das Abrißverhalten verbessert. Dies erfolgt durch temporäre Weichmachung. Die Einbeziehung einer größeren Men¬ ge üblicher Weichmacher ist nachteilig, wie bereits oben gezeigt, da diese die Ab- deckschicht dauerhaft weichmachen würde. Dies hätte unter anderem zur Folge, daß ein unerwünschtes Ausbluten der abgedeckten Schriftzüge oder sogar ein Durchbluten auftreten würde. Beim Beschreiben einer derartigen Übertragungsschicht mit Tinte würde diese auslaufen. Darüber hinaus führt der Einsatz der feinen flexiblen, wasser¬ haltigen Hohlteilchen dazu, daß beispielsweise beim Einsatz von teuren Pigmenten, insbesondere beispielsweise Titandioxid, die Menge an Pigment herabgesetzt werden kann.The performance characteristics of the transmission tape according to the invention are particularly comprehensively improved. Thus, the long-term storage of the pressure-sensitive adhesive layer, if it has largely dried out, is at least slightly moistened and the adhesive force is improved in this way if it contains the hollow particles described. By including them together with a solid alcohol in the transfer layer, their cohesion is reduced and thus the tear behavior is improved. This is done by temporary softening. The inclusion of a larger amount of conventional plasticizers is disadvantageous, as already shown above, since this would permanently soften the cover layer. One of the consequences of this would be that undesired bleeding of the covered lettering or even bleeding would occur. Writing on such a transfer layer with ink would cause it to leak. In addition, the use of the fine, flexible, water-containing hollow particles means that, for example when using expensive pigments, in particular, for example, titanium dioxide, the amount of pigment can be reduced.
Die Erfindung wird nachfolgend anhand von Beispielen noch näher erläutert.The invention is explained in more detail below with the aid of examples.
Beispiel 1 (Ausführungsform der Übertragungsschicht)Example 1 (embodiment of the transfer layer)
Es wird folgende wäßrige Dispersion zur Ausbildung der farbmittelhaltigen Übertra¬ gungsschicht hergestellt: The following aqueous dispersion is produced to form the colorant-containing transfer layer:
Wäßrige Acrylatd ispers ionAqueous acrylic dispersion
(25 % ig in Wasser / Handelsprodukt Worleecryl® 7712W der Firma Worlee Chemie GmbH, Hamburg) 23,42 Gew. -Teile(25% strength in water / commercial product Worleecryl 7712W ® from Worlee Chemie GmbH, Hamburg) 23.42 parts by wt.
Lactimon® WS (Alkylammoniumsalze von Polycarbonsäuren undLactimon ® WS (alkyl ammonium salts of polycarboxylic acids and
Polysiloxancopolymer) 0,8 Gew. -TeilePolysiloxane copolymer) 0.8 parts by weight
2-Butoxyethanol 1,5 Gew. -Teile2-butoxyethanol 1.5 parts by weight
Byk®-034Byk ® -034
(Flydrophobe, silikonartige Komponenten in Mineralöl) 0,2 Gew. -Teile Byk®-307(Flydrophobic, silicone-like components in mineral oil) 0.2 parts by weight of Byk ® -307
(Polyethermodifiziertes Dimethylpolysiloxancopolymer) 0,02 Gew. -Teile(Polyether modified dimethylpolysiloxane copolymer) 0.02 part by weight
Sorbit 5,00 Gew. -TeileSorbitol 5.00 parts by weight
Kieselsäure 4,00 Gew. -TeileSilica 4.00 parts by weight
Titandioxid 35,00 Gew. -Teile Elfenbeinschwarz 0,06 Gew. -Teile wäßrige Dispersion von feinen Hohlkugeln 30.00 Gew. -TeileTitanium dioxide 35.00 parts by weight ivory black 0.06 parts by weight aqueous dispersion of fine hollow spheres 30.00 parts by weight
100,00 Gew. -Teile100.00 parts by weight
Die oben bezeichnete wäßrige Hohlkugeldispersion wird wie folgt hergestellt:The above-mentioned aqueous hollow sphere dispersion is prepared as follows:
