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EP2479040B1 - Method for manufacturing a pen with elevated structure - Google Patents

Method for manufacturing a pen with elevated structure Download PDF

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Publication number
EP2479040B1
EP2479040B1 EP12151265.1A EP12151265A EP2479040B1 EP 2479040 B1 EP2479040 B1 EP 2479040B1 EP 12151265 A EP12151265 A EP 12151265A EP 2479040 B1 EP2479040 B1 EP 2479040B1
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EP
European Patent Office
Prior art keywords
photoinitiator
plastic composition
monomer
soft
proportion
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EP12151265.1A
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German (de)
French (fr)
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EP2479040A1 (en
Inventor
Udo Beck
Dr. Gerhard Lugert
Walter Oetter
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Faber Castell AG
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Faber Castell AG
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Priority to EP12151265.1A priority Critical patent/EP2479040B1/en
Publication of EP2479040A1 publication Critical patent/EP2479040A1/en
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B43—WRITING OR DRAWING IMPLEMENTS; BUREAU ACCESSORIES
    • B43K—IMPLEMENTS FOR WRITING OR DRAWING
    • B43K19/00—Non-propelling pencils; Styles; Crayons; Chalks
    • B43K19/14—Sheathings
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B43—WRITING OR DRAWING IMPLEMENTS; BUREAU ACCESSORIES
    • B43K—IMPLEMENTS FOR WRITING OR DRAWING
    • B43K19/00—Non-propelling pencils; Styles; Crayons; Chalks
    • B43K19/16—Making non-propelling pencils
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B43—WRITING OR DRAWING IMPLEMENTS; BUREAU ACCESSORIES
    • B43K—IMPLEMENTS FOR WRITING OR DRAWING
    • B43K23/00—Holders or connectors for writing implements; Means for protecting the writing-points
    • B43K23/008—Holders comprising finger grips
    • A—HUMAN NECESSITIES
    • A45—HAND OR TRAVELLING ARTICLES
    • A45D—HAIRDRESSING OR SHAVING EQUIPMENT; EQUIPMENT FOR COSMETICS OR COSMETIC TREATMENTS, e.g. FOR MANICURING OR PEDICURING
    • A45D40/00—Casings or accessories specially adapted for storing or handling solid or pasty toiletry or cosmetic substances, e.g. shaving soaps or lipsticks
    • A45D40/20—Pencil-like cosmetics; Simple holders for handling stick-shaped cosmetics or shaving soap while in use

