EP2499932A1 - Casing body - Google Patents

Casing body Download PDF

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Publication number
EP2499932A1
EP2499932A1 EP11002218A EP11002218A EP2499932A1 EP 2499932 A1 EP2499932 A1 EP 2499932A1 EP 11002218 A EP11002218 A EP 11002218A EP 11002218 A EP11002218 A EP 11002218A EP 2499932 A1 EP2499932 A1 EP 2499932A1
Authority
EP
European Patent Office
Prior art keywords
polyamide
sleeve body
body according
shells
shell
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
EP11002218A
Other languages
German (de)
French (fr)
Other versions
EP2499932B1 (en
Inventor
Heinz Caviezel
Roland Treutlein
Ulrich Presenz
Mark Pfleghar
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.)
EMS Patent AG
Original Assignee
EMS Patent AG
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 EMS Patent AG filed Critical EMS Patent AG
Priority to ES11002218.3T priority Critical patent/ES2578732T3/en
Priority to EP11002218.3A priority patent/EP2499932B1/en
Priority to PL11002218.3T priority patent/PL2499932T3/en
Priority to US13/421,541 priority patent/US20120237708A1/en
Priority to KR20120027034A priority patent/KR101495095B1/en
Priority to CN201210072691.7A priority patent/CN102669920B/en
Publication of EP2499932A1 publication Critical patent/EP2499932A1/en
Application granted granted Critical
Publication of EP2499932B1 publication Critical patent/EP2499932B1/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

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Classifications

    • 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
    • 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
    • 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
    • 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
    • Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
    • Y10T428/1352—Polymer or resin containing [i.e., natural or synthetic]
    • Y10T428/1376—Foam or porous material containing

Definitions

  • the invention relates to a sleeve body made of a thermoplastic material with a shell structure, wherein at least three shells are provided and one, an intermediate shell forming shell contains polyamide foam and at least one other shell polyamide and / or consists thereof.
  • the invention further relates to the use of such a sleeve body, in particular for cosmetic pencils, pens and industrial applications.
  • Sleeve body for cosmetic pencils and pens or cosmetic pencils and pens, which have a sheath made of plastic, are known in the art.
  • Foamed PVC has hitherto been used as plastic in the prior art.
  • a sleeve body made of a thermoplastic material, in particular for cosmetic pencils or pens, which in addition to the freedom from chlorine and excellent feel and good barrier property against the solvents of the mine.
  • these sleeve bodies should be able to be produced at a high production speed in order to increase the production costs reduce.
  • the sleeve body has at least one to a maximum of ten outer shells an intermediate shell and at least one to at most ten inner shells, wherein the intermediate shell contains polyamide foam and at least one of the other shells polyamide and / or consists thereof.
  • the inventively proposed layer structure has many advantages. Thus, it is possible to produce the sleeve body by means of a co-extrusion process in a single operation, wherein the inventors were able to show that significantly higher production speeds could be achieved with respect to the prior art. It should also be emphasized that the shell structure can also be used to specifically influence the mechanical and physical properties. Thus, excellent barrier properties can be produced by deliberately influencing the shell material and, furthermore, by providing a specifically selected outer shell, the feel of the sleeve body to be produced can also be specifically controlled.
  • the use of polyamide as a shell material has the further advantage that it can be guaranteed freedom from chlorine and that it is possible to improve by adding eg selected additives and the mechanical properties and the sharpenability.
  • the intermediate shell is formed of polyamide foam.
  • This intermediate shell of polyamide foam then preferably has a greater layer thickness than the layer thickness of the other shells, i. the inner shells surrounding the cavity and those shells facing outwards.
  • the intermediate shell Z preferably has a layer thickness of 1000 to 3000 .mu.m, preferably from 1100 to 2500 .mu.m, more preferably from 1200 to 2100 microns and most preferably from 1300 to 1800 microns.
  • the shells containing polyamide have a layer thickness of 50 to 600 .mu.m, preferably from 80 to 500 .mu.m, more preferably from 100 to 400 .mu.m and most preferably from 150 to 300 .mu.m.
  • An inventive sleeve body as described above has excellent maximum forces in the bending test, which are preferably in the range of 85 to 250 N, more preferably 90 to 180 N and most preferably in the range of 100 to 170 N.
  • the sleeve body is constructed so that the polyamide foam forming the intermediate layer is composed of an amorphous polyamide and / or a partially crystalline polyamide and a polyamide elastomer and / or modified polyolefin elastomer.
  • the polyamide foam is preferably composed of an amorphous or partially crystalline polyamide and a polyamide elastomer and / or a modified polyolefin elastomer.
  • the polyamide foam contains per se conventional blowing agents. Examples of blowing agents are bicarbonates, hydrogen citrates, Azodicarbonamides, citric acid, hydrazides, semicarbazides, borohydrides and mixtures thereof.
  • blowing agents are usually diluted by the addition of diluents, such as starch or calcium carbonate, so that 20 to 50 wt .-% - mixtures are used.
  • diluents such as starch or calcium carbonate
  • Preferred as blowing agents are bicarbonates, hydrogen citrates, azodicarbonamides, citric acid and mixtures thereof.
  • Particularly preferred blowing agents are mixtures of sodium bicarbonate, citric acid and calcium carbonate.
  • the polyamide foam is 50 to 80% by weight, more preferably 60 to 75% by weight, most preferably 65 to 75% by weight of polyamide, and 20 to 50% by weight preferably 35 to 25 wt .-%, most preferably 65 to 75 wt .-%, of a polyamide elastomer and / or modified polyolefin elastomer.
  • Propellant mixtures containing from 30 to 35% by weight of propellant usually contain from 0.4 to 0.75% by weight, preferably from 0.45 to 0.65% by weight.
  • amorphous polyamides for the polyamide foam preference is given to those which have a glass transition temperature of the amorphous polyamide of from 90 to 210 ° C., preferably from 100 to 180 ° C., particularly preferably from 100 to 170 ° C.
  • a glass transition temperature of the amorphous polyamide of from 90 to 210 ° C., preferably from 100 to 180 ° C., particularly preferably from 100 to 170 ° C.
  • the relative viscosity of the amorphous polyamides measured on solutions of 0.5 g of polyamide in 100 ml of solvent in m-cresol at 20 ° C., is 1.50 to 1.85, preferably 1.55 to 1.80, particularly preferably 1, 55 to 1.75.
  • the proportion of isophthalic acid in the polyamide PA 6I / 6T is 90 to 57 mol%, preferably 85 to 60 mol%, particularly preferably 75 to 60 mol%, very particularly preferably 72 to 63 mol%, wherein the sum of the two Dicarboxylic acids 100 mol% results.
  • the proportion of isophthalic acid in the polyamide PA 6I / 66/69 is 50 to 80 mol%, preferably 60 to 80 mol%, particularly preferably 65 to 75 mol%, wherein the sum of the three dicarboxylic acids gives 100 mol%.
  • the molar ratio of adipic acid: sebacic acid in polyamide PA 6I / 66/69 is 1: 2 to 2: 1, preferably 1: 1.5 to 1.5: 1, more preferably 1: 1.
  • the melting point of the partially crystalline polyamides of the polyamide foam is preferably in the range from 120 to 295 ° C., more preferably from 150 to 280 ° C., more preferably from 170 to 270 ° C., most preferably from 190 to 255 ° C.
  • particularly suitable semicrystalline polyamides are PA MXD6, PA MXD6 / MXDI, PA MXD6 / 66/610, PACM12, PA 6 and PA 6/66.
  • the relative viscosity of the partially crystalline polyamides containing MXD or PACM measured on solutions of 0.5 g of polyamide in 100 ml of solvent in m-cresol at 20 ° C., is 1.40 to 1.90, preferably 1.50 to 1.80, more preferably 1.55 to 1.75.
  • the relative viscosity of the partially crystalline polyamides PA 6 or PA 6/66 measured on solutions of 1.0 g of polyamide in 100 ml of solvent in 96% strength sulfuric acid at 20 ° C., is 3.40 to 6.0, preferably 3, 7 to 5.70, more preferably 4.0 to 5.50.
  • the proportion of isophthalic acid in the polyamide PA MXD6 / MXDI is 2 to 15 mol%, preferably 2 to 12 mol%, particularly preferably 2 to 8 mol%, wherein the sum of the two dicarboxylic acids gives 100 mol%.
  • the proportion of meta-xylylenediamine (MXD) in the polyamide PA MXD6 / 66/610 is 40 to 90 mol%, preferably 50 to 85 mol%, particularly preferably 60 to 80 mol%, very particularly preferably 70 to 80 mol% %, the sum of the two diamines being 100 mol%.
  • polyetheramides In the polyamide elastomers for the polyamide foam, polyetheramides, polyesteretheramides and / or polyesteramides are preferred.
  • the polyolefin elastomers are preferably selected from acid-modified copolyolefin elastomers and acid-modified blends of several copolyolefin elastomers.
  • An acid-modified blend of several copolyolefin elastomers is to be understood as meaning a mixture of the components ethylene-propylene copolymer, ethylene-but-1-ene copolymer, propylene-but-1-ene copolymer, polyethylene and / or polypropylene.
  • the mixture is homogenized in the melt, whereby the acid modification by grafting takes place, so that the modification degree 0.3 to 1.5 wt .-%, preferably 0.4 to 1.2 wt .-%, particularly preferably 0.4 to 1.0 wt .-%, based on the mixture.
  • the mixture of the copolyolefin elastomers is used as a dry blend, ie without homogenization in the melt, then at least some of the components are already acid-modified, for example to such an extent that the degree of modification of the total dry blend is from 0.3 to 1.5% by weight. -%, preferably 0.4 to 1.2 wt .-%, particularly preferably 0.4 to 1.0 wt .-%, is. Possibly In addition, such a dry blend can additionally be homogenized in the melt.
  • the copolyolefin elastomer contains said monomers d) to f) in the specified preferred molar proportions, but also includes the possibility of mixing a plurality of copolyolefin elastomers each containing two of the monomers d ) to f), ie d) and e), d) and f) or e) and f), so that the monomers d) to f) are present in the preferred molar proportions in the mixture.
  • the mixture particularly preferably consists of a copolyolefin elastomer of the monomers d) and e) and a copolyolefin elastomer of the monomers d) and f), so that the monomers d) to f) are present in the preferred molar proportions in the mixture.
  • the acid modification of the copolyolefin elastomer or the blend of several copolyolefin elastomers by grafting with unsaturated carboxylic acids and / or unsaturated carboxylic acid derivatives preferably a carboxylic acid derivative selected from the group consisting of unsaturated carboxylic acid esters and unsaturated carboxylic acid anhydrides, in particular with an unsaturated carboxylic acid selected from the group consisting of acrylic acid, methacrylic acid, alpha-ethylacrylic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, aconitic acid, tetrahydrophthalic acid and / or butenylsuccinic acid, takes place, ie the copolyolefin elastomer contains grafted unsaturated carboxylic acids and / or unsaturated carboxylic acid derivatives in the molecule.
  • the weight fractions of the unsaturated carboxylic acids and / or unsaturated carboxylic acid derivatives on the copolyolefin elastomer or on the blend of several copolyolefin elastomers are 0.3 to 1.5% by weight, preferably 0.4 to 1.2 Wt .-%, particularly preferably from 0.4 to 1.0 wt .-%.
  • polyamide of the other polyamide-containing or consisting of polyamide shells aliphatic, cycloaliphatic, aromatic polyamides and / or blends thereof are mentioned.
  • polyamides of polyamide-containing or polyamide-containing shells are: PA 6, PA 11, PA 12, PA 46, PA 410, PA 412, PA 66, PA 69, PA 610, PA 612, PA 1010, PA 1212, PA 6/11, PA 6/12, PA 6/66, PA 6/68, PA 6/610, PA 66/11, PA 66/12, PA 66/610, PA 6/66/11, PA 6/66/12, PA 6/66/69, PA 6/66/610, PA 6/66/612, PA 6/610/11, PA 6/610 / 12, PA 6I, PA 6I / 6T, PA 6I / 66/69, PA 6I / 66/610, PA 6-3-T, PA MXD6, PA MXD6 / MXDI, PA MXD6 / 66/610, PA MXDI / 61, PA MACM12, PA PACM12, PA MACM14 / 1014, PA MACM12 / PACM12, PA MAM /
  • the alphabetical abbreviations of the monomers mean: I isophthalic T terephthalic acid MACM Bis (4-amino-3-methyl-cyclohexyl) -methane MXD Meta-xylylenediamine PACM Bis (4-amino-cyclohexyl) methane (PACM).
  • the polyamide PA 6-3-T is composed of trimethylhexamethylenediamine and terephthalic acid.
  • both the intermediate shell and the inner shells and the outer shells contain polyamide and / or consist of polyamide.
  • the sleeve body is thus constructed exclusively of polyamide.
  • the invention also includes embodiments in which at least one of the shells which are directed outwards and / or one of the inner shells does not contain polyamide and / or consist of polyamide, but that here another shell material is used depending on the desired properties can be.
  • the thickness of this shell is, except when using adhesion promoters, in the range of polyamide-containing shells.
  • Trays formed from one or more adhesion promoters have thicknesses of from 3 to 100 .mu.m, preferably from 5 to 50 .mu.m, particularly preferably from 7 to 20 .mu.m.
  • polyesters examples include polyethylene terephthalate (PET), polybutylene terephthalate (PBT) and polyethylene naphthalate (PEN) are preferable.
  • PET polyethylene terephthalate
  • PBT polybutylene terephthalate
  • PEN polyethylene naphthalate
  • polyolefin in this context includes homopolyolefins, such as PE or PP, copolyolefins, cycloolefin copolymers (COC), thermoplastic elastomers (TPE), grafted polyolefins, grafted copolyolefins, ionomers, adhesion promoters and copolymers of olefins with acrylic acid, acrylic acid derivatives (eg methacrylic acid , Acrylonitrile, methyl methacrylate, butyl methacrylate, glycidyl methacrylate, etc.), vinyl acetate, maleic anhydride, other olefins and / or styrene.
  • acrylic acid derivatives eg methacrylic acid , Acrylonitrile, methyl methacrylate, butyl methacrylate, glycidyl methacrylate, etc.
  • vinyl acetate maleic anhydride
  • the components of the polyamide foam, amorphous polyamide and / or partially crystalline polyamide and polyamide elastomer and / or modified polyolefin elastomer, are used in the preparation of the polyamide foam as a compound or dry blend.
  • the components are mixed in the melt state. This is done on conventional compounding machines, such as single- or twin-screw extruders or screw kneaders.
  • the components are individually dosed into the feeder or supplied in the form of a dry blend.
  • the dried granules and optionally further additives are mixed. This mixture is homogenized by means of a tumbling mixer, Rhönradmischers or tumble dryer for 10 to 40 minutes. To avoid moisture absorption, this can be done under dried inert gas.
  • the compounding takes place at set cylinder temperatures of 200 ° C to 340 ° C. Vacuum can be applied in front of the nozzle or degassed atmospherically.
  • the melt is discharged in strand form, cooled in a water bath at 10 to 80 ° C and then granulated.
  • the granules are dried for 12 to 24 hours at 80 to 120 ° C under nitrogen or in vacuo to a water content of less than 0.1 wt .-%.
  • the blowing agent is added to the compound or dry blend only before processing to foam, so before the coextrusion of the tubes.
  • the homogenization takes place as in dryblend.
  • the shell structure of the sleeve body consists of 1 to 10 inner shells of an intermediate shell and 1 to 10 outer shells.
  • the shell structure can be carried out asymmetrically or symmetrically starting from the intermediate shell Z. It is preferred if the number of shells is a total of 3 to 9, preferably 3 to 7 and very particularly preferably 3 to 5. Examples for a preferred shell construction are given below.
  • A1 stands for the first, starting from the intermediate shell Z starting shell.
  • A2 is then the second outer shell. The same applies to the inner shell I.
  • the invention also encompasses embodiments in which bonding agent layers are still provided between the shells as explained above.
  • the choice of primer layer depends on how the shell construction has been chosen. It is also possible to incorporate a bonding agent in the material of the shells.
  • additives can be added to the materials of the shells.
  • the additive is selected from the group consisting of inorganic stabilizers, organic stabilizers, lubricants, colorants and markers, inorganic pigments, organic pigments, antistatic agents, antiblocking agents, nucleating agents, crystallization accelerators, crystallization retardants, chain-extending additives, mold release agents, release agents, optical brighteners, metallic pigments , Metal flakes, metal-coated particles, fillers and reinforcing materials, in particular nanoscale fillers and reinforcing materials, such as minerals with a particle size of at most 100 nm or unmodified or modified, natural or synthetic phyllosilicates or mixtures thereof.
  • At least one shell A, I and / or Z can also be colored.
  • the shells can be designed differently in color.
  • the sheath body according to the invention can also be used to produce strong colors of the entire color spectrum, including black and white.
  • Preferred uses for the sleeve bodies described above are eyeshadow pens, lip contour pens, eye contour pens, eyebrow pencils, sun protection pens, anti-paging pins, anti-sore pens, pens, crayons, and / or industrial applications, e.g. Media-leading systems in apparatus construction.
  • FIG. 1 In section, an inventive sleeve body 1 is shown.
  • the sleeve body according to the embodiment according to FIG. 1 is cylindrical and consists of an intermediate shell Z, an outer shell A1 and an inner shell 11.
  • the cavity is designated H.
  • FIG. 1 trained sleeve body according to the invention experiments were carried out by means of various materials, which in the tables (in the Figures 3 and 4 ) are indicated.
  • 3-layer tubes of dimensions 7.8 ⁇ 1.8 mm were produced by coextrusion with the following materials and layer thicknesses: outer shell A1 made of PA 6 150 ⁇ m, intermediate shell Z made of polyamide foam according to the invention 1450 ⁇ m, inner shell I1 made of PA 6I / 6T 200 ⁇ m. The following temperatures were used: outer shell A1 260 ° C, intermediate shell Z 250 ° C, inner shell I1 230 ° C. The endless tube was cut into 120 mm long tubes.
  • Relative viscosity ISO 307 0.5% strength by weight m-cresol solution or 1.0% strength by weight solution in 96% strength by weight sulfuric acid at 20 ° C. Calculation of the relative viscosity (RV) after RV t / t 0 in accordance with section 11 of the standard.
  • Tg Melting point and glass transition temperature (Tg) ISO standard 11357-1 / -2 granules Differential Scanning Calorimetry (DSC) was performed at a rate of 20 K / min. At the melting point the temperature is indicated at the peak maximum, at the glass transition temperature the temperature at the onset.
  • the maximum force is determined on five tubes each.
  • the arithmetic mean of the measured maximum forces in N. is given.
  • the sharpener used was a commercial pencil sharpener from KUM GmbH & Co. KG: Magnesium single sharpener with a carbon steel blade, block shape.
  • the torque was measured by means of an electronic agitator with torque indicator from Heidolph Instruments GmbH & Co. KG: Heidolph RZR 2051 control.
  • the sharpener was clamped by means of a Stielfeilklobens in the stirrer.
  • the measurement of the torque was carried out at 200 U / min.
  • the tube was pressed by means of a helical compression spring of a standard stand clamp in the sharpener and read the torque maximum.
  • the measurement is carried out twice on three tubes.
  • the specified payload is the arithmetic mean of the measured maximum torques in Ncm.
  • the sleeve body according to the invention have a maximum force in the bending test, which is above 100 N, and a production speed of at least 25 m / min. In some examples, even the production rate is over 50 m / min. The sharpenability is always greater than 11 N ⁇ cm.
  • the production rate of mono-tubes made of foamed PVC is 8 to 11 m / min.
  • a 120 mm long foam PVC monotube measuring 7.8 x 1.8 mm was found to have a flexural strength of 83 N and a toughness of 11 N cm.
  • FIG. 2 a further embodiment of a sleeve body according to the invention is shown.
  • the embodiment according to FIG. 2 now shows a sleeve body, which consists of a total of 5 shells, wherein the intermediate shell Z, which consists of polyamide foam, each surrounded by two shells.
  • the sleeve body in the embodiment after FIG. 2 via two inner shells I1 and I2 and via two outer shells A1 and A2.
  • polyamides have again been used as shell materials.
  • the invention also includes embodiments in which an asymmetric shell structure is realized.
  • the sleeve body so that 3 shells are provided starting from the intermediate shell Z to the outside, ie outer shell A1, A2 and A3, and that the sleeve body then has only two inner shells I1 and I2.
  • the number The shells also depend on the application, so it is possible, in particular in the outer area still attach an additional shell, with which the feel and / or the optical properties of the sleeve body can be influenced.
  • Additional shells for example of ethylene-vinyl alcohol copolymers or polypropylene (PP), especially indoors, can further improve, for example, the barrier effect of the sleeve body towards components of the mine. In this case, no adhesion promoter is necessary between a shell of ethylene-vinyl alcohol copolymers and a shell which contains polyamide and / or consists thereof.
  • an adhesive layer is provided between this shell, e.g. made of polypropylene and the adjacent shells.

