EP2684628B1 - Binder system for powder injection moulding mass - Google Patents
Binder system for powder injection moulding mass Download PDFInfo
- Publication number
- EP2684628B1 EP2684628B1 EP13170584.0A EP13170584A EP2684628B1 EP 2684628 B1 EP2684628 B1 EP 2684628B1 EP 13170584 A EP13170584 A EP 13170584A EP 2684628 B1 EP2684628 B1 EP 2684628B1
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- EP
- European Patent Office
- Prior art keywords
- binder system
- fatty alcohol
- acid
- carbon atoms
- fatty
- 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.)
- Revoked
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- 239000011230 binding agent Substances 0.000 title claims description 99
- 239000000843 powder Substances 0.000 title claims description 69
- 238000001746 injection moulding Methods 0.000 title claims description 42
- 125000004432 carbon atom Chemical group C* 0.000 claims description 91
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 77
- 229930195729 fatty acid Natural products 0.000 claims description 77
- 239000000194 fatty acid Substances 0.000 claims description 77
- 150000004665 fatty acids Chemical class 0.000 claims description 74
- -1 hydroxybenzoic acid fatty alcohol ester Chemical class 0.000 claims description 69
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 59
- 239000000203 mixture Substances 0.000 claims description 56
- 150000002191 fatty alcohols Chemical class 0.000 claims description 51
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 claims description 41
- UKMSUNONTOPOIO-UHFFFAOYSA-N docosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCC(O)=O UKMSUNONTOPOIO-UHFFFAOYSA-N 0.000 claims description 36
- 239000002184 metal Substances 0.000 claims description 22
- 235000021314 Palmitic acid Nutrition 0.000 claims description 19
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 claims description 19
- 235000021357 Behenic acid Nutrition 0.000 claims description 18
- 235000021355 Stearic acid Nutrition 0.000 claims description 18
- 229940116226 behenic acid Drugs 0.000 claims description 17
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 17
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 17
- 239000008117 stearic acid Substances 0.000 claims description 15
- 229920000642 polymer Polymers 0.000 claims description 12
- 239000004952 Polyamide Substances 0.000 claims description 10
- 239000000919 ceramic Substances 0.000 claims description 10
- 229920002647 polyamide Polymers 0.000 claims description 10
- 238000000465 moulding Methods 0.000 claims description 4
- 239000000463 material Substances 0.000 claims 9
- 230000008018 melting Effects 0.000 description 23
- 238000002844 melting Methods 0.000 description 23
- 239000004413 injection moulding compound Substances 0.000 description 22
- 229920006395 saturated elastomer Polymers 0.000 description 10
- 230000000694 effects Effects 0.000 description 9
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 7
- TUNFSRHWOTWDNC-UHFFFAOYSA-N Myristic acid Natural products CCCCCCCCCCCCCC(O)=O TUNFSRHWOTWDNC-UHFFFAOYSA-N 0.000 description 6
- 150000002148 esters Chemical class 0.000 description 6
- KEMQGTRYUADPNZ-UHFFFAOYSA-N heptadecanoic acid Chemical compound CCCCCCCCCCCCCCCCC(O)=O KEMQGTRYUADPNZ-UHFFFAOYSA-N 0.000 description 6
- ISYWECDDZWTKFF-UHFFFAOYSA-N nonadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCCC(O)=O ISYWECDDZWTKFF-UHFFFAOYSA-N 0.000 description 6
- 239000012778 molding material Substances 0.000 description 5
- 238000000113 differential scanning calorimetry Methods 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- CKDDRHZIAZRDBW-UHFFFAOYSA-N henicosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCC(O)=O CKDDRHZIAZRDBW-UHFFFAOYSA-N 0.000 description 4
- VKOBVWXKNCXXDE-UHFFFAOYSA-N icosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCC(O)=O VKOBVWXKNCXXDE-UHFFFAOYSA-N 0.000 description 4
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- TWJNQYPJQDRXPH-UHFFFAOYSA-N 2-cyanobenzohydrazide Chemical compound NNC(=O)C1=CC=CC=C1C#N TWJNQYPJQDRXPH-UHFFFAOYSA-N 0.000 description 2
- IJFXRHURBJZNAO-UHFFFAOYSA-N 3-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=CC(O)=C1 IJFXRHURBJZNAO-UHFFFAOYSA-N 0.000 description 2
- 229940090248 4-hydroxybenzoic acid Drugs 0.000 description 2
- 235000021360 Myristic acid Nutrition 0.000 description 2
- 229920002614 Polyether block amide Polymers 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- KFEVDPWXEVUUMW-UHFFFAOYSA-N docosanoic acid Natural products CCCCCCCCCCCCCCCCCCCCCC(=O)OCCC1=CC=C(O)C=C1 KFEVDPWXEVUUMW-UHFFFAOYSA-N 0.000 description 2
- 150000005165 hydroxybenzoic acids Chemical class 0.000 description 2
- CBFCDTFDPHXCNY-UHFFFAOYSA-N icosane Chemical compound CCCCCCCCCCCCCCCCCCCC CBFCDTFDPHXCNY-UHFFFAOYSA-N 0.000 description 2
- YAQXGBBDJYBXKL-UHFFFAOYSA-N iron(2+);1,10-phenanthroline;dicyanide Chemical compound [Fe+2].N#[C-].N#[C-].C1=CN=C2C3=NC=CC=C3C=CC2=C1.C1=CN=C2C3=NC=CC=C3C=CC2=C1 YAQXGBBDJYBXKL-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N methyl undecanoic acid Natural products CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 2
- 229920000571 Nylon 11 Polymers 0.000 description 1
- 229920000299 Nylon 12 Polymers 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 229920006147 copolyamide elastomer Polymers 0.000 description 1
- ZOMIMPCSKRRCJI-UHFFFAOYSA-N docosyl 2-hydroxybenzoate Chemical compound CCCCCCCCCCCCCCCCCCCCCCOC(=O)C1=CC=CC=C1O ZOMIMPCSKRRCJI-UHFFFAOYSA-N 0.000 description 1
- DLCYTEDPEMSRHN-UHFFFAOYSA-N icosyl 2-hydroxybenzoate Chemical compound CCCCCCCCCCCCCCCCCCCCOC(=O)C1=CC=CC=C1O DLCYTEDPEMSRHN-UHFFFAOYSA-N 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- OZAVCEALUDNEKN-UHFFFAOYSA-N octadecyl 2-hydroxybenzoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)C1=CC=CC=C1O OZAVCEALUDNEKN-UHFFFAOYSA-N 0.000 description 1
- 230000002028 premature Effects 0.000 description 1
- 150000003138 primary alcohols Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/22—Manufacture 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
- B22F3/225—Manufacture 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/10—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material
- B22F1/107—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material containing organic material comprising solvents, e.g. for slip casting
Definitions
- metal injection molding also called metal injection molding (MIM).
- MIM metal injection molding
- Polyamide is often used as the polymeric binder component.
- the publication DE 10 2008 054 615 A1 describes a process for preparing an ester of a hydroxybenzoic acid and a fatty alcohol for use in a binder system for powder injection molding and a corresponding binder system.
- the WO 2011/133100 A1 to take a binder system containing 20 wt .-% to 30 wt .-% of an olefinic polymer and 30 wt .-% to 80 wt .-% of a wax.
- the present invention is a binder system for a powder injection molding material, for example a metal and / or ceramic powder injection molding compound, in particular a metal powder injection molding composition which comprises at least one polymer and at least one Hydroxybenzoeklaalkoholester.
- a fatty alcohol may in particular be understood to mean a saturated or unsaturated, linear or branched monohydric primary alcohol having a carbon chain length of ⁇ 8 carbon atoms to ⁇ 24 carbon atoms.
- the binder system in particular comprises at least one fatty acid.
- a fatty acid may in particular be understood to mean a saturated or unsaturated, linear or branched carboxylic acid having a carbon chain length of ⁇ 8 carbon atoms to ⁇ 24 carbon atoms.
- the addition of fatty acids can advantageously improve the dispersion properties of the binder system and thus the homogeneity of the powder injection molding compound, reduce the tendency to disperse deflections and flow front and reduce the viscosity. Overall, a more homogeneous distribution of the powder injection molding compound in the cavity of the injection molding tool can thus be achieved.
- the emphasis in the powder injection molding process can be reduced by the addition of fatty acid.
- the addition of fatty acid makes it possible to easily adjust the melting range of the binder system. For example, it has been found that by adding fatty acids, the melting range can be lowered and broadened. By lowering and broadening the melting range, the powder injection molding compound solidifies more slowly and more uniformly in the cavity of the injection molding tool, which has a particularly advantageous effect on the roundness of bores or the roundness of rotationally symmetrical components themselves.
- the binder system comprises at least one fatty acid having a lower or equal carbon chain length than the fatty alcohol of the hydroxybenzoic acid fatty alcohol ester having the longest fatty alcohol carbon chain length.
- the binder system may comprise at least one fatty acid having a lower carbon chain length than the fatty alcohol of the hydroxybenzoic acid fatty alcohol ester having the longest fatty alcohol carbon chain length.
- Binder system thereby comprise at least one fatty acid having a lower or equal, especially lower, carbon chain length than the average carbon chain length of the fatty alcohols contained in the binder system Hydroxybenzoeklaalkoholester or as the fatty alcohols of all present in the binder system Hydroxybenzoeklaalkoholester in detail.
- the binder system may comprise one or more fatty acids having, on average or even all, a lower or equal, especially lower, carbon chain length than the average carbon chain length of the fatty alcohols of all hydroxybenzoic acid fatty alcohol esters contained in the binder system or as the fatty alcohols of all hydroxybenzoic acid fatty alcohol esters included in the binder system exhibit.
- the carbon chain length of the at least one fatty acid for example of a fatty acid or of at least one fatty acid, optionally also of several fatty acids or even of all fatty acids, for example by at least 2 carbon atoms, for example by at least 3 carbon atoms or by at least 4 carbon atoms, for example at least 5 carbon atoms or at least 6 carbon atoms, shorter than the carbon chain length of the fatty alcohol of the hydroxybenzoic acid fatty alcohol ester having the longest fatty alcohol carbon chain length, optionally also as the average carbon chain lengths of the fatty alcohols of all hydroxybenzoic acid fatty alcohol esters contained in the binder system or even as the carbon chain length of the fatty alcohols of all in the binder system Hydroxybenzoic acid fatty alcohol esters in detail.
- the carbon chain length of the at least one fatty acid may be shorter than the carbon chain length of Fatty alcohol of the hydroxybenzoic acid fatty alcohol ester having the longest fatty alcohol carbon chain length, optionally also as the average carbon chain lengths of the fatty alcohols of all contained in the binder system Hydroxybenzoeklaalkoholester or even as the carbon chain length of the fatty alcohols of all present in the binder system Hydroxybenzoeklafettalkoholester in detail.
- the structure of the at least one shorter-chain or equal-length, in particular shorter-chain, fatty acid may in particular be similar to the structure of the fatty alcohol.
- both the at least one short-chain or equivalent, in particular shorter-chain, fatty acid and the fatty alcohol of the hydroxybenzoic acid fatty alcohol ester may be saturated or unsaturated or linear or branched, in particular saturated and optionally linear.
- the melting range of the binder system can be shifted towards lower temperatures as well as broadened.
- the melting range of the binder system can be particularly effectively shifted towards lower temperatures and broadened.
- the at least one fatty acid has a carbon chain length of ⁇ 14 carbon atoms to ⁇ 24 carbon atoms.
- the at least one fatty acid may have a carbon chain length of ⁇ 14 carbon atoms to ⁇ 22 carbon atoms, especially ⁇ 14 carbon atoms or ⁇ 15 carbon atoms or ⁇ 16 carbon atoms or ⁇ 17 carbon atoms to ⁇ 22 carbon atoms or ⁇ 21 carbon atoms or ⁇ 20 carbon atoms or ⁇ 19 carbon atoms or ⁇ 18 carbon atoms, for example from ⁇ 16 carbon atoms or ⁇ 17 carbon atoms to ⁇ 22 carbon atoms or ⁇ 20 carbon atoms or ⁇ 19 carbon atoms, for example from 18 carbon atoms.