Definitions

  • the invention relates to a method for producing a pen, in particular for writing, painting, drawing and cosmetic purposes, protruding from the surface of raised structures.
  • Pins of the type in question comprise a shaft made of materials such as wood, wood composite material, plastic and metal and are optionally coated with a coating, e.g. with a paint coat, coated.
  • the structures are present at least at a longitudinal portion of the pin and serve to increase the grip of the pins. They are for example formed in the manner of nubs and are applied in the form of a flowable plastic material in a desired pattern or grid on the pin surface and then cured. The curing takes place for example by a physical drying. In the case of aqueous polymer compositions, the very long, up to two days drying time is disadvantageous. Although the drying time is shortened in the case of plastic materials based on organic solvents, elaborate measures are required to prevent contamination of the environment with solvent vapors.
  • pins are provided whose structures consist of UV-cured plastic materials.
  • a UV-curable, a photoinitiator-containing plastic mass is applied in flowable form on the pin surface and then irradiated with UV light. The curing takes place within seconds, so that a bleeding of the flowable plastic mass is prevented shortly after its application to the pin surface.
  • the grip of a pen does not arise now only by the mere presence of the structures, it is rather determined to a not inconsiderable degree by the haptic properties of the plastic mass used in their cured or crosslinked state.
  • the object of the invention is therefore to provide a method by means of which raised structures based on urethane-acrylate polymers with improved feel and feel can be produced on a pin.
  • a flowable crosslinkable that is a not yet cured or crosslinked plastic mass is applied to the pin surface, a urethane acrylate oligomer and a crosslinking with this oligomer monomer under UV irradiation, a soft-touch additive and a photoinitiator from the group of bis-acyl-phosphine oxides.
  • a co-photoinitiator from another chemical group is not or only in a lower proportion than the main photoinitiator.
  • the UV radiation forms the corresponding polymer from the urethane-acrylate oligomer and the monomer, initiated by the main and optionally present co-initiator.
  • a soft-touch additive a urethane-acrylate oligomer, a monomer, a photoinitiator or other constituent
  • a soft-touch additive a urethane-acrylate oligomer, a monomer, a photoinitiator or other constituent
  • at least one constituent of the type mentioned is present.
  • two different urethane-acrylate oligomers or several different main photoinitiators from the mentioned group may be present.
  • the percentages given in the claims and elsewhere are by weight.
  • a monomer of the abovementioned type is in liquid form at room temperature and is also referred to as a reactive monomer diluent, since it serves as a solvent. In the process, however, it is incorporated in the course of crosslinking into the resulting polymer molecules.
  • a monofunctional monomer ie containing only one double bond
  • acrylate monomers in particular Trimethylolpropanformalacrylat
  • this proportion can be kept so low that the positive effect of the main photoinitiator is not impaired, if at all, only insignificantly.
  • the soft-touch additives are also present at the end of the crosslinking reaction present on the surface of the raised structures, ie, they partially protrude from the surface of the structures, and can accordingly develop their haptic effect, which is not or not sufficiently the case with the structures of the known pens.
  • a plastic material containing a co-photoinitiator its proportion is preferably limited to a maximum of 75%, in particular to a maximum of 15%, based on the proportion of the main photoinitiator. Especially with the last-mentioned content upper limit, it is ensured in almost all possible co-photoinitiators that the haptic effect based on the presence of the main photoinitiator is essentially achieved.
  • Co-photoinitiators which are particularly advantageous in this sense are those from the group of the alpha-hydroxy ketones, for example, the photoinitiators Irgacure 127, Irgacure 184 and Darocure 1173 available from BASF.
  • the invention is applicable to both pens with painted or unpainted shanks.
  • a corona or plasma treatment of the respective surface may be expedient in order to improve the adhesion of the plastic compound.
  • the flowable UV-curable plastic composition contains 20-98% urethane-acrylate oligomer, 0.1% to 60% monomer, 0.1-30% soft-touch additive and 0.1-30% photoinitiator from the chemical group acyl phosphine oxides.
  • a content of 50% to 65% of the urethane acrylate oligomer and 10% to 25% of the monomer in the plastic composition is particularly preferred since very soft and non-slip structures can be obtained here, especially if the plastic composition Contains 0.5% to 6% of photoinitiator and the content of soft-touch additive is limited to 5% to 20%.
  • soft-touch additives from the group aluminum silicate hollow spheres (Schwarzheder textile works), expanded hollow spheres (Akzo Nobel), polyurethane or acrylate softfeeling beads (Grolman / Dainichiseika) are particularly suitable.
  • Silicone rubber beads Dow Corning
  • micronized plastics shamrock
  • PE polypropylene
  • PE polypropylene
  • PP polypropylene
  • PTFE PTFE
  • PA waxes and their dispersions are particularly suitable.
  • the parentheses are examples of manufacturers / suppliers for the mentioned Softtouch additives indicated.
  • Soft-touch additives in combination with at least one photoinitiator from the group of bis-acyl-phosphine oxides, since these act more on the hardening of the applied mass, so that Softtouch additives have enough time to orient themselves to the surface before it hardens too.
  • the effect of the photoinitiator can be increased by adding a co-initiator, for example Darocure 1173 (BASF), in a proportion of 0.5 to 3%.
  • BASF Darocure 1173
  • the plastic mass may also contain 0% to 40% of colorant, 0% to 60% of filler, 0% to 10% of a rheological additive, 0% to 1% of defoamer and 0% to 10% of other additives.
  • a filler is used to vary the consistency of the plastic mass, the proportion of which is up to 60%.
  • at least one filler from the group kaolin, talc, barium sulfate, titanium white, calcium carbonate and mica is added.
  • the plastic composition may contain colorants, such as organic or inorganic pigments, as well as soluble dyes, wherein preferably an upper content limit of 40% is maintained.
  • a rheological additive may be added, for example to adjust a viscosity suitable for the particular type of application of the flowable plastic compound to the pin surface. In this case, a content range of 0.5% to 3% is preferred.
  • a rheological additive is mainly amorphous silica in question. Foaming during the processing of the plastic mass is prevented or at least reduced by a defoamer.
  • the plastic composition can contain up to 40% of an organic solvent, for example butylglycol acetate, if this is necessary, for example, to achieve a specific viscosity or for other reasons.
  • the solvent evaporates virtually completely from the structures during the crosslinking reaction and / or a subsequent drying step.
  • the attached drawing shows a pin 1 with a pen shank 3 formed, for example, by a wood casing 2.
  • a pen shank 3 formed, for example, by a wood casing 2.
  • pin shank 3 raised structures protruding from the surface 6 are present.
  • These are produced by a flowable plastic composition of the type described above, for example, with the in the in EP 2 110 185 A1 applied device is exposed and exposed to UV radiation. This usually happens at room temperature. To control the viscosity of the plastic mass but can also be heated (up to 60 ° C).
  • nubs With the known device structures can be produced in the form of nubs. Instead of nubs other structures may be applied to the pin surface, for example, extending in the pen longitudinal strip-shaped or any other structures.
  • knob-like structures were obtained by applying an inventive (A), (B), (C) and a known flowable plastic compound (D), (E) to the surface of an aqueous PU-Acrylatlack coated wood pencil and applied to a plastic shaft and crosslinked by UV radiation.
  • Plastic compound E (Example 1D from EP 2110185 A1)

Landscapes

  • Macromonomer-Based Addition Polymer (AREA)
  • Paints Or Removers (AREA)

Description

Die Erfindung betrifft ein Verfahren zur Herstellung eines Stiftes insbesondere für Schreib-, Mal-, Zeichen- und Kosmetikzwecke, aus dessen Oberfläche erhabene Strukturen hervorstehen. Stifte der in Rede stehenden Art umfassen einen Schaft aus Werkstoffen wie Holz, Holzverbundwerkstoff, Kunststoff und Metall und sind gegebenenfalls mit einer Beschichtung, z.B. mit einem Farblack, überzogen. Die Strukturen sind zumindest an einem Längsabschnitt des Stiftes vorhanden und dienen zur Erhöhung der Griffigkeit der Stifte. Sie sind beispielsweise nach Art von Noppen ausgebildet und werden in Form einer fließfähigen Kunststoffmasse in einem gewünschten Raster oder Muster auf die Stiftoberfläche aufgebracht und anschließend ausgehärtet. Das Aushärten erfolgt beispielsweise durch eine physikalische Trocknung. Bei wässrigen Kunststoffmassen ist dabei die sehr lange, bis zu zwei Tage dauernde Trockenzeit nachteilig. Bei Kunststoffmassen auf der Basis organischer Lösungsmittel ist zwar die Trockenzeit verkürzt, es sind jedoch aufwändige Maßnahmen erforderlich, um eine Kontamination der Umgebung mit Lösungsmitteldämpfen zu verhindern.The invention relates to a method for producing a pen, in particular for writing, painting, drawing and cosmetic purposes, protruding from the surface of raised structures. Pins of the type in question comprise a shaft made of materials such as wood, wood composite material, plastic and metal and are optionally coated with a coating, e.g. with a paint coat, coated. The structures are present at least at a longitudinal portion of the pin and serve to increase the grip of the pins. They are for example formed in the manner of nubs and are applied in the form of a flowable plastic material in a desired pattern or grid on the pin surface and then cured. The curing takes place for example by a physical drying. In the case of aqueous polymer compositions, the very long, up to two days drying time is disadvantageous. Although the drying time is shortened in the case of plastic materials based on organic solvents, elaborate measures are required to prevent contamination of the environment with solvent vapors.