800 Gew-Teile der im Handel erhältlichen Ropaque®-Emulsion Op-62 LO-E der Fir¬ ma Rohm & Haas Company, Philadelphia, USA (bestehend aus einem nicht- filmbildenden Polymer eines effektiven Feststoffgehaltes von 52 % sowie eines tat¬ sächlichen Feststoffgehaltes von 37,5 % und eines pH-Wertes von 8,0 bis 8,7 (Teilchendurchmesser 0,4 μm, Innendurchmesser 0,28 μm) werden mit 176 Gew.- Teilen Wasser und 2 Gew. -Teilen eines Entschäumeradditivs (Byk® -034) (hydrophobe, silikonhaltige Komponenten in Mineralöl) und 22 Gew. -Teilen einer Ameisensäure-Lösung (hergestellt durch Vermischen vn 100 Gew. -Teilen Ameisen¬ säure konz. un 900 Gew. -Teilen Wasser) gemischt. Von dieser angesäuterten Disper¬ sion werden in der obigen Rezeptur 30 Gew. -Teile eingesetzt.800 parts by weight of the Ropaque ® emulsion commercially available Op-62 LO-E of Fir¬ ma Rohm & Haas Company, Philadelphia, USA (consisting of a non-film-forming polymer of an effective solid content of 52% and a tat¬ extraneous solids content (microns particle diameter 0.4, inner diameter 0.28 microns) of 37.5% and a pH of 8.0 to 8.7 are 176 parts by weight of water and 2 wt. parts by a Entschäumeradditivs (Byk ® -034) (hydrophobic, silicone-containing components in mineral oil) and 22 parts by weight of a formic acid solution (produced by mixing 100 parts by weight of formic acid and 900 parts by weight of water), from which the dispersed acid ¬ sion 30 parts by weight are used in the above recipe.
Die vorstehende Abdeckmasse wird mit einer Rakel in einer Menge von 18 g/m2 auf einen silikonisierten Papierträger aufgetragen. Dann wird das Wasser bei etwa 80°C durch Überleiten warmer Luft abgedampft.The above masking compound is applied with a doctor blade in an amount of 18 g / m 2 onto a siliconized paper carrier. Then the water is evaporated at about 80 ° C by passing warm air over it.
Anschließend wird eine wäßrige Dispersion, die aus folgenden Bestandteilen besteht, mit einer Rakel auf die Oberfläche der farbmittelhaltigen Abdeckschicht aufgetragen. Haftkleber auf Acrylatbasis 57,3 Gew. -TeileAn aqueous dispersion consisting of the following constituents is then applied with a doctor blade to the surface of the colorant-containing cover layer. Acrylic-based pressure sensitive adhesive 57.3 parts by weight
(Kunststoff-Dispersion VP 859/6 der Firma Freihoff) (Copolymer auf Basis von Acrylsäureester) Wasser 41, 1 Gew. -Teile(Plastic dispersion VP 859/6 from Freihoff) (copolymer based on acrylic acid ester) water 41.1 parts by weight
Ammoniak 1.6 Gew. -TeileAmmonia 1.6 parts by weight
100,0 Gew. -Teile100.0 parts by weight
Die Haftklebemasse wird mit einer Rakel in einer Stärke von 3 g/m aufgetragen. Dann wird der Wasseranteil der Haftklebemasse bei etwa 80°C durch Überleiten von Luft abgedampft. Das Wasser innerhalb der Hohlkugeln in der Übertragungsschicht verbleibt hierbei darin.The PSA is applied with a doctor blade in a thickness of 3 g / m. Then the water portion of the PSA is evaporated at about 80 ° C by passing air over it. The water inside the hollow spheres in the transfer layer remains in it.
Das erhaltene Übertragungsband ist besonders zum Abdecken von auf Papier be- schriebenen Schriftzeichen geeignet. Es führt zum schnellen und gleichmäßigen Auf¬ bringen eines unmittelbar wiederbeschreibbaren Abdeckstreifens, wobei das Auftragen durch einen im Handel erhältlichen Handroller erfolgt. Neu aufgetragene Schriftzei¬ chen sind klar und zeigen bei mikroskopischer Betrachtung in den Randbereichen kein Auslaufen.The transfer tape obtained is particularly suitable for covering characters written on paper. It leads to the rapid and uniform application of an immediately rewritable cover strip, the application being carried out using a commercially available hand roller. Newly applied characters are clear and, when viewed microscopically, show no leakage in the edge areas.
Beispiel 2 (Ausführungsform zur Übertragungsschicht)Example 2 (embodiment for the transmission layer)