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Abstract

A sleeve component is made ?[deg] f a thermoplastic compound, and has cavity enclosed with three-layered structure comprising 1-10 outer shells, an intermediate shell and 1-10 inner shells. The intermediate shell contains polyamide foam, and at least one of inner and outer shells are made of polyamide or its derivative.

Description

Die Erfindung betrifft einen Hülsenkörper aus einem thermoplastischen Kunststoff mit einem Schalenaufbau, wobei mindestens drei Schalen vorgesehen sind und eine, eine Zwischenschale bildende Schale Polyamidschaum und mindestens eine andere Schale Polyamid enthält und/oder daraus besteht. Die Erfindung betrifft weiterhin die Verwendung eines derartigen Hülsenkörpers, insbesondere für Kosmetikstifte, Schreibstifte und industrielle Anwendungen.The invention relates to a sleeve body made of a thermoplastic material with a shell structure, wherein at least three shells are provided and one, an intermediate shell forming shell contains polyamide foam and at least one other shell polyamide and / or consists thereof. The invention further relates to the use of such a sleeve body, in particular for cosmetic pencils, pens and industrial applications.

Hülsenkörper für Kosmetikstifte und Schreibstifte bzw. Kosmetikstifte und Schreibstifte, die eine Ummantelung aus Kunststoff aufweisen, sind im Stand der Technik bekannt.Sleeve body for cosmetic pencils and pens or cosmetic pencils and pens, which have a sheath made of plastic, are known in the art.

So ist z.B. in dem britischen Patent 1 538 188 beschrieben, dass die für die Kosmetikstifte verwendete Mine aus einer kosmetischen Masse in den Hülsenkörper des Stiftes eingegossen wird. Darüber hinaus beschreibt das deutsche Patent 40 05 894 ein Verfahren und Kosmetikstifte mit einer relativ dünnen Mine sowie einen spitzbaren Hülsenkörper aus Kunststoff unter Verwendung axial beweglicher Gießnadeln. Bekannt sind ferner auch Verfahren zur Herstellung von Hülsenkörpern für Kosmetikstifte mittels Spritzguss, wobei diese Hülsen mit einer durch Erhitzen verflüssigten Kosmetikmasse befüllt werden können. Hierzu genannt seien beispielsweise die US-Patente 4,413,921 und 5,957,607 .For example, in the British patent 1 538 188 described that the mine used for the cosmetic pencils from a cosmetic mass in the sleeve body of the pin is poured. In addition, the German patent describes 40 05 894 a method and cosmetic pencils with a relatively thin refill and a sharpenable plastic sleeve body using axially movable casting needles. Also known are methods for the production of sleeve bodies for cosmetic pencils by injection molding, these sleeves can be filled with a liquefied by heating cosmetic mass. These may be mentioned, for example, the U.S. Patents 4,413,921 and 5,957,607 ,

Als Kunststoff wird dabei bisher im Stand der Technik bevorzugt geschäumtes PVC eingesetzt.Foamed PVC has hitherto been used as plastic in the prior art.

Nachteilig ist bei Hülsenkörpern bzw. bei Kosmetikstiften, die einen geschäumten PVC-Mantel aufweisen, dass die Barriereeigenschaften gegenüber dem Lösungsmittel der Mine, meist Isododecan, nur ungenügend sind. Weiterhin ist beim Stand der Technik zu kritisieren, dass bei der Herstellung derartiger Stifte nur eine geringe Produktionsgeschwindigkeit realisierbar ist. Nachteilig ist auch, dass bei Verwendung von PVC als Umhüllungsmaterial keine Chlorfreiheit garantiert werden kann und dass die Haptik der Stifte verbesserungswürdig ist.A disadvantage of sleeve bodies or cosmetic pencils, which have a foamed PVC jacket, that the barrier properties against the solvent of the mine, usually isododecane, are only insufficient. Furthermore, it should be criticized in the prior art that in the production of such pins only a low production speed can be realized. Another disadvantage is that when using PVC as wrapping material no chlorine freedom can be guaranteed and that the feel of the pins is in need of improvement.

Ausgehend hiervon ist es deshalb die Aufgabe der vorliegenden Erfindung, einen Hülsenkörper aus einem thermoplastischen Kunststoff, insbesondere für Kosmetikstifte oder Schreibstifte, anzugeben, der neben der Chlorfreiheit und einer ausgezeichneten Haptik auch gute Barriereeigenschaft gegenüber den Lösungsmitteln der Mine aufweist. Gleichzeitig sollen diese Hülsenkörper mit einer hohen Produktionsgeschwindigkeit herstellbar sein, um die Produktionskosten zu senken.Based on this, it is therefore the object of the present invention to provide a sleeve body made of a thermoplastic material, in particular for cosmetic pencils or pens, which in addition to the freedom from chlorine and excellent feel and good barrier property against the solvents of the mine. At the same time, these sleeve bodies should be able to be produced at a high production speed in order to increase the production costs reduce.