Unter anderem aus diesen Gründen werden Stifte vorgesehen, deren Strukturen aus UV-gehärteten Kunststoffmassen bestehen. Wie beispielsweise bei dem aus EP 2 110 185 bekannten Verfahren, wird zur Herstellung solcher Stifte eine UV-härtbare, einen Photoinitiator enthaltende Kunststoffmasse in fließfähiger Form auf die Stiftoberfläche aufgebracht und anschließend mit UV-Licht bestrahlt. Die Aushärtung geschieht dabei binnen Sekunden, so dass ein Verlaufen der fließfähigen Kunststoffmasse schon kurz nach deren Aufbringen auf die Stiftoberfläche verhindert ist. Die Griffigkeit eines Stiftes ergibt sich nun nicht allein durch die bloße Anwesenheit der Strukturen, sie wird vielmehr in nicht unerheblichem Maße auch durch die haptischen Eigenschaften der jeweils verwendeten Kunststoffmasse in deren ausgehärtetem bzw. vernetztem Zustand bestimmt. Im Zuge der Strahlungshärtung entstehen jedoch, bedingt durch den in Form einer radikalischen Vernetzung ablaufenden Härtungsprozess vielfach Strukturen, die relativ hart sind. Wünschenswert sind jedoch weiche Strukturen mit einer angenehmen Haptik und hoher Griffigkeit. Bei dem bekannten Herstellungsverfahren werden Kunststoffmassen auf Urethan-Acrylatbasis eingesetzt. Zur Verbesserung der Haptik und Griffigkeit der Strukturen werden den auf eine Stiftoberfläche zu applizierenden Kunststoffmassen Softtouch-Additive wie PE-Wachse und Aluminiumsilikat-Hohlkugeln zugesetzt. Trotz dieser Maßnahme sind die Strukturen hinsichtlich Haptik und Griffigkeit noch nicht zufriedenstellend.Among other things, for these reasons, pins are provided whose structures consist of UV-cured plastic materials. For example, in the case of EP 2 110 185 known methods, for the production of such pens, a UV-curable, a photoinitiator-containing plastic mass is applied in flowable form on the pin surface and then irradiated with UV light. The curing takes place within seconds, so that a bleeding of the flowable plastic mass is prevented shortly after its application to the pin surface. The grip of a pen does not arise now only by the mere presence of the structures, it is rather determined to a not inconsiderable degree by the haptic properties of the plastic mass used in their cured or crosslinked state. In the course of radiation curing, however, arise due to the running in the form of a radical crosslinking hardening process often structures that are relatively hard. However, soft structures with a pleasant feel and high grip are desirable. In the known manufacturing process, plastic compositions are used on urethane-acrylate. To improve the feel and feel of the structures, soft-touch additives such as PE waxes and aluminum silicate hollow spheres are added to the plastic compositions to be applied to a pin surface. Despite this measure, the structures in terms of feel and grip are still unsatisfactory.

Die Aufgabe der Erfindung besteht daher darin, ein Verfahren anzugeben, mit dem sich auf einem Stift erhabene Strukturen auf der Basis von Urethan-Acrylatpolymeren mit verbesserter Haptik und Griffigkeit erzeugen lassen.The object of the invention is therefore to provide a method by means of which raised structures based on urethane-acrylate polymers with improved feel and feel can be produced on a pin.

Diese Aufgabe wird durch ein Verfahren nach Anspruch 1 gelöst. Bei diesem Verfahren wird eine fließfähige vernetzbare, also eine noch nicht ausgehärtete bzw. vernetzte Kunststoffmasse auf die Stiftoberfläche aufgebracht, die ein Urethan-Acrylat-Oligomer sowie ein mit diesem Oligomer unter UV-Bestrahlung vernetzendes Monomer, ein Softtouch-Additiv und einen Photoinitiator aus der Gruppe der Bis-Acyl-Phosphinoxide enthält. Dabei ist ein Co-Photoinitiator aus einer anderen chemischen Gruppe nicht oder nur mit einem geringeren Anteil enthalten, als der Haupt-Photoinitiator. Durch die UV-Bestrahlung bildet sich aus dem Urethan-Acrylat-Oligomer und dem Monomer, initiert durch den Haupt- und gegebenenfalls vorhandenen Co-Initiator, das entsprechende Polymer. Wenn hier davon gesprochen wird, dass ein Softtouch-Additiv, ein Urethan-Acrylat-Oligomer, ein Monomer, ein Photoinitiator oder ein sonstiger Bestandteil vorhanden sind, so ist damit gemeint, dass jeweils wenigstens ein Bestandteil der genannten Art vorhanden ist. Es können also beispielsweise zwei verschiedene Urethan-Acrylat-Oligomere oder mehrere unterschiedliche Haupt-Photoinitiatoren aus der genannten Gruppe vorhanden sein. Anzumerken ist noch, dass die in den Ansprüchen und an sonstiger Stelle gemachten Prozentangaben Gewichtsprozente sind.This object is achieved by a method according to claim 1. In this process, a flowable crosslinkable, that is a not yet cured or crosslinked plastic mass is applied to the pin surface, a urethane acrylate oligomer and a crosslinking with this oligomer monomer under UV irradiation, a soft-touch additive and a photoinitiator from the group of bis-acyl-phosphine oxides. In this case, a co-photoinitiator from another chemical group is not or only in a lower proportion than the main photoinitiator. The UV radiation forms the corresponding polymer from the urethane-acrylate oligomer and the monomer, initiated by the main and optionally present co-initiator. When it is said here that a soft-touch additive, a urethane-acrylate oligomer, a monomer, a photoinitiator or other constituent are present, it is meant that in each case at least one constituent of the type mentioned is present. Thus, for example, two different urethane-acrylate oligomers or several different main photoinitiators from the mentioned group may be present. It should also be noted that the percentages given in the claims and elsewhere are by weight.