Es wird folgende wäßrige Dispersion zur Ausbildung der farbmittelhaltigen Übertra- gungsschicht hergestellt: The following aqueous dispersion for producing the colorant-containing transfer layer is produced:
Wäßrige Acrylatd ispers ionAqueous acrylic dispersion
(25 % ig in Wasser / Handelsprodukt Worleecryl® 7712W der Firma Worlee Chemie GmbH, Hamburg) 20,42 Gew. -Teile(25% strength in water / commercial product Worleecryl 7712W ® from Worlee Chemie GmbH, Hamburg) 20.42 parts by wt.
Lactimon® WS (Alkylammoniumsalze von Polycarbonsäuren undLactimon ® WS (alkyl ammonium salts of polycarboxylic acids and
Polysiloxancopolymer) 0,8 Gew. -TeilePolysiloxane copolymer) 0.8 parts by weight
2-Butoxyethanol 1,5 Gew. -Teile2-butoxyethanol 1.5 parts by weight
Byk®~034Byk ® ~ 034
(Hydrophobe, silikonhaltige Komponenten in Mineralöl) 0,2 Gew. -Teile Byk®-307(Hydrophobic, silicone-containing components in mineral oil) 0.2 parts by weight of Byk ® -307
(Polyethermodifiziertes Dimethylpolysiloxancopolymer) 0,02 Gew. -Teile(Polyether modified dimethylpolysiloxane copolymer) 0.02 part by weight
Sorbit 8,00 Gew. -TeileSorbitol 8.00 parts by weight
Kieselsäure 4,00 Gew. -TeileSilica 4.00 parts by weight
Titandioxid 35,00 Gew. -Teile Elfenbeinschwarz 0,06 Gew. -Teile wäßrige Dispersion von Hohlkugeln 30.00 Gew. -TeileTitanium dioxide 35.00 parts by weight of ivory black 0.06 parts by weight of aqueous dispersion of hollow spheres 30.00 parts by weight
100,00 Gew. -Teile100.00 parts by weight
Diese Dispersion wurde in der gleichen Weise eingesetzt, wie sie in Beispiel 1 be- schrieben ist. Das gleiche gilt auch für die Ausbildung der Haftkleberschicht.This dispersion was used in the same manner as described in Example 1. The same applies to the formation of the pressure sensitive adhesive layer.
Beispiel 3 (Ausführungsform zur Haftkleberschicht)Example 3 (embodiment for the pressure-sensitive adhesive layer)
Es wird folgende wäßrige Dispersion zur Ausbildung der.farbmittelhaltigen Übertra- gungsschicht hergestellt:The following aqueous dispersion is produced to form the colorant-containing transfer layer:
Haftkleberrezeptur -Ausführungsbeispiel 1Pressure sensitive adhesive formulation - exemplary embodiment 1
Wasser 16, 1 Gew. -Teile Haftkleber auf Acrylatbasis (50% ig) 57,3 Gew. -TeileWater 16.1 parts by weight of pressure sensitive adhesive based on acrylate (50%) 57.3 parts by weight
(Kunststoffdispersion VP 859/6 der Firma Freihoff)(Plastic dispersion VP 859/6 from Freihoff)
Ammoniak 1,6 Gew. -TeileAmmonia 1.6 parts by weight
Sorbit 10,0 Gew. -TeileSorbitol 10.0 parts by weight
Ropaque® OP-62 LO-E (37,5 % ig) 15,0 Gew. -TeileRopaque ® OP-62 LO-E (37.5%) 15.0 parts by weight
100,0 Gew. -Teile100.0 parts by weight
Die Ausbildung der Haftkleberschicht erfolgte entsprechend Beispiel 1. Beispiel 4 (Ausführungsform zur Haftkleberschicht)The pressure-sensitive adhesive layer was formed in accordance with Example 1. Example 4 (embodiment of the pressure-sensitive adhesive layer)
Es wird folgende wäßrige Dispersion zur Ausbildung der farbmittelhaltigen Übertra¬ gungsschicht hergestellt:The following aqueous dispersion is produced to form the colorant-containing transfer layer:
Haftkleberrezeptur - Ausführungsbeispiel 2Pressure sensitive adhesive formulation - working example 2
Wasser 21, 1 Gew. -TeileWater 21, 1 parts by weight
Haftkleber auf Acrylatbasis (50% ig) 57,3 Gew. -TeileAcrylic-based pressure sensitive adhesive (50%) 57.3 parts by weight
(Kunststoffdispersion VP 859/6 der Firma Freihoff)(Plastic dispersion VP 859/6 from Freihoff)
Ammoniak 1,6 Gew. -TeileAmmonia 1.6 parts by weight
Sorbit 5,0 Gew. -TeileSorbitol 5.0 parts by weight
Ropaque® OP-62 LO-E (37,5 % ig) 15.0 Gew. -TeileRopaque ® OP-62 LO-E (37.5%) 15.0 parts by weight
100,0 Gew. -Teile100.0 parts by weight
Die Ausbildung der Haftkleberschicht erfolgte entsprechend Beispiel 1. The pressure-sensitive adhesive layer was formed in accordance with Example 1.