- the at least one fatty acid may be a saturated carboxylic acid, for example a saturated and linear carboxylic acid.
- the at least one fatty acid may be selected from the group consisting of behenic acid (C 22 H 44 O 2 , docosanoic acid), heneicosanoic acid (C 21 H 42 O 2 ), arachidic acid (C 20 H 40 O 2 , eicosane / lcosanoic acid ), Nonadecanoic acid (C 19 H 38 O 2 ), stearic acid (C 18 H 36 O 2 , octadecanoic acid), heptadecanoic acid (C 17 H 34 O 2 ), palmitic acid (C 16 H 32 O 2 , hexadecanoic acid), pentadecanoic acid (C 15 H 30 O 2 ), myristic acid (C 14 H 28 O 2 , tetradecanoic acid) and mixtures thereof.
- behenic acid C 22 H 44 O 2
- docosanoic acid heneicosanoic acid
- arachidic acid C 20 H 40 O 2
- the binder system comprises only one fatty acid, for example whose carbon chain length is in a range of ⁇ 16 carbon atoms and ⁇ 20 carbon atoms, in particular 17 carbon atoms and ⁇ 19 carbon atoms, for example 18 carbon atoms.
- the binder system comprises at least two fatty acids.
- the binder system comprises at least two fatty acids.
- the at least two fatty acids may also be selected from the group consisting of behenic acid (C 22 H 44 O 2 , docosanoic acid), heneicosanoic acid (C 21 H 42 O 2 ), arachidic acid (C 20 H 40 O 2 , eicosan / lcosanoic acid), Nonadecanoic acid (C 19 H 38 O 2 ), stearic acid (C 18 H 36 O 2 , octadecanoic acid), heptadecanoic acid (C 17 H 34 O 2 ), palmitic acid (C 16 H 32 O 2 , hexadecanoic acid), pentadecanoic acid (C 15 H 30 O 2 ), myristic acid (C 14 H 28 O 2 , tetradecanoic acid) and mixtures thereof.
- behenic acid C 22 H 44 O 2
- docosanoic acid heneicosanoic acid
- arachidic acid C 20 H 40 O 2
- the binder system comprises at least two fatty acids, then their average carbon chain length is less than or equal to, in particular lower, than the fatty alcohol of the hydroxybenzoic acid fatty alcohol ester having the longest fatty alcohol carbon chain length.
- the binder system comprises at least two fatty acids whose average carbon chain length is less than or equal to the fatty alcohol of the Hydroxybenzoic acid fatty alcohol ester having the longest fatty alcohol carbon chain length.
- the binder system may comprise at least two fatty acids whose average carbon chain length is less than the carbon chain length of the fatty alcohol of the hydroxybenzoic acid fatty alcohol ester having the longest fatty alcohol carbon chain length.
- the binder system may comprise at least two fatty acids whose average carbon chain length is less than or equal to, in particular less than, the average carbon chain length of the fatty alcohols of all hydroxybenzoic fatty acid alcohol esters contained in the binder system, or even less than or equal to, in particular less than, the carbon chain length of the fatty alcohols of all in the binder system
- the hydroxybenzoic acid fatty alcohol ester contained in detail is contained.
- the average carbon chain length of the fatty acids may be shorter than the carbon chain length of the fatty alcohol of the hydroxybenzoic acid fatty alcohol ester having the longest fatty alcohol carbon chain length, optionally also the average carbon chain lengths of the fatty alcohols of all Binder system, or even as the carbon chain length of the fatty alcohols of all hydroxybenzoic acid fatty alcohol esters contained in the binder system.
- the average carbon chain length of the fatty acids may be, for example, at most 8 carbon atoms, for example at most 7 carbon atoms or at most 6 carbon atoms, shorter than the carbon chain length of the fatty alcohol of the hydroxybenzoic acid fatty alcohol ester having the longest fatty alcohol carbon chain length, optionally also the average carbon chain lengths of the fatty alcohols of all Binder system, or even as the carbon chain length of the fatty alcohols of all hydroxybenzoic acid fatty alcohol esters contained in the binder system.
- the binder system may comprise at least two fatty acids whose average carbon chain length is in a range of ⁇ 16 carbon atoms and ⁇ 20 carbon atoms, especially 17 carbon atoms and ⁇ 19 carbon atoms, for example, 18 carbon atoms.
- the binder system comprises palmitic acid and / or behenic acid and / or stearic acid.
- the binder system may comprise stearic or palmitic or palmitic and behenic or palmitic and stearic or stearic and behenic acids.
- These fatty acids or fatty acid combinations have proved to be particularly advantageous for a low and wide melting binder system and to achieve a good roundness of round components.
- Palmitic acid has been found to be particularly advantageous for lowering the melting temperature.
- the binder system in particular at least, comprises palmitic acid.
- the binder system comprises only one fatty acid, it has been found to be advantageous if it has a carbon chain length in a range of ⁇ 17 carbon atoms and ⁇ 19 carbon atoms.
- the binder system may comprise, as the sole fatty acid, nonadecanoic acid or stearic acid or heptadecanoic acid, especially stearic acid.
- the fatty acid weight fraction of the binder system is less than the hydroxybenzoic acid fatty alcohol ester weight fraction of the binder system. This has proven to be particularly advantageous in order to effect a good dispersion of the components of the powder injection molding composition and to achieve a homogeneous distribution of the components of the powder injection molding material in the melt.
- the fatty acid weight fraction of the binder system less than or equal to half, in particular less than or equal to one-third, of the Hydroxybenzoeklafettalkoholesterissanteils of the binder system.
- the at least one hydroxybenzoic acid fatty alcohol ester has a carbon chain length of ⁇ 14 carbon atoms to ⁇ 24 carbon atoms.
- the at least one hydroxybenzoic acid fatty alcohol ester may be an ester of a saturated fatty alcohol, for example a saturated and linear fatty alcohol.
- the at least one hydroxybenzoic acid fatty alcohol ester may be selected from the group consisting of hydroxybenzoic acid arnoceryl ester (C 31 H 54 O 3 ), hydroxybenzoic acid behenyl ester (C 29 H 50 O 3 ), hydroxybenzoic acid arachidyl ester (C 27 H 46 O 3 ), hydroxybenzoic acid stearyl ester (C 25 H 42 O 3 ), hydroxybenzoic acid palmitate ester (C 23 H 38 O 3 ), myristate hydroxybenzoate (C 21 H 34 O 3 ) and mixtures thereof.
- the binder system may one or more, as in the document DE 10 2008 054 615 A1 described hydroxybenzoic acid fatty alcohol esters include.
- the binder system preferably comprises at least one hydroxybenzoic acid fatty alcohol ester whose fatty alcohol has a carbon chain length of ⁇ 14 carbon atoms to ⁇ 22 carbon atoms, in particular from ⁇ 14 carbon atoms to ⁇ 20 carbon atoms, for example from ⁇ 14 carbon atoms, or, for example, ⁇ 15 carbon atoms or ⁇ 16 carbon atoms or ⁇ 17 Carbon atoms, up to ⁇ 20 carbon atoms, or for example ⁇ 19 carbon atoms or ⁇ 18 carbon atoms or ⁇ 17 carbon atoms or ⁇ 16 carbon atoms.
- the binder system comprises at least two hydroxybenzoic acid fatty alcohol esters, for example with fatty alcohols of different lengths of carbon chain length.
- a particularly wide melting range can also be achieved.
- the binder system comprises at least one first hydroxybenzoic acid fatty alcohol ester and one second hydroxybenzoic acid fatty alcohol ester, the fatty alcohol of the second hydroxybenzoic acid fatty alcohol ester having a lower carbon chain length than the fatty alcohol of the first hydroxybenzoic acid fatty alcohol ester.
- the fatty alcohols of the first and second Hydroxybenzoeklaalkoholesters can in particular have a similar structure.
- both the fatty alcohol of the first hydroxybenzoic acid fatty alcohol ester and the fatty alcohol of the second hydroxybenzoic acid fatty alcohol ester may be saturated or unsaturated or linear or branched, in particular saturated and optionally linear.
- the melting range of the binder system can be both effectively shifted towards lower temperatures and broadened. This in turn can be used to cause the powder injection molding compound to solidify more slowly in the cavity of the injection molding tool, which has a particularly advantageous effect on the roundness of round components made therefrom.
- the first hydroxybenzoic acid fatty alcohol ester may be a fatty alcohol having a carbon chain length of ⁇ 20 carbon atoms to ⁇ 24 carbon atoms and the second hydroxybenzoic acid fatty alcohol ester a
- This combination has proved to be particularly advantageous for a low and wide melting binder system and thus for achieving a good roundness of round components.
- the binder system may comprise two or more hydroxybenzoic acid fatty alcohol esters whose fatty alcohols have an average carbon chain length in a range of ⁇ 16 carbon atoms and ⁇ 20 carbon atoms, especially ⁇ 17 carbon atoms and ⁇ 19 carbon atoms, for example 18 carbon atoms.
- the weight fraction of the second hydroxybenzoic acid fatty alcohol ester of the binder system is less than the weight fraction of the first hydroxybenzoic acid fatty alcohol ester of the binder system.
- the proportion by weight of the second hydroxybenzoic acid fatty alcohol ester of the binder system may be less than or equal to half, in particular less than or equal to one third, for example less than or equal to a quarter or fifth, of the weight fraction of the first hydroxybenzoic acid fatty alcohol ester of the binder system.
- the proportion by weight of the first hydroxybenzoic acid fatty alcohol ester can be ⁇ 80% by weight to ⁇ 99.9% by weight and the weight fraction of the second hydroxybenzoic acid fatty alcohol ester ⁇ 0.1% by weight to ⁇ 20% by weight, based on the total weight of the Hydroxybenzoeklaalkoholester the binder system, amount.
- the polymer weight fraction of the binder system may in particular also be less than the hydroxybenzoic acid fatty alcohol ester weight fraction of the binder system.
- the polymer weight fraction of the binder system may also be less than or equal to two-thirds, optionally less than or equal to half of the hydroxybenzoic acid fatty alcohol ester weight fraction of the binder system.
- the at least one polymer comprises a polyamide.
- the at least one polymer may be a polyamide or a polyamide blend or a polyamide (block) copolymer.
- the at least one polymer may be a copolyamide 612, a blend of polyamide 11 and polyamide 12, or a polyether block amide (PEBA).
- the hydroxybenzoic acid fatty alcohol ester (s) may in principle be either fatty alcohol esters of ortho-hydroxybenzoic acid or meta-hydroxybenzoic acid or para-hydroxybenzoic acid or a mixture of these hydroxybenzoic acids.
- the hydroxybenzoic acid fatty alcohol esters may be fatty alcohol esters of ortho-hydroxybenzoic acid or para-hydroxybenzoic acid or a mixture of these hydroxybenzoic acids.
- a further subject matter of the present invention is a powder injection molding compound (feedstock), for example a metal and / or ceramic powder injection molding compound, in particular a metal powder injection molding compound which comprises a binder system according to the invention and at least one metal powder and / or at least one ceramic powder, in particular at least one metal powder.
- feedstock for example a metal and / or ceramic powder injection molding compound, in particular a metal powder injection molding compound which comprises a binder system according to the invention and at least one metal powder and / or at least one ceramic powder, in particular at least one metal powder.
- the powder injection molding composition based on the total weight of the powder injection molding composition, ⁇ 70 wt .-% to ⁇ 99 wt .-% metal and / or ceramic powder, in particular metal powder, and ⁇ 1 wt .-% to ⁇ 30 wt. -% binder system.