Ein Monomer der oben genannten Art liegt bei Raumtemperatur in flüssiger Form vor und wird auch als reaktiver Monomer-Verdünner bezeichnet, da es quasi als Lösungsmittel dient. Dabei wird es aber im Zuge der Vernetzung in die entstehenden Polymermoleküle eingebaut. Im Hinblick auf die Erzielung von weichen Strukturen wird vorzugsweise ein monofunktionales, d.h. nur eine Doppelbindung enthaltendes Monomer eingesetzt, wobei Acrylat-Monomere, insbesondere
Trimethylolpropanformalacrylat, die besten Ergebnisse ergeben.A monomer of the abovementioned type is in liquid form at room temperature and is also referred to as a reactive monomer diluent, since it serves as a solvent. In the process, however, it is incorporated in the course of crosslinking into the resulting polymer molecules. With regard to the achievement of soft structures, preference is given to using a monofunctional monomer, ie containing only one double bond, with acrylate monomers, in particular
Trimethylolpropanformalacrylat, give the best results.

Die mit der Zugabe eines oder mehrerer Softtouch-Additive angestrebte Wirkung, nämlich den Strukturen eine weiche Haptik zu verleihen, ist bei den mit dem Verfahren von EP 2 110 185 hergestellten Stiften nur in nicht zufriedenstellendem Ausmaß vorhanden. Die Softtouch-Additive werden scheinbar so fest in das bei der Vernetzungsreaktion entstehende Polymer-Netzwerk eingebunden, dass sie an der Oberfläche der Strukturen ihre Wirkung nicht entfalten können. Es war nun überraschend, dass bei Verwendung eines Haupt-Photoinitiators aus der Gruppe der Bis-Acyl-Phosphinoxide Strukturen mit signifikant verbesserten Softtouch-Eigenschaften erhalten werden können, sofern wie oben ausgeführt, entweder kein Co-Photoinitiator aus einer anderen chemischen Gruppe als jener der Bis-Acyl-Phosphinoxide vorhanden ist oder allenfalls mit einem geringeren Anteil. Dieser Anteil kann je nach Art des verwendeten Co-Photoinitiators so gering gehalten werden, dass die positive Wirkung des Haupt-Photoinitiators nicht oder allenfalls nur unwesentlich beeinträchtigt wird Bei Verwendung des in Rede stehenden Haupt-Photoinitiators sind die Softtouch-Additive am Ende der Vernetzungsreaktion auch an der Oberfläche der erhabenen Strukturen vorhanden, d.h. sie stehen teilweise aus der Oberfläche der Strukturen hervor, und können dementsprechend ihre haptische Wirkung entfalten, was bei den Strukturen der bekannten Stifte nicht oder nicht in ausreichendem Maße der Fall ist.The effect aimed at with the addition of one or more soft-touch additives, namely to give the structures a soft feel, is similar to that achieved with the method of EP 2 110 185 produced pins only to unsatisfactory extent. The soft-touch additives seem to be so tight in involved in the crosslinking reaction polymer network involved that they can not unfold their effect on the surface of the structures. It was now surprising that when using a major photoinitiator from the group of bis-acyl-phosphine oxides structures with significantly improved soft-touch properties can be obtained, as stated above, either no co-photoinitiator from a chemical group other than that Bis-acyl-phosphine is present or at best with a lower proportion. Depending on the type of co-photoinitiator used, this proportion can be kept so low that the positive effect of the main photoinitiator is not impaired, if at all, only insignificantly. When using the main photoinitiator in question, the soft-touch additives are also present at the end of the crosslinking reaction present on the surface of the raised structures, ie, they partially protrude from the surface of the structures, and can accordingly develop their haptic effect, which is not or not sufficiently the case with the structures of the known pens.

Vorzugsweise ist im Falle der Verwendung einer einen Co-Photoinitiator enthaltenden Kunststoffmasse dessen Anteil auf maximal 75%, insbesondere auf maximal 15% - bezogen auf den Anteil des Haupt-Phototinitiators - begrenzt. Vor allem mit der letztgenannten Gehalts-Obergrenze ist bei nahezu allen in Frage kommenden Co-Photoinitiatoren gewährleistet, dass die auf die Anwesenheit des Haupt-Photoinitiators basierende haptische Wirkung im Wesentlichen erzielt wird. Co-Photoinitiatoren die in diesem Sinne besonders vorteilhaft sind, sind solche aus der Gruppe der Alpha-hydroxyketone, beispielsweise die von der BASF erhältlichen Photoinitiatoren Irgacure 127, Irgacure 184 und Darocure 1173.In the case of using a plastic material containing a co-photoinitiator, its proportion is preferably limited to a maximum of 75%, in particular to a maximum of 15%, based on the proportion of the main photoinitiator. Especially with the last-mentioned content upper limit, it is ensured in almost all possible co-photoinitiators that the haptic effect based on the presence of the main photoinitiator is essentially achieved. Co-photoinitiators which are particularly advantageous in this sense are those from the group of the alpha-hydroxy ketones, for example, the photoinitiators Irgacure 127, Irgacure 184 and Darocure 1173 available from BASF.

Die Erfindung ist sowohl bei Stiften mit lackierten oder unlackierten Schäften anwendbar. Je nach Art des Schaftmaterials oder eines auf die Schaftoberfläche aufgebrachten Lack-überzugs kann eine Corona- oder Plasmabehandlung der jeweiligen Oberfläche zweckmäßig sein, um die Haftung der Kunststoffmasse zu verbessern.The invention is applicable to both pens with painted or unpainted shanks. Depending on the nature of the shaft material or of a coating applied to the shaft surface, a corona or plasma treatment of the respective surface may be expedient in order to improve the adhesion of the plastic compound.

