CH707572B1 - Binder, useful in injection molding composition, which is useful for making metal/ceramic part for watch industry, comprises polymeric base containing copolymers of ethylene and methacrylic/acrylic acid, wax mixture and surfactant - Google Patents

Binder, useful in injection molding composition, which is useful for making metal/ceramic part for watch industry, comprises polymeric base containing copolymers of ethylene and methacrylic/acrylic acid, wax mixture and surfactant Download PDF

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Publication number
CH707572B1
CH707572B1 CH01258/13A CH12582013A CH707572B1 CH 707572 B1 CH707572 B1 CH 707572B1 CH 01258/13 A CH01258/13 A CH 01258/13A CH 12582013 A CH12582013 A CH 12582013A CH 707572 B1 CH707572 B1 CH 707572B1
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Switzerland
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binder
ethylene
powder
mixture
oxide
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CH01258/13A
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French (fr)
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Damien Cartier
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Comadur Sa
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    • C04B35/63Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B using additives specially adapted for forming the products, e.g.. binder binders
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    • C04B35/634Polymers
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
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    • BPERFORMING OPERATIONS; TRANSPORTING
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    • B22F3/225Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces for producing castings from a slip by injection molding
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Abstract

Binder comprises 35-54 vol.% of a polymeric base, 40-55 vol.% of a wax mixture, and 10 vol.% of a surfactant. The polymeric base contains copolymers of ethylene and methacrylic or acrylic acid, copolymers of ethylene and vinyl acetate, or copolymers of ethylene comprising maleic anhydride or mixture of these copolymers, as well as polyethylene, polypropylene and acrylic resin. An independent claim is included for an injection molding composition, preferably feedstock, comprising 76-96 wt.% of an inorganic powder, and 4-24 wt.% of the binder.

Description

[0001] L'invention concerne une composition de liant pour moulage par injection ainsi qu'une composition de moulage par injection (feedstock) destinée à la fabrication de pièces de forme métalliques ou céramiques [0001] The invention relates to a binder composition for injection molding and an injection molding composition (feedstock) for the manufacture of metallic or ceramic shaped parts

[0002] Dans la fabrication de matériaux durs pour la bijouterie et l'industrie horlogère, ou encore pour des applications techniques telles que le médical, l'électronique, la téléphonie, l'outillage, les plaquettes de coupe d'usinage, l'industrie des biens de consommation, et notamment en ce qui concerne des matériaux durs généralement désignés sous le nom générique de «céramiques» inorganiques, on met en œuvre des techniques de métallurgie des poudres. [0002] In the manufacture of hard materials for jewelery and watch industry, or for technical applications such as medical, electronics, telephony, tooling, machining cutting inserts, the consumer goods industry, particularly as regards hard materials generally referred to generically as "ceramics" inorganic, it is implementing powder metallurgy techniques. On appellera ici «céramique» le matériau de synthèse inorganique obtenu, quelle que soit la nature de ce matériau, saphir, rubis, diamant artificiel, glace saphir, céramique, micro-aimant, métal, alliage, ou autre. Here we call "ceramic" inorganic synthetic material obtained, regardless of the nature of this material, sapphire, ruby, artificial diamond, sapphire crystal, ceramic, micro-magnet, metal, alloy, or otherwise.

[0003] Les matières premières de base sont de différente nature, de façon générale, et comportent au moins d'une part de la poudre de céramique et d'autre part des liants organiques, tels que résines ou matières plastiques ou similaires qui permettent l'injection et la bonne tenue du composant réalisé avec le mélange de l'ensemble des matières premières. [0003] The basic raw materials are of different nature, in general, and comprise at least a part of the ceramic powder and the other organic binders, such as resins or plastics or similar that allow injection and good holding component produced with the mixture of all raw materials. D'autres additifs peuvent être incorporés au mélange. Other additives may be incorporated into the mixture. Ces matières premières peuvent également être de différentes textures: solide, pulvérulente, liquide, ou encore pâteuse. These raw materials can also be of different textures: solid, powder, liquid or paste. Le mélange peut en outre changer de structure au cours de son élaboration, en particulier, et non limitativement, quand des composants complémentaires d'une résine subissent une réaction de polymérisation. The mixture may also change during its elaboration structure, in particular, and without limitation, when complementary components of a resin undergo a polymerization reaction.