- a metal powder injection molding composition based on the total weight of the powder injection molding composition, ⁇ 90 wt .-% to ⁇ 99 wt .-% metal powder and ⁇ 1 wt .-% to ⁇ 10 wt .-% binder system include.
- a ceramic powder injection molding compound may in particular, based on the total weight of the powder injection molding material, comprise ⁇ 70 wt .-% to ⁇ 90 wt .-% ceramic powder and ⁇ 10 wt .-% to ⁇ 30 wt .-% binder system.
- the binder system based on the total weight of the powder injection molding composition, ⁇ 0.1 wt .-% to ⁇ 5 wt .-% of polymers, ⁇ 0.1 wt .-% to ⁇ 10 wt .-% of Hydroxybenzoeklaalkoholestern and ⁇ 0.1 wt .-% to ⁇ 5 wt .-% of fatty acids.
- the binder system based on the total weight of the powder injection molding compound, ⁇ 1 wt .-% to ⁇ 3 wt .-% of polymers, 2 wt .-% to ⁇ 6 wt .-% of Hydroxybenzoeklaalkoholestern and ⁇ 0.5 wt. % to ⁇ 2% by weight of fatty acids.
- Such binder systems or powder injection molding compounds are particularly easy to process and have proven to be advantageous for the production of round components with a good roundness.
- the present invention relates to the use of a binder system according to the invention or of a powder injection molding composition according to the invention, in particular by means of powder injection molding, for example by means of metal and / or ceramic powder injection molding, for producing a molded part.
- the molded part may be a rounded or round component.
- the molded part may be a valve body or a multi-hole valve.
- valve bodies were made from several powder injection molding compounds of comparable composition.
- the powder injection molding compositions each contained a metal powder, a polyamide, a Hydroxybenzoeklaalkoholester and optionally one or more fatty acids.
- the fatty acid-containing powder injection molding compounds were more homogeneous than the fatty acid-free powder injection molding compounds and could advantageously be injection-molded at a lower holding pressure.
- a more homogeneous distribution of the powder injection molding material in the cavity of the injection molding tool could be effected with the fatty acid-containing powder injection molding compounds, which had an advantageous effect on the quality of the valve body produced.
- Hydroxybenzoic acid fatty alcohol esters 22 C
- Behenic acid 22 C
- Stearic acid 18 C
- Palmitic acid (16 C) 0 100% by weight - - - 1 91% by weight 9% by weight - - 2 76% by weight - 24% by weight - 3 76% by weight - - 24% by weight 4 76% by weight 12% by weight 12% by weight - 5 76% by weight - 12% by weight 12% by weight 6 76% by weight 12% by weight - 12% by weight
- compositions Nos. 0 to 6 were melted in high-walled vials on a hot plate and allowed to cool with agitation. Subsequently, the melting ranges were investigated by means of differential scanning calorimetry (DSC). The results of the differential scanning calorimetry are shown in Table 2. The results of differential scanning calorimetry are also available in FIG. 1 shown in the form of a bar chart. Table 2: DSC results of the compositions given in Table 1 composition melting range No. from [° C] up to [° C] ⁇ [K] 0 72.6 78.7 6.1 1 69.6 76.7 7.1 2 67.1 74.6 7.5 3 56 74.7 18.7 4 57 74.8 17.8 5 50 74.3 24.3 6 48 74.4 26.4
- Table 2 and FIG. 1 show that the melt range 1 of the behenic acid-containing Composition No. 1 is slightly widened and shifted toward lower temperatures compared with the melting range 0 of the fatty acid-free Composition No. 0.
- Table 2 and FIG. 1 also show that by the addition of stearic acid instead of behenic acid, the melting range 2 of stearic acid-containing composition No. 2 - compared to the melting range 1 of the behenic acid-containing composition No. 1 - slightly widened and could be shifted towards lower temperatures.
- Table 2 and FIG. 1 in that the addition of palmitic acid, which has a significantly lower carbon chain length (C16) than the fatty alcohol of the ester (C22), enabled the melting range of the palmitic acid-containing composition No. 3 to be significantly broadened and shifted to significantly lower temperatures.
- Table 2 and FIG. 1 moreover show that by adding a fatty acid combination, namely behenic acid and stearic acid in composition no. 4, an effect comparable to that of the palmitic acid-containing composition no. 3 can be achieved.
- Composition Nos. 1 to 6 were each mixed with metal powder and polyamide into powder injection molding compounds, and valve bodies were made from the resulting powder injection molding compositions by metal injection molding (MIM).
- Table 3 shows in particular that good roundness values can be achieved by adding a fatty acid or fatty acid mixture.
- compositions Nos. 1 to 3 show that by using the shorter-chain fatty acids stearic acid and palmitic acid in Compositions Nos. 2 and 3, respectively, the roundness can be improved instead of the longer-chain behenic acid used in Composition No. 1.
- the addition of stearic acid in Composition No. 2 shows the most significant effect on the roundness of the components when using only one fatty acid.
- Table 3 further shows that also by a combination of fatty acids, the roundness can be improved compared to the behenic acid-containing composition No. 1.
- the combination of the two fatty acids behenic acid and stearic acid in composition No. 4 with a roundness of 43.9 ⁇ m is clearly better than the composition containing behenic acid only, the addition of the shorter-chain palmitic acid in the stearic acid and palmitic acid-containing composition shows No. 5 and the behenic acid and palmitic acid-containing composition No. 6 have an even more pronounced effect on the roundness.
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Description
Eine Methode zur Formgebung von komplexen metallischen Bauteilen ist das Metallpulverspritzguss-Verfahren, auch Metal Injection Molding (MIM) genannt. Um eine spritzbare Masse, einen so genannten Feedstock, zu erhalten, wird dabei Metallpulver mit Binderkomponenten vermengt.One method of forming complex metallic components is metal injection molding, also called metal injection molding (MIM). In order to obtain a sprayable mass, a so-called feedstock, while metal powder is mixed with binder components.
Als polymere Binderkomponente werden häufig Polyamide eingesetzt.Polyamide is often used as the polymeric binder component.
Die Druckschrift
Darüber hinaus ist der
Weiterhin ist der
Gegenstand der vorliegenden Erfindung ist ein Bindersystem für eine Pulverspritzgussmasse, beispielsweise eine Metall- und/oder Keramikpulverspritzgussmasse, insbesondere eine Metallpulverspritzgussmasse, welches mindestens ein Polymer und mindestens einen Hydroxybenzoesäurefettalkoholester umfasst.The present invention is a binder system for a powder injection molding material, for example a metal and / or ceramic powder injection molding compound, in particular a metal powder injection molding composition which comprises at least one polymer and at least one Hydroxybenzoesäurefettalkoholester.
Unter einem Fettalkohol kann insbesondere ein gesättigter oder ungesättigter, linearer oder verzweigter, einwertiger primärer Alkohol mit einer Kohlenstoffkettenlänge von ≥ 8 Kohlenstoffatomen bis ≤ 24 Kohlenstoffatomen verstanden werden.A fatty alcohol may in particular be understood to mean a saturated or unsaturated, linear or branched monohydric primary alcohol having a carbon chain length of ≥ 8 carbon atoms to ≦ 24 carbon atoms.
Um die Homogenität und Verarbeitbarkeit der Pulverspritzgussmasse zu verbessern, umfasst das Bindersystem insbesondere mindestens eine Fettsäure.In order to improve the homogeneity and processability of the powder injection molding composition, the binder system in particular comprises at least one fatty acid.
Unter einer Fettsäure kann dabei insbesondere eine gesättigte oder ungesättigte, lineare oder verzweigte Carbonsäure mit einer Kohlenstoffkettenlänge von ≥ 8 Kohlenstoffatomen bis ≤ 24 Kohlenstoffatomen verstanden werden.A fatty acid may in particular be understood to mean a saturated or unsaturated, linear or branched carboxylic acid having a carbon chain length of ≥ 8 carbon atoms to ≦ 24 carbon atoms.
Durch den Fettsäurezusatz können vorteilhafterweise die Dispersionseigenschaften des Bindersystems und damit die Homogenität der Pulverspritzgussmasse verbessert, die Tendenz zu Entmischungen an Umlenkungen und Fließfront verringert und die Viskosität verringert werden. Insgesamt kann so auch eine homogenere Verteilung der Pulverspritzgussmasse in der Kavität des Spritzgusswerkzeugs erzielt werden. Zudem kann durch den Fettsäurezusatz der Nachdruck beim Pulverspritzgussprozess verringert werden. Insbesondere ermöglicht es der Fettsäurezusatz den Schmelzbereich des Bindersystems auf einfache Weise einzustellen. Zum Beispiel hat sich gezeigt, dass durch den Zusatz von Fettsäuren der Schmelzbereich erniedrigt und verbreitert werden kann. Durch die Erniedrigung und Verbreiterung des Schmelzbereiches erstarrt die Pulverspritzgussmasse langsamer und gleichmäßiger in der Kavität des Spritzgusswerkzeugs, was sich besonders vorteilhaft auf die Rundheit von Bohrungen beziehungsweise die Rundheit von rotationssymmetrischen Bauteilen selbst auswirkt.The addition of fatty acids can advantageously improve the dispersion properties of the binder system and thus the homogeneity of the powder injection molding compound, reduce the tendency to disperse deflections and flow front and reduce the viscosity. Overall, a more homogeneous distribution of the powder injection molding compound in the cavity of the injection molding tool can thus be achieved. In addition, the emphasis in the powder injection molding process can be reduced by the addition of fatty acid. In particular, the addition of fatty acid makes it possible to easily adjust the melting range of the binder system. For example, it has been found that by adding fatty acids, the melting range can be lowered and broadened. By lowering and broadening the melting range, the powder injection molding compound solidifies more slowly and more uniformly in the cavity of the injection molding tool, which has a particularly advantageous effect on the roundness of bores or the roundness of rotationally symmetrical components themselves.
Im Rahmen einer Ausführungsform umfasst das Bindersystem mindestens eine Fettsäure, die eine geringere oder gleiche Kohlenstoffkettenlänge aufweist als der Fettalkohol des Hydroxybenzoesäurefettalkoholesters mit der längsten Fettalkoholkohlenstoffkettenlänge. Insbesondere kann das Bindersystem mindestens eine Fettsäure umfassen, die eine geringere Kohlenstoffkettenlänge aufweist als der Fettalkohol des Hydroxybenzoesäurefettalkoholesters mit der längsten Fettalkoholkohlenstoffkettenlänge. Beispielsweise kann das Bindersystem dabei mindestens eine Fettsäure umfassen, die eine geringere oder gleiche, insbesondere geringere, Kohlenstoffkettenlänge als die durchschnittliche Kohlenstoffkettenlänge der Fettalkohole aller in dem Bindersystem enthaltenen Hydroxybenzoesäurefettalkoholester oder als die Fettalkohole aller in dem Bindersystem enthaltenen Hydroxybenzoesäurefettalkoholester im Einzelnen aufweist. Zum Beispiel kann das Bindersystem dabei eine oder mehrere Fettsäure umfassen, die durchschnittlich oder sogar alle eine geringere oder gleiche, insbesondere geringere, Kohlenstoffkettenlänge als die durchschnittliche Kohlenstoffkettenlänge der Fettalkohole aller in dem Bindersystem enthaltenen Hydroxybenzoesäurefettalkoholester oder als die Fettalkohole aller in dem Bindersystem enthaltenen Hydroxybenzoesäurefettalkoholester im Einzelnen aufweisen.In one embodiment, the binder system comprises at least one fatty acid having a lower or equal carbon chain length than the fatty alcohol of the hydroxybenzoic acid fatty alcohol ester having the longest fatty alcohol carbon chain length. In particular, the binder system may comprise at least one fatty acid having a lower carbon chain length than the fatty alcohol of the hydroxybenzoic acid fatty alcohol ester having the longest fatty alcohol carbon chain length. For example, that can Binder system thereby comprise at least one fatty acid having a lower or equal, especially lower, carbon chain length than the average carbon chain length of the fatty alcohols contained in the binder system Hydroxybenzoesäurefettalkoholester or as the fatty alcohols of all present in the binder system Hydroxybenzoesäurefettalkoholester in detail. For example, the binder system may comprise one or more fatty acids having, on average or even all, a lower or equal, especially lower, carbon chain length than the average carbon chain length of the fatty alcohols of all hydroxybenzoic acid fatty alcohol esters contained in the binder system or as the fatty alcohols of all hydroxybenzoic acid fatty alcohol esters included in the binder system exhibit.