Claims

Patentansprüche claims
1. Mehrschichtiges, flexibles Ubertragungsband mit einem Hilfsträger und einer Haftkleberschicht, wobei zwischen dem Hilfsträger und der Haftkleberschicht eine bindemittelhaltige Übertragungsschicht, die zur Haftkleberschicht eine stärkere Haf¬ tung als zum Hilfsträger aufweist, vorliegt, dadurch gekennzeichnet, daß a) die bin¬ demittelhaltige Übertragungsschicht und/oder b) die Haftkleberschicht feine Hohlteil¬ chen und einen wasserlöslichen, festen Alkohol enthalten.1. Multilayer, flexible transfer belt with an auxiliary carrier and a pressure-sensitive adhesive layer, a binder-containing transfer layer being present between the auxiliary carrier and the pressure-sensitive adhesive layer, which has a stronger adhesion to the pressure-sensitive adhesive layer than to the auxiliary carrier, characterized in that a) the binder-containing transfer layer and / or b) the pressure-sensitive adhesive layer contains fine hollow particles and a water-soluble, solid alcohol.
2. Ubertragungsband nach Anspruch 1 , dadurch gekennzeichnet, daß die feinen Hohlteilchen flexible, wasserhaltige Hohlteilchen poröser Wandung darstellen.2. Transfer belt according to claim 1, characterized in that the fine hollow particles are flexible, water-containing hollow particles porous wall.
3. Ubertragungsband nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß die Hohlteilchen im Falle des Vorliegens in der bindemittelhaltigen Übertragungsschicht einen Durchmesser von etwa 0,3 bis 10 μm aufweisen und im Falle des Vorliegens in der Haftkleberschicht einen Durchmesser von etwa 0,3 bis 2 μm aufweisen.3. Transfer belt according to claim 1 or 2, characterized in that the hollow particles in the presence of the binder-containing transfer layer have a diameter of about 0.3 to 10 microns and in the presence of the pressure-sensitive adhesive layer a diameter of about 0.3 to Have 2 μm.
4. Ubertragungsband nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, daß das Hohlraumvolumen der Hohlteilchen etwa 20 bis 55 %, insbesondere etwa 25 bis4. Transfer belt according to one of claims 1 to 3, characterized in that the void volume of the hollow particles is about 20 to 55%, in particular about 25 to
40% , beträgt.40%.
5. Ubertragungsband nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, daß die bindemittelhaltige Übertragungsschicht etwa 3 bis 25 Gew.- % wasserlöslichen, festen Alkohol enthält.5. Transfer belt according to one of claims 1 to 4, characterized in that the binder-containing transfer layer contains about 3 to 25% by weight of water-soluble, solid alcohol.
6. Ubertragungsband nach Anspruch 4, dadurch gekennzeichnet, daß in der bindemit¬ telhaltigen Übertragungsschicht etwa 1 bis 25 Gew.- % Hohlteilchen vorliegen.6. Transfer belt according to claim 4, characterized in that about 1 to 25% by weight of hollow particles are present in the binder-containing transfer layer.
7. Ubertragungsband nach Anspruch 4, dadurch gekennzeichnet, daß in der Haftkle- berschicht etwa 1 bis 25 Gew.- % Hohlteilchen vorliegen. 7. Transfer belt according to claim 4, characterized in that about 1 to 25% by weight of hollow particles are present in the pressure-sensitive adhesive layer.