Diese Aufgabe wird durch die kennzeichnenden Merkmale des Patentanspruches 1 gelöst. Die Unteransprüche zeigen vorteilhafte Weiterbildungen auf.This object is solved by the characterizing features of claim 1. The dependent claims show advantageous developments.

Erfindungsgemäß wird somit vorgeschlagen, dass der Hülsenkörper mindestens eine bis maximal zehn äußere Schalen eine Zwischenschale und mindestens eine bis höchstens zehn innere Schalen aufweist, wobei die Zwischenschale Polyamidschaum und mindestens eine der anderen Schalen Polyamid enthält und/oder daraus besteht.According to the invention it is thus proposed that the sleeve body has at least one to a maximum of ten outer shells an intermediate shell and at least one to at most ten inner shells, wherein the intermediate shell contains polyamide foam and at least one of the other shells polyamide and / or consists thereof.

Der erfindungsgemäß vorgeschlagene Lagenaufbau weist zahlreiche Vorteile auf. So ist es möglich, den Hülsenkörper mittels eines Coextrusionsverfahrens in einem Arbeitsgang herzustellen, wobei die Erfinder zeigen konnten, dass damit gegenüber dem Stand der Technik deutlich erhöhte Produktionsgeschwindigkeiten erreicht werden konnten. Weiter ist hervorzuheben, dass durch den Schalenaufbau auch eine gezielte Beeinflussung der mechanischen und physikalischen Eigenschaften erreicht werden kann. So können ausgezeichnete Barriereeigenschaften durch gezielte Beeinflussung des Schalenmaterials hergestellt werden und weiterhin kann durch das Vorsehen einer spezifisch ausgewählten Außenschale auch die Haptik der herzustellenden Hülsenkörper gezielt gesteuert werden. Die Verwendung von Polyamid als Schalenmaterial hat den weiteren Vorteil, dass damit eine Chlorfreiheit garantiert werden kann und dass es möglich ist, durch Zusatz z.B. von ausgewählten Additiven auch die mechanischen Eigenschaften und die Spitzbarkeit zu verbessern.The inventively proposed layer structure has many advantages. Thus, it is possible to produce the sleeve body by means of a co-extrusion process in a single operation, wherein the inventors were able to show that significantly higher production speeds could be achieved with respect to the prior art. It should also be emphasized that the shell structure can also be used to specifically influence the mechanical and physical properties. Thus, excellent barrier properties can be produced by deliberately influencing the shell material and, furthermore, by providing a specifically selected outer shell, the feel of the sleeve body to be produced can also be specifically controlled. The use of polyamide as a shell material has the further advantage that it can be guaranteed freedom from chlorine and that it is possible to improve by adding eg selected additives and the mechanical properties and the sharpenability.

Wesentliches Element der vorliegenden Erfindung ist, dass die Zwischenschale aus Polyamidschaum gebildet ist. Diese Zwischenschale aus Polyamidschaum weist dann bevorzugterweise eine größere Schichtdicke auf als die Schichtdicke der anderen Schalen, d.h. der innenliegenden Schalen, die den Hohlraum umschließen und derjenigen Schalen, die nach außen gerichtet sind. Die Zwischenschale Z weist bevorzugt eine Schichtdicke von 1000 bis 3000 µm, bevorzugt von 1100 bis 2500 µm, besonders bevorzugt von 1200 bis 2100 µm und ganz besonders bevorzugt von 1300 bis 1800 µm auf.An essential element of the present invention is that the intermediate shell is formed of polyamide foam. This intermediate shell of polyamide foam then preferably has a greater layer thickness than the layer thickness of the other shells, i. the inner shells surrounding the cavity and those shells facing outwards. The intermediate shell Z preferably has a layer thickness of 1000 to 3000 .mu.m, preferably from 1100 to 2500 .mu.m, more preferably from 1200 to 2100 microns and most preferably from 1300 to 1800 microns.

Die Schalen, die Polyamid enthalten, weisen hingegen eine Schichtdicke von 50 bis 600 µm, bevorzugt von 80 bis 500 µm, besonders bevorzugt von 100 bis 400 µm und ganz besonders bevorzugt von 150 bis 300 µm auf.The shells containing polyamide, however, have a layer thickness of 50 to 600 .mu.m, preferably from 80 to 500 .mu.m, more preferably from 100 to 400 .mu.m and most preferably from 150 to 300 .mu.m.

Ein wie vorstehend beschriebener erfindungsgemäßer Hülsenkörper weist ausgezeichnete Maximalkräfte im Biegetest auf, die bevorzugt im Bereich von 85 bis 250 N, weiter bevorzugt 90 bis 180 N und ganz besonders bevorzugt im Bereich von 100 bis 170 N liegen.An inventive sleeve body as described above has excellent maximum forces in the bending test, which are preferably in the range of 85 to 250 N, more preferably 90 to 180 N and most preferably in the range of 100 to 170 N.

Von der stofflichen Seite her ist der Hülsenkörper so aufgebaut, dass der Polyamidschaum, der die Zwischenlage bildet, aus einem amorphen Polyamid und/oder einem teilkristallinen Polyamid und einem Polyamidelastomer und/oder modifizierten Polyolefinelastomer aufgebaut ist. Der Polyamidschaum ist dabei bevorzugt aus einem amorphen oder teilkristallinen Polyamid sowie einem Polyamidelastomer und/oder einem modifizierten Polyolefinelastomer aufgebaut. Wie im Stand der Technik bekannt, enthält der Polyamidschaum an und für sich gebräuchliche Treibmittel. Beispiele für Treibmittel sind Hydrogencarbonate, Hydrogencitrate, Azodicarbonamide, Zitronensäure, Hydrazide, Semicarbazide, Borhydride und Mischungen davon. Die Treibmittel werden meist durch Zusatz von Streckmitteln, wie Stärke oder Calciumcarbonat, verdünnt, so dass 20 bis 50 Gew.-%-ige Mischungen zum Einsatz kommen. Als Treibmittel bevorzugt sind Hydrogencarbonate, Hydrogencitrate, Azodicarbonamide, Zitronensäure und Mischungen davon. Als Treibmittel besonders bevorzugt sind Mischungen aus Natriumhydrogencarbonat, Zitronensäure und Calciumcarbonat.From the material side, the sleeve body is constructed so that the polyamide foam forming the intermediate layer is composed of an amorphous polyamide and / or a partially crystalline polyamide and a polyamide elastomer and / or modified polyolefin elastomer. The polyamide foam is preferably composed of an amorphous or partially crystalline polyamide and a polyamide elastomer and / or a modified polyolefin elastomer. As known in the art, the polyamide foam contains per se conventional blowing agents. Examples of blowing agents are bicarbonates, hydrogen citrates, Azodicarbonamides, citric acid, hydrazides, semicarbazides, borohydrides and mixtures thereof. The blowing agents are usually diluted by the addition of diluents, such as starch or calcium carbonate, so that 20 to 50 wt .-% - mixtures are used. Preferred as blowing agents are bicarbonates, hydrogen citrates, azodicarbonamides, citric acid and mixtures thereof. Particularly preferred blowing agents are mixtures of sodium bicarbonate, citric acid and calcium carbonate.

Von der mengenmäßigen Zusammensetzung ist bevorzugt, wenn der Polyamidschaum 50 bis 80 Gew.-%, besonders bevorzugt 60 bis 75 Gew.-%, ganz besonders bevorzugt 65 bis 75 Gew.-% Polyamid, und 20 bis 50 Gew.-%, besonders bevorzugt 35 bis 25 Gew.-%, ganz besonders bevorzugt 65 bis 75 Gew.-%, eines Polyamidelastomers und/oder modifizierten Polyolefinelastomers enthält. An Treibmittelmischungen mit einem Gehalt an Treibmittel von 30 bis 35 Gew.-% sind gewöhnlicherweise 0,4 bis 0,75 Gew.-%, bevorzugt 0,45 bis 0,65 Gew.-% enthalten.Of the quantitative composition, it is preferred if the polyamide foam is 50 to 80% by weight, more preferably 60 to 75% by weight, most preferably 65 to 75% by weight of polyamide, and 20 to 50% by weight preferably 35 to 25 wt .-%, most preferably 65 to 75 wt .-%, of a polyamide elastomer and / or modified polyolefin elastomer. Propellant mixtures containing from 30 to 35% by weight of propellant usually contain from 0.4 to 0.75% by weight, preferably from 0.45 to 0.65% by weight.

Bei den amorphen Polyamiden für den Polyamidschaum sind diejenigen bevorzugt, die eine Glasübergangstemperatur des amorphen Polyamids von 90 bis 210 °C, bevorzugt 100 bis 180 °C, besonders bevorzugt 100 bis 170 °C aufweisen. Beispiele hierfür sind PA 6I, PA 6I/6T, PA 6I/66/69, PA 6-3-T, PA MACM12 und PA MACMI/12.In the case of the amorphous polyamides for the polyamide foam, preference is given to those which have a glass transition temperature of the amorphous polyamide of from 90 to 210 ° C., preferably from 100 to 180 ° C., particularly preferably from 100 to 170 ° C. Examples of these are PA 6I, PA 6I / 6T, PA 6I / 66/69, PA 6-3-T, PA MACM12 and PA MACMI / 12.

Die relative Viskosität der amorphen Polyamide, gemessen an Lösungen von 0,5 g Polyamid in 100 ml Lösungsmittel in m-Kresol bei 20 °C beträgt 1,50 bis 1,85, bevorzugt 1,55 bis 1,80, besonders bevorzugt 1,55 bis 1,75.The relative viscosity of the amorphous polyamides, measured on solutions of 0.5 g of polyamide in 100 ml of solvent in m-cresol at 20 ° C., is 1.50 to 1.85, preferably 1.55 to 1.80, particularly preferably 1, 55 to 1.75.

Der Anteil der Isophthalsäure im Polyamid PA 6I/6T beträgt 90 bis 57 Mol-%, bevorzugt 85 bis 60 Mol-%, besonders bevorzugt 75 bis 60 Mol-%, ganz besonders bevorzugt 72 bis 63 Mol-%, wobei die Summe der beiden Dicarbonsäuren 100 Mol-% ergibt.The proportion of isophthalic acid in the polyamide PA 6I / 6T is 90 to 57 mol%, preferably 85 to 60 mol%, particularly preferably 75 to 60 mol%, very particularly preferably 72 to 63 mol%, wherein the sum of the two Dicarboxylic acids 100 mol% results.

Der Anteil der Isophthalsäure im Polyamid PA 6I/66/69 beträgt 50 bis 80 Mol-%, bevorzugt 60 bis 80 Mol-%, besonders bevorzugt 65 bis 75 Mol-%, wobei die Summe der drei Dicarbonsäuren 100 Mol-% ergibt. Das Molverhältnis von Adipinsäure:Sebazinsäure im Polyamid PA 6I/66/69 beträgt 1:2 bis 2:1, bevorzugt 1:1,5 bis 1,5:1, besonders bevorzugt 1:1.The proportion of isophthalic acid in the polyamide PA 6I / 66/69 is 50 to 80 mol%, preferably 60 to 80 mol%, particularly preferably 65 to 75 mol%, wherein the sum of the three dicarboxylic acids gives 100 mol%. The molar ratio of adipic acid: sebacic acid in polyamide PA 6I / 66/69 is 1: 2 to 2: 1, preferably 1: 1.5 to 1.5: 1, more preferably 1: 1.

Der Schmelzpunkt der teilkristallinen Polyamide des Polyamidschaums liegt bevorzugt im Bereich von 120 bis 295 °C, weiter bevorzugt bei 150 bis 280 °C, besonders bevorzugt bei 170 bis 270 °C, ganz besonders bevorzugt bei 190 bis 255 °C. Beispiele für besonders geeignete teilkristalline Polyamide sind PA MXD6, PA MXD6/MXDI, PA MXD6/66/610, PACM12, PA 6 und PA 6/66.The melting point of the partially crystalline polyamides of the polyamide foam is preferably in the range from 120 to 295 ° C., more preferably from 150 to 280 ° C., more preferably from 170 to 270 ° C., most preferably from 190 to 255 ° C. Examples of particularly suitable semicrystalline polyamides are PA MXD6, PA MXD6 / MXDI, PA MXD6 / 66/610, PACM12, PA 6 and PA 6/66.

Die relative Viskosität der teilkristallinen Polyamide enthaltend MXD oder PACM, gemessen an Lösungen von 0,5 g Polyamid in 100 ml Lösungsmittel in m-Kresol bei 20 °C beträgt 1,40 bis 1,90, bevorzugt 1,50 bis 1,80, besonders bevorzugt 1,55 bis 1,75.The relative viscosity of the partially crystalline polyamides containing MXD or PACM, measured on solutions of 0.5 g of polyamide in 100 ml of solvent in m-cresol at 20 ° C., is 1.40 to 1.90, preferably 1.50 to 1.80, more preferably 1.55 to 1.75.