Die fließfähige UV-vernetzbare Kunststoffmasse enthält 20-98 % Urethan-Acrylat-Oligomer, 0,1% bis 60% Monomer, 0,1-30% Softtouch-Additiv und 0,1-30 % Photoinitiator aus der chemischen Gruppe der Bis-Acyl-Phosphinoxide.The flowable UV-curable plastic composition contains 20-98% urethane-acrylate oligomer, 0.1% to 60% monomer, 0.1-30% soft-touch additive and 0.1-30% photoinitiator from the chemical group acyl phosphine oxides.

Bei allen Rezepturvarianten ist ein Gehalt von 50 % bis 65 % des Urethan-Acrylat-Oligomers und 10% bis 25% des Monomers in der Kunststoffmasse besonders bevorzugt, da hiermit sehr weiche und griffige Strukturen erhalten werden können, vor allem dann, wenn die Kunststoffmasse 0,5 % bis 6% Photoinitiator enthält und der Gehalt an Softtouch-Additiv auf 5% bis 20% eingeschränkt wird.In all formulation variants, a content of 50% to 65% of the urethane acrylate oligomer and 10% to 25% of the monomer in the plastic composition is particularly preferred since very soft and non-slip structures can be obtained here, especially if the plastic composition Contains 0.5% to 6% of photoinitiator and the content of soft-touch additive is limited to 5% to 20%.

Zur Beeinflussung der taktilen Eigenschaften der Oberflächen der erhabenen Strukturen eignen sich in besonderer Weise sogenannte Softtouch-Additive aus der Gruppe Aluminiumsilikat-Hohlkugeln (Schwarzwälder Textilwerke), expandierte Hohlkugeln (Akzo Nobel), Polyurethan- oder Acrylat-Softfeeling-Kügelchen (Grolman/Dainichiseika), Silikonkautschuk-Kügelchen (Dow Corning), mikronisierte Kunststoffe (Shamrock) wie Polypropylen oder PE-, PP-, PTFE-, und PA-Wachse sowie deren Dispersionen. In den Klammern sind beispielhaft Hersteller/Lieferanten für die genannten Softtouch-Additive angegeben. Wie oben erwähnt ist es wichtig, derartige Softtouch-Additive in Kombination mit wenigstens einem Photoinitiator aus der Gruppe der Bis-Acyl-Phosphinoxide einzusetzen, da diese verstärkt auf die Durchhärtung der aufgebrachten Masse wirken, so dass Softtouchadditive genügend Zeit haben sich zur Oberfläche zu orientieren, bevor diese ebenfalls aushärtet. Die Wirkung des Photoinitiators kann durch Zusatz eines Co-Initiators, beispielsweise Darocure 1173 (BASF), mit einem Anteil von 0,5 bis 3% verstärkt werden.In order to influence the tactile properties of the surfaces of the raised structures, so-called soft-touch additives from the group aluminum silicate hollow spheres (Schwarzwälder textile works), expanded hollow spheres (Akzo Nobel), polyurethane or acrylate softfeeling beads (Grolman / Dainichiseika) are particularly suitable. , Silicone rubber beads (Dow Corning), micronized plastics (shamrock) such as polypropylene or PE, PP, PTFE, and PA waxes and their dispersions. The parentheses are examples of manufacturers / suppliers for the mentioned Softtouch additives indicated. As mentioned above, it is important to use such soft-touch additives in combination with at least one photoinitiator from the group of bis-acyl-phosphine oxides, since these act more on the hardening of the applied mass, so that Softtouch additives have enough time to orient themselves to the surface before it hardens too. The effect of the photoinitiator can be increased by adding a co-initiator, for example Darocure 1173 (BASF), in a proportion of 0.5 to 3%.

Neben den genannten Bestandteilen kann die Kunststoffmasse noch 0% bis 40 % Farbmittel, 0% bis 60% Füllstoff, 0% bis 10% eines rheologischen Additivs, 0% bis 1% Entschäumer und 0% bis 10% sonstiger Additive enthalten.In addition to the constituents mentioned, the plastic mass may also contain 0% to 40% of colorant, 0% to 60% of filler, 0% to 10% of a rheological additive, 0% to 1% of defoamer and 0% to 10% of other additives.

Ein Füllstoff wird z.B. verwendet, um die Konsistenz der Kunststoffmasse zu variieren, wobei dessen Anteil bis zu 60% beträgt. Vorzugsweise wird wenigstens ein Füllstoff aus der Gruppe Kaolin, Talkum, Bariumsulfat, Titanweiß, Calciumcarbonat und Glimmer zugesetzt. Desweiteren kann die Kunststoffmasse Farbmittel, wie organische oder anorganische Pigmente, sowie lösliche Farbstoffe enthalten, wobei vorzugsweise eine obere Gehaltsgrenze von 40% eingehalten wird. Ein rheologisches Additiv kann zugesetzt werden, beispielsweise um eine für die jeweilige Art des Auftrags der fließfähigen Kunststoffmasse auf die Stiftoberfläche geeignete Viskosität einzustellen. Dabei ist ein Gehaltsbereich von 0,5% bis 3% bevorzugt. Als rheologisches Additiv kommt vor allem amorphes Siliziumdioxid in Frage. Eine Schaumbildung bei der Verarbeitung der Kunststoffmasse wird durch einen Entschäumer verhindert oder zumindest verringert.For example, a filler is used to vary the consistency of the plastic mass, the proportion of which is up to 60%. Preferably, at least one filler from the group kaolin, talc, barium sulfate, titanium white, calcium carbonate and mica is added. Furthermore, the plastic composition may contain colorants, such as organic or inorganic pigments, as well as soluble dyes, wherein preferably an upper content limit of 40% is maintained. A rheological additive may be added, for example to adjust a viscosity suitable for the particular type of application of the flowable plastic compound to the pin surface. In this case, a content range of 0.5% to 3% is preferred. As a rheological additive is mainly amorphous silica in question. Foaming during the processing of the plastic mass is prevented or at least reduced by a defoamer.