[0004] Le procédé global de fabrication d'un composant céramique inorganique comporte au moins les étapes suivantes: préparation des matières premières; [0004] The overall process of manufacturing an inorganic ceramic component comprises at least the following steps: preparation of raw materials; mélange(s) des matières premières, ou/et pré-mélange deux à deux (ou plus) si nécessaire; mixture (s) of raw materials, and / or two premixing to two (or more) if necessary; d'homogénéisation; homogenization; granulation; granulation; pressage, notamment dans une chambre de moulage, d'une quantité de poudre ou de granulés feedstock issue du malaxage et de la granulation, pour la réalisation d'une ébauche de composant. pressing, particularly in a molding chamber, a quantity of powder or granular feedstock after the kneading and granulating, for producing a component blank. Ce pressage peut être réalisé par injection, sous pression, notamment dans un injecteur à vis comportant des moyens de mise en température de cette quantité de poudre ou de granulés feedstock issue du malaxage et de la granulation; This pressing may be accomplished by injection, under pressure, in particular in a screw injector having tempering means that amount of powder or granular feedstock after the mixing and granulation; étuvage de déliantage pour la combustion ou/et la dissolution de certains composants du mélange; parboiling debinding for combustion and / or the dissolution of some components of the mixture; traitement thermique de l'ébauche en sortie de déliantage, pour le frittage donnant sa cohérence finale au composant fini. heat treatment of the preform at the output of debinding, sintering for giving its final consistency to the finished component. Ce traitement thermique entraîne un retrait dimensionnel, qui permet l'obtention d'un composant en cotes finies; This heat treatment causes a dimensional shrinkage, which allows the production of a component finished dimensions; traitement de finition d'aspect du composant. finishing treatment of component appearance.

[0005] L'invention vise plus particulièrement à proposer un liant pour composition de moulage par injection optimisé facilitant le malaxage en métallurgie des poudres pour l'obtention de céramiques ou de métaux, de façon à obtenir une production de qualité très reproductible, avec un coefficient de retrait maîtrisé. [0005] The invention aims more particularly to provide a binder for optimized injection molding composition facilitating the mixing powder metallurgy for obtaining metals or ceramics, so as to obtain a production of very reproducible quality, with a controlled shrinkage coefficient.

[0006] On connaît déjà, par exemple le brevet US 5 145 900, des matériaux thermoplastiques (feedstock) pour la fabrication de pièces moulées céramiques qui contiennent une poudre inorganique frittable et un liant organique polymérique, celui-ci étant essentiellement constitué d'un mélange de polyoxyméthylène et de copolymères de polyoxyméthylène et de polyoxolanes. [0006] There are already known, for example U.S. Patent 5,145,900, thermoplastic materials (feedstock) for producing ceramic molded parts containing a sinterable inorganic powder and a polymeric organic binder, the latter consisting essentially of a mixture of polyoxymethylene and copolymers of polyoxymethylene and polyoxolanes.

[0007] Ces feedstocks ont révélé toutefois de nombreux inconvénients, comme par exemple une fluidité insuffisante en moulage par injection, et des problèmes de tenue des pièces de formes moulées qui présentent des fissures et du feuilletage, ceci surtout lorsque la forme des pièces est complexe; [0007] These feedstocks revealed many drawbacks, however, such as insufficient fluidity in injection molding, and handling problems in parts molded shapes with cracks and lamination, this especially when the shape of the parts is complex ; ils sont en outre responsables de problèmes environnementaux dus à la nécessité d'utiliser des produits agressifs, tels que l'acide nitrique, plus particulièrement pour l'élimination finale de la phase organique. they are also responsible of environmental problems due to the need to use aggressive products, such as nitric acid, in particular for the final removal of the organic phase. De plus, l'utilisation d'eau dans ce processus d'élimination du liant organique est problématique dans le cas où les feedstocks contiennent des matériaux métalliques qui risquent d'être oxydés. In addition, the use of water in this process of removing the organic binder is problematic in the case where the feedstocks contain metal materials that may be oxidized.