Die relative Viskosität der teilkristallinen Polyamide PA 6 bzw. PA 6/66, gemessen an Lösungen von 1,0 g Polyamid in 100 ml Lösungsmittel in 96 %-iger Schwefelsäure bei 20 °C beträgt 3,40 bis 6,0, bevorzugt 3,7 bis 5,70, besonders bevorzugt 4,0 bis 5,50.The relative viscosity of the partially crystalline polyamides PA 6 or PA 6/66, measured on solutions of 1.0 g of polyamide in 100 ml of solvent in 96% strength sulfuric acid at 20 ° C., is 3.40 to 6.0, preferably 3, 7 to 5.70, more preferably 4.0 to 5.50.

Der Anteil der Isophthalsäure im Polyamid PA MXD6/MXDI beträgt 2 bis 15 Mol-%, bevorzugt 2 bis 12 Mol-%, besonders bevorzugt 2 bis 8 Mol-%, wobei die Summe der beiden Dicarbonsäuren 100 Mol-% ergibt.The proportion of isophthalic acid in the polyamide PA MXD6 / MXDI is 2 to 15 mol%, preferably 2 to 12 mol%, particularly preferably 2 to 8 mol%, wherein the sum of the two dicarboxylic acids gives 100 mol%.

Der Anteil an Meta-Xylylendiamin (MXD) im Polyamid PA MXD6/66/610 beträgt 40 bis 90 Mol-%, bevorzugt 50 bis 85 Mol-%, besonders bevorzugt 60 bis 80 Mol-%, ganz besonders bevorzugt 70 bis 80 Mol-%, wobei die Summe der beiden Diamine 100 Mol-% ergibt.The proportion of meta-xylylenediamine (MXD) in the polyamide PA MXD6 / 66/610 is 40 to 90 mol%, preferably 50 to 85 mol%, particularly preferably 60 to 80 mol%, very particularly preferably 70 to 80 mol% %, the sum of the two diamines being 100 mol%.

Bei den Polyamidelastomeren für den Polyamidschaum sind Polyetheramide, Polyesteretheramide und/oder Polyesteramide bevorzugt. Die Polyolefinelastomere sind bevorzugt ausgewählt aus säuremodifizierten Copolyolefinen-Elastomeren und säuremodifizierten Blends mehrerer Copolyolefinelastomere.In the polyamide elastomers for the polyamide foam, polyetheramides, polyesteretheramides and / or polyesteramides are preferred. The polyolefin elastomers are preferably selected from acid-modified copolyolefin elastomers and acid-modified blends of several copolyolefin elastomers.

Unter einem säuremodifizierten Blend mehrerer Copolyolefin-Elastomerer ist eine Mischung aus den Komponenten Ethylen-Propylen-Copolymer, Ethylen-But-1-en-Copolymer, Propylen-But-1-en-Copolymer, Polyethylen und/oder Polypropylen zu verstehen. Die Mischung wird in der Schmelze homogenisiert, dabei erfolgt auch die Säuremodifikation durch Pfropfung, so dass der Modifizierungsgrad 0,3 bis 1,5 Gew.-%, bevorzugt 0,4 bis 1,2 Gew.-%, besonders bevorzugt 0,4 bis 1,0 Gew.-% beträgt, bezogen auf die Mischung.An acid-modified blend of several copolyolefin elastomers is to be understood as meaning a mixture of the components ethylene-propylene copolymer, ethylene-but-1-ene copolymer, propylene-but-1-ene copolymer, polyethylene and / or polypropylene. The mixture is homogenized in the melt, whereby the acid modification by grafting takes place, so that the modification degree 0.3 to 1.5 wt .-%, preferably 0.4 to 1.2 wt .-%, particularly preferably 0.4 to 1.0 wt .-%, based on the mixture.

Wird die Mischung der Copolyolefin-Elastomere als Dryblend, also ohne Homogenisierung in der Schmelze, verwendet, so ist zumindest ein Teil der Komponenten bereits säuremodifiziert, z.B. in einem solchen Maße, dass der Modifizierungsgrad des gesamten Dryblends 0,3 bis 1,5 Gew.-%, bevorzugt 0,4 bis 1,2 Gew.-%, besonders bevorzugt 0,4 bis 1,0 Gew.-%, beträgt. Gegebenenfalls kann ein solches Dryblend zusätzlich noch in der Schmelze homogenisiert werden.If the mixture of the copolyolefin elastomers is used as a dry blend, ie without homogenization in the melt, then at least some of the components are already acid-modified, for example to such an extent that the degree of modification of the total dry blend is from 0.3 to 1.5% by weight. -%, preferably 0.4 to 1.2 wt .-%, particularly preferably 0.4 to 1.0 wt .-%, is. Possibly In addition, such a dry blend can additionally be homogenized in the melt.

Weiter ist bevorzugt, dass das mindestens eine säuremodifizierte Copolyolefin-Elastomer oder das mindestens eine säuremodifizierte Blend mehrerer Copolyolefin-Elastomeren aus monomeren Einheiten zusammengesetzt ist, die ausgewählt sind aus der Gruppe bestehend aus Ethylen d), Propylen e) und But-1-en f), wobei bevorzugt die zuvor genannten Monomere in folgenden molaren Anteilen verwendet werden:

  • d) Ethylen: 65-90 mol-%, bevorzugt 65-87 mol-%, besonders bevorzugt 71-84 mol-%,
  • e) Propylen: 8-33 mol-%, bevorzugt 10-25 mol-%, besonders bevorzugt 12-20 mol-%, sowie
  • f) But-1-en: 2-25 mol-%, bevorzugt 3-20 mol-%, besonders bevorzugt 4-15 mol-%, ganz besonders bevorzugt 4-9 mol-%,
It is further preferred that the at least one acid-modified copolyolefin elastomer or the at least one acid-modified blend of a plurality of copolyolefin elastomers is composed of monomeric units selected from the group consisting of ethylene d), propylene e) and but-1-ene f ), wherein preferably the abovementioned monomers are used in the following molar proportions:
  • d) ethylene: 65-90 mol%, preferably 65-87 mol%, particularly preferably 71-84 mol%,
  • e) Propylene: 8-33 mol%, preferably 10-25 mol%, particularly preferably 12-20 mol%, and
  • f) but-1-ene: 2-25 mol%, preferably 3-20 mol%, particularly preferably 4-15 mol%, very particularly preferably 4-9 mol%,

und wobei sich die Komponenten d), bis f) zu 100 mol-% addieren.and wherein components d) to f) add up to 100 mol%.

Gemäß dieser Ausführungsform kann somit vorgesehen sein, dass das Copolyolefin-Elastomer die genannten Monomere d) bis f) in den angegebenen bevorzugten molaren Anteilen enthält, jedoch ist ebenso die Möglichkeit umfasst, dass mehrere Copolyolefin-Elastomere gemischt werden, die jeweils zwei der Monomere d) bis f), d.h. d) und e), d) und f) oder e) und f), enthalten, so dass in der Mischung die Monomere d) bis f) in den bevorzugten molaren Anteilen vorliegen. Besonders bevorzugt besteht die Mischung aus einem Copolyolefin-Elastomer der Monomere d) und e) und einem Copolyolefin-Elastomer der Monomere d) und f), so dass in der Mischung die Monomere d) bis f) in den bevorzugten molaren Anteilen vorliegen.Thus, according to this embodiment, it may be provided that the copolyolefin elastomer contains said monomers d) to f) in the specified preferred molar proportions, but also includes the possibility of mixing a plurality of copolyolefin elastomers each containing two of the monomers d ) to f), ie d) and e), d) and f) or e) and f), so that the monomers d) to f) are present in the preferred molar proportions in the mixture. The mixture particularly preferably consists of a copolyolefin elastomer of the monomers d) and e) and a copolyolefin elastomer of the monomers d) and f), so that the monomers d) to f) are present in the preferred molar proportions in the mixture.

Weiter ist es vorteilhaft, dass die Säuremodifikation des Copolyolefin-Elastomeren oder des Blends mehrerer Copolyolefin-Elastomerer durch Pfropfen mit ungesättigten Carbonsäuren und/oder ungesättigten Carbonsäurederivaten, bevorzugt einem Carbonsäurederivat ausgewählt aus der Gruppe bestehend aus ungesättigten Carbonsäureestern und ungesättigten Carbonsäureanhydriden, insbesondere mit einer ungesättigten Carbonsäure ausgewählt aus der Gruppe bestehend aus Acrylsäure, Methacrylsäure, alpha-Ethylacrylsäure, Maleinsäure, Fumarsäure, Itaconsäure, Citraconsäure, Aconitsäure, Tetrahydrophthalsäure und/oder Butenylsuccinsäure, erfolgt, d.h. dass das Copolyolefin-Elastomer aufgepfropfte ungesättigte Carbonsäuren und/oder ungesättigte Carbonsäurederivate im Molekül enthält. Die Bedingungen, unter denen die Pfropfung des Copolyolefin-Elastomers abläuft, sind dem Fachmann hinlänglich bekannt.Further, it is advantageous that the acid modification of the copolyolefin elastomer or the blend of several copolyolefin elastomers by grafting with unsaturated carboxylic acids and / or unsaturated carboxylic acid derivatives, preferably a carboxylic acid derivative selected from the group consisting of unsaturated carboxylic acid esters and unsaturated carboxylic acid anhydrides, in particular with an unsaturated carboxylic acid selected from the group consisting of acrylic acid, methacrylic acid, alpha-ethylacrylic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, aconitic acid, tetrahydrophthalic acid and / or butenylsuccinic acid, takes place, ie the copolyolefin elastomer contains grafted unsaturated carboxylic acids and / or unsaturated carboxylic acid derivatives in the molecule. The conditions under which the grafting of the copolyolefin elastomer proceeds are well known to those skilled in the art.

Vorteilhafte Modifizierungsgrade, also die Gewichtsanteile der ungesättigten Carbonsäuren und/oder ungesättigten Carbonsäurederivate am Copolyolefin-Elastomeren oder am Blend mehrerer Copolyolefin-Elastomerer, liegen dabei bei 0,3 bis 1,5 Gew.-%, bevorzugt bei 0,4 bis 1,2 Gew.-%, besonders bevorzugt bei 0,4 bis 1,0 Gew.-%.Advantageous degrees of modification, ie the weight fractions of the unsaturated carboxylic acids and / or unsaturated carboxylic acid derivatives on the copolyolefin elastomer or on the blend of several copolyolefin elastomers, are 0.3 to 1.5% by weight, preferably 0.4 to 1.2 Wt .-%, particularly preferably from 0.4 to 1.0 wt .-%.

Bezüglich des Polyamids der anderen Polyamid enthaltenden bzw. aus Polyamid bestehenden Schalen sind aliphatische, cycloaliphatische, aromatische Polyamide und/oder Blends hiervon zu nennen.With regard to the polyamide of the other polyamide-containing or consisting of polyamide shells aliphatic, cycloaliphatic, aromatic polyamides and / or blends thereof are mentioned.

Geeignete Beispiele für Polyamide der Polyamid enthaltenden bzw. aus Polyamid bestehenden Schalen sind: PA 6, PA 11, PA 12, PA 46, PA 410, PA 412, PA 66, PA 69, PA 610, PA 612, PA 1010, PA 1212, PA 6/11, PA 6/12, PA 6/66, PA 6/68, PA 6/610, PA 66/11, PA 66/12, PA 66/610, PA 6/66/11, PA 6/66/12, PA 6/66/69, PA 6/66/610, PA 6/66/612, PA 6/610/11, PA 6/610/12, PA 6I, PA 6I/6T, PA 6I/66/69, PA 6I/66/610, PA 6-3-T, PA MXD6, PA MXD6/MXDI, PA MXD6/66/610, PA MXDI/61, PA MACM12, PA PACM12, PA MACM14/1014, PA MACM12/PACM12, PA MACM14/PACM14, PA MACMI/PACMI/12, PA MACMI/12, PA MACMT/12, PA MACMI/MACMT/12, PA 6I/MACMI/12, PA 6I/6T/MACMI/MACMT, PA 6I/6T/MACMI/MACMT/12, PA MACM6/11, PA 6I/6T/MACMI/MACMT/MACM12/612, Polyetheramide, Polyesteretheramide und/oder Polyesteramide.Suitable examples of polyamides of polyamide-containing or polyamide-containing shells are: PA 6, PA 11, PA 12, PA 46, PA 410, PA 412, PA 66, PA 69, PA 610, PA 612, PA 1010, PA 1212, PA 6/11, PA 6/12, PA 6/66, PA 6/68, PA 6/610, PA 66/11, PA 66/12, PA 66/610, PA 6/66/11, PA 6/66/12, PA 6/66/69, PA 6/66/610, PA 6/66/612, PA 6/610/11, PA 6/610 / 12, PA 6I, PA 6I / 6T, PA 6I / 66/69, PA 6I / 66/610, PA 6-3-T, PA MXD6, PA MXD6 / MXDI, PA MXD6 / 66/610, PA MXDI / 61, PA MACM12, PA PACM12, PA MACM14 / 1014, PA MACM12 / PACM12, PA MACM14 / PACM14, PA MACMI / PACMI / 12, PA MACMI / 12, PA MACMT / 12, PA MACMI / MACMT / 12, PA 6I / MACMI / 12, PA 6I / 6T / MACMI / MACMT, PA 6I / 6T / MACMI / MACMT / 12, PA MACM6 / 11, PA 6I / 6T / MACMI / MACMT / MACM 12/612, polyetheramides, polyesteretheramides and / or polyesteramides.