8. Ubertragungsband nach mindestens einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, daß die Haftkleberschicht etwa 1 bis 40 Gew.-% wasserlöslichen, festen Alkohol enthält.8. Transfer belt according to at least one of the preceding claims, characterized in that the pressure-sensitive adhesive layer contains approximately 1 to 40% by weight of water-soluble, solid alcohol.
9. Verfahren zur Herstellung eines mehrschichtigen, flexiblen Übertragungsbandes nach mindestens einem der Ansprüche 1 bis 8, dadurch gekennzeichnet, daß eine pigmenthaltige Kunststoffdispersion nach üblichen Auftragstechnologien auf einen flexiblen Hilfsträger aufgetragen, das Dispersionsmittel abgedampft, darauf eine einen Haftkleber enthaltende wäßrige Dispersion nach üblichen Auftragstechnologien auf die ausgebildete Übertragungsschicht aufgetragen und danach das Wasser abgedampft wird, wobei a) die pigmenthaltige Kunststoffdispersion einen wasserlöslichen, festen Alkohol und feine Hohlteilchen enthält und/oder b) die den Haftkleber enthaltende wäßrige Dispersion einen wasserlöslichen festen Alkohol und feine Hohlteilchen enthält.9. A process for the production of a multilayer, flexible transfer belt according to at least one of claims 1 to 8, characterized in that a pigment-containing plastic dispersion applied by customary application technologies to a flexible auxiliary carrier, the dispersant is evaporated, then an aqueous dispersion containing a pressure sensitive adhesive according to conventional application technologies the transfer layer formed is applied and then the water is evaporated off, a) the pigment-containing plastic dispersion containing a water-soluble, solid alcohol and fine hollow particles and / or b) the aqueous dispersion containing the pressure sensitive adhesive contains a water-soluble solid alcohol and fine hollow particles.
10. Verwendung des Übertragungsbandes nach einem der Ansprüche 1 bis 8 in aufge¬ rollter Form in einem Handgerät, wobei die Haftkleberschicht zur Rückseite des Hilfsträgers eine Haftung aufweist, die kleiner als die Haftung zwischen der Übertra- gungsschicht und Haftkleberschicht und kleiner als die Haftung zwischen Übertra¬ gungsschicht und Hilfsträger ist. 10. Use of the transfer tape according to one of claims 1 to 8 in rolled up form in a hand-held device, the pressure-sensitive adhesive layer to the back of the auxiliary carrier having an adhesion which is less than the adhesion between the transfer layer and the pressure-sensitive adhesive layer and less than the adhesion between Transfer layer and subcarrier.
EP96904856A 1995-03-14 1996-02-23 Multi-layer, flexible transfer strip, a process for its production and its use in a hand device Expired - Lifetime EP0814963B1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19509124 1995-03-14
DE19509124 1995-03-14
PCT/EP1996/000757 WO1996028308A1 (en) 1995-03-14 1996-02-23 Multi-layer, flexible transfer strip, a process for its production and its use in a hand device