Dabei kann die Kohlenstoffkettenlänge der mindestens einen Fettsäure, beispielsweise von einer Fettsäure oder von zumindest einer Fettsäure, gegebenenfalls auch von mehreren Fettsäuren oder sogar von allen Fettsäuren, zum Beispiel um mindestens 2 Kohlenstoffatome, beispielsweise um mindestens 3 Kohlenstoffatome oder um mindestens 4 Kohlenstoffatome, zum Beispiel um mindestens 5 Kohlenstoffatome oder um mindestens 6 Kohlenstoffatome, kürzer sein als die Kohlenstoffkettenlänge des Fettalkohols des Hydroxybenzoesäurefettalkoholesters mit der längsten Fettalkoholkohlenstoffkettenlänge, gegebenenfalls auch als die durchschnittliche Kohlenstoffkettenlängen der Fettalkohole aller in dem Bindersystem enthaltenen Hydroxybenzoesäurefettalkoholester oder sogar als die Kohlenstoffkettenlänge der Fettalkohole aller in dem Bindersystem enthaltenen Hydroxybenzoesäurefettalkoholester im Einzelnen. Gegebenenfalls kann die Kohlenstoffkettenlänge der mindestens einen Fettsäure, beispielsweise von zumindest einer Fettsäure, gegebenenfalls auch von mehreren Fettsäuren oder sogar von allen Fettsäuren, zum Beispiel um höchstens 8 Kohlenstoffatome, beispielsweise um höchstens 7 Kohlenstoffatome oder um höchstens 6 Kohlenstoffatome, kürzer sein als die Kohlenstoffkettenlänge des Fettalkohols des Hydroxybenzoesäurefettalkoholesters mit der längsten Fettalkoholkohlenstoffkettenlänge, gegebenenfalls auch als die durchschnittliche Kohlenstoffkettenlängen der Fettalkohole aller in dem Bindersystem enthaltenen Hydroxybenzoesäurefettalkoholester oder sogar als die Kohlenstoffkettenlänge der Fettalkohole aller in dem Bindersystem enthaltenen Hydroxybenzoesäurefettalkoholester im Einzelnen.In this case, the carbon chain length of the at least one fatty acid, for example of a fatty acid or of at least one fatty acid, optionally also of several fatty acids or even of all fatty acids, for example by at least 2 carbon atoms, for example by at least 3 carbon atoms or by at least 4 carbon atoms, for example at least 5 carbon atoms or at least 6 carbon atoms, shorter than the carbon chain length of the fatty alcohol of the hydroxybenzoic acid fatty alcohol ester having the longest fatty alcohol carbon chain length, optionally also as the average carbon chain lengths of the fatty alcohols of all hydroxybenzoic acid fatty alcohol esters contained in the binder system or even as the carbon chain length of the fatty alcohols of all in the binder system Hydroxybenzoic acid fatty alcohol esters in detail. Optionally, the carbon chain length of the at least one fatty acid, for example of at least one fatty acid, optionally also of several fatty acids or even of all fatty acids, for example by at most 8 carbon atoms, for example at most 7 carbon atoms or at most 6 carbon atoms, may be shorter than the carbon chain length of Fatty alcohol of the hydroxybenzoic acid fatty alcohol ester having the longest fatty alcohol carbon chain length, optionally also as the average carbon chain lengths of the fatty alcohols of all contained in the binder system Hydroxybenzoesäurefettalkoholester or even as the carbon chain length of the fatty alcohols of all present in the binder system Hydroxybenzoesäurefettalkoholester in detail.
Die Struktur der mindestens einen kürzerkettigen oder gleichlangen, insbesondere kürzerkettigen, Fettsäure kann dabei insbesondere ähnlich der Struktur des Fettalkohols sein. Zum Beispiel kann sowohl die mindestens eine kürzerkettige beziehungsweise gleichlange, insbesondere kürzerkettige, Fettsäure als auch der Fettalkohol des Hydroxybenzoesäurefettalkoholesters gesättigt oder ungesättigt beziehungsweise linear oder verzweigt, insbesondere gesättigt und gegebenenfalls linear, sein. Durch den Einsatz einer oder mehrerer Fettsäuren mit einer - verglichen mit dem Fettalkoholester - geringeren oder gleichlangen Kohlenstoffkettenlänge und gegebenenfalls ähnlichen Struktur, kann vorteilhafterweise der Schmelzbereich des Bindersystems zu niedrigeren Temperaturen hin verschoben als auch verbreitert werden. Durch den Einsatz einer oder mehrerer Fettsäuren mit einer - verglichen mit dem Fettalkoholester - geringeren Kohlenstoffkettenlänge und gegebenenfalls ähnlichen Struktur, kann vorteilhafterweise der Schmelzbereich des Bindersystems besonders effektiv zu niedrigeren Temperaturen hin verschoben und verbreitert werden.The structure of the at least one shorter-chain or equal-length, in particular shorter-chain, fatty acid may in particular be similar to the structure of the fatty alcohol. For example, both the at least one short-chain or equivalent, in particular shorter-chain, fatty acid and the fatty alcohol of the hydroxybenzoic acid fatty alcohol ester may be saturated or unsaturated or linear or branched, in particular saturated and optionally linear. By using one or more fatty acids with a - compared to the fatty alcohol ester - less or equal length carbon chain length and optionally similar structure, advantageously, the melting range of the binder system can be shifted towards lower temperatures as well as broadened. By using one or more fatty acids with a - compared to the fatty alcohol esters - lower carbon chain length and optionally similar structure, advantageously, the melting range of the binder system can be particularly effectively shifted towards lower temperatures and broadened.
Im Rahmen einer Ausführungsform weist die mindestens eine Fettsäure eine Kohlenstoffkettenlänge von ≥ 14 Kohlenstoffatomen bis ≤ 24 Kohlenstoffatomen auf. Beispielsweise kann die mindestens eine Fettsäure eine Kohlenstoffkettenlänge von ≥ 14 Kohlenstoffatomen bis ≤ 22 Kohlenstoffatomen, insbesondere von ≥ 14 Kohlenstoffatomen oder ≥ 15 Kohlenstoffatomen oder ≥ 16 Kohlenstoffatomen oder ≥ 17 Kohlenstoffatomen bis ≤ 22 Kohlenstoffatomen oder ≤ 21 Kohlenstoffatomen oder ≤ 20 Kohlenstoffatomen oder ≤ 19 Kohlenstoffatomen oder ≤ 18 Kohlenstoffatomen, zum Beispiel von ≥ 16 Kohlenstoffatomen oder ≥ 17 Kohlenstoffatomen bis ≤ 22 Kohlenstoffatomen oder ≤ 20 Kohlenstoffatomen oder ≤ 19 Kohlenstoffatomen, beispielsweise von 18 Kohlenstoffatomen, aufweisen.In one embodiment, the at least one fatty acid has a carbon chain length of ≥ 14 carbon atoms to ≦ 24 carbon atoms. For example, the at least one fatty acid may have a carbon chain length of ≥ 14 carbon atoms to ≤ 22 carbon atoms, especially ≥ 14 carbon atoms or ≥ 15 carbon atoms or ≥ 16 carbon atoms or ≥ 17 carbon atoms to ≤ 22 carbon atoms or ≤ 21 carbon atoms or ≤ 20 carbon atoms or ≤ 19 carbon atoms or ≤ 18 carbon atoms, for example from ≥ 16 carbon atoms or ≥ 17 carbon atoms to ≤ 22 carbon atoms or ≤ 20 carbon atoms or ≤ 19 carbon atoms, for example from 18 carbon atoms.
Insbesondere kann die mindestens eine Fettsäure eine gesättigte Carbonsäure, zum Beispiel eine gesättigte und lineare Carbonsäure, sein.In particular, the at least one fatty acid may be a saturated carboxylic acid, for example a saturated and linear carboxylic acid.
Zum Beispiel kann die mindestens eine Fettsäure ausgewählt sein, aus der Gruppe bestehend aus Behensäure (C22H44O2, Docosansäure), Heneicosansäure (C21H42O2), Arachinsäure (C20H40O2, Eicosan-/lcosansäure), Nonadecansäure (C19H38O2), Stearinsäure (C18H36O2, Octadecansäure), Heptadecansäure (C17H34O2), Palmitinsäure (C16H32O2, Hexadecansäure), Pentadecansäure (C15H30O2), Myristinsäure (C14H28O2, Tetradecansäure) und Mischungen davon.For example, the at least one fatty acid may be selected from the group consisting of behenic acid (C 22 H 44 O 2 , docosanoic acid), heneicosanoic acid (C 21 H 42 O 2 ), arachidic acid (C 20 H 40 O 2 , eicosane / lcosanoic acid ), Nonadecanoic acid (C 19 H 38 O 2 ), stearic acid (C 18 H 36 O 2 , octadecanoic acid), heptadecanoic acid (C 17 H 34 O 2 ), palmitic acid (C 16 H 32 O 2 , hexadecanoic acid), pentadecanoic acid (C 15 H 30 O 2 ), myristic acid (C 14 H 28 O 2 , tetradecanoic acid) and mixtures thereof.
Es ist möglich, dass das Bindersystem lediglich eine Fettsäure umfasst, beispielsweise deren Kohlenstoffkettenlänge in einem Bereich von ≥ 16 Kohlenstoffatomen und ≤ 20 Kohlenstoffatomen, insbesondere von ≥ 17 Kohlenstoffatomen und ≤ 19 Kohlenstoffatomen, zum Beispiel bei 18 Kohlenstoffatomen, liegt.It is possible that the binder system comprises only one fatty acid, for example whose carbon chain length is in a range of ≥ 16 carbon atoms and ≦ 20 carbon atoms, in particular 17 carbon atoms and ≦ 19 carbon atoms, for example 18 carbon atoms.
Im Rahmen einer weiteren Ausführungsform umfasst das Bindersystem jedoch mindestens zwei Fettsäuren. So kann vorteilhafterweise ein besonders breiter Schmelzbereich erzielt werden.In a further embodiment, however, the binder system comprises at least two fatty acids. Thus, advantageously, a particularly wide melting range can be achieved.
Die mindestens zwei Fettsäuren können dabei ebenfalls aus der Gruppe, bestehend aus Behensäure (C22H44O2, Docosansäure), Heneicosansäure (C21H42O2), Arachinsäure (C20H40O2, Eicosan-/lcosansäure), Nonadecansäure (C19H38O2), Stearinsäure (C18H36O2, Octadecansäure), Heptadecansäure (C17H34O2), Palmitinsäure (C16H32O2, Hexadecansäure), Pentadecansäure (C15H30O2), Myristinsäure (C14H28O2, Tetradecansäure) und Mischungen davon, ausgewählt sein.The at least two fatty acids may also be selected from the group consisting of behenic acid (C 22 H 44 O 2 , docosanoic acid), heneicosanoic acid (C 21 H 42 O 2 ), arachidic acid (C 20 H 40 O 2 , eicosan / lcosanoic acid), Nonadecanoic acid (C 19 H 38 O 2 ), stearic acid (C 18 H 36 O 2 , octadecanoic acid), heptadecanoic acid (C 17 H 34 O 2 ), palmitic acid (C 16 H 32 O 2 , hexadecanoic acid), pentadecanoic acid (C 15 H 30 O 2 ), myristic acid (C 14 H 28 O 2 , tetradecanoic acid) and mixtures thereof.