[0008] En conséquence, le but de la présente invention consiste à fournir un liant pour composition de moulage qui obvie aux inconvénients susmentionnés, et plus particulièrement qui vise à améliorer l'homogénéité et la fluidité du feedstock pour permettre la fabrication de pièces métalliques ou céramiques de formes plus complexes, de réduire les temps de cycle en production, d'augmenter la résistance mécanique des corps verts et déliantes aux contraintes de production (manipulation et diverses opérations de reprise), et enfin qui supprime la nécessité d'utiliser des produits agressifs pour l'environnement pour l'élimination du liant organique, en remplaçant ceux-ci par des solvants non polluants pouvant être éliminés par simple traitement thermique. [0008] Accordingly, the object of the present invention to provide a binder composition for molding which obviates the aforementioned drawbacks, and more particularly aimed at improving the homogeneity and fluidity of the feedstock to enable the manufacture of metal parts or ceramics more complex forms, reduce production cycle time, increase the strength of the green body and unbinding to production constraints (handling and various recovery operations) and finally eliminating the need to use products aggressive to the environment for removal of the organic binder, replacing them by non-polluting solvents that may be removed by simple thermal treatment.

[0009] A cet effet, l'invention a pour objet un liant pour composition de moulage par injection comprenant: – de 35 à 54% vol. [0009] To this end, the invention relates to a binder for injection molding composition comprising: - 35 to 54% vol. d'une base polymérique, – de 40 à 55% vol. a polymer base - 40 to 55% vol. d'un mélange de cires, – et environ 10% vol. a mixture of waxes, - about 10% vol. d'un surfactant, dans lequel la base polymérique contient des copolymères d'éthylène et d'acide méthacrylique ou acrylique, ou des copolymères d'éthylène et d'acétate de vinyle, ou des copolymères d'éthylène comprenant un anhydride maléique ou un mélange de ces copolymères, ainsi que du polyéthylène, du polypropylène et une résine acrylique. of a surfactant, wherein the base polymer contains ethylene and methacrylic or acrylic acid, or copolymers of ethylene and vinyl acetate, or ethylene copolymers comprising maleic anhydride or a mixture of such copolymers and polyethylene, polypropylene and an acrylic resin.

[0010] De préférence, le liant de l'invention comprend de 2 à 7% vol. [0010] Preferably, the binder of the invention comprises from 2 to 7% vol. d'un desdits copolymères ou de leurs mélanges, environ 25% vol. one of said copolymers or mixtures thereof, about 25% vol. de polyéthylène, de 2 à 15% vol. polyethylene, 2-15% vol. de polypropylène et de 6 à 15% vol. polypropylene and 6-15% vol. de résine acrylique. acrylic resin.

[0011] Selon un mode de réalisation préféré, le copolymère d'éthylène et d'acide méthacrylique ou acrylique contient de 3 à 10% pds. [0011] According to a preferred embodiment, the copolymer of ethylene and methacrylic or acrylic acid contains from 3 to 10% wt. de comonomère méthacrylique ou acrylique, le copolymère d'éthylène et d'acétate de vinyle contient de 7 à 18% pds. methacrylic or acrylic comonomer, the copolymer of ethylene and vinyl acetate contains from 7 to 18% wt. de comonomère acétate de vinyle, et le copolymère d'éthylène et d'anhydride est un copolymère statistique (random) d'éthylène et d'anhydride maléique ayant un point de fusion de 100 à 110 °C ou un copolymère de polyéthylène HD et d'un anhydride modifié ayant une point de fusion de 130 à 134 °C. vinyl acetate comonomer, and the ethylene copolymer anhydride is a random copolymer (random) ethylene and maleic anhydride having a melting point of 100 to 110 ° C or a copolymer of polyethylene HD and a modified anhydride having a melting point of 130 to 134 ° C.