Die alphabetischen Abkürzungen der Monomere bedeuten: I Isophthalsäure T Terephthalsäure MACM Bis-(4-amino-3-methyl-cyclohexyl)methan MXD Meta-Xylylendiamin PACM Bis-(4-amino-cyclohexyl)methan (PACM). The alphabetical abbreviations of the monomers mean: I isophthalic T terephthalic acid MACM Bis (4-amino-3-methyl-cyclohexyl) -methane MXD Meta-xylylenediamine PACM Bis (4-amino-cyclohexyl) methane (PACM).

Das Polyamid PA 6-3-T setzt sich zusammen aus Trimethylhexamethylendiamin und Terephthalsäure.The polyamide PA 6-3-T is composed of trimethylhexamethylenediamine and terephthalic acid.

Beim erfindungsgemäßen Hülsenkörper ist es besonders bevorzugt, wenn sowohl die Zwischenschale als auch die inneren Schalen und die äußeren Schalen Polyamid enthalten und/oder aus Polyamid bestehen. Für diesen Fall ist somit der Hülsenkörper ausschließlich aus Polyamid aufgebaut.In the case of the sleeve body according to the invention, it is particularly preferred if both the intermediate shell and the inner shells and the outer shells contain polyamide and / or consist of polyamide. For this case, the sleeve body is thus constructed exclusively of polyamide.

Die Erfindung umfasst aber auch Ausführungsformen, bei denen mindestens eine der Schalen, die nach außen gerichtet sind und/oder eine der inneren Schalen nicht Polyamid enthalten und/oder aus Polyamid bestehen, sondern dass hier ein anderes Schalenmaterial in Abhängigkeit von den gewünschten Eigenschaften eingesetzt werden kann. Gemäß der vorliegenden Erfindung ist es hier nur erforderlich, dass mindestens eine der Schalen, die insgesamt für den Schalenaufbau verwendet werden, aus einem anderen Polymer gebildet ist. Die Dicke dieser Schale liegt, außer bei Verwendung von Haftvermittlern, im Bereich der Polyamid enthaltenden Schalen. Schalen, die aus einem oder mehreren Haftvermittlern gebildet werden, weisen Dicken von 3 bis 100 µm, bevorzugt von 5 bis 50 µm, besonders bevorzugt von 7 bis 20 µm auf. Beispiele für andere Polymere sind Polyolefine, Polyester, Polycarbonate, Ethylen-Vinylalkoholcopolymere und/oder Schalen, die aus Recyclingmaterial, das aus dem Herstellungsprozess des Hülsenkörpers stammt, gebildet sind. Bei den Polyestern sind Polyethylenterephthalat (PET), Polybutylenterephthalat (PBT) und Polyethylennaphthalat (PEN) bevorzugt. Der Begriff Polyolefin umfasst in diesem Zusammenhang Homopolyolefine, wie z.B. PE oder PP, Copolyolefine, Cycloolefin-Copolymere (COC), thermoplastische Elastomere (TPE), gepfropfte Polyolefine, gepfropfte Copolyolefine, Ionomere, Haftvermittler und Copolymere aus Olefinen mit Acrylsäure, Acrylsäurederivaten (z.B. Methacrylsäure, Acrylnitril, Methacrylsäuremethylester, Methacrylsäurebutylester, Glycidylmethacrylat usw.), Vinylacetat, Maleinsäureanhydrid, weiteren Olefinen und/oder Styrol. Bei den Polyolefinen sind Polypropylen, Cycloolefin-Copolymere (COC) und Haftvermittler besonders bevorzugt.However, the invention also includes embodiments in which at least one of the shells which are directed outwards and / or one of the inner shells does not contain polyamide and / or consist of polyamide, but that here another shell material is used depending on the desired properties can be. According to the present invention, it is only necessary here that at least one of the shells used as a whole for the shell construction is formed from a different polymer. The thickness of this shell is, except when using adhesion promoters, in the range of polyamide-containing shells. Trays formed from one or more adhesion promoters have thicknesses of from 3 to 100 .mu.m, preferably from 5 to 50 .mu.m, particularly preferably from 7 to 20 .mu.m. Examples of other polymers are polyolefins, polyesters, polycarbonates, ethylene-vinyl alcohol copolymers, and / or shells formed from recycled material derived from the manufacturing process of the sleeve body. In the polyesters, polyethylene terephthalate (PET), polybutylene terephthalate (PBT) and polyethylene naphthalate (PEN) are preferable. The term polyolefin in this context includes homopolyolefins, such as PE or PP, copolyolefins, cycloolefin copolymers (COC), thermoplastic elastomers (TPE), grafted polyolefins, grafted copolyolefins, ionomers, adhesion promoters and copolymers of olefins with acrylic acid, acrylic acid derivatives (eg methacrylic acid , Acrylonitrile, methyl methacrylate, butyl methacrylate, glycidyl methacrylate, etc.), vinyl acetate, maleic anhydride, other olefins and / or styrene. In the case of the polyolefins, polypropylene, cycloolefin copolymers (COC) and adhesion promoters are particularly preferred.

Die Komponenten des Polyamidschaums, amorphes Polyamid und/oder teilkristallines Polyamid und Polyamidelastomer und/oder modifiziertes Polyolefinelastomer, werden bei der Herstellung des Polyamidschaums als Compound oder Dryblend verwendet. Beim Compound werden die Komponenten im schmelzeförmigen Zustand gemischt. Dies geschieht auf üblichen Compoundiermaschinen, wie z.B. ein- oder zweiwelligen Extrudern oder Schneckenknetern. Die Komponenten werden dabei einzeln in den Einzug dosiert oder in Form eines Dryblends zugeführt.The components of the polyamide foam, amorphous polyamide and / or partially crystalline polyamide and polyamide elastomer and / or modified polyolefin elastomer, are used in the preparation of the polyamide foam as a compound or dry blend. In the compound, the components are mixed in the melt state. This is done on conventional compounding machines, such as single- or twin-screw extruders or screw kneaders. The components are individually dosed into the feeder or supplied in the form of a dry blend.

Zur Dryblendherstellung werden die getrockneten Granulate und gegebenenfalls weitere Zusatzstoffe vermischt. Diese Mischung wird mittels eines Taumelmischers, Rhönradmischers oder Taumeltrockners 10 bis 40 Minuten lang homogenisiert. Zur Vermeidung der Feuchtigkeitsaufnahme kann dies unter getrocknetem Schutzgas erfolgen.For dryblend production, the dried granules and optionally further additives are mixed. This mixture is homogenized by means of a tumbling mixer, Rhönradmischers or tumble dryer for 10 to 40 minutes. To avoid moisture absorption, this can be done under dried inert gas.

Die Compoundierung erfolgt bei eingestellten Zylindertemperaturen von 200 °C bis 340 °C. Vor der Düse kann Vakuum angelegt oder atmosphärisch entgast werden. Die Schmelze wird in Strangform ausgetragen, im Wasserbad bei 10 bis 80 °C abgekühlt und anschließend granuliert. Das Granulat wird für 12 bis 24 Stunden bei 80 bis 120 °C unter Stickstoff oder im Vakuum auf einen Wassergehalt von unter 0,1 Gew.-% getrocknet.The compounding takes place at set cylinder temperatures of 200 ° C to 340 ° C. Vacuum can be applied in front of the nozzle or degassed atmospherically. The melt is discharged in strand form, cooled in a water bath at 10 to 80 ° C and then granulated. The granules are dried for 12 to 24 hours at 80 to 120 ° C under nitrogen or in vacuo to a water content of less than 0.1 wt .-%.

Das Treibmittel wird dem Compound bzw. Dryblend erst vor der Verarbeitung zum Schaum, also vor der Coextrusion der Röhrchen zugesetzt. Die Homogenisierung erfolgt wie beim Dryblend.The blowing agent is added to the compound or dry blend only before processing to foam, so before the coextrusion of the tubes. The homogenization takes place as in dryblend.

Gemäß der vorliegenden Erfindung ist es vorgesehen, dass der Schalenaufbau des Hülsenkörpers aus 1 bis 10 inneren Schalen einer Zwischenschale und 1 bis 10 äußeren Schalen besteht. Der Schalenaufbau kann dabei ausgehend von der Zwischenschale Z asymmetrisch oder auch symmetrisch erfolgen. Bevorzugt ist es, wenn die Anzahl der Schalen insgesamt 3 bis 9, bevorzugt 3 bis 7 und ganz besonders bevorzugt 3 bis 5 beträgt. Beispiele für einen bevorzugten Schalenaufbau sind nachfolgend angeführt. A1 steht dabei für die erste, von der Zwischenschale Z ausgehend angeordnete Schale. A2 ist dann die zweite Außenschale. Entsprechendes gilt für die innere Schale I. 4 Schalen: A2/A1/Z/I1 A1/Z/I1/I2 5 Schalen: A3/A2/A1/Z/I1 A1/Z/I1/I2/I3 6 Schalen: A3/A2/A1/Z/I1/I2 A2/A1/Z/I1/I2/I3 According to the present invention, it is provided that the shell structure of the sleeve body consists of 1 to 10 inner shells of an intermediate shell and 1 to 10 outer shells. The shell structure can be carried out asymmetrically or symmetrically starting from the intermediate shell Z. It is preferred if the number of shells is a total of 3 to 9, preferably 3 to 7 and very particularly preferably 3 to 5. Examples for a preferred shell construction are given below. A1 stands for the first, starting from the intermediate shell Z starting shell. A2 is then the second outer shell. The same applies to the inner shell I. 4 bowls: A2 / A1 / Z / I1 A1 / Z / I1 / I2 5 bowls: A3 / A2 / A1 / Z / I1 A1 / Z / I1 / I2 / I3 6 bowls: A3 / A2 / A1 / Z / I1 / I2 A2 / A1 / Z / I1 / I2 / I3

Die Erfindung umfasst dabei selbstverständlich auch Ausführungsformen, bei denen zwischen den Schalen wie vorstehend erläutert noch Haftvermittlerschichten vorgesehen sind. Die Auswahl der Haftvermittlerschicht hängt davon ab, wie der Schalenaufbau gewählt worden ist. Auch ist es möglich, einen Haftvermittler mit in das Material der Schalen einzuarbeiten.Of course, the invention also encompasses embodiments in which bonding agent layers are still provided between the shells as explained above. The choice of primer layer depends on how the shell construction has been chosen. It is also possible to incorporate a bonding agent in the material of the shells.

Den Materialien der Schalen können bis zu 5 Gew.-%, bevorzugt 0,1 bis 4 Gew.-%, besonders bevorzugt 0,1 bis 2 Gew.-%, Zusatzstoffe zugegeben werden.Up to 5% by weight, preferably 0.1 to 4% by weight, particularly preferably 0.1 to 2% by weight, of additives can be added to the materials of the shells.

Der Zusatzstoff ist ausgewählt aus der Gruppe bestehend aus anorganischen Stabilisatoren, organischen Stabilisatoren, Gleitmitteln, Farb- und Markierungsstoffen, anorganischen Pigmenten, organischen Pigmenten, Antistatika, Antiblockmitteln, Nukleierungsmitteln, Kristallisationsbeschleunigern, Kristallisationsverzögerern, kettenverlängernden Additiven, Entformungsmitteln, Trennmitteln, optischen Aufhellern, metallischen Pigmenten, Metallflittern, metallbeschichteten Partikeln, Füll- und Verstärkungsstoffen, insbesondere nanoskaligen Füll- und Verstärkungsstoffen, wie z.B. Mineralen mit einer Partikelgröße von maximal 100 nm oder unmodifizierte oder modifizierte, natürliche oder synthetische Phyllosilicate oder Mischungen davon.The additive is selected from the group consisting of inorganic stabilizers, organic stabilizers, lubricants, colorants and markers, inorganic pigments, organic pigments, antistatic agents, antiblocking agents, nucleating agents, crystallization accelerators, crystallization retardants, chain-extending additives, mold release agents, release agents, optical brighteners, metallic pigments , Metal flakes, metal-coated particles, fillers and reinforcing materials, in particular nanoscale fillers and reinforcing materials, such as minerals with a particle size of at most 100 nm or unmodified or modified, natural or synthetic phyllosilicates or mixtures thereof.