Es hat sich herausgestellt, dass es vorteilhaft ist, wenn das Bindersystem mindestens zwei Fettsäuren umfasst, dass dann deren durchschnittliche Kohlenstoffkettenlänge geringer oder gleichlang, insbesondere geringer, als der Fettalkohol des Hydroxybenzoesäurefettalkoholesters mit der längsten Fettalkoholkohlenstoffkettenlänge, ist.It has been found that it is advantageous if the binder system comprises at least two fatty acids, then their average carbon chain length is less than or equal to, in particular lower, than the fatty alcohol of the hydroxybenzoic acid fatty alcohol ester having the longest fatty alcohol carbon chain length.
Im Rahmen einer speziellen Ausgestaltung, umfasst daher das Bindersystem mindestens zwei Fettsäuren, deren durchschnittliche Kohlenstoffkettenlänge geringer oder gleich als der Fettalkohol des Hydroxybenzoesäurefettalkoholesters mit der längsten Fettalkoholkohlenstoffkettenlänge, ist. Insbesondere kann das Bindersystem mindestens zwei Fettsäuren umfassen, deren durchschnittliche Kohlenstoffkettenlänge geringer als die Kohlenstoffkettenlänge des Fettalkohols des Hydroxybenzoesäurefettalkoholesters mit der längsten Fettalkoholkohlenstoffkettenlänge ist. Beispielsweise kann das Bindersystem dabei mindestens zwei Fettsäuren umfassen, deren durchschnittliche Kohlenstoffkettenlänge geringer oder gleich, insbesondere geringer, als die durchschnittliche Kohlenstoffkettenlänge der Fettalkohole aller in dem Bindersystem enthaltenen Hydroxybenzoesäurefettalkoholester oder sogar geringer oder gleich, insbesondere geringer, als die Kohlenstoffkettenlänge der Fettalkohole aller in dem Bindersystem enthaltenen Hydroxybenzoesäurefettalkoholester im Einzelnen ist.In a specific embodiment, therefore, the binder system comprises at least two fatty acids whose average carbon chain length is less than or equal to the fatty alcohol of the Hydroxybenzoic acid fatty alcohol ester having the longest fatty alcohol carbon chain length. In particular, the binder system may comprise at least two fatty acids whose average carbon chain length is less than the carbon chain length of the fatty alcohol of the hydroxybenzoic acid fatty alcohol ester having the longest fatty alcohol carbon chain length. For example, the binder system may comprise at least two fatty acids whose average carbon chain length is less than or equal to, in particular less than, the average carbon chain length of the fatty alcohols of all hydroxybenzoic fatty acid alcohol esters contained in the binder system, or even less than or equal to, in particular less than, the carbon chain length of the fatty alcohols of all in the binder system The hydroxybenzoic acid fatty alcohol ester contained in detail is contained.
Dabei kann die durchschnittliche Kohlenstoffkettenlänge der Fettsäuren zum Beispiel um mindestens 2 Kohlenstoffatome, beispielsweise um mindestens 3 Kohlenstoffatome oder um mindestens 4 Kohlenstoffatome, kürzer sein als die Kohlenstoffkettenlänge des Fettalkohols des Hydroxybenzoesäurefettalkoholesters mit der längsten Fettalkoholkohlenstoffkettenlänge, gegebenenfalls auch als die durchschnittliche Kohlenstoffkettenlängen der Fettalkohole aller in dem Bindersystem enthaltenen Hydroxybenzoesäurefettalkoholester oder sogar als die Kohlenstoffkettenlänge der Fettalkohole aller in dem Bindersystem enthaltenen Hydroxybenzoesäurefettalkoholester im Einzelnen. Gegebenenfalls kann die durchschnittliche Kohlenstoffkettenlänge der Fettsäuren zum Beispiel um höchstens 8 Kohlenstoffatome, beispielsweise um höchstens 7 Kohlenstoffatome oder um höchstens 6 Kohlenstoffatome, kürzer sein als die Kohlenstoffkettenlänge des Fettalkohols des Hydroxybenzoesäurefettalkoholesters mit der längsten Fettalkoholkohlenstoffkettenlänge, gegebenenfalls auch als die durchschnittliche Kohlenstoffkettenlängen der Fettalkohole aller in dem Bindersystem enthaltenen Hydroxybenzoesäurefettalkoholester oder sogar als die Kohlenstoffkettenlänge der Fettalkohole aller in dem Bindersystem enthaltenen Hydroxybenzoesäurefettalkoholester im Einzelnen.The average carbon chain length of the fatty acids, for example by at least 2 carbon atoms, for example by at least 3 carbon atoms or by at least 4 carbon atoms, may be shorter than the carbon chain length of the fatty alcohol of the hydroxybenzoic acid fatty alcohol ester having the longest fatty alcohol carbon chain length, optionally also the average carbon chain lengths of the fatty alcohols of all Binder system, or even as the carbon chain length of the fatty alcohols of all hydroxybenzoic acid fatty alcohol esters contained in the binder system. Optionally, the average carbon chain length of the fatty acids may be, for example, at most 8 carbon atoms, for example at most 7 carbon atoms or at most 6 carbon atoms, shorter than the carbon chain length of the fatty alcohol of the hydroxybenzoic acid fatty alcohol ester having the longest fatty alcohol carbon chain length, optionally also the average carbon chain lengths of the fatty alcohols of all Binder system, or even as the carbon chain length of the fatty alcohols of all hydroxybenzoic acid fatty alcohol esters contained in the binder system.
Beispielsweise kann das Bindersystem mindestens zwei Fettsäuren umfassen, deren durchschnittliche Kohlenstoffkettenlänge in einem Bereich von ≥ 16 Kohlenstoffatomen und ≤ 20 Kohlenstoffatomen, insbesondere von ≥ 17 Kohlenstoffatomen und ≤ 19 Kohlenstoffatomen, zum Beispiel bei 18 Kohlenstoffatomen, liegt.For example, the binder system may comprise at least two fatty acids whose average carbon chain length is in a range of ≥ 16 carbon atoms and ≦ 20 carbon atoms, especially 17 carbon atoms and ≦ 19 carbon atoms, for example, 18 carbon atoms.
Es hat sich als vorteilhaft herausgestellt, wenn das Bindersystem Palmitinsäure und/oder Behensäure und/oder Stearinsäure umfasst.It has proved to be advantageous if the binder system comprises palmitic acid and / or behenic acid and / or stearic acid.
Insbesondere kann das Bindersystem Stearinsäure oder Palmitinsäure oder Palmitinsäure und Behensäure oder Palmitinsäure und Stearinsäure oder Stearinsäure und Behensäure umfassen. Diese Fettsäuren beziehungsweise Fettsäuren-Kombinationen haben sich für ein niedrig und breit schmelzendes Bindersystem und zum Erzielen einer guten Rundheit von runden Bauteilen als besonders vorteilhaft erwiesen.In particular, the binder system may comprise stearic or palmitic or palmitic and behenic or palmitic and stearic or stearic and behenic acids. These fatty acids or fatty acid combinations have proved to be particularly advantageous for a low and wide melting binder system and to achieve a good roundness of round components.
Zur Senkung der Schmelztemperatur hat sich dabei Palmitinsäure als besonders vorteilhaft herausgestellt.Palmitic acid has been found to be particularly advantageous for lowering the melting temperature.
Im Rahmen einer weiteren Ausführungsform umfasst daher das Bindersystem, insbesondere zumindest, Palmitinsäure.Within the scope of a further embodiment, therefore, the binder system, in particular at least, comprises palmitic acid.
Insofern das Bindersystem nur eine Fettsäure umfasst, hat es sich jedoch als vorteilhaft herausgestellt, wenn diese eine Kohlenstoffkettenlänge in einem Bereich von ≥ 17 Kohlenstoffatomen und ≤ 19 Kohlenstoffatomen umfasst. Zum Beispiel kann das Bindersystem als alleinige Fettsäure Nonadecansäure oder Stearinsäure oder Heptadecansäure, insbesondere Stearinsäure, umfassen.However, inasmuch as the binder system comprises only one fatty acid, it has been found to be advantageous if it has a carbon chain length in a range of ≥ 17 carbon atoms and ≦ 19 carbon atoms. For example, the binder system may comprise, as the sole fatty acid, nonadecanoic acid or stearic acid or heptadecanoic acid, especially stearic acid.
Im Rahmen einer weiteren Ausführungsform ist der Fettsäuregewichtsanteil des Bindersystems geringer als der Hydroxybenzoesäurefettalkoholestergewichtsanteil des Bindersystems. Dies hat sich als besonders vorteilhaft herausgestellt, um eine gute Dispersion der Bestandteile der Pulverspritzgussmasse zu bewirken und eine homogene Verteilung der Bestandteile der Pulverspritzgussmasse in der Schmelze zu erzielen. Beispielsweise kann der Fettsäuregewichtsanteil des Bindersystems, kleiner oder gleich der Hälfte, insbesondere kleiner oder gleich einem Drittel, des Hydroxybenzoesäurefettalkoholestergewichtsanteils des Bindersystems sein.In a further embodiment, the fatty acid weight fraction of the binder system is less than the hydroxybenzoic acid fatty alcohol ester weight fraction of the binder system. This has proven to be particularly advantageous in order to effect a good dispersion of the components of the powder injection molding composition and to achieve a homogeneous distribution of the components of the powder injection molding material in the melt. For example, the fatty acid weight fraction of the binder system, less than or equal to half, in particular less than or equal to one-third, of the Hydroxybenzoesäurefettalkoholestergewichtsanteils of the binder system.
Im Rahmen einer weiteren Ausführungsform weist der mindestens eine Hydroxybenzoesäurefettalkoholester eine Kohlenstoffkettenlänge von ≥ 14 Kohlenstoffatomen bis ≤ 24 Kohlenstoffatomen auf.In a further embodiment, the at least one hydroxybenzoic acid fatty alcohol ester has a carbon chain length of ≥ 14 carbon atoms to ≦ 24 carbon atoms.
Insbesondere kann es sich bei dem mindestens einen Hydroxybenzoesäurefettalkoholester um einen Ester eines gesättigten Fettalkohols, zum Beispiel eines gesättigten und linearen Fettalkohols, handeln. Zum Beispiel kann der mindestens eine Hydroxybenzoesäurefettalkoholester ausgewählt sein, aus der Gruppe bestehend aus Hydroxybenzoesäurelignocerylester (C31H54O3), Hydroxybenzoesäurebehenylester (C29H50O3), Hydroxybenzoesäurearachidylester (C27H46O3), Hydroxybenzoesäurestearylester (C25H42O3), Hydroxybenzoesäurepalmitylester (C23H38O3), Hydroxybenzoesäuremyristylester (C21H34O3) und Mischungen davon.In particular, the at least one hydroxybenzoic acid fatty alcohol ester may be an ester of a saturated fatty alcohol, for example a saturated and linear fatty alcohol. For example, the at least one hydroxybenzoic acid fatty alcohol ester may be selected from the group consisting of hydroxybenzoic acid arnoceryl ester (C 31 H 54 O 3 ), hydroxybenzoic acid behenyl ester (C 29 H 50 O 3 ), hydroxybenzoic acid arachidyl ester (C 27 H 46 O 3 ), hydroxybenzoic acid stearyl ester (C 25 H 42 O 3 ), hydroxybenzoic acid palmitate ester (C 23 H 38 O 3 ), myristate hydroxybenzoate (C 21 H 34 O 3 ) and mixtures thereof.