Die Kunststoffmasse kann bis zu 40% eines organischen Lösungsmittels, beispielsweise Butylglycolacetat, enthalten, falls dies beispielsweise zur Erzielung einer bestimmten Viskosität oder aus sonstigen Gründen erforderlich ist. Das Lösungsmittel verdampft bei Vernetzungsreaktion und/oder einem anschließenden Trocknungsschritt praktisch vollständig aus den Strukturen.The plastic composition can contain up to 40% of an organic solvent, for example butylglycol acetate, if this is necessary, for example, to achieve a specific viscosity or for other reasons. The solvent evaporates virtually completely from the structures during the crosslinking reaction and / or a subsequent drying step.

Die beigefügte Zeichnung zeigt einen Stift 1 mit einem beispielsweise von einer Holzummantelung 2 gebildeten Stiftschaft 3. Auf der Oberfläche 4 des unlackierten oder mit einer Lackbeschichtung 5 versehenen Stiftschaftes 3 sind erhaben aus der Oberfläche vorstehende Strukturen 6 vorhanden. Diese werden erzeugt, indem eine fließfähige Kunststoffmasse der oben beschriebenen Art, beispielsweise mit der in der in EP 2 110 185 A1 beschriebenen Vorrichtung aufgebracht und einer UV-Strahlung ausgesetzt wird. Dies geschieht üblicherweise bei Raumtemperatur. Zur Steuerung der Viskosität kann die Kunststoffmasse aber auch erwärmt werden (bis 60°C). Mit der bekannten Vorrichtung lassen sich Strukturen in der Form von Noppen herstellen. Anstelle von Noppen können auch andere Strukturen auf die Stiftoberfläche aufgebracht sein, beispielsweise sich in Stiftlängsrichtung erstreckende leistenförmige oder beliebige andere Strukturen.The attached drawing shows a pin 1 with a pen shank 3 formed, for example, by a wood casing 2. On the surface 4 of the unpainted or coated with a lacquer coating 5 pin shank 3 raised structures protruding from the surface 6 are present. These are produced by a flowable plastic composition of the type described above, for example, with the in the in EP 2 110 185 A1 applied device is exposed and exposed to UV radiation. This usually happens at room temperature. To control the viscosity of the plastic mass but can also be heated (up to 60 ° C). With the known device structures can be produced in the form of nubs. Instead of nubs other structures may be applied to the pin surface, for example, extending in the pen longitudinal strip-shaped or any other structures.

Um den Unterschied zwischen erhabenen Strukturen aus einer Kunststoffmasse gemäß EP 2 110 185 und erfindungsgemäßen Strukturen aufzuzeigen, wurden Vergleichsversuche durchgeführt. Dabei wurden noppenartige Strukturen durch Aufbringen einer erfindungsgemäßen (A), (B), (C) und einer bekannten fließfähigen Kunststoffmasse (D), (E) auf die Oberfläche eines mit einem wässrigen PU-Acrylatlack beschichteten Holzstiftes und auf einen Kunststoffschaft aufgebracht und durch UV-Strahlung vernetzt.According to the difference between raised structures made of a plastic mass according to EP 2 110 185 and show structures according to the invention, comparative experiments were carried out. In this case, knob-like structures were obtained by applying an inventive (A), (B), (C) and a known flowable plastic compound (D), (E) to the surface of an aqueous PU-Acrylatlack coated wood pencil and applied to a plastic shaft and crosslinked by UV radiation.

Kunststoffmasse APlastic compound A

Handelsname (Lieferant)Trade name (supplier) Chemische Bezeichnung/FunktionChemical name / function Konzentrationconcentration Laromer UA 9030 (BASF)Laromer UA 9030 (BASF) Urethanacrylat, Oligomer, BindemittelUrethane acrylate, oligomer, binder 70,3 %70.3% Laromer LR 8887 (BASF)Laromer LR 8887 (BASF) Trimethylolpropanformalacrylat, MonomerTrimethylolpropane formalacrylate, monomer 15 %15% Deuteron UV RS 20 (Deuteron)Deuteron UV RS 20 (Deuterone) PE-Wachsdispersion, SofttouchadditivPE wax dispersion, soft touch additive 8 %8th % Irgacure 819 (BASF)Irgacure 819 (BASF) Haupt-Photoinitiator (Bis-Acyl-Phosphinoxid)Main photoinitiator (bis-acyl-phosphine oxide) 4 %4% Aerosil 380 (Evonik)Aerosil 380 (Evonik) Amorphes Siliziumdioxid, Rheologisches AdditivAmorphous silica, rheological additive 2 %2% Tego Glide 432 (Evonik)Tego Glide 432 (Evonik) Tensid, Verlaufs- und GleitmittelSurfactant, leveling agent and lubricant 0,5 %0.5% Tego Airex 920 (Evonik)Tego Airex 920 (Evonik) Entschäumerdefoamers 0,2 %0.2%

Kunststoffmasse BPlastic compound B

Handelsname (Lieferant)Trade name (supplier) Chemische Bezeichnung/FunktionChemical name / function Konzentrationconcentration Laromer UA 9030 (BASF)Laromer UA 9030 (BASF) Urethanacrylat, Oligomer, BindemittelUrethane acrylate, oligomer, binder 70,3 %70.3% Laromer LR 8887 (BASF)Laromer LR 8887 (BASF) Trimethylolpropanformalacrylat, MonomerTrimethylolpropane formalacrylate, monomer 15 %15% Deuteron UV RS 20 (Deuteron)Deuteron UV RS 20 (Deuterone) PE-Wachsdispersion, SofttouchadditivPE wax dispersion, soft touch additive 8 %8th % Irgacure 819 (BASF)Irgacure 819 (BASF) Haupt-Photoinitiator (Bis-Acyl-Phosphinoxid)Main photoinitiator (bis-acyl-phosphine oxide) 3,4 %3.4% Irgacure 127 (BASF)Irgacure 127 (BASF) Co-Initiator (α-Hydroxyketon)Co-initiator (α-hydroxyketone) 0,6%0.6% Aerosil 380 (Evonik)Aerosil 380 (Evonik) Amorphes Siliziumdioxid, Rheologisches AdditivAmorphous silica, rheological additive 2 %2% Tego Glide 432 (Evonik)Tego Glide 432 (Evonik) Tensid, Verlaufs- und GleitmittelSurfactant, leveling agent and lubricant 0,5 %0.5% Tego Airex 920 (Evonik)Tego Airex 920 (Evonik) Entschäumerdefoamers 0,2 %0.2%