Erfindungsgemäß kann auch mindestens eine Schale A, I und/oder Z eingefärbt sein. Die Schalen können farblich auch unterschiedlich ausgeführt sein. Im Gegensatz zu den geschäumten PVC-Röhrchen, welche nur in Pastelltönen einzufärben sind, können bei dem erfindungsgemäßen Hülsenkörper auch kräftige Farben des gesamten Farbspektrums, einschließlich schwarz und weiß, realisiert werden.According to the invention, at least one shell A, I and / or Z can also be colored. The shells can be designed differently in color. In contrast to the foamed PVC tubes, which are to be colored only in pastel shades, the sheath body according to the invention can also be used to produce strong colors of the entire color spectrum, including black and white.

Bevorzugte Verwendungen für die vorstehend beschriebenen Hülsenkörper sind Lidschattenstifte, Lippenkonturstifte, Augenkonturstifte, Augenbrauenstifte, Sonnenschutzstifte, Antiagingstifte, Antiaknestifte, Schreibstifte, Malstifte und/oder industrielle Anwendungen, wie z.B. medienführende Systeme im Apparatebau.Preferred uses for the sleeve bodies described above are eyeshadow pens, lip contour pens, eye contour pens, eyebrow pencils, sun protection pens, anti-paging pins, anti-sore pens, pens, crayons, and / or industrial applications, e.g. Media-leading systems in apparatus construction.

Die Erfindung wird nachfolgend anhand der Figuren 1 und 2 und der Messergebnisse (Figuren 3 bis 6) näher erläutert.The invention will be described below with reference to FIGS. 1 and 2 and the measurement results ( FIGS. 3 to 6 ) explained in more detail.

In Figur 1 ist im Schnitt ein erfindungsgemäßer Hülsenkörper 1 dargestellt. Der Hülsenkörper nach der Ausführungsform nach Figur 1 ist zylindrisch ausgebildet und besteht aus einer Zwischenschale Z, einer Außenschale A1 sowie einer Innenschale 11. Der Hohlraum ist mit H bezeichnet. Mit einem gemäß Figur 1 ausgebildeten erfindungsgemäßen Hülsenkörper wurden mittels verschiedener Materialien Versuche durchgeführt, die in den Tabellen (in den Figuren 3 und 4) angegeben sind.In FIG. 1 In section, an inventive sleeve body 1 is shown. The sleeve body according to the embodiment according to FIG. 1 is cylindrical and consists of an intermediate shell Z, an outer shell A1 and an inner shell 11. The cavity is designated H. With one according to FIG. 1 trained sleeve body according to the invention experiments were carried out by means of various materials, which in the tables (in the Figures 3 and 4 ) are indicated.

Für die Beispiele 1 bis 20 wurden durch Coextrusion 3-Schicht-Röhrchen mit der Dimension 7,8 x 1,8 mm mit folgenden Materialien und Schichtdicken hergestellt: Außenschale A1 aus PA 6 150 µm, Zwischenschale Z aus erfindungsgemäßem Polyamidschaum 1450 µm, Innenschale I1 aus PA 6I/6T 200 µm. Es wurden dabei folgende Temperaturen verwendet: Außenschale A1 260 °C, Zwischenschale Z 250 °C, Innenschale I1 230 °C. Das Endlosröhrchen wurde in 120 mm lange Röhrchen geschnitten.For examples 1 to 20, 3-layer tubes of dimensions 7.8 × 1.8 mm were produced by coextrusion with the following materials and layer thicknesses: outer shell A1 made of PA 6 150 μm, intermediate shell Z made of polyamide foam according to the invention 1450 μm, inner shell I1 made of PA 6I / 6T 200 μm. The following temperatures were used: outer shell A1 260 ° C, intermediate shell Z 250 ° C, inner shell I1 230 ° C. The endless tube was cut into 120 mm long tubes.

Die in den Beispielen verwendeten Materialien sind aus den Tabellen (Figur 5 und Figur 6) zu entnehmen.The materials used in the examples are from the tables ( FIG. 5 and FIG. 6 ) refer to.

Es wurden folgende Messvorschriften verwendet.The following measurement instructions were used.

Relative Viskosität
ISO 307
0,5 Gew.-%-ige m-Kresollösung bzw. 1,0 Gew.-%-ige Lösung in 96 Gew.-%-iger Schwefelsäure Temperatur 20 °C
Berechnung der relativen Viskosität (RV) nach
RV = t/t0 in Anlehnung an Abschnitt 11 der Norm.Relative viscosity
ISO 307
0.5% strength by weight m-cresol solution or 1.0% strength by weight solution in 96% strength by weight sulfuric acid at 20 ° C.
Calculation of the relative viscosity (RV) after
RV = t / t 0 in accordance with section 11 of the standard.

Schmelzpunkt und Glasumwandlungstemperatur (Tg)
ISO-Norm 11357-1/-2
Granulat
Die Differential Scanning Calorimetry (DSC) wurde mit Aufheizrate von 20 K/min durchgeführt.
Beim Schmelzpunkt wird die Temperatur am Peakmaximum, bei der Glasumwandlungstemperatur die Temperatur am Onset angegeben.Melting point and glass transition temperature (Tg)
ISO standard 11357-1 / -2
granules
Differential Scanning Calorimetry (DSC) was performed at a rate of 20 K / min.
At the melting point the temperature is indicated at the peak maximum, at the glass transition temperature the temperature at the onset.

Maximalkraft im Biegeversuch
EN ISO-Norm 178
120 mm lange Röhrchen der Dimension 7,8 x 1,8 mm
Temperatur: 23 °C
Prüfgeschwindigkeit 2 mm/min
Stützweite 80 mmMaximum force in bending test
EN ISO standard 178
120 mm long tubes measuring 7.8 x 1.8 mm
Temperature: 23 ° C
Test speed 2 mm / min
Support width 80 mm

Die Maximalkraft wird an jeweils fünf Röhrchen bestimmt. Angegeben wird das arithmetische Mittel der gemessenen Maximalkräfte in N.The maximum force is determined on five tubes each. The arithmetic mean of the measured maximum forces in N. is given.

Spitzbarkeitsharpenability

Zur Bestimmung der Spitzbarkeit wurde das Drehmoment während dem Spitzen gemessen. Als Spitzer wurde ein handelsüblicher Bleistiftspitzer der KUM GmbH & Co. KG verwendet: Magnesium-Einfachspitzer mit Hartstahlmesser, Blockform. Das Drehmoment wurde mittels eines elektronischen Rührwerks mit Drehmomentanzeige der Heidolph Instruments GmbH & Co. KG gemessen: Heidolph RZR 2051 control. Der Spitzer wurde mittels eines Stielfeilklobens in den Rührer eingespannt.To determine the spikeability, the torque was measured during the spike. The sharpener used was a commercial pencil sharpener from KUM GmbH & Co. KG: Magnesium single sharpener with a carbon steel blade, block shape. The torque was measured by means of an electronic agitator with torque indicator from Heidolph Instruments GmbH & Co. KG: Heidolph RZR 2051 control. The sharpener was clamped by means of a Stielfeilklobens in the stirrer.

Die Messung des Drehmoments erfolgte bei 200 U/min. Dazu wurde das Röhrchen mittels einer Schraubendruckfeder einer Standardstativklemme in den Spitzer gedrückt und das Drehmomentmaximum abgelesen. Die Messung wird an drei Röhrchen jeweils zweimal durchgeführt. Die angegebene Spitzbarkeit ist das arithmetische Mittel der gemessenen maximalen Drehmomente in Ncm.The measurement of the torque was carried out at 200 U / min. For this purpose, the tube was pressed by means of a helical compression spring of a standard stand clamp in the sharpener and read the torque maximum. The measurement is carried out twice on three tubes. The specified payload is the arithmetic mean of the measured maximum torques in Ncm.

Wie aus der Tabelle (Figuren 3 und 4) hervorgeht, weisen somit die erfindungsgemäßen Hülsenkörper eine Maximalkraft im Biegetest auf, die über 100 N liegt, und eine Produktionsgeschwindigkeit von mindestens 25 m/min. In einigen Beispielen liegt sogar die Produktionsgeschwindigkeit über 50 m/min. Die Spitzbarkeit ist immer größer als 11 N · cm.As from the table ( Figures 3 and 4 ), therefore, the sleeve body according to the invention have a maximum force in the bending test, which is above 100 N, and a production speed of at least 25 m / min. In some examples, even the production rate is over 50 m / min. The sharpenability is always greater than 11 N · cm.

Im Vergleich hierzu beträgt die Produktionsgeschwindigkeit von Monoröhrchen aus geschäumtem PVC 8 bis 11 m/min. An 120 mm langen Monoröhrchen aus geschäumtem PVC mit den Dimensionen 7,8 x 1,8 mm wurde eine Biegefestigkeit von 83 N und eine Spitzbarkeit von 11 N cm gemessen.In comparison, the production rate of mono-tubes made of foamed PVC is 8 to 11 m / min. A 120 mm long foam PVC monotube measuring 7.8 x 1.8 mm was found to have a flexural strength of 83 N and a toughness of 11 N cm.

Überraschenderweise ergibt sich somit, dass mit dem Schalenaufbau nach der Erfindung eine Produktionsgeschwindigkeit (ausgedrückt in m/min) erreicht werden kann, die deutlich über der liegt, wie sie bisher im Stand der Technik von Hülsenkörpern aus geschäumtem PVC bekannt war. Ergänzend ist darauf hinzuweisen, dass zusätzlich die Spitzbarkeit der Hülsenkörper und die Maximalkraft im Biegetest besser als im Stand der Technik sind.Surprisingly, it follows that with the shell structure according to the invention, a production speed (expressed in m / min) can be achieved, which is well above that, as was previously known in the art of sleeve bodies made of foamed PVC. In addition, it should be noted that in addition the sharpenability of the sleeve body and the maximum force in the bending test are better than in the prior art.

In Figur 2 ist eine weitere Ausführungsform eines erfindungsgemäßen Hülsenkörpers dargestellt. Die Ausführungsform nach Figur 2 zeigt nun einen Hülsenkörper, der aus insgesamt 5 Schalen besteht, wobei die Zwischenschale Z, die aus Polyamidschaum besteht, jeweils von zwei Schalen umgeben ist. So verfügt der Hülsenkörper in der Ausführungsform nach Figur 2 über zwei Innenschalen I1 und I2 und über zwei Außenschalen A1 und A2. Bei der Ausführungsform nach der Figur 2 sind jeweils wieder Polyamide als Schalenmaterialien verwendet worden.In FIG. 2 a further embodiment of a sleeve body according to the invention is shown. The embodiment according to FIG. 2 now shows a sleeve body, which consists of a total of 5 shells, wherein the intermediate shell Z, which consists of polyamide foam, each surrounded by two shells. Thus, the sleeve body in the embodiment after FIG. 2 via two inner shells I1 and I2 and via two outer shells A1 and A2. In the embodiment of the FIG. 2 In each case, polyamides have again been used as shell materials.

Die Erfindung umfasst aber auch Ausführungsformen, bei denen ein asymmetrischer Schalenaufbau verwirklicht wird. So ist es möglich, den Hülsenkörper so auszubilden, dass ausgehend von der Zwischenschale Z nach außen hin 3 Schalen vorgesehen sind, d.h. Außenschale A1, A2 und A3, und dass der Hülsenkörper dann über nur zwei Innenschalen I1 und I2 verfügt. Die Anzahl der Schalen richtet sich hierbei auch nach dem Anwendungsfall, so ist es möglich, insbesondere im Außenbereich noch eine zusätzliche Schale anzubringen, mit der die Haptik und/oder die optischen Eigenschaften des Hülsenkörpers beeinflusst werden können. Zusätzliche Schalen, z.B. aus Ethylen-Vinylalkoholcopolymeren oder Polypropylen (PP), insbesondere im Innenbereich, können z.B. die Barrierewirkung des Hülsenkörpers gegenüber Bestandteilen der Mine noch weiter verbessern. Dabei sind zwischen einer Schale aus Ethylen-Vinylalkoholcopolymeren und einer Schale, die Polyamid enthält und/oder daraus besteht, keine Haftvermittler nötig.However, the invention also includes embodiments in which an asymmetric shell structure is realized. Thus, it is possible to form the sleeve body so that 3 shells are provided starting from the intermediate shell Z to the outside, ie outer shell A1, A2 and A3, and that the sleeve body then has only two inner shells I1 and I2. The number The shells also depend on the application, so it is possible, in particular in the outer area still attach an additional shell, with which the feel and / or the optical properties of the sleeve body can be influenced. Additional shells, for example of ethylene-vinyl alcohol copolymers or polypropylene (PP), especially indoors, can further improve, for example, the barrier effect of the sleeve body towards components of the mine. In this case, no adhesion promoter is necessary between a shell of ethylene-vinyl alcohol copolymers and a shell which contains polyamide and / or consists thereof.