[0012] De préférence, la résine acrylique présente un poids moléculaire compris entre 50 000 et 220 000 et une viscosité de 0,21 à 0,83, et est choisie parmi le groupe comprenant les polymères méthacrylate d'isobutyle, de méthyle, d'éthyle et de N-butyle, et les copolymères méthacrylates d'isobutyle et de N-butyle et méthacrylates de méthyle et de N-butyle ou un mélanges de ces polymères et/ou copolymères. [0012] Preferably, the acrylic resin has a molecular weight between 50 000 and 220 000 and a viscosity from 0.21 to 0.83, and is selected from the group comprising the methacrylate polymers isobutyl, methyl, d ethyl and N-butyl, methacrylates and copolymers isobutyl and n-butyl and methyl methacrylate and N-butyl or mixtures of these polymers and / or copolymers.

[0013] De manière avantageuse, la cire est une cire de Carnauba ou une cire de paraffine, ou une huile de palme, ou un mélange de ces éléments. [0013] Advantageously, the wax is a carnauba wax or paraffin wax, or a palm oil, or a mixture thereof.

[0014] Selon une autre caractéristique préférée, le surfactant est un NN ́-éthylène-bis(stéaramide) ou un mélange d'acides stéarique et palmitique (stéarine), ou un mélange de ces éléments. [0014] According to another preferred feature, the surfactant is an N, N-ethylene-bis (stearamide) or a mixture of stearic and palmitic acid (stearin), or a mixture thereof.

[0015] L'invention a également pour objet une composition de moulage par injection (feedstock) destinée à la fabrication de pièces de forme métalliques ou céramiques comprenant 76 à 96% pds. [0015] The invention also relates to an injection molding composition (feedstock) for the manufacture of metallic or ceramic shaped parts comprising 76-96% by weight. d'une poudre inorganique et 4 à 24% pds. of an inorganic powder and 4 to 24 wt%. de liant comprenant: – de 35 à 54% vol. binder comprising: - 35 to 54% vol. d'une base polymérique, – de 40 à 55% vol. a polymer base - 40 to 55% vol. d'un mélange de cires, – et environ 10% vol. a mixture of waxes, - about 10% vol. d'un surfactant, dans lequel la base polymérique contient des copolymères d'éthylène et d'acide méthacrylique ou acrylique, ou des copolymères d'éthylène et d'acétate de vinyle, ou des copolymères d'éthylène comprenant un anhydride maléique ou un mélange de ces copolymères, ainsi que du polyéthylène, du polypropylène et une résine acrylique. of a surfactant, wherein the base polymer contains ethylene and methacrylic or acrylic acid, or copolymers of ethylene and vinyl acetate, or ethylene copolymers comprising maleic anhydride or a mixture of such copolymers and polyethylene, polypropylene and an acrylic resin.

[0016] Selon une caractéristique particulière, la poudre inorganique de la composition de moulage par injection peut être choisie parmi l'ensemble comprenant une poudre d'oxyde, de nitrure, de carbure, de métal, ou un mélange de ces dites poudres et de préférence la poudre inorganique est choisie parmi l'ensemble comprenant une poudre d'alumine, une poudre d'oxyde de zirconium, une poudre de carbure de chrome, une poudre de carbure de titane ou une poudre de carbure de tungstène, une poudre de tungstène métallique ou de nitrure de silicium, une poudre d'acier inoxydable, une poudre de titane métallique ou une mélanges de ces poudres. [0016] According to a particular feature, the inorganic powder for the injection molding composition may be selected from the group consisting of an oxide powder, nitride, carbide, metal, or a mixture of these said powders and preferably the inorganic powder is selected from the group consisting of an alumina powder, a zirconium oxide powder, chromium carbide powder, titanium carbide powder or tungsten carbide powder, tungsten powder metal or silicon nitride, stainless steel powder, titanium powder metal or mixtures of these powders.