Insbesondere kann das Bindersystem einen oder mehrere, wie in der Druckschrift
Vorzugsweise umfasst das Bindersystem mindestens einen Hydroxybenzoesäurefettalkoholester, dessen Fettalkohol eine Kohlenstoffkettenlänge von ≥ 14 Kohlenstoffatomen bis ≤ 22 Kohlenstoffatomen, insbesondere von ≥ 14 Kohlenstoffatomen bis ≤ 20 Kohlenstoffatomen, beispielsweise von ≥ 14 Kohlenstoffatomen, oder zum Beispiel ≥ 15 Kohlenstoffatomen oder ≥ 16 Kohlenstoffatomen oder ≥ 17 Kohlenstoffatomen, bis ≤ 20 Kohlenstoffatomen, oder zum Beispiel ≤ 19 Kohlenstoffatomen oder ≤ 18 Kohlenstoffatomen oder ≤ 17 Kohlenstoffatomen oder ≤ 16 Kohlenstoffatomen, aufweist.The binder system preferably comprises at least one hydroxybenzoic acid fatty alcohol ester whose fatty alcohol has a carbon chain length of ≥ 14 carbon atoms to ≦ 22 carbon atoms, in particular from ≥ 14 carbon atoms to ≦ 20 carbon atoms, for example from ≥ 14 carbon atoms, or, for example, ≥ 15 carbon atoms or ≥ 16 carbon atoms or ≥ 17 Carbon atoms, up to ≤ 20 carbon atoms, or for example ≤ 19 carbon atoms or ≤ 18 carbon atoms or ≤ 17 carbon atoms or ≤ 16 carbon atoms.
Durch den Einsatz eines Hydroxybenzoesäurefettalkoholesters mit einem kurzkettigen Fettalkohol kann vorteilhafterweise der Schmelzbereich der Pulverspritzgussmasse erniedrigt und verbreitert werden. Dies ermöglicht es zum Einen beim Pulverspritzgussprozess einen geringeren Nachdruck anzuwenden. Zum Anderen kann dadurch bewirkt werden, dass die Pulverspritzgussmasse langsamer in der Kavität des Spritzgusswerkzeugs erstarrt, was sich besonders vorteilhaft auf die Rundheit von daraus hergestellten runden Bauteilen auswirkt.By using a Hydroxybenzoesäurefettalkoholesters with a short-chain fatty alcohol advantageously the melting range of the powder injection molding material can be reduced and widened. This makes it possible for To apply a lower emphasis in the powder injection molding process. On the other hand, this can cause the powder injection molding compound to solidify more slowly in the cavity of the injection molding tool, which has a particularly advantageous effect on the roundness of round components made therefrom.
Im Rahmen einer weiteren Ausführungsform umfasst das Bindersystem mindestens zwei Hydroxybenzoesäurefettalkoholester, beispielsweise mit Fettalkoholen unterschiedlich langer Kohlenstoffkettenlänge. So kann vorteilhafterweise ebenfalls ein besonders breiter Schmelzbereich erzielt werden.Within the scope of a further embodiment, the binder system comprises at least two hydroxybenzoic acid fatty alcohol esters, for example with fatty alcohols of different lengths of carbon chain length. Thus, advantageously, a particularly wide melting range can also be achieved.
Im Rahmen einer Ausgestaltung dieser Ausführungsform umfasst das Bindersystem zumindest einen ersten Hydroxybenzoesäurefettalkoholester und einen zweiten Hydroxybenzoesäurefettalkoholester, wobei der Fettalkohol des zweiten Hydroxybenzoesäurefettalkoholesters eine geringere Kohlenstoffkettenlänge als der Fettalkohol des ersten Hydroxybenzoesäurefettalkoholesters aufweist. Die Fettalkohole des ersten und zweiten Hydroxybenzoesäurefettalkoholesters können dabei insbesondere eine einander ähnliche Struktur aufweisen. Zum Beispiel kann sowohl der Fettalkohol des ersten Hydroxybenzoesäurefettalkoholesters als auch der Fettalkohol des zweiten Hydroxybenzoesäurefettalkoholesters gesättigt oder ungesättigt beziehungsweise linear oder verzweigt, insbesondere gesättigt und gegebenenfalls linear, sein. Durch den Einsatz eines Hydroxybenzoesäurefettalkoholesters dessen Fettalkohol - verglichen mit dem Fettalkohol des anderen Hydroxybenzoesäurefettalkoholesters - eine geringere Kohlenstoffkettenlänge und gegebenenfalls eine ähnlich Struktur aufweist, kann vorteilhafterweise ebenfalls der Schmelzbereich des Bindersystems besonders effektiv sowohl zu niedrigeren Temperaturen hin verschoben als auch verbreitert werden. Dadurch kann wiederum bewirkt werden, dass die Pulverspritzgussmasse langsamer in der Kavität des Spritzgusswerkzeugs erstarrt, was sich besonders vorteilhaft auf die Rundheit von daraus hergestellten runden Bauteilen auswirkt.Within the context of one embodiment of this embodiment, the binder system comprises at least one first hydroxybenzoic acid fatty alcohol ester and one second hydroxybenzoic acid fatty alcohol ester, the fatty alcohol of the second hydroxybenzoic acid fatty alcohol ester having a lower carbon chain length than the fatty alcohol of the first hydroxybenzoic acid fatty alcohol ester. The fatty alcohols of the first and second Hydroxybenzoesäurefettalkoholesters can in particular have a similar structure. For example, both the fatty alcohol of the first hydroxybenzoic acid fatty alcohol ester and the fatty alcohol of the second hydroxybenzoic acid fatty alcohol ester may be saturated or unsaturated or linear or branched, in particular saturated and optionally linear. By using a Hydroxybenzoesäurefettalkoholesters whose fatty alcohol - compared with the fatty alcohol of the other Hydroxybenzoesäurefettalkoholesters - has a lower carbon chain length and optionally a similar structure, advantageously also the melting range of the binder system can be both effectively shifted towards lower temperatures and broadened. This in turn can be used to cause the powder injection molding compound to solidify more slowly in the cavity of the injection molding tool, which has a particularly advantageous effect on the roundness of round components made therefrom.
Zum Beispiel kann der erste Hydroxybenzoesäurefettalkoholester einen Fettalkohol mit einer Kohlenstoffkettenlänge von ≥ 20 Kohlenstoffatomen bis ≤ 24 Kohlenstoffatomen und der zweite Hydroxybenzoesäurefettalkoholester einen Fettalkohol mit einer Kohlenstoffkettenlänge von ≥ 14 Kohlenstoffatomen bis ≤ 20, insbesondere von ≥ 14 Kohlenstoffatomen bis ≤ 18, zum Beispiel von ≥ 14 Kohlenstoffatomen bis ≤ 16, beispielsweise von 14 Kohlenstoffatomen, aufweisen. Diese Kombination hat sich für ein niedrig und breit schmelzendes Bindersystem und damit zum Erzielen einer guten Rundheit von runden Bauteilen als besonders vorteilhaft erwiesen.For example, the first hydroxybenzoic acid fatty alcohol ester may be a fatty alcohol having a carbon chain length of ≥ 20 carbon atoms to ≤ 24 carbon atoms and the second hydroxybenzoic acid fatty alcohol ester a Have fatty alcohol having a carbon chain length of ≥ 14 carbon atoms to ≤ 20, in particular from ≥ 14 carbon atoms to ≤ 18, for example from ≥ 14 carbon atoms to ≤ 16, for example of 14 carbon atoms. This combination has proved to be particularly advantageous for a low and wide melting binder system and thus for achieving a good roundness of round components.
Insbesondere kann das Bindersystem zwei oder mehr Hydroxybenzoesäurefettalkoholester umfassen, deren Fettalkohole eine durchschnittliche Kohlenstoffkettenlänge in einem Bereich von ≥ 16 Kohlenstoffatomen und ≤ 20 Kohlenstoffatomen, insbesondere von ≥ 17 Kohlenstoffatomen und ≤ 19 Kohlenstoffatomen, zum Beispiel von 18 Kohlenstoffatomen, aufweisen.In particular, the binder system may comprise two or more hydroxybenzoic acid fatty alcohol esters whose fatty alcohols have an average carbon chain length in a range of ≥ 16 carbon atoms and ≤ 20 carbon atoms, especially ≥ 17 carbon atoms and ≤ 19 carbon atoms, for example 18 carbon atoms.
Vorzugsweise ist der Gewichtsanteil des zweiten Hydroxybenzoesäurefettalkoholesters des Bindersystems geringer als der Gewichtsanteil des ersten Hydroxybenzoesäurefettalkoholesters des Bindersystems. So kann vorteilhafterweise eine gute Entformbarkeit des Bauteils aus der Kavität gewährleistet werden. Beispielsweise kann der Gewichtsanteil des zweiten Hydroxybenzoesäurefettalkoholesters des Bindersystems kleiner oder gleich der Hälfte, insbesondere kleiner oder gleich einem Drittel, beispielsweise kleiner oder gleich einem Viertel beziehungsweise Fünftel, des Gewichtsanteil des ersten Hydroxybenzoesäurefettalkoholesters des Bindersystems sein.Preferably, the weight fraction of the second hydroxybenzoic acid fatty alcohol ester of the binder system is less than the weight fraction of the first hydroxybenzoic acid fatty alcohol ester of the binder system. Thus, advantageously, a good releasability of the component from the cavity can be ensured. For example, the proportion by weight of the second hydroxybenzoic acid fatty alcohol ester of the binder system may be less than or equal to half, in particular less than or equal to one third, for example less than or equal to a quarter or fifth, of the weight fraction of the first hydroxybenzoic acid fatty alcohol ester of the binder system.
Insbesondere kann dabei der Gewichtsanteil des ersten Hydroxybenzoesäurefettalkoholesters ≥ 80 Gew.-% bis ≤ 99,9 Gew.-% und der Gewichtsanteil des zweiten Hydroxybenzoesäurefettalkoholesters ≥ 0,1 Gew.-% bis ≤ 20 Gew.-%, bezogen auf das Gesamtgewicht der Hydroxybenzoesäurefettalkoholester des Bindersystems, betragen.In particular, the proportion by weight of the first hydroxybenzoic acid fatty alcohol ester can be ≥ 80% by weight to ≦ 99.9% by weight and the weight fraction of the second hydroxybenzoic acid fatty alcohol ester ≥ 0.1% by weight to ≦ 20% by weight, based on the total weight of the Hydroxybenzoesäurefettalkoholester the binder system, amount.
Der Polymergewichtsanteil des Bindersystems kann insbesondere ebenfalls geringer als der Hydroxybenzoesäurefettalkoholestergewichtsanteil des Bindersystems sein. Beispielsweise kann der Polymergewichtsanteil des Bindersystems ebenfalls kleiner oder gleich der Zweidrittel, gegebenenfalls kleiner oder gleich der Hälfte, des Hydroxybenzoesäurefettalkoholestergewichtsanteils des Bindersystems sein.The polymer weight fraction of the binder system may in particular also be less than the hydroxybenzoic acid fatty alcohol ester weight fraction of the binder system. For example, the polymer weight fraction of the binder system may also be less than or equal to two-thirds, optionally less than or equal to half of the hydroxybenzoic acid fatty alcohol ester weight fraction of the binder system.
Im Rahmen einer weiteren Ausführungsform umfasst das mindestens eine Polymer ein Polyamid. Insbesondere kann das mindestens eine Polymer ein Polyamid oder eine Polyamid-Mischung oder ein Polyamid-(block-)Copolymer sein. Zum Beispiel kann das mindestens eine Polymer ein Copolyamid 612, eine Mischung aus Polyamid 11 und Polyamid 12 oder ein Polyether-Blockamid (PEBA) sein.In a further embodiment, the at least one polymer comprises a polyamide. In particular, the at least one polymer may be a polyamide or a polyamide blend or a polyamide (block) copolymer. For example, the at least one polymer may be a copolyamide 612, a blend of polyamide 11 and polyamide 12, or a polyether block amide (PEBA).