Bei Verwendung einer weiteren Schale, die nicht Polyamid enthält und/oder aus Polyamid besteht, kann es erforderlich sein, dass zwischen dieser Schale, z.B. aus Polypropylen und den anliegenden Schalen, eine Haftvermittlerschicht vorgesehen ist.When using a further shell which does not contain polyamide and / or consists of polyamide, it may be necessary that between this shell, e.g. made of polypropylene and the adjacent shells, an adhesive layer is provided.

Claims (20)

Hülsenkörper (1) aus einem thermoplastischen Kunststoff, insbesondere für Kosmetikstifte oder Schreibstifte, dessen Hohlraum H von einem mindestens dreischaligen Aufbau A, Z, I umschlossen ist,
dadurch gekennzeichnet, dass er 1 bis 10 äußere Schalen A, eine Zwischenschale Z und 1 bis 10 innere Schalen I aufweist, wobei die Zwischenschale Z Polyamidschaum und mindestens eine der anderen Schalen A, I Polyamid enthält und/oder daraus besteht.Sleeve body (1) made of a thermoplastic material, in particular for cosmetic pencils or pens, whose cavity H is enclosed by an at least three-shell structure A, Z, I,
characterized in that it comprises 1 to 10 outer shells A, an intermediate shell Z and 1 to 10 inner shells I, wherein the intermediate shell Z polyamide foam and at least one of the other shells A, I contains polyamide and / or consists thereof. Hülsenkörper nach Anspruch 1,
dadurch gekennzeichnet, dass die Zwischenschale Z, die aus Polyamidschaum gebildet ist, eine größere Schichtdicke aufweist als die anderen Schalen A und I.Sleeve body according to claim 1,
characterized in that the intermediate shell Z, which is formed from polyamide foam, has a greater layer thickness than the other shells A and I. Hülsenkörper nach Anspruch 1 oder 2,
dadurch gekennzeichnet, dass die Zwischenschale Z eine Schichtdicke von 1000 bis 3000 µm, bevorzugt 1100 bis 2500 µm, besonders bevorzugt 1200 bis 2100 µm, ganz besonders bevorzugt 1300 bis 1800 µm, aufweisen.Sleeve body according to claim 1 or 2,
characterized in that the intermediate shell Z has a layer thickness of 1000 to 3000 .mu.m, preferably 1100 to 2500 .mu.m, more preferably 1200 to 2100 microns, most preferably 1300 to 1800 microns have. Hülsenkörper nach mindestens einem der Ansprüche 1 bis 3,
dadurch gekennzeichnet, dass die Schalen von A und/oder von I, die Polyamid enthalten, eine Schichtdicke von 50 bis 600 µm, bevorzugt 80 bis 500 µm, besonders bevorzugt 100 bis 400 µm, ganz besonders bevorzugt 150 bis 300 µm, aufweisen.Sleeve body according to at least one of claims 1 to 3,
characterized in that the shells of A and / or I containing polyamide, a layer thickness of 50 to 600 microns, preferably 80 to 500 .mu.m, more preferably 100 to 400 .mu.m, most preferably 150 to 300 .mu.m. Hülsenkörper nach mindestens einem der Ansprüche 1 bis 4,
dadurch gekennzeichnet, dass er spitzbar ist.Sleeve body according to at least one of claims 1 to 4,
characterized in that it is sharpenable. Hülsenkörper nach mindestens einem der Ansprüche 1 bis 5,
dadurch gekennzeichnet, dass seine Maximalkraft im Biegetest im Bereich von 85 bis 250 N, bevorzugt 90 bis 180 N, besonders bevorzugt 100 bis 170 N, liegt.Sleeve body according to at least one of claims 1 to 5,
characterized in that its maximum force in the bending test in the range of 85 to 250 N, preferably 90 to 180 N, more preferably 100 to 170 N, is located. Hülsenkörper nach mindestens einem der Ansprüche 1 bis 6,
dadurch gekennzeichnet, dass der Polyamidschaum aus einem amorphen Polyamid und/oder einem teilkristallinen Polyamid und einem Polyamidelastomer und/oder modifiziertem Polyolefinelastomer aufgebaut ist.Sleeve body according to at least one of claims 1 to 6,
characterized in that the polyamide foam is composed of an amorphous polyamide and / or a partially crystalline polyamide and a polyamide elastomer and / or modified polyolefin elastomer. Hülsenkörper nach Anspruch 7,
dadurch gekennzeichnet, dass der Polyamidschaum 50 bis 80 Gew.-% Polyamid und 20 bis 50 Gew.-% eines Polyamidelastomers und/oder modifizierten Polyolefinelastomers enthält.Sleeve body according to claim 7,
characterized in that the polyamide foam contains 50 to 80% by weight of polyamide and 20 to 50% by weight of a polyamide elastomer and / or modified polyolefin elastomer. Hülsenkörper nach einem der Ansprüche 7 oder 8, dadurch gekennzeichnet, dass die Glasübergangstemperatur des amorphen Polyamids 90 bis 210 °C, bevorzugt 100 bis 180 °C, besonders bevorzugt 110 bis 170 °C, beträgt.Sleeve body according to one of claims 7 or 8, characterized in that the glass transition temperature of the amorphous polyamide 90 to 210 ° C, preferably 100 to 180 ° C, particularly preferably 110 to 170 ° C, is. Hülsenkörper nach einem der Ansprüche 7 oder 8, dadurch gekennzeichnet, dass der Schmelzpunkt des teilkristallinen Polyamids 120 bis 295 °C, bevorzugt 150 bis 280 °C, besonders bevorzugt 170 bis 270 °C, ganz besonders bevorzugt 180 bis 255 °C, beträgt.Sleeve body according to one of claims 7 or 8, characterized in that the melting point of the partially crystalline polyamide 120 to 295 ° C, preferably 150 to 280 ° C, particularly preferably 170 to 270 ° C, most preferably 180 to 255 ° C, is. Hülsenkörper nach einem der Ansprüche 7 oder 8, dadurch gekennzeichnet, dass das Polyamidelastomer ausgewählt ist aus Polyetheramiden, Polyesteretheramiden und/oder Polyesteramiden und das Polyolefinelastomer ausgewählt ist aus einem säuremodifizierten Copolyolefin-Elastomeren und/oder einem säuremodifizierten Blend mehrerer Copolyolefin-Elastomerer.A sleeve body according to one of claims 7 or 8, characterized in that the polyamide elastomer is selected from polyetheramides, polyesteretheramides and / or polyesteramides and the polyolefin elastomer is selected from an acid-modified copolyolefin elastomer and / or an acid-modified blend of a plurality of copolyolefin elastomers. Hülsenkörper nach mindestens einem der Ansprüche 1 bis 11,
dadurch gekennzeichnet, dass das Polyamid der Polyamid enthaltenden und/oder aus Polyamid bestehenden Schalen von A und/oder von I aus aliphatischen, cycloaliphatischen, aromatischen Polyamiden und/oder Blends hiervon ausgewählt ist.Sleeve body according to at least one of claims 1 to 11,
characterized in that the polyamide polyamide-containing and / or consisting of polyamide shells of A and / or I is selected from aliphatic, cycloaliphatic, aromatic polyamides and / or blends thereof. Hülsenkörper nach Anspruch 12,
dadurch gekennzeichnet, dass das Polyamid ausgewählt ist aus PA 6, PA 11, PA 12, PA 46, PA 410, PA 412, PA 66, PA 69, PA 610, PA 612, PA 1010, PA 1212, PA 6/11, PA 6/12, PA 6/66, PA 6/68,
PA 6/610, PA 66/11, PA 66/12, PA 66/610, PA 6/66/11, PA 6/66/12, PA 6/66/69, PA 6/66/610, PA 6/66/612, PA 6/610/11, PA 6/610/12, PA 6I, PA 6I/6T, PA 6I/66/69, PA 6I/66/610, PA 6-3-T, PA MXD6, PA MXD6/MXDI, PA MXD6/66/610, PA MXDI/6I, PA MACM12, PA PACM12, PA MACM14/1014, PA MACM12/PACM12, PA MACM14/PACM14, PA MACMI/PACMI/12, PA MACMI/12, PA MACMT/12, PA MACMI/MACMT/12, PA 6I/MACMI/12, PA 6I/6T/MACMI/MACMT, PA 6I/6T/MACMI/MACMT/12, PA MACM6/11, und PA 6I/6T/MACMI/MACMT/MACM12/612, Polyetheramide, Polyesteretheramide und/oder Polyesteramide.Sleeve body according to claim 12,
characterized in that the polyamide is selected from PA 6, PA 11, PA 12, PA 46, PA 410, PA 412, PA 66, PA 69, PA 610, PA 612, PA 1010, PA 1212, PA 6/11, PA 6/12, PA 6/66, PA 6/68,
PA 6/610, PA 66/11, PA 66/12, PA 66/610, PA 6/66/11, PA 6/66/12, PA 6/66/69, PA 6/66/610, PA 6 / 66/612, PA 6/610/11, PA 6/610/12, PA 6I, PA 6I / 6T, PA 6I / 66/69, PA 6I / 66/610, PA 6-3-T, PA MXD6 , PA MXD6 / MXDI, PA MXD6 / 66/610, PA MXDI / 6I, PA MACM12, PA PACM12, PA MACM14 / 1014, PA MACM12 / PACM12, PA MACM14 / PACM14, PA MACMI / PACMI / 12, PA MACMI / 12 , PA MACMT / 12, PA MACMI / MACMT / 12, PA 6I / MACMI / 12, PA 6I / 6T / MACMI / MACMT, PA 6I / 6T / MACMI / MACMT / 12, PA MACM6 / 11, and PA 6I / 6T / MACMI / MACMT / MACM12 / 612 Polyetheramides, polyesteretheramides and / or polyesteramides. Hülsenkörper nach mindestens einem der Ansprüche 1 bis 13,
dadurch gekennzeichnet, dass die Schalen von A und von I Polyamid enthalten und/oder aus Polyamid bestehen und die Polyamide von mindestens zwei Schalen von A und/oder von I unterschiedlich sind.Sleeve body according to at least one of claims 1 to 13,
characterized in that the shells of A and I contain polyamide and / or consist of polyamide and the polyamides of at least two shells of A and / or I are different. Hülsenkörper nach mindestens einem der Ansprüche 1 bis 13,
dadurch gekennzeichnet, dass mindestens eine der Schalen von A und/oder von I Polyolefin, Polycarbonat, Polyester, Polyesterelastomere, Ethylen-Vinylalkohol-Copolymer und/oder Recyclingmaterial aus dem Herstellungsprozess des Hülsenkörpers (1) enthalten und/oder daraus bestehen.Sleeve body according to at least one of claims 1 to 13,
characterized in that at least one of the shells of A and / or I polyolefin, polycarbonate, polyester, polyester elastomers, ethylene-vinyl alcohol copolymer and / or recycled material from the manufacturing process of the sleeve body (1) and / or consist thereof. Hülsenkörper nach mindestens einem der Ansprüche 1 bis 15,
dadurch gekennzeichnet, dass die Anzahl der Schalen A, Z und I insgesamt 3 bis 9, bevorzugt 3 bis 7 und besonders bevorzugt 3 bis 5 ist.Sleeve body according to at least one of claims 1 to 15,
characterized in that the number of shells A, Z and I is a total of 3 to 9, preferably 3 to 7 and particularly preferably 3 to 5. Hülsenkörper nach mindestens einem der Ansprüche 1 bis 16,
dadurch gekennzeichnet, dass zwischen mindestens zwei Schalen von A, I und/oder Z eine Haftvermittlerschicht vorgesehen ist.Sleeve body according to at least one of claims 1 to 16,
characterized in that between at least two shells of A, I and / or Z, a bonding agent layer is provided. Hülsenkörper nach mindestens einem der Ansprüche 1 bis 17,
dadurch gekennzeichnet, dass in mindestens einer der Schalen von A, I und/oder Z Zusatzstoffe in einer Menge von bis zu 5 Gew.-%, bezogen auf die Gesamtzusammensetzung der Schale, enthalten sind.Sleeve body according to at least one of claims 1 to 17,
characterized in that in at least one of the shells of A, I and / or Z additives in an amount of up to 5 wt .-%, based on the Total composition of the shell, are included. Hülsenkörper nach mindestens einem der Ansprüche 1 bis 18,
dadurch gekennzeichnet, dass mindestens eine Schale von A, I und/oder Z eingefärbt ist.Sleeve body according to at least one of claims 1 to 18,
characterized in that at least one shell of A, I and / or Z is colored. Verwendung eines Hülsenkörpers nach mindestens einem der Ansprüche 1 bis 19 für Lidschattenstifte, Lippenkonturstifte, Augenkonturstifte, Augenbrauenstifte, Sonnenschutzstifte, Antiagingstifte, Antiaknestifte, Schreibstifte, Malstifte und/oder industrielle Anwendungen.Use of a sleeve body according to at least one of claims 1 to 19 for eyeshadow pens, lip contour pens, eye contour pens, eyebrow pencils, sun protection pens, anti-paging pins, anti-acne pins, pens, crayons and / or industrial applications.
EP11002218.3A 2011-03-17 2011-03-17 Casing body Active EP2499932B1 (en)