[0017] Selon des modes de réalisation préférés de la composition de moulage par injection, cette dernière contient en % poids: <tb>•<SEP>76 à 88% d'alumine et 12 à 24% de liant selon l'invention tel que défini plus haut, ou <tb>•<SEP>76 à 88% d'alumine et 0.1 à 0.6% d'oxyde de magnésium et 12 à 24% de liant de l'invention, ou <tb>•<SEP>58 à 86.5% d'oxyde zirconium et 3.9 à 4.6% d'oxyde d'yttrium et 0.18 à 18.5% d'alumine et 9 à 22% de liant de l'invention, ou <tb>•<SEP>61.5 à 84% d'oxyde de zirconium et 3.9 à 4.6% d'oxyde d'yttrium et 0.2 à 9% d'alumine et 2 à 5.5% de pigments inorganique d'une liste comprenant de l'oxyde de fer, de l'oxyde de cobalt, de l'oxyde de chrome, de l'oxyde de titane, de l'oxyde de manganèse, de l'oxyde de zinc ou d'un mélange des dits oxydes et de 9 à 22% de liant de l'invention, ou <tb>•<SEP>de 88 à 91% de carbure de chrome ou de titane, et de 9 à 12% de liant de l'invention, ou <tb>•<SEP>de 93 à 96% de carbure de tungs [0017] According to preferred embodiments of the injection molding composition, the latter contains in% by weight: <tb> • <SEP> 76-88% alumina and 12 to 24% binder of the invention as defined above, or <tb> • <September> 76-88% alumina and 0.1 to 0.6% magnesium oxide and 12 to 24% binder of the invention, or <tb> • <September> 58 to 86.5% zirconium oxide and 3.9 to 4.6% yttrium oxide and 0.18 to 18.5% alumina and 9-22% binder of the invention, or <tb> • <September> 61.5 to 84 % zirconium oxide and 3.9 to 4.6% yttrium oxide and 0.2 to 9% alumina and 2 to 5.5% inorganic pigments of a list comprising iron oxide, the oxide of cobalt, chromium oxide, titanium oxide, manganese oxide, zinc oxide or a mixture of said oxides and 9-22% binder of the invention, or <tb> • <SEP> from 88 to 91% of chromium or titanium carbide, and 9 to 12% binder of the invention, or <tb> • <SEP> from 93 to 96% carbide Tungs tène ou de tungstène métallique et de 4 à 7% de liant de l'invention, ou <tb>•<SEP>de 78 à 85% de nitrure de silicium et de 15 à 22% de liant de l'invention. Tène or tungsten metal and 4 to 7% binder of the invention, or <tb> • <SEP> from 78 to 85% silicon nitride and 15 to 22% binder of the invention.

[0018] La présente invention sera maintenant illustrée plus en détails par les exemples non limitatifs qui suivent. [0018] The present invention will now be further illustrated by non-limiting examples.

Exemple 1 example 1

[0019] On mélange la partie polymérique du liant à une poudre d'oxyde zirconium noir (de type St. Gobain Zir Black) à une température d'environ 150 °C pour former un prémix. [0019] was mixed polymer component of the binder in a black zirconium oxide powder (St. Gobain Zir Black type) at a temperature of about 150 ° C to form a premix. A ce prémix sont ajoutés les cires et le surfactant, et la température est à nouveau augmentée jusqu'à environ 180 °C pour former une sorte de pâte homogène, laquelle est alors refroidie puis granulée jusqu'à solidification, puis conservée pour constituer le feedstock utilisable dans la fabrication d'une pièce de forme par injection selon une technique connue. To this premix were added the surfactant and waxes and the temperature is again increased to about 180 ° C to form a sort of homogeneous paste, which is then cooled and then granulated to solidify, and then stored to form the feedstock use in the manufacture of an injection molded part using a known technique.