Publications (2)

Publication Number Publication Date
EP0814963A1 true EP0814963A1 (en) 1998-01-07
EP0814963B1 EP0814963B1 (en) 1998-12-09

Family

ID=7756603

Family Applications (1)

Application Number Title Priority Date Filing Date
EP96904856A Expired - Lifetime EP0814963B1 (en) 1995-03-14 1996-02-23 Multi-layer, flexible transfer strip, a process for its production and its use in a hand device

Country Status (17)

Country Link
US (1) US5891562A (en)
EP (1) EP0814963B1 (en)
JP (1) JPH11502477A (en)
KR (1) KR19980703021A (en)
AT (1) ATE174270T1 (en)
AU (1) AU692366B2 (en)
BR (1) BR9607353A (en)
CA (1) CA2215388A1 (en)
CR (1) CR5280A (en)
CZ (1) CZ285897A3 (en)
DE (2) DE19606839C2 (en)
FI (1) FI105087B (en)
NO (1) NO309182B1 (en)
RU (1) RU2155676C2 (en)
TW (1) TW306896B (en)
WO (1) WO1996028308A1 (en)
ZA (1) ZA962019B (en)

Families Citing this family (23)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19617850C1 (en) * 1996-05-03 1997-06-05 Henkel Kgaa Multilayered flexible transfer strip with auxiliary support and pressure sensitive adhesive layer
US6277368B1 (en) * 1996-07-25 2001-08-21 The Regents Of The University Of California Cancer immunotherapy using autologous tumor cells combined with cells expressing a membrane cytokine
DE19744956C2 (en) * 1997-10-10 2002-10-31 Pelikan Produktions Ag Egg Thermal transfer ribbon for luminescent characters
DE69813202D1 (en) * 1997-04-10 2003-05-15 Stephane Christopher Martel DEVICE FOR DOSED DIFFUSION FROM ONE OR MORE FLOWING MEDIA
FR2761928B1 (en) * 1997-04-10 1999-05-14 Stephan Christopher Martell TEMPORARY TATTOO APPLICATION DEVICE
GB9718238D0 (en) * 1997-08-28 1997-11-05 Trip Productions B V Decalcamania having solvent-activated adhesive layers
DE19744957C1 (en) * 1997-10-10 1999-07-29 Pritt Produktionsgesellschaft Multi-layer, flexible correction tape
FR2780341B1 (en) * 1998-06-29 2000-09-29 Stephane Christopher Martel DEVICE FOR APPLYING AN ADHESIVE TEMPORARY TATTOO
FR2780342B1 (en) * 1998-06-29 2000-09-29 Stephane Christopher Martel DEVICE FOR APPLYING AN ADHESIVE TEMPORARY TATTOO
DE10106596A1 (en) * 2001-02-09 2002-08-22 Deotexis Inc Process for area-wise printing of a textile material
JP4079617B2 (en) * 2001-10-01 2008-04-23 ゼネラル株式会社 Transfer tape, transfer tool, and method for cutting adhesive layer of transfer tape
AU2003292727A1 (en) * 2002-12-27 2004-07-29 Nagase Chemtex Corporation Method for producing fiber-reinforced thermoplastic plastic and fiber-reinforced thermoplastic prastic
US20050056377A1 (en) * 2003-09-17 2005-03-17 General Co., Ltd. Transfer tool
US7332046B2 (en) * 2003-09-26 2008-02-19 Eastman Chemical Company Methods of blocking stains on a substrate to be painted, and composites suitable for use in such methods
JP2006168164A (en) * 2004-12-15 2006-06-29 Tombow Pencil Co Ltd Pressure-sensitive transfer correction tape
US20060177649A1 (en) * 2005-02-07 2006-08-10 Clark Mark D Methods of blocking stains on a substrate to be painted, and composites suitable for use in such methods
US20070038807A1 (en) * 2005-08-11 2007-02-15 International Business Machines Corporation Reduced stress relaxation in elastomeric compression structures adapted for use with electrical components
US8397784B2 (en) 2010-08-31 2013-03-19 Sanford, L.P. Correction tape dispenser with variable clutch mechanism
US8578999B2 (en) 2010-12-29 2013-11-12 Sanford, L.P. Variable clutch mechanism and correction tape dispenser with variable clutch mechanism
US8746313B2 (en) 2010-12-29 2014-06-10 Sanford, L.P. Correction tape re-tensioning mechanism and correction tape dispenser comprising same
US8746316B2 (en) 2011-12-30 2014-06-10 Sanford, L.P. Variable clutch mechanism and correction tape dispenser with variable clutch mechanism
US9606098B2 (en) * 2013-03-29 2017-03-28 Weyerhaeuser Nr Company Moisture indicator for wood substrates
US10639921B2 (en) 2016-07-26 2020-05-05 Hewlett-Packard Development Company, L.P. Transfer printing