Kunststoffmasse CPlastic compound C

Handelsname (Lieferant)Trade name (supplier) Chemische Bezeichnung/FunktionChemical name / function Konzentrationconcentration Laromer UA 9030 (BASF)Laromer UA 9030 (BASF) Urethanacrylat, Oligomer, BindemittelUrethane acrylate, oligomer, binder 70,3 %70.3% Laromer LR 8887 (BASF)Laromer LR 8887 (BASF) Trimethylolpropanformalacrylat, MonomerTrimethylolpropane formalacrylate, monomer 15 %15% Deuteron UV RS 20 (Deuteron)Deuteron UV RS 20 (Deuterone) PE-Wachsdispersion, SofttouchadditivPE wax dispersion, soft touch additive 8 %8th % Irgacure 819 (BASF)Irgacure 819 (BASF) Haupt-Photoinitiator (Bis-Acyl-Phosphinoxid)Main photoinitiator (bis-acyl-phosphine oxide) 3,2 %3.2% Irgacure 184 (BASF)Irgacure 184 (BASF) Co-Initiator (α-Hydroxyketon)Co-initiator (α-hydroxyketone) 0,8 %0.8% Aerosil 380 (Evonik)Aerosil 380 (Evonik) Amorphes Siliziumdioxid, Rheologisches AdditivAmorphous silica, rheological additive 2 %2% Tego Glide 432 (Evonik)Tego Glide 432 (Evonik) Tensid, Verlaufs- und GleitmittelSurfactant, leveling agent and lubricant 0,5 %0.5% Tego Airex 920 (Evonik)Tego Airex 920 (Evonik) Entschäumerdefoamers 0,2 %0.2%

Vergleichsbeispiele:

  • Kunststoffmasse D (Beispiel 1C aus EP 2110185 A1)
Handelsname (Lieferant) Chemische Bezeichnung/Funktion Konzentration Roskydal UA VP LS 2258 (Bayer Material Science) Urethanacrylat-Oligomer 57,3 % Roskydal UA XP 2491 (Bayer Material Science) 20 % Laromer TPGDA (BASF) Tripropylenglycoltriacrylat-Monomer 18 % Irgacure 2959 (BASF) Photoinitiator (α-Hydroxyketon) 2 % HDK T30 (Wacker Chemie AG) Amorphes Siliziumdioxid, Rheologisches Additiv 2 % Tego Glide 440 (Evonik) Tensid, Verlaufs- und Gleitmittel 0,5 % Byk 021 (BYK-Chemie) Entschäumer 0,2 % Comparative Examples:
  • Plastic compound D (Example 1C from EP 2110185 A1)
Trade name (supplier) Chemical name / function concentration Roskydal UA VP LS 2258 (Bayer Material Science) Urethane acrylate oligomer 57.3% Roskydal UA XP 2491 (Bayer Material Science) 20% Laromer TPGDA (BASF) Tripropylenglycoltriacrylat monomer 18% Irgacure 2959 (BASF) Photoinitiator (α-hydroxyketone) 2% HDK T30 (Wacker Chemie AG) Amorphous silica, rheological additive 2% Tego Glide 440 (Evonik) Surfactant, leveling agent and lubricant 0.5% Byk 021 (BYK-Chemie) defoamers 0.2%

Kunststoffmasse E (Beispiel 1D aus EP 2110185 A1)Plastic compound E (Example 1D from EP 2110185 A1)

Handelsname (Lieferant)Trade name (supplier) Chemische Bezeichnung/FunktionChemical name / function Konzentrationconcentration Roskydal UA VP LS 2258 (Bayer Material Science)Roskydal UA VP LS 2258 (Bayer Material Science) Urethanacrylat-OligomerUrethane acrylate oligomer 75,8 %75.8% Roskydal UA XP 2491 (Bayer Material Science)Roskydal UA XP 2491 (Bayer Material Science) 20 %20% Laromer TPGDA (BASF)Laromer TPGDA (BASF) Tripropylenglycoltriacrylat-MonomerTripropylenglycoltriacrylat monomer -- Irgacure 2959 (BASF)Irgacure 2959 (BASF) Haupt-Photoinitiator (α-Hydroxyketon)Main photoinitiator (α-hydroxyketone) 2 %2% Irgacure 819 (BASF)Irgacure 819 (BASF) Co-Photoinitiator Bis-Acyl-Phosphinoxid)Co-photoinitiator bis-acyl-phosphine oxide) 1 %1 % HDK T30 (Wacker Chemie AG)HDK T30 (Wacker Chemie AG) Amorphes Siliziumdioxid, Rheologisches AdditivAmorphous silica, rheological additive 2 %2% Tego Glide 440 (Evonik)Tego Glide 440 (Evonik) Tensid, Verlaufs- und GleitmittelSurfactant, leveling agent and lubricant 0,5 %0.5% Byk 021 (BYK-Chemie)Byk 021 (BYK-Chemie) Entschäumerdefoamers 0,2 %0.2%