[0020] Dans cet exemple, on a utilisé plus particulièrement 17,2 kg de la poudre de zircone (86% pds.) et 2,8 kg du liant (env. 14% pds) ayant la composition volumique suivante: 24% de polyéthyiène HD 10% de polypropylène 4% de copolymère d'éthylène et d'acide méthacrylique (à 6,5% pds. d'acide méthacrylique, par exemple du type «Nucrel (TM)» de DuPont) 10% d'une résine polymère méthacrylate d'iso-butyle ayant un poids moléculaire de 195 000 (par exemple du type «Elvacite (TM) 2045» de Lucite International) 1% d'une résine copolymère méthacrylate d'isobutyle et N-butyle ayant un poids moléculaire de 165 000 (par exemple du type «Elvacite (TM) 2046» de Lucite International) 11% de cire Carnauba 31% d'une cire de paraffine (par exemple du type «Carisma 54 T (TM)» de Alpha Wax BV) 6% de bis-stéaramide de N, N ́-éthylène 3% d'un mélange d'acides stéarique et palmitique (par exemple du type Stéarine Dubois). [0020] In this example, especially was used 17.2 kg of zirconia powder (86% wt.) And 2.8 kg of the binder having the following composition by volume (approx 14% wt.): 24% polyéthyiène HD 10% 4% polypropylene copolymer of ethylene and methacrylic acid (6.5% wt. of methacrylic acid, for example of the type "Nucrel (TM)" from DuPont) 10% resin isobutyl methacrylate polymer having a molecular weight of 195,000 (e.g., type "Elvacite (TM) 2045" Lucite International) 1% of a resin copolymer of isobutyl methacrylate and N-butyl having a molecular weight of 165 000 (e.g. type "Elvacite (TM) 2046" Lucite International) 11% Carnauba wax 31% of a paraffin wax (e.g., type "Carisma 54 T (TM)" Alpha wax BV) 6 % bis-stearamide, N, N-ethylene 3% of a mixture of stearic and palmitic acids (e.g. of the type Stearine Dubois).

Exemple 2 example 2

[0021] Le même type de feedstock que dans l'Exemple 1 ci-dessus est préparé en remplaçant l'oxyde de zirconium noir par de l'oxyde de zirconium blanc, et en utilisant des valeurs légèrement différentes des divers composants du liant, plus particulièrement: 26% du polyéthyiène HD 10% de polypropylène 4% de copolymère d'éthylène et d'acide méthacrylique 11% de la résine «Elvacite 2045» 1% de résine «Elvacite 2046» 11% de cire de Carnauba 29% de la cire de paraffine 8% de la bis-stéaramide de N, N ́-éthylène [0021] The same type of feedstock as in Example 1 above was prepared by substituting black zirconium oxide of white zirconium oxide, and using slightly different values ​​for the various components of the binder, more particularly 26% of polyéthyiène HD 10% 4% polypropylene copolymer of ethylene and methacrylic acid 11% of the resin "Elvacite 2045" resin 1% "Elvacite 2046" 11% Carnauba wax 29% paraffin wax 8% bis-stearamide, N, N-ethylene

Exemple 3 example 3

[0022] Toujours avec les mêmes composants du liant organique, avec des proportions volumiques légèrement différentes, d'autres feedstocks peuvent être préparés avec divers poudres céramiques ou métalliques, plus particulièrement de l'alumine, avec indice de retrait de 1,19 ou 1,30 (translucide), du carbure de chrome ou du carbure de titane, du carbure de tungstène (de différentes qualités) et du tungstène métallique, selon le Tableau suivant. [0022] Still with the same components of the organic binder, with slightly different proportions by volume, other feedstocks can be prepared with various ceramic or metallic powders, particularly alumina, with 1.19 shrinkage ratio of one or , 30 (translucent), chromium carbide or titanium carbide, tungsten carbide (different grades) and tungsten metal according to the following Table.