Family Cites Families (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3413168A (en) * 1967-05-03 1968-11-26 Minnesota Mining & Mfg Adhesive bonding method permitting precise positioning
US3869393A (en) * 1970-05-21 1975-03-04 Everlube Corp Of America Solid lubricant adhesive film
CA1180474A (en) * 1979-06-26 1985-01-02 Alexander Kowalski Sequential heteropolymer dispersion and a particulate material obtainable therefrom useful in coating compositions as a thickening and/or opacifying agent
US4427836A (en) * 1980-06-12 1984-01-24 Rohm And Haas Company Sequential heteropolymer dispersion and a particulate material obtainable therefrom, useful in coating compositions as a thickening and/or opacifying agent
JPS58142944A (en) * 1982-02-19 1983-08-25 Pentel Kk Solid coating material
US4654256A (en) * 1985-02-08 1987-03-31 Minnesota Mining And Manufacturing Company Article containing microencapsulated materials
JP2500934B2 (en) * 1985-03-27 1996-05-29 ティーディーケイ株式会社 Magnetic recording media
US4891260A (en) * 1987-12-03 1990-01-02 Pelikan Aktiengesellschaft Multilayer flexible transfer ribbon
US5135798A (en) * 1987-12-03 1992-08-04 Pelikan Aktiengesellschaft Multilayer, flexible transfer strip
DE3741022C3 (en) * 1987-12-03 1994-12-22 Pelikan Ag Multilayer, flexible transfer belt
JP2809229B2 (en) * 1988-05-12 1998-10-08 三菱製紙株式会社 Thermal recording material
DE3918616A1 (en) * 1989-06-07 1990-12-13 Minnesota Mining & Mfg DUCT TAPE
DE3925130A1 (en) * 1989-07-28 1991-01-31 Pelikan Ag MULTILAYER, FLEXIBLE MARKING BAND
US5344705A (en) * 1993-05-05 1994-09-06 Minnesota Mining And Manufacturing Company Retroreflective transfer sheet material

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9628308A1 *

Also Published As

Publication number Publication date
NO973603D0 (en) 1997-08-05
ZA962019B (en) 1996-09-26
KR19980703021A (en) 1998-09-05
DE59600968D1 (en) 1999-01-21
NO309182B1 (en) 2000-12-27
FI105087B (en) 2000-06-15
WO1996028308A1 (en) 1996-09-19
FI973672A0 (en) 1997-09-12
DE19606839C2 (en) 1998-09-24
TW306896B (en) 1997-06-01
NO973603L (en) 1997-08-05
JPH11502477A (en) 1999-03-02
CA2215388A1 (en) 1996-09-19
AU4880096A (en) 1996-10-02
EP0814963B1 (en) 1998-12-09
CZ285897A3 (en) 1998-03-18
FI973672A (en) 1997-09-12
BR9607353A (en) 1997-12-30
AU692366B2 (en) 1998-06-04
DE19606839A1 (en) 1996-09-19
US5891562A (en) 1999-04-06
ATE174270T1 (en) 1998-12-15
MX9706983A (en) 1997-11-29
CR5280A (en) 1996-11-22
RU2155676C2 (en) 2000-09-10