Die mit Kunststoffmassen der o.g. Beispiele und Vergleichsbeispiele erzeugten Strukturen wurden einer vergleichenden Bewertung hinsichtlich Haftung, Softtouch-Eigenschaften, Härte, Trockenzeit und Kratzfestigkeit unterzogen. Das Ergebnis der Bewertung ist in der untenstehenden Tabelle zusammengefasst. Bewertungskriterium Beisp. A-C Beisp. D, E Haftung auf lackierten Holzoberflächen +++++ ++ Haftung auf Kunststoffoberflächen (ABS) ++++ +++++ Softtouch-Eigenschaften +++++ +++ Trockenzeit +++++ +++++ Kratzfestigkeit +++++ +++++ Bewertungsschema:
+++++ = sehr gut
++++ = gut
+++ = akzeptabel
++ = schlecht
+ = sehr schlecht The structures produced with the plastics compositions of the above-mentioned examples and comparative examples were subjected to a comparative evaluation with regard to adhesion, soft-to-touch properties, hardness, drying time and scratch resistance. The result of the evaluation is summarized in the table below. evaluation criterion Ex. AC Ex. D, E Adhesion to painted wood surfaces +++++ ++ Adhesion on plastic surfaces (ABS) ++++ +++++ Soft Touch Properties +++++ +++ dry season +++++ +++++ scratch resistance +++++ +++++ Evaluation scheme:
+++++ = very good
++++ = good
+++ = acceptable
++ = bad
+ = very bad

Während die erfindungsgemäßen Rezepturbeispiele A-C in allen fünf bewerteten Kategorien sehr gute oder gute Ergebnisse erzielten, zeigt der UV-Lack aus den Beispielen D und E schlechte Werte für die Haftung auf lackierten Holzoberflächen und nur akzeptable Softtoucheigenschaften.While Formulation Examples A-C according to the invention achieved very good or good results in all five evaluated categories, the UV varnish from Examples D and E shows poor adhesion values on lacquered wood surfaces and only acceptable soft-touch properties.

Claims (15)

  1. Method for manufacturing a pen, wherein a flowing UV-crosslinkable plastic composition is applied to the surface of the pen and cured by UV radiation, wherein the plastic composition contains
    - 20% - 98% of a urethane-acrylate oligomer,
    - 0.1% to 60% of a monomer crosslinking with this oligomer when subjected to UV radiation,
    - 0.1% - 30% of a soft-touch additive and
    - 0.1% - 30% of a main photoinitiator from the chemical group of bis-acyl phosphinoxides, and a co-photoinitiator from another chemical group is not present as the main photoinitiator or only in a smaller proportion.
  2. Method according to claim 1,
    characterised by the use of a plastic composition with a proportion of co-photoinitiator that is 75% maximum of the proportion of the main photoinitiator.
  3. Method according to claim 2,
    characterised by the use of a plastic composition with a proportion of co-photoinitiator that is 15%maximum of the proportion of the main photoinitiator.
  4. Method according to one of the preceding claims,
    characterised in that,
    a plastic composition is used in which 0.5% to 6% of main photoinitiator is present.
  5. Method according to one of the preceding claims,
    characterised in that,
    a photoinitiator from the group of alpha hydroxy ketones is used as the co-photoinitiator.
  6. Method according to one of the preceding claims,
    characterised in that,
    a simple functional monomer is used.
  7. Method according to one of the preceding claims,
    characterised in that,
    an acrylate monomer is used as the monomer.
  8. Method according to claim 7,
    characterised by the use of trimethylolpropane formacrylate as the acrylate monomer.
  9. Method according to one of the preceding claims,
    characterised in that,
    a plastic composition is used that contains 0% to 40% colourant, 0% to 60% filler, 0% to 10% of a rheological additive, 0% to 1% defoamer and 0% to 10% of other additives.
  10. Method according to claim 9,
    characterised by
    the use of a plastic composition containing 50% to 65% of the urethane-acrylate oligomer and 10% to 25% of the monomer.
  11. Method according to one of the preceding claims,
    characterised by
    the use of a plastic composition with a content of soft-touch additive from 5% to 20%.
  12. Method according to one of the preceding claims,
    characterised in that,
    the plastic composition has at least one soft-touch additive from the group aluminium silicate hollow balls, expanded hollow balls, polyurethane soft-feeling pellets, silicon rubber pellets, micronized plastics, PE, PF, PTFE and PA wax and dispersions of these waxes.
  13. Method according to one of the preceding claims,
    characterised by
    the use of a plastic composition, in which 0.5% to 3% rheological additive is present.
  14. Method according to claim 13,
    characterised in that,
    the rheological additive is amorphous silicon dioxide.
  15. Method according to one of the preceding claims,
    characterised in that,
    a plastic composition containing up to 40% of an organic solvent is used.
EP12151265.1A 2011-01-19 2012-01-16 Method for manufacturing a pen with elevated structure Active EP2479040B1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
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EP11151411 2011-01-19
EP12151265.1A EP2479040B1 (en) 2011-01-19 2012-01-16 Method for manufacturing a pen with elevated structure

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US9394436B2 (en) * 2013-08-26 2016-07-19 Dymax Corporation Form in-place gasket with tack free surface
JP7018871B2 (en) 2015-08-07 2022-02-14 アルケマ フランス One-component curable soft feel coating
TWI682976B (en) 2016-03-02 2020-01-21 阿科瑪法國公司 Dual cure soft touch coatings
CN110382631A (en) 2017-03-28 2019-10-25 阿科玛法国公司 The method for being used to form flexible touch applicator
US20200102472A1 (en) 2017-03-28 2020-04-02 Arkema France Compositions useful for forming soft touch coatings

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Publication number Priority date Publication date Assignee Title
EP1700713B1 (en) * 2005-03-09 2007-10-10 Faber-Castell AG Process for manufacturing of coatings with structured surface, applied especially for pencils, and object with structured surface
EP2110185B1 (en) 2008-04-17 2013-06-12 Faber-Castell AG Method for creating embossed structures of the surface of a pen
EP2248675A1 (en) * 2009-05-04 2010-11-10 Faber-Castell AG Stylus, in particular for writing, painting and cosmetic purposes

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BR102012001252A2 (en) 2013-07-16
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DE202012012632U1 (en) 2013-07-03

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