[0023] <img class="EMIRef" id="319275196-ib0002" /> [0023] <img class = "EMIRef" id = "319275196-ib0002" />

Claims (10)

1. Liant pour composition de moulage par injection comprenant: – de 35 à 54% vol. 1. A binder for injection molding composition comprising: - 35 to 54% vol. d'une base polymérique, – de 40 à 55% vol. a polymer base - 40 to 55% vol. d'un mélange de cires, – et environ 10% vol. a mixture of waxes, - about 10% vol. d'un surfactant, dans lequel la base polymérique contient des copolymères d'éthylène et d'acide méthacrylique ou acrylique, ou des copolymères d'éthylène et d'acétate de vinyle, ou des copolymères d'éthylène comprenant un anhydride maléique ou un mélange de ces copolymères, ainsi que du polyéthylène, du polypropylène et une résine acrylique. of a surfactant, wherein the base polymer contains ethylene and methacrylic or acrylic acid, or copolymers of ethylene and vinyl acetate, or ethylene copolymers comprising maleic anhydride or a mixture of such copolymers and polyethylene, polypropylene and an acrylic resin.
2. Liant selon la revendication 1 comprenant de 2 à 7% vol. 2. A binder according to claim 1 comprising from 2 to 7% vol. d'un desdits copolymères ou de leurs mélanges, environ 25% vol. one of said copolymers or mixtures thereof, about 25% vol. de polyéthylène, de 2 à 15% vol. polyethylene, 2-15% vol. de polypropylène et de 6 à 15% vol. polypropylene and 6-15% vol. de résine acrylique. acrylic resin.
3. Liant selon la revendication 1 ou la revendication 2, dans lequel le copolymère d'éthylène et d'acide méthacrylique ou acrylique contient de 3 à 10% pds. 3. A binder according to claim 1 or claim 2, wherein the copolymer of ethylene and methacrylic or acrylic acid contains from 3 to 10 wt%. de comonomère méthacrylique ou acrylique, le copolymère d'éthylène et d'acétate de vinyle contient de 7 à 18% pds. methacrylic or acrylic comonomer, the copolymer of ethylene and vinyl acetate contains from 7 to 18% wt. de comonomère acétate de vinyle, et le copolymère d'éthylène et d'anhydride est un copolymère statistique, random, d'éthylène et d'anhydride maléique ayant un point de fusion de 100 à 110 °C ou un copolymère de polyéthylène HD et d'un anhydride modifié ayant une point de fusion de 130 à 134 °C. vinyl acetate comonomer, and the ethylene-anhydride copolymer is a statistical, random, of ethylene and maleic anhydride having a melting point of 100 to 110 ° C or a copolymer of polyethylene HD and a modified anhydride having a melting point of 130 to 134 ° C.
4. Liant selon l'une des revendications précédentes, dans lequel la résine acrylique présente un poids moléculaire compris entre 50 000 et 220 000 et une viscosité de 0,21 à 0,83, et est choisie parmi les polymères méthacrylate d'isobutyle, de méthyle, d'éthyle et de N-butyle, et les copolymères méthacrylates d'isobutyle et de N-butyle et méthacrylates de méthyle et de N-butyle ou un mélanges de ces polymères et/ou copolymères. 4. A binder according to one of the preceding claims, wherein the acrylic resin has a molecular weight between 50 000 and 220 000 and a viscosity from 0.21 to 0.83, and is selected from polymers of isobutyl methacrylate, methyl, ethyl and N-butyl, methacrylates and copolymers isobutyl and n-butyl and methyl methacrylate and N-butyl or mixtures of these polymers and / or copolymers.
5. Liant selon l'une des revendications précédentes, dans lequel le mélange de cires comprend une cire de Carnauba ou une cire de paraffine ou une huile de palme ou un mélanges de ces éléments. 5. A binder according to one of the preceding claims, wherein the mixture of waxes comprises a carnauba wax or paraffin wax or a palm oil or mixtures thereof.
6. Liant selon l'une des revendications précédentes, dans lequel le surfactant est un NN ́-éthylène-bis(stéaramide), ou un mélange d'acides stéarique et palmitique, stéarine, ou un mélange de ces éléments. 6. A binder according to any preceding claim, wherein the surfactant is an N, N-ethylene-bis (stearamide), or a mixture of stearic and palmitic acids, stearin, or a mixture thereof.