Bei dem oder den Hydroxybenzoesäurefettalkoholestern kann es sich grundsätzlich sowohl um Fettalkoholester der ortho-Hydroxybenzoesäure oder der meta-Hydroxybenzoesäure oder der para-Hydroxybenzoesäure oder einer Mischung dieser Hydroxybenzoesäuren handeln. Insbesondere kann es sich dem oder den Hydroxybenzoesäurefettalkoholestern um Fettalkoholester der ortho-Hydroxybenzoesäure oder para-Hydroxybenzoesäure oder einer Mischung dieser Hydroxybenzoesäuren handeln.The hydroxybenzoic acid fatty alcohol ester (s) may in principle be either fatty alcohol esters of ortho-hydroxybenzoic acid or meta-hydroxybenzoic acid or para-hydroxybenzoic acid or a mixture of these hydroxybenzoic acids. In particular, the hydroxybenzoic acid fatty alcohol esters may be fatty alcohol esters of ortho-hydroxybenzoic acid or para-hydroxybenzoic acid or a mixture of these hydroxybenzoic acids.
Hinsichtlich weiterer technischer Merkmale und Vorteile des erfindungsgemäßen Bindersystems wird hiermit explizit auf die Erläuterungen im Zusammenhang mit der erfindungsgemäßen Pulverspritzgussmasse, den Ausführungsbeispielen sowie den Figuren verwiesen.With regard to further technical features and advantages of the binder system according to the invention, reference is hereby explicitly made to the explanations in connection with the powder injection molding compound according to the invention, the exemplary embodiments and the figures.
Ein weiterer Gegenstand der vorliegenden Erfindung ist eine Pulverspritzgussmasse (Feedstock), beispielsweise eine Metall- und/oder Keramikpulverspritzgussmasse, insbesondere eine Metallpulverspritzgussmasse, welche ein erfindungsgemäßes Bindersystem und mindestens ein Metallpulver und/oder mindestens ein Keramikpulver, insbesondere mindestens ein Metallpulver, umfasst.A further subject matter of the present invention is a powder injection molding compound (feedstock), for example a metal and / or ceramic powder injection molding compound, in particular a metal powder injection molding compound which comprises a binder system according to the invention and at least one metal powder and / or at least one ceramic powder, in particular at least one metal powder.
Im Rahmen einer Ausführungsform umfasst die Pulverspritzgussmasse, bezogen auf das Gesamtgewicht der Pulverspritzgussmasse, ≥ 70 Gew.-% bis ≤ 99 Gew.-% Metall- und/oder Keramikpulver, insbesondere Metallpulver, und ≥ 1 Gew.-% bis ≤ 30 Gew.-% Bindersystem.In one embodiment, the powder injection molding composition, based on the total weight of the powder injection molding composition, ≥ 70 wt .-% to ≤ 99 wt .-% metal and / or ceramic powder, in particular metal powder, and ≥ 1 wt .-% to ≤ 30 wt. -% binder system.
Insbesondere kann eine Metallpulverspritzgussmasse, bezogen auf das Gesamtgewicht der Pulverspritzgussmasse, ≥ 90 Gew.-% bis ≤ 99 Gew.-% Metallpulver und ≥ 1 Gew.-% bis ≤ 10 Gew.-% Bindersystem umfassen.
Eine Keramikpulverspritzgussmasse kann insbesondere, bezogen auf das Gesamtgewicht der Pulverspritzgussmasse, ≥ 70 Gew.-% bis ≤ 90 Gew.-% Keramikpulver und ≥ 10 Gew.-% bis ≤ 30 Gew.-% Bindersystem umfassen.
Im Rahmen einer weiteren Ausführungsform umfasst das Bindersystem, bezogen auf das Gesamtgewicht der Pulverspritzgussmasse, ≥ 0,1 Gew.-% bis ≤ 5 Gew.-% an Polymeren, ≥ 0,1 Gew.-% bis ≤ 10 Gew.-% an Hydroxybenzoesäurefettalkoholestern und ≥ 0,1 Gew.-% bis ≤ 5 Gew.-% an Fettsäuren. Insbesondere kann das Bindersystem, bezogen auf das Gesamtgewicht der Pulverspritzgussmasse, ≥ 1 Gew.-% bis ≤ 3 Gew.-% an Polymeren, 2 Gew.-% bis ≤ 6 Gew.-% an Hydroxybenzoesäurefettalkoholestern und ≥ 0,5 Gew.-% bis ≤ 2 Gew.-% an Fettsäuren umfassen.
Derartige Bindersysteme beziehungsweise Pulverspritzgussmassen sind besonders gut verarbeitbar und haben sich zur Herstellung von runden Bauteilen mit einer guten Rundheit als vorteilhaft erwiesen.
Hinsichtlich weiterer technischer Merkmale und Vorteile der erfindungsgemäßen Pulverspritzgussmasse wird hiermit explizit auf die Erläuterungen im Zusammenhang mit dem erfindungsgemäßen Bindersystem, den Ausführungsbeispielen sowie den Figuren verwiesen.In particular, a metal powder injection molding composition, based on the total weight of the powder injection molding composition, ≥ 90 wt .-% to ≤ 99 wt .-% metal powder and ≥ 1 wt .-% to ≤ 10 wt .-% binder system include.
A ceramic powder injection molding compound may in particular, based on the total weight of the powder injection molding material, comprise ≥ 70 wt .-% to ≤ 90 wt .-% ceramic powder and ≥ 10 wt .-% to ≤ 30 wt .-% binder system.
In a further embodiment, the binder system, based on the total weight of the powder injection molding composition, ≥ 0.1 wt .-% to ≤ 5 wt .-% of polymers, ≥ 0.1 wt .-% to ≤ 10 wt .-% of Hydroxybenzoesäurefettalkoholestern and ≥ 0.1 wt .-% to ≤ 5 wt .-% of fatty acids. In particular, the binder system, based on the total weight of the powder injection molding compound, ≥ 1 wt .-% to ≤ 3 wt .-% of polymers, 2 wt .-% to ≤ 6 wt .-% of Hydroxybenzoesäurefettalkoholestern and ≥ 0.5 wt. % to ≤ 2% by weight of fatty acids.
Such binder systems or powder injection molding compounds are particularly easy to process and have proven to be advantageous for the production of round components with a good roundness.
With regard to further technical features and advantages of the powder injection molding composition according to the invention, reference is hereby explicitly made to the explanations in connection with the binder system according to the invention, the exemplary embodiments and the figures.
Ferner betrifft die vorliegende Erfindung die Verwendung eines erfindungsgemäßen Bindersystems oder aus einer erfindungsgemäßen Pulverspritzgussmasse, insbesondere mittels Pulverspritzguss, beispielsweise mittels Metall- und/oder Keramik-Pulverspritzguss, zur Herstellung eines Formteils. Insbesondere kann es sich bei dem Formteil um ein abgerundetes oder rundes Bauteil handeln. Beispielsweise kann es sich bei dem Formteil um einen Ventilkörper oder ein Mehrlochventil handeln.Furthermore, the present invention relates to the use of a binder system according to the invention or of a powder injection molding composition according to the invention, in particular by means of powder injection molding, for example by means of metal and / or ceramic powder injection molding, for producing a molded part. In particular, the molded part may be a rounded or round component. For example, the molded part may be a valve body or a multi-hole valve.
Hinsichtlich weiterer technischer Merkmale und Vorteile des erfindungsgemäßen Formteils wird hiermit explizit auf die Erläuterungen im Zusammenhang mit dem erfindungsgemäßen Bindersystem, der erfindungsgemäßen Pulverspritzgussmasse den Ausführungsbeispielen sowie den Figuren verwiesen.With regard to further technical features and advantages of the molding according to the invention, reference is hereby explicitly made to the explanations in connection with the binder system according to the invention, the powder injection molding composition according to the invention, the exemplary embodiments and the figures.
Weitere Vorteile und vorteilhafte Ausgestaltungen der erfindungsgemäßen Gegenstände werden durch die Ausführungsbeispiele und Zeichnungen veranschaulicht und in der nachfolgenden Beschreibung erläutert. Dabei ist zu beachten, dass die Ausführungsbeispiele und Zeichnungen nur beschreibenden Charakter haben und nicht dazu gedacht sind, die Erfindung in irgendeiner Form einzuschränken.Further advantages and advantageous embodiments of the subject invention are illustrated by the embodiments and drawings and explained in the following description. It should be noted that the embodiments and drawings are only descriptive in nature and are not intended to limit the invention in any way.
Zur Untersuchung des Einflusses von Fettsäuren auf die Eigenschaften von Pulverspritzgussmassen und daraus spritzgegossenen Formteilen, wurden Ventilkörper aus mehreren Pulverspritzgussmassen vergleichbarer Zusammensetzung hergestellt. Die Pulverspritzgussmassen enthielten dabei jeweils ein Metallpulver, ein Polyamid, einen Hydroxybenzoesäurefettalkoholester und optional eine oder mehrere Fettsäuren.To investigate the influence of fatty acids on the properties of powder injection molding compounds and moldings injection molded from them, valve bodies were made from several powder injection molding compounds of comparable composition. The powder injection molding compositions each contained a metal powder, a polyamide, a Hydroxybenzoesäurefettalkoholester and optionally one or more fatty acids.
Es zeigte sich, dass die fettsäurehaltigen Pulverspritzgussmassen homogener als die fettsäurefreien Pulverspritzgussmassen waren und vorteilhafterweise mit einem geringeren Nachdruck spritzgegossen werden konnten. Zudem konnte mit den fettsäurehaltigen Pulverspritzgussmassen eine homogenere Verteilung der Pulverspritzgussmasse in der Kavität des Spritzgusswerkzeugs bewirkt werden, was sich vorteilhaft auf die Qualität der hergestellten Ventilkörper auswirkte.It was found that the fatty acid-containing powder injection molding compounds were more homogeneous than the fatty acid-free powder injection molding compounds and could advantageously be injection-molded at a lower holding pressure. In addition, a more homogeneous distribution of the powder injection molding material in the cavity of the injection molding tool could be effected with the fatty acid-containing powder injection molding compounds, which had an advantageous effect on the quality of the valve body produced.
Um den Einfluss von unterschiedlichen Fettsäuren beziehungsweise Fettsäuremischungen auf Hydroxybenzoesäurefettalkoholester enthaltende Zusammensetzungen zu untersuchen, wurde ein Hydroxybenzoesäurefettalkoholester und eine oder mehrere Fettsäuren wie in Tabelle 1 angegeben eingewogen und gemischt. Die Gewichtsprozentangaben in Tabelle 1 beziehen sich auf das Gesamtgewicht der Bestandteile jeweiligen Zusammensetzung.
Die Zusammensetzungen Nr. 0 bis 6 wurden in hochwandigen Präparate-Gläschen auf einer Heizplatte aufgeschmolzen und unter Bewegung wieder abgekühlt. Anschließend wurden die Schmelzbereiche mittels dynamischer Differenzkalorimetrie (DSC) untersucht. Die Ergebnisse der dynamischen Differenzkalorimetrie sind in Tabelle 2 wiedergegeben. Die Ergebnisse der dynamischen Differenzkalorimetrie sind zudem in
Tabelle 2 und
Tabelle 2 und
Weiterhin zeigen Tabelle 2 und
Tabelle 2 und
Die in Tabelle 2 und
Zur Untersuchung des Einflusses von Hydroxybenzoesäurefettalkoholester-Fettsäure-Zusammensetzungen auf die Eigenschaften von Pulverspritzgussmassen und daraus spritzgegossenen Formteilen wurden, die Zusammensetzungen Nr. 1 bis 6 jeweils mit Metallpulver und Polyamid zu Pulverspritzgussmassen vermischt und aus den resultierenden Pulverspritzgussmassen Ventilkörper mittels Metallpulverspritzguss (MIM) hergestellt.To investigate the influence of hydroxybenzoic acid fatty alcohol ester fatty acid compositions on the properties of powder injection molding compounds and moldings molded therefrom, Composition Nos. 1 to 6 were each mixed with metal powder and polyamide into powder injection molding compounds, and valve bodies were made from the resulting powder injection molding compositions by metal injection molding (MIM).
Die Rundheit der hergestellten Ventilkörper wurde mittels eines Koordinatenmessgerätes (KMG) überprüft.
Die Ergebnisse der Rundheitsmessungen zeigen, dass durch die Zusammensetzungen Nr. 1 bis 6 bewirkte Schmelztemperaturerniedrigung und Schmelzbereichsaufweitung ein vorzeitiges Erstarren der Pulverspritzgussmassen in der Kavität des Spritzgusswerkzeugs vermieden und somit eine homogenere Verteilung der Spritzgussmasse in der Kavität erzielt werden kann.The results of the roundness measurements show that melting temperature reduction and melting range broadening caused by compositions Nos. 1 to 6 prevent premature solidification of the powder injection molding compounds in the cavity of the injection molding tool and thus a more homogeneous distribution of the injection molding compound in the cavity can be achieved.
Tabelle 3 zeigt insbesondere, dass durch den Zusatz einer Fettsäure oder Fettsäuremischung gute Rundheitswerte erzielt werden können.Table 3 shows in particular that good roundness values can be achieved by adding a fatty acid or fatty acid mixture.
Die Messergebnisse der Zusammensetzungen Nr. 1 bis 3 zeigen, dass durch den Einsatz der kürzerkettigen Fettsäuren Stearinsäure und Palmitinsäure in den Zusammensetzungen Nr. 2 beziehungsweise 3 anstelle der in Zusammensetzung Nr. 1 eingesetzten längerkettigen Behensäure die Rundheit noch verbessert werden kann. Dabei zeigt die Zugabe von Stearinsäure in Zusammensetzung Nr. 2 die deutlichste Auswirkung auf die Rundheit der Bauteile beim Einsatz lediglich einer Fettsäure.The measurement results of compositions Nos. 1 to 3 show that by using the shorter-chain fatty acids stearic acid and palmitic acid in Compositions Nos. 2 and 3, respectively, the roundness can be improved instead of the longer-chain behenic acid used in Composition No. 1. The addition of stearic acid in Composition No. 2 shows the most significant effect on the roundness of the components when using only one fatty acid.
Tabelle 3 zeigt weiterhin, dass auch durch eine Kombination von Fettsäuren die Rundheit verglichen mit der Behensäure enthaltenden Zusammensetzung Nr. 1 verbessert werden kann. Dabei ist die Kombination der beiden Fettsäuren Behensäure und Stearinsäure in Zusammensetzung Nr. 4 mit einer Rundheit von 43,9 µm zwar deutlich besser als die ausschließlich Behensäure enthaltende Zusammensetzung Nr.1, allerdings zeigt der Zusatz der kürzerkettigeren Palmitinsäure in der Stearinsäure und Palmitinsäure enthaltenden Zusammensetzung Nr. 5 und der Behensäure und Palmitinsäure enthaltenden Zusammensetzung Nr. 6 einen noch ausgeprägteren Effekt auf die Rundheit.Table 3 further shows that also by a combination of fatty acids, the roundness can be improved compared to the behenic acid-containing composition No. 1. Although the combination of the two fatty acids behenic acid and stearic acid in composition No. 4 with a roundness of 43.9 μm is clearly better than the composition containing behenic acid only, the addition of the shorter-chain palmitic acid in the stearic acid and palmitic acid-containing composition shows No. 5 and the behenic acid and palmitic acid-containing composition No. 6 have an even more pronounced effect on the roundness.
Dies kann dadurch erklärt werden, dass anscheinend auch eine geringere durchschnittliche Kohlenstoffkettenlänge der in der Fettsäuremischung enthaltenen Fettsäuren, welche im Fall von Zusammensetzung Nr. 4 bei 20 Kohlenstoffatomen, im Fall der Zusammensetzungen Nr. 5 und 6 jedoch bei 17 Kohlenstoffatomen beziehungsweise 19 Kohlenstoffatomen liegt, einen positiven Einfluss auf die Rundheit hat.This can be explained by the fact that apparently also a lower average carbon chain length of the fatty acids contained in the fatty acid mixture, which is 20 carbon atoms in the case of composition No. 4, but 17 carbon atoms or 19 carbon atoms in the case of compositions Nos. 5 and 6, has a positive influence on the roundness.
Insgesamt scheint eine alleinige oder durchschnittliche Fettsäurenkohlenstoffkettenlänge in einem Bereich von ≥ 16 Kohlenstoffatomen bis ≤ 20 Kohlenstoffatomen, insbesondere in einem Bereich von ≥ 17 Kohlenstoffatomen bis ≤ 19 Kohlenstoffatomen, sich vorteilhaft auf die Rundheit auszuwirken.Overall, a single or average fatty acid carbon chain length in a range of ≥ 16 carbon atoms to ≦ 20 carbon atoms, especially in a range of ≥ 17 carbon atoms to ≦ 19 carbon atoms, appears to favorably affect the roundness.
Dass eine Verbesserung der Rundheit dabei auch durch Fettsäurekombinationen erzielbar ist, ist unter diesem Aspekt besonders vorteilhaft, da dadurch zum Einen eine breitere Vielfalt an miteinander kombinierbaren Rohstoffen zur Verfügung gestellt wird und zum Anderen dadurch auch durchschnittliche Kettenlängen einstellbar sind, bei denen die dazu korrespondierende Einzelfettsäure teuer oder schlecht erhältlich oder nicht herstellbar wäre, wobei diese wiederum ermöglicht die Rundheit noch stärker zu optimieren.The fact that an improvement in the roundness can also be achieved by fatty acid combinations is particularly advantageous in this respect, since on the one hand a broader variety of combinable raw materials is made available and on the other hand also average chain lengths are adjustable in which the corresponding single fatty acid expensive or poorly available or could not be produced, which in turn makes it possible to optimize the roundness even more.
Claims (15)
- Binder system for a powder injection moulding material, in particular a metal and/or ceramic powder injection moulding material, comprising- at least one polymer and- at least one hydroxybenzoic acid fatty alcohol ester and- at least one fatty acid.
- Binder system according to Claim 1, wherein the binder system comprises at least one fatty acid having a carbon chain length which is less than or equal to, in particular less than, that of the fatty alcohol of the hydroxybenzoic acid fatty alcohol ester having the longest fatty alcohol carbon chain length.
- Binder system according to Claim 1 or 2, wherein the at least one fatty acid has a carbon chain length of ≥ 14 carbon atoms to ≤ 24 carbon atoms.
- Binder system according to any of Claims 1 to 3, wherein the binder system comprises at least two fatty acids.
- Binder system according to any of Claims 1 to 4, wherein the binder system comprises at least two fatty acids whose average carbon chain length is less than or equal to, in particular less than, that of the fatty alcohol of the hydroxybenzoic acid fatty alcohol ester having the longest fatty alcohol carbon chain length, in particular wherein the binder system comprises at least two fatty acids whose average carbon chain length is in a range from ≥ 16 carbon atoms to ≤ 20 carbon atoms.
- Binder system according to any of Claims 1 to 5, wherein the binder system comprises behenic acid and/or stearic acid and/or palmitic acid.
- Binder system according to any of Claims 1 to 6, wherein the binder system comprises at least palmitic acid.
- Binder system according to any of Claims 1 to 7, wherein the fatty acid weight fraction of the binder system is less than the hydroxybenzoic acid fatty alcohol ester weight fraction of the binder system.
- Binder system according to any of Claims 1 to 8, wherein the at least one hydroxybenzoic acid fatty alcohol ester has a carbon chain length of ≥ 14 carbon atoms to ≤ 24 carbon atoms.
- Binder system according to any of Claims 1 to 9, wherein the binder system comprises at least a first hydroxybenzoic acid fatty alcohol ester and a second hydroxybenzoic acid fatty alcohol ester, wherein the fatty alcohol of the second hydroxybenzoic acid fatty alcohol ester has a carbon chain length less than that of the fatty alcohol of the first hydroxybenzoic acid fatty alcohol ester, in particular wherein the first hydroxybenzoic acid fatty alcohol ester has a fatty alcohol having a carbon chain length of ≥ 20 carbon atoms to ≤ 24 carbon atoms and the second hydroxybenzoic acid fatty alcohol ester has a fatty alcohol having a carbon chain length of ≥ 14 carbon atoms to ≤ 18.
- Binder system according to any of Claims 1 to 10, wherein the at least one polymer comprises a polyamide or is a polyamide or a polyamide mixture or a polyamide copolymer.
- Powder injection moulding material, comprising a binder system according to any of Claims 1 to 11 and at least one metal powder and/or at least one ceramic powder, in particular at least one metal powder.
- Powder injection moulding material according to Claim 12, wherein based on the total weight of the powder injection moulding material the powder injection moulding material comprises- ≥ 70% by weight to ≤ 99% by weight of metal and/or ceramic powder, in particular metal powder, and- ≥ 1% by weight to ≤ 30% by weight of binder system.
- Powder injection moulding material according to Claim 12 or 13, wherein based on the total weight of the powder injection moulding material the binder system comprises- ≥ 0.1% by weight to ≤ 5% by weight of polymers,- ≥ 0.1% by weight to ≤ 10% by weight of hydroxybenzoic acid fatty alcohol esters and- ≥ 0.1% by weight to ≤ 5% by weight of fatty acids.
- Use of a binder system according to any of Claims 1 to 11 or a powder injection moulding material according to any of Claims 12 to 14 for producing a moulding.
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DE102012212018.1A DE102012212018A1 (en) | 2012-07-10 | 2012-07-10 | Binder system for powder injection molding compound |
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KR102364527B1 (en) | 2018-05-28 | 2022-02-17 | 제이에프이 스틸 가부시키가이샤 | Powder mixture for powder metallurgy and manufacturing method thereof |
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EP1881025A1 (en) | 2006-07-20 | 2008-01-23 | Cognis Oleochemicals GmbH | Use of esters of polyethylenglycol and fatty acids as lubricants for thermoplastic materials |
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DE102008054615A1 (en) | 2008-12-15 | 2010-06-17 | Robert Bosch Gmbh | Process for the preparation of an ester and binder system |
DE102009008685A1 (en) | 2009-02-06 | 2010-08-12 | Adform Ag | Producing component such as connection sleeve for brake disk of motor vehicle by injection-molding, comprises mixing metal- and/or ceramic powder with binder to homogeneous mass, and subsequently producing molded body from homogeneous mass |
DE102010029610A1 (en) | 2010-06-02 | 2011-12-08 | Evonik Goldschmidt Gmbh | Quaternary dialkanolamine esters |
DE102012212018A1 (en) | 2012-07-10 | 2014-01-16 | Robert Bosch Gmbh | Binder system for powder injection molding compound |
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US5877270A (en) * | 1994-03-14 | 1999-03-02 | Kabushiki Kaisha Komatsu Seisakusho | Water solvent extraction degreasing method and molded products produced therewith |
JP2005179773A (en) * | 2003-11-26 | 2005-07-07 | Sumitomo Metal Mining Co Ltd | Rare earth-iron-manganese based master alloy powder and its production method, anisotropic rare earth-iron-manganese-nitrogen based magnet powder obtained by using the same and its production method, composition for rare earth bond magnet obtained by using the same, and rare earth bond magnet |
US20130064708A1 (en) * | 2010-04-20 | 2013-03-14 | Seco Tools Ab | Method for producing cemented carbide products |
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- 2013-06-05 EP EP13170584.0A patent/EP2684628B1/en not_active Revoked
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US20090160105A1 (en) | 2006-07-06 | 2009-06-25 | Plansee Se | Process for Producing an Extruded Shaped Body |
EP1881025A1 (en) | 2006-07-20 | 2008-01-23 | Cognis Oleochemicals GmbH | Use of esters of polyethylenglycol and fatty acids as lubricants for thermoplastic materials |
DE102008054615A1 (en) | 2008-12-15 | 2010-06-17 | Robert Bosch Gmbh | Process for the preparation of an ester and binder system |
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