Priority Applications (6)

Application Number Priority Date Filing Date Title
ES11002218.3T ES2578732T3 (en) 2011-03-17 2011-03-17 Sleeve body
EP11002218.3A EP2499932B1 (en) 2011-03-17 2011-03-17 Casing body
PL11002218.3T PL2499932T3 (en) 2011-03-17 2011-03-17 Casing body
US13/421,541 US20120237708A1 (en) 2011-03-17 2012-03-15 Casing body
KR20120027034A KR101495095B1 (en) 2011-03-17 2012-03-16 Casing body
CN201210072691.7A CN102669920B (en) 2011-03-17 2012-03-19 Set of shells

Applications Claiming Priority (1)

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EP11002218.3A EP2499932B1 (en) 2011-03-17 2011-03-17 Casing body

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EP2499932B1 EP2499932B1 (en) 2016-05-11

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014114421A1 (en) * 2013-01-23 2014-07-31 J.S. Staedtler Gmbh & Co. Kg Component for writing, drawing, painting and/or cosmetic implements and method for the production thereof
CN104442094A (en) * 2014-11-26 2015-03-25 武汉光禾笔业有限公司 Coated pencil
US10308063B2 (en) 2014-12-17 2019-06-04 Conte Paper pencil lead
WO2020127209A1 (en) * 2018-12-18 2020-06-25 Societe Bic Lead casing for pencil, and pencil thereof for writing, drawing, marking, plotting, and coloring
WO2020127203A1 (en) * 2018-12-18 2020-06-25 Societe Bic Lead casing for pencil, and pencil thereof for writing, drawing, marking, plotting, and coloring
EP4349562A3 (en) * 2016-08-26 2024-06-26 A.W. Faber-Castell Cosmetics GmbH Use of a one-piece injection-moulded coating sleeve

Families Citing this family (24)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2060607B2 (en) * 2007-11-16 2019-11-27 Ems-Patent Ag Filled polyamide moulding materials
ES2429814T3 (en) * 2010-03-12 2013-11-18 Ems-Patent Ag Modified polyamide molding mass for impact resistance as well as container formed from it
EP2412757B1 (en) 2010-07-30 2013-11-13 Ems-Patent Ag Polyamide moulding composition for producing moulded articles with a soft touch surface and corresponding articles
EP2666803B1 (en) 2012-05-23 2018-09-05 Ems-Patent Ag Scratch-proof, transparent and ductile copolyamide moulding materials, moulded parts produced from same and use of same
EP2716716B1 (en) 2012-10-02 2018-04-18 Ems-Patent Ag Polyamide moulding compositions and their use in the production of moulded articles
PL2746339T3 (en) 2012-12-18 2015-05-29 Ems Patent Ag Polyamide form mass and moulded parts produced from same
EP2778190B1 (en) 2013-03-15 2015-07-15 Ems-Patent Ag Polyamide moulding material and moulded body produced from the same
US8998519B2 (en) * 2013-05-13 2015-04-07 Hemant Patel Process and formulation for a plastic pencil
DE102013217241A1 (en) 2013-08-29 2015-03-05 Ems-Patent Ag Polyamide molding compounds and moldings produced therefrom
CN105440390A (en) * 2015-12-21 2016-03-30 江西省吉水县吉星文化用品有限公司 Plastic pencil and preparation method thereof
EP3184577A1 (en) 2015-12-23 2017-06-28 Ems-Patent Ag Method and container for storing and transporting polyamide pellets and correspondingly stored or transported polyamide pellets and shaped articles obtained therefrom
WO2018036847A1 (en) 2016-08-26 2018-03-01 A.W. Faber-Castell Cosmetics Gmbh Pencil comprising an integrally injection-moulded layered casing
EP3312224B1 (en) 2016-10-21 2018-12-26 Ems-Patent Ag Polyamide moulding composition and multi-layered structure made herefrom
EP3444113B1 (en) 2017-08-18 2021-01-20 Ems-Chemie Ag Reinforced polyamide moulding compounds with low haze and moulds therefrom
EP3444112B1 (en) 2017-08-18 2020-12-23 Ems-Chemie Ag Reinforced polyamide moulding compounds with low haze and moulds therefrom
EP3444114B1 (en) 2017-08-18 2023-10-25 Ems-Chemie Ag Reinforced polyamide moulding compounds with low haze and moulds therefrom
EP3450481B1 (en) 2017-08-31 2020-10-21 Ems-Chemie Ag Polyamide moulding material having high gloss and high notch impact strength
EP3502191B1 (en) 2017-12-22 2021-02-17 Ems-Chemie Ag Polyamide moulding material
EP3502164B1 (en) 2017-12-22 2022-10-05 Ems-Chemie Ag Polyamide moulding material
CN108338482B (en) * 2018-02-09 2023-09-01 浙江正庄实业有限公司 Environment-friendly high-rigidity antistatic single-tube eyebrow pencil and preparation method thereof
EP3636406B1 (en) 2018-10-09 2021-04-28 Ems-Chemie Ag Toughened polyamide moulding masses
EP3670184A1 (en) 2018-12-20 2020-06-24 EMS-Patent AG Fluid transport line and its use
EP3772520B1 (en) 2019-08-09 2023-07-12 Ems-Chemie Ag Polyamide moulding compound and use thereof and moulded bodies produced from said moulding compound
EP3842496A1 (en) 2019-12-23 2021-06-30 Ems-Chemie Ag Polyamide moulding compositions for hypochlorite resistant applications

Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR60608E (en) * 1948-12-20 1954-11-22 Manufacture of pencils with a lead and synthetic plastics
US3551064A (en) * 1967-04-18 1970-12-29 Bernard I Bartner Unitary composite article and method of manufacturing the same
DE2821333A1 (en) * 1977-05-16 1978-11-30 Borg Warner TUBE MADE OF THERMOPLASTIC MATERIAL AND THE METHOD OF ITS MANUFACTURING
GB1538188A (en) 1976-07-27 1979-01-10 Oreal Make-up pencil
DE2937441A1 (en) * 1979-09-15 1982-04-01 Schwan-Stabilo Schwanhäußer GmbH & Co, 8500 Nürnberg Cosmetic pencil esp. with non castable core - has surrounding shell esp. of polyolefin cast around core
GB2084084A (en) * 1980-09-22 1982-04-07 Oreal Pencil, having a sleeve made of plastic, and process for the manufacture of same
US4413921A (en) 1978-09-05 1983-11-08 Revlon, Inc. Cosmetic pencil having a sharpenable polyethylene casing
DE4005894A1 (en) 1990-02-24 1991-12-12 Schwan Stabilo Schwanhaeusser Cosmetic stick prodn. method - consists of sleeve leading into mould, with duct and front end
DE69200023T2 (en) * 1991-03-19 1994-05-11 Conte Sa Process for producing a pen or colored pencil by tri-extrusion and then produced pen or colored pencil with a protective layer for the lead.
US5957607A (en) 1998-06-17 1999-09-28 Tsai; Felix J. Cosmetic pencil structure
DE202009008403U1 (en) * 2009-06-18 2010-01-28 Gauss, Anna Pencil with a shock absorbing sheath

Family Cites Families (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3625788A (en) * 1969-09-04 1971-12-07 Bernard I Bartner Method of manufacturing a unitary composite article comprised of a core and lining
US4322260A (en) * 1979-04-04 1982-03-30 Monsanto Company Process for the continuous extrusion forming of a plastic double-walled foam-core conduit
EP0325923A3 (en) * 1988-01-19 1990-03-14 Caran D'ache S.A. Process for enclosing a pencil, lead and pencil lead obtained by this process
DE9001242U1 (en) * 1990-02-04 1991-02-28 J. S. Staedtler GmbH & Co, 8500 Nürnberg Writing or painting pen
PL315481A1 (en) * 1995-08-02 1997-02-03 Inventa Ag Optical fibre shield made of plastic material
MY120047A (en) * 1997-06-30 2005-08-30 Kisco Ltd Polyamide resin composition
US6158912A (en) * 1999-05-24 2000-12-12 Color Access, Inc. Flexible wall cosmetic container
JP2001048202A (en) 1999-08-11 2001-02-20 Takeuchi Press Ind Co Ltd Multilayered blow tube container for hair dye
FR2802148B1 (en) * 1999-12-13 2003-01-24 Conte PROCESS FOR THE MANUFACTURE BY TRI-EXTRUSION OF A PENCIL TO BE WRITING OR TO BE COLORED AND THE PENCIL TO BE WRITING OR TO BE COLORED COMPRISING A PROTECTIVE INTERMEDIATE LAYER
JP3952959B2 (en) * 2002-02-25 2007-08-01 株式会社村田製作所 Ultrasonic horn and ultrasonic bonding apparatus using this ultrasonic horn
GB0500985D0 (en) * 2005-01-18 2005-02-23 Zotefoams Plc Polyamide foams, process to make them and applications thereof
CN101357515A (en) * 2007-07-30 2009-02-04 衡阳凌云特种材料有限公司 Preparation method of high temperature resistant heat insulation composite bushing
CN201741455U (en) * 2010-07-01 2011-02-09 成都西南电工有限公司 Class 220 polyimide/polyamide enamelled round copper wire

Patent Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR60608E (en) * 1948-12-20 1954-11-22 Manufacture of pencils with a lead and synthetic plastics
US3551064A (en) * 1967-04-18 1970-12-29 Bernard I Bartner Unitary composite article and method of manufacturing the same
GB1538188A (en) 1976-07-27 1979-01-10 Oreal Make-up pencil
DE2821333A1 (en) * 1977-05-16 1978-11-30 Borg Warner TUBE MADE OF THERMOPLASTIC MATERIAL AND THE METHOD OF ITS MANUFACTURING
US4413921A (en) 1978-09-05 1983-11-08 Revlon, Inc. Cosmetic pencil having a sharpenable polyethylene casing
DE2937441A1 (en) * 1979-09-15 1982-04-01 Schwan-Stabilo Schwanhäußer GmbH & Co, 8500 Nürnberg Cosmetic pencil esp. with non castable core - has surrounding shell esp. of polyolefin cast around core
GB2084084A (en) * 1980-09-22 1982-04-07 Oreal Pencil, having a sleeve made of plastic, and process for the manufacture of same
DE4005894A1 (en) 1990-02-24 1991-12-12 Schwan Stabilo Schwanhaeusser Cosmetic stick prodn. method - consists of sleeve leading into mould, with duct and front end
DE69200023T2 (en) * 1991-03-19 1994-05-11 Conte Sa Process for producing a pen or colored pencil by tri-extrusion and then produced pen or colored pencil with a protective layer for the lead.
US5957607A (en) 1998-06-17 1999-09-28 Tsai; Felix J. Cosmetic pencil structure
DE202009008403U1 (en) * 2009-06-18 2010-01-28 Gauss, Anna Pencil with a shock absorbing sheath

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014114421A1 (en) * 2013-01-23 2014-07-31 J.S. Staedtler Gmbh & Co. Kg Component for writing, drawing, painting and/or cosmetic implements and method for the production thereof
CN104968507A (en) * 2013-01-23 2015-10-07 J.S.斯达德勒两合公司 Component for writing, drawing, painting and/or cosmetic implements and method for the production thereof
EP2948317B1 (en) 2013-01-23 2021-09-29 STAEDTLER Mars GmbH & Co. KG Pen and manufacturing method
CN104442094A (en) * 2014-11-26 2015-03-25 武汉光禾笔业有限公司 Coated pencil
US10308063B2 (en) 2014-12-17 2019-06-04 Conte Paper pencil lead
EP4349562A3 (en) * 2016-08-26 2024-06-26 A.W. Faber-Castell Cosmetics GmbH Use of a one-piece injection-moulded coating sleeve
WO2020127209A1 (en) * 2018-12-18 2020-06-25 Societe Bic Lead casing for pencil, and pencil thereof for writing, drawing, marking, plotting, and coloring
WO2020127203A1 (en) * 2018-12-18 2020-06-25 Societe Bic Lead casing for pencil, and pencil thereof for writing, drawing, marking, plotting, and coloring
CN113165417A (en) * 2018-12-18 2021-07-23 法国比克公司 Pencil lead sheath and pencil comprising the same for writing, drawing, marking, drawing and coloring
CN113165417B (en) * 2018-12-18 2023-03-03 法国比克公司 Pencil lead sleeve and pencil thereof
US11865855B2 (en) 2018-12-18 2024-01-09 SOCIéTé BIC Lead casing for pencil, and pencil thereof for writing, drawing, marking, plotting, and coloring

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CN102669920A (en) 2012-09-19
ES2578732T3 (en) 2016-07-29
US20120237708A1 (en) 2012-09-20
PL2499932T3 (en) 2016-12-30
EP2499932B1 (en) 2016-05-11
CN102669920B (en) 2016-05-25
KR20120106637A (en) 2012-09-26
KR101495095B1 (en) 2015-02-23

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