7. Composition de moulage par injection, feedstock, destinée à la fabrication de pièces de forme métalliques ou céramiques comprenant 76 à 96% pds. 7. An injection molding composition, feedstock, for producing metallic or ceramic shaped parts comprising 76-96% by weight. d'une poudre inorganique et 4 à 24% pds. of an inorganic powder and 4 to 24 wt%. du liant selon l'une des revendications 1 à 6. the binder according to one of claims 1 to 6.
8. Composition de moulage selon la revendication 7, dans laquelle la poudre inorganique est choisie parmi l'ensemble comprenant une poudre d'oxyde, de nitrure, de carbure, de métal, ou un mélange de celles-ci. 8. A molding composition according to claim 7, wherein the inorganic powder is selected from the group consisting of an oxide powder, nitride, carbide, metal, or a mixture thereof.
9. Composition de moulage selon la revendication 8, dans laquelle la poudre inorganique est choisie parmi l'ensemble comprenant une poudre d'alumine, une poudre d'oxyde de zirconium, une poudre de carbure de chrome, une poudre de carbure de titane ou une poudre de carbure de tungstène, une poudre de tungstène métallique ou de nitrure de silicium, une poudre d'acier inoxydable, une poudre de titane métallique, ou un mélange de ces poudres. 9. A molding composition according to claim 8, wherein the inorganic powder is selected from the group consisting of an alumina powder, a zirconia powder, chromium carbide powder, titanium carbide powder or a tungsten carbide powder, a metal powder or tungsten silicon nitride, stainless steel powder, a titanium metal powder, or a mixture of these powders.
10. Composition de moulage selon la revendication 8 ou 9, qui contient en % poids: – soit 76 à 88% d'alumine et 12 à 24% de liant, – soit 76 à 88% d'alumine et 0.1 à 0.6% d'oxyde de magnésium et 12 à 24% de liant, – soit 58 à 86.5% d'oxyde zirconium et 3.9 à 4.6% d'oxyde d'yttrium et 0.18 à 18.5% d'alumine et 9 à 22% de liant, – soit 61.5 à 84% d'oxyde de zirconium et 3.9 à 4.6% d'oxyde d'Yttrium et 0.2 à 9% d'alumine et 2 à 5.5% de pigments inorganique d'une liste comprenant de l'oxyde de fer, de l'oxyde de cobalt, de l'oxyde de chrome, de l'oxyde de titane, de l'oxyde de manganèse, de l'oxyde de zinc ou d'un mélange des dits oxydes et de 9 à 22% de liant, – soit de 88 à 91% de carbure de chrome ou de titane et de 9 à 12% de liant, – soit de 93 à 96% de carbure de tungstène ou de tungstène métallique et de 4 à 7% de liant, – soit de 78 à 85% de Nitrure de silicium et de 15 à 22% de liant. 10. A molding composition according to claim 8 or 9 which contains in weight%: - either 76-88% alumina and 12 to 24% of binder, - or from 76 to 88% alumina and 0.1 to 0.6% of magnesium oxide and 12 to 24% of binder, - 58 to 86.5% zirconium oxide and 3.9 to 4.6% yttrium oxide and 0.18 to 18.5% alumina and 9-22% binder, - is 61.5 to 84% zirconium oxide and 3.9 to 4.6% yttrium oxide and 0.2 to 9% alumina and 2 to 5.5% inorganic pigments of a list comprising iron oxide, cobalt oxide, chromium oxide, titanium oxide, manganese oxide, zinc oxide or a mixture of said oxides and 9-22% binder, or - from 88 to 91% chromium carbide or titanium and from 9 to 12% of binder, - or from 93 to 96% of tungsten carbide or tungsten metal and 4 to 7% of binder, or - from 78 to 85% silicon nitride and 15 to 22% of binder.
CH01258/13A 2013-07-15 2013-07-15 Binder, useful in injection molding composition, which is useful for making metal/ceramic part for watch industry, comprises polymeric base containing copolymers of ethylene and methacrylic/acrylic acid, wax mixture and surfactant CH707572B1 (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3332897A1 (en) 2016-12-08 2018-06-13 The Swatch Group Research and Development Ltd Binder for injection-moulding composition

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3332897A1 (en) 2016-12-08 2018-06-13 The Swatch Group Research and Development Ltd Binder for injection-moulding composition

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