Similar Documents

Publication Publication Date Title
EP0814963B1 (en) Multi-layer, flexible transfer strip, a process for its production and its use in a hand device
EP0410248B1 (en) Multilayer flexible marking tape
US5135798A (en) Multilayer, flexible transfer strip
DE19617850C1 (en) Multilayered flexible transfer strip with auxiliary support and pressure sensitive adhesive layer
EP0318804B1 (en) Multilayer flexible transfer ribbon
DE3118980C2 (en)
DE69916130T2 (en) CORRECTION BAND WITH COLOR TRANSMISSION BLOCKING PROPERTIES
EP0886580B1 (en) Multi-layer correcting and/or marking material, process for its manufacture and its use
DE6911299U (en) IMAGE CARRIERS, THE CHARACTERS OF WHICH ARE TRANSFERRED BY PRINTING ON A PAD
DE2335838C3 (en) Transmission material and process for its manufacture
DE2842139C2 (en) Process for making signs
DE2332527C2 (en) Pressure sensitive imaging materials
MXPA97006983A (en) Flexible transfer tape, of multiple layers, a process for the production of the same and as use in a man apparatus
MXPA98009138A (en) Flexible layer band of multip layers
DE2454117B2 (en) Printable or writable, rollable adhesive tape
DE2222106A1 (en) Transferable prints - applied to foil or siliconised paper by using pigments and encapsulated solvents

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 19970905

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE CH DE DK ES FR GB GR IE IT LI LU MC NL PT SE

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

17Q First examination report despatched

Effective date: 19980130

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE CH DE DK ES FR GB GR IE IT LI LU MC NL PT SE

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 19981209

Ref country code: IT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRE;WARNING: LAPSES OF ITALIAN PATENTS WITH EFFECTIVE DATE BEFORE 2007 MAY HAVE OCCURRED AT ANY TIME BEFORE 2007. THE CORRECT EFFECTIVE DATE MAY BE DIFFERENT FROM THE ONE RECORDED.SCRIBED TIME-LIMIT

Effective date: 19981209

Ref country code: GR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19981209

Ref country code: ES

Free format text: THE PATENT HAS BEEN ANNULLED BY A DECISION OF A NATIONAL AUTHORITY

Effective date: 19981209

REF Corresponds to:

Ref document number: 174270

Country of ref document: AT

Date of ref document: 19981215

Kind code of ref document: T

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REF Corresponds to:

Ref document number: 59600968

Country of ref document: DE

Date of ref document: 19990121

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

Free format text: GERMAN

ET Fr: translation filed
PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19990223

Ref country code: AT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19990223

GBT Gb: translation of ep patent filed (gb section 77(6)(a)/1977)

Effective date: 19990210

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 19990309

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 19990309

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 19990309

NLV1 Nl: lapsed or annulled due to failure to fulfill the requirements of art. 29p and 29m of the patents act
PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19990820

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MC

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19990831

REG Reference to a national code

Ref country code: IE

Ref legal event code: FD4D

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed
PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20000229

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20000229

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

REG Reference to a national code

Ref country code: GB

Ref legal event code: IF02

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20020212

Year of fee payment: 7

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 20020227

Year of fee payment: 7

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20020314

Year of fee payment: 7

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: BE

Payment date: 20020418

Year of fee payment: 7

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20030223

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20030228

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20030902

GBPC Gb: european patent ceased through non-payment of renewal fee
PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20031031

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST