WO2019030267A1 - Procédé pour fabriquer un objet tridimensionnel présentant une partie d'objet individualisée et produite par l'intermédiaire d'une impression 3d - Google Patents

Procédé pour fabriquer un objet tridimensionnel présentant une partie d'objet individualisée et produite par l'intermédiaire d'une impression 3d Download PDF

Info

Publication number
WO2019030267A1
WO2019030267A1 PCT/EP2018/071477 EP2018071477W WO2019030267A1 WO 2019030267 A1 WO2019030267 A1 WO 2019030267A1 EP 2018071477 W EP2018071477 W EP 2018071477W WO 2019030267 A1 WO2019030267 A1 WO 2019030267A1
Authority
WO
WIPO (PCT)
Prior art keywords
printing
object section
section
diisocyanate
acrylate
Prior art date
Application number
PCT/EP2018/071477
Other languages
German (de)
English (en)
Inventor
Dirk Achten
Thomas BÜSGEN
Nicolas Degiorgio
Jonas KÜNZEL
Original Assignee
Covestro Deutschland Ag
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Covestro Deutschland Ag filed Critical Covestro Deutschland Ag
Publication of WO2019030267A1 publication Critical patent/WO2019030267A1/fr

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y10/00—Processes of additive manufacturing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
    • B29C64/10—Processes of additive manufacturing
    • B29C64/106—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material
    • A—HUMAN NECESSITIES
    • A43—FOOTWEAR
    • A43B—CHARACTERISTIC FEATURES OF FOOTWEAR; PARTS OF FOOTWEAR
    • A43B13/00—Soles; Sole-and-heel integral units
    • A43B13/02—Soles; Sole-and-heel integral units characterised by the material
    • A43B13/04—Plastics, rubber or vulcanised fibre
    • A—HUMAN NECESSITIES
    • A43—FOOTWEAR
    • A43B—CHARACTERISTIC FEATURES OF FOOTWEAR; PARTS OF FOOTWEAR
    • A43B13/00—Soles; Sole-and-heel integral units
    • A43B13/02—Soles; Sole-and-heel integral units characterised by the material
    • A43B13/08—Wood
    • A—HUMAN NECESSITIES
    • A43—FOOTWEAR
    • A43B—CHARACTERISTIC FEATURES OF FOOTWEAR; PARTS OF FOOTWEAR
    • A43B13/00—Soles; Sole-and-heel integral units
    • A43B13/02—Soles; Sole-and-heel integral units characterised by the material
    • A43B13/12—Soles with several layers of different materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y70/00—Materials specially adapted for additive manufacturing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y80/00—Products made by additive manufacturing

Definitions

  • the invention relates to a method for producing a 3-dimensional object comprising at least a first and a second object section, wherein the first object section is generated by means of a 3D printing method directly on the second object section, which is not generated via a 3D printing method.
  • 3D printing is still a very inefficient method of applying large quantities of material, and therefore, the use of 3D printing to efficiently create complex and / or individually modified surfaces of existing 3D bodies contributes to desired acceleration and optimal value creation.
  • the object of the invention was thus to provide a method by means of which 3D semi-finished products can be modified by means of a 3D printing process, the resulting product having improved adhesion between the object section produced by conventional methods and 3D printing has generated on this object section.
  • the method should allow an efficient targeted surface modification of the object section produced by conventional methods.
  • This object is achieved by a method for producing a 3-dimensional object comprising at least a first and a second object section, wherein the first object section is generated directly on the second object section by means of a 3D printing method, which is not generated via a 3D printing method, the method being characterized in that the first object section produced by means of a 3D printing method contains or consists of a polyurethane resin.
  • a further advantage of the method according to the invention is that it is possible to resort to base bodies which are not produced by 3D printing processes, for example a mattress or the like, which can be customized by means of the method according to the invention by means of 3D printing, that is to say adapted to a specific requirement profile. This is advantageous insofar as the production of individualized objects is more cost-effective and can be carried out more quickly.
  • the polyurethane resin is supplied to the 3D printing process as a reactive resin mixture and cured. Curing can take place during and / or after printing, preferably after printing.
  • a reactive resin mixture for example, a 1-K or a 2-K polyurethane system can be used.
  • a 2-K polyurethane system the mixing of the two components takes place immediately before processing, for example in a supply line to the print head in a suitable mixer, for example a static mixer.
  • Suitable 1-K polyurethane systems are, for example, hotmelts based on moisture-curing isocyanate-terminated polyurethane hotmelt adhesives, urethane acrylates, moisture-curing isocyanate-terminated urethane acrylates, mixtures of blocked isocyanates with alcohols and / or thiols, and / or carboxylic acids, and / or epoxides, and / or amines.
  • 2-K polyurethane systems for example, combinations of double bond-containing compounds with free isocyanate groups and or mixtures of blocked isocyanates with alcohols and / or thiols, and / or carboxylic acids, and / or epoxides, and / or amines or isocyanate-containing resins in combination with mixtures of blocked isocyanates with alcohols and / or thiols, and / or carboxylic acids, and / or epoxides, and / or amines.
  • the reactive polyurethane systems are free-radically crosslinkable resins having a viscosity (23 ° C., DIN EN ISO 2884-1) of> 500 mPas to ⁇ 70000 mPas. More preferably, the viscosity is in the range of> 1000 mPas to ⁇ 50,000 mPas.
  • the free-radically crosslinkable resin comprises functional groups which are selected from vinyl, propenyl, allyl, vinyl ether, maleyl, fumaryl, maleimide, dicyclopentadienyl, acrylamide and (meth) acrylate. Groups or a combination of at least two of them. Preference is given to (meth) acrylate groups.
  • the radically crosslinkable resin comprises a urethane (meth) acrylate.
  • the radically crosslinkable resin comprises at least one isocyanate-functional compound having at least one radiation-curing group selected from: vinyl, propenyl, allyl, vinyl ether, maleyl, fumaryl, maleimide, dicyclopentadienyl, acrylamide and (Meth) acrylate groups or a combination of at least two thereof, (component A) and at least one polyol (component B).
  • this radically crosslinkable resin further contains an unsaturated urethane acrylate which does not carry isocyanate groups, (component C) and at least one (meth) acrylate component (component D).
  • the isocyanate-functional compounds which can be used in accordance with the invention are composed, for example, of polyisocyanates, a portion of the NCO groups originally present having hydroxy-functional compounds, the functional groups selected from the group consisting of vinyl, propenyl, allyl, vinyl ether, maleinyl and fumaryl compounds. , Maleimide, dicyclopentadienyl, acrylamide and (meth) acrylate groups, or a combination of at least two thereof, such that the isocyanate functional compound vinyl, propenyl, allyl, vinyl ether, maleinyl, fumaryl , Maleimide, dicyclopentadienyl, acrylamide and / or (meth) acrylate groups and isocyanate groups.
  • the polyisocyanates used are typically aromatic, aliphatic and cycloaliphatic polyisocyanates having a number average molecular weight of less than 800 g / mol.
  • TDI 2,4- / 2,6-toluene diisocyanate
  • MDI methylene diphenyl diisocyanate
  • TIN triisocyanatononane
  • NDI nap
  • MCI isocyanatocyclohexane
  • TXDI 1,3-dioctylcyanato-4-methylcyclohexane
  • Preferred starting materials for the preparation of the isocyanate-functional compounds are hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI) and / or 4,4'-diisocyanatodicyclohexylmethane.
  • polyisocyanates are reaction products of the abovementioned isocyanates with themselves or with one another to uretdiones, or isocyanurates.
  • examples include Desmodur® N3300, Desmodur® N3400 or Desmodur® N3600 (all Covestro AG, Leverkusen, DE).
  • derivatives of isocyanates such as allophanates or biurets. Examples include Desmodur® N100, Desmodur® N75MPA / BA or Desmodur® VPLS2102 (all Covestro AG, Leverkusen, DE).
  • hydroxyl-containing compounds having radiation-curing groups are 2-hydroxyethyl (meth) acrylate, poly (ethylene oxide) mono (meth) acrylate (eg PEA6 / PEM6; Laporte Performance Chemicals Ltd., UK), polypropylene oxide mono (meth) acrylate (eg PPA6, PPM5S Laporte Performance Chemicals Ltd., UK), polyalkyleneoxide mono (meth) acrylate (eg PEM63P, Laporte Performance Chemicals Ltd., UK), poly (8-caprolactone) mono (meth) acrylates such as Tone Ml 00® (Dow, Schwalbach, DE), 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, hydroxybutyl vinyl ether, 3-hydroxy-2,2-dimethylpropyl (meth) acrylate, the hydroxy-functional mono-, di - or as far as possible higher acrylates such as Glycerol di (meth) acrylate,
  • Dipentaerythritol penta (meth) acrylate which are accessible by reacting polyvalent optionally alkoxylated alcohols such as trimethylolpropane, glycerol, pentaerythritol, dipentaerythritol.
  • the reaction products of double bond-containing acids with optionally double bond-containing epoxy compounds such as the reaction products of (meth) acrylic acid with glycidyl (meth) acrylate or bisphenol A diglycidyl ether, used in the urethanization become.
  • the isocyanate-functional compound having at least one radiation-curing group selected from the group consisting of vinyl ether, maleyl, fumaryl, maleimide, dicyclopentadienyl, acrylamide, (meth) acrylate groups or a combination of at least two thereof, an isocyanate-functional urethane acrylate.
  • a urethane acrylate is understood as meaning those compounds which have at least one isocyanate group and at least one acrylate group per molecule.
  • Such systems are known per se and have the property of free-radical polymerization via an NCO / OH reaction with polyols or polyamines, as well as via the acrylate function by means of UV light or electron radiation. There two Various mechanisms of polymerization of these compounds will be apparent in compositions containing such compounds, also referred to as "dual-cure" systems.
  • the isocyanate-functional urethane acrylates which can be used according to the invention are composed, for example, of polyisocyanates, a portion of the NCO groups originally present being reacted with hydroxy-functional acrylates or methacrylates, so that the molecule carries terminal (meth) acrylate groups and isocyanate groups.
  • Suitable starting compounds for isocyanate-functional urethane acrylates are monomeric diioder triisocyanates.
  • suitable monomeric polyisocyanates are 1,5-naphthylene diisocyanate, 2,2'-, 2,4- and / or 4,4'-diphenylmethane diisocyanate (MDI), hydrogenated MDI (H12MDI), xylylene diisocyanate (XDI), tetramethylxylylene diisocyanate (TMXDI) , 4,4'-diphenyldimethylmethane diisocyanate, 4,4'-dibenzyldiisocyanate, 1,3-phenylenediisocyanate, 1,4-phenylenediisocyanate, tolylenediisocyanate (TDI), 1-methyl-2,4-diisocyanato-cyclohexane, 1,6- Diisocyanato-2,2,4-trimethylhexane, 1,6
  • hydroxy-functional acrylates or methacrylates contain at least one monohydric hydroxy-functional ester of (meth) acrylic acid.
  • monohydric hydroxy-functional ester of (meth) acrylic acid include both a free hydroxyl-containing ester of acrylic acid or methacrylic acid with dihydric alcohols such as 2-hydroxyethyl, 2- or 3-hydroxypropyl or 2-, 3- or 4-hydroxybutyl (meth) acrylate and any mixtures of such compounds.
  • n is an integer or fractional number from greater than 2 to 4, preferably 3, and wherein per mole of said alcohols of (n-0.8) to (n-1,2), preferably (n-1 ) Mol (meth) acrylic acid can be used.
  • These compounds or product mixtures include, for example, the reaction products of glycerol, trimethylolpropane and / or pentaerythritol, of low molecular weight alkoxylation products of such alcohols, such as, for example, ethoxylated or propoxylated trimethylolpropane, such as for example, the adduct of ethylene oxide with trimethylolpropane of the OH number 550 or of any mixtures of such at least trihydric alcohols with dihydric alcohols such as ethylene glycol or propylene glycol with (ii) (meth) acrylic acid in said molar ratio.
  • urethane acrylates which can be used according to the invention, it is likewise possible to start from a polymeric compound selected from the group consisting of polyester (meth) acrylates, polyether (meth) acrylates, polyetherester (meth) acrylates, unsaturated polyesters with allyl ether structural units and polyepoxy (meth) acrylates.
  • This polymeric compound forms the polymer backbone and is reacted with polyisocyanates to produce the urethane acrylate.
  • the isocyanate groups of the resulting urethane acrylates can then in turn be reacted with monomeric compounds each having a hydroxy function and at least one (meth) acrylate group, thereby producing terminal acrylate groups.
  • the isocyanate-functional urethane acrylate has an NCO functionality of 0.8 to 6, preferably 1 to 4, more preferably 1.2 to 3, very particularly preferably 1.5 to 2.5 and in particular 2.
  • the double bond functionality of the isocyanate-functional urethane acrylate can vary over a wide range.
  • the double bond functionality is preferably from 0.5 to 6, preferably from 1 to 4, more preferably from 1.5 to 3.
  • the double bond functionality is defined here as the statistical average number of double bonds per molecule of the isocyanate-functional urethane acrylate.
  • the isocyanate-functional urethane acrylate has an average molecular weight of 150 to 5000, in particular from 300 to 2500 g / mol.
  • this resin composition contains at least one polyol (component B).
  • polyol which is known in the prior art, for example for the preparation of polyurethane polymers.
  • Suitable for this purpose are in particular polyether polyols, polyester polyols, polyether polyester polyols, polycarbonate polyols, polyester carbonate polyols or polyether carbonate polyols.
  • Further examples are aliphatic alcohols and polyols having 1-6 OH groups per molecule and 2 to about 30 C atoms.
  • Suitable aliphatic polyols are, for example, ethylene glycol, 1,2-propanediol or 1,3-diol, 1,4-butanediol, 1,3-butanediol, 2,3-butanediol, 1,4-butanediol, 1,5-pentanediol, pentenediols, Hexanediol-1,6, octanediol-1,8, dodecanediol and higher homologs, isomers and mixtures of such compounds.
  • higher functional Alcohols such as glycerol, trimethylolpropane, pentaerythritol or sugar alcohols, such as sorbitol or glucose, and oligomeric ethers or reaction products with ethylene or propylene oxide.
  • the reaction products of low molecular weight polyfunctional alcohols with alkylene oxides so-called polyether polyols, can be used.
  • the alkylene oxides preferably have from two to about four carbon atoms.
  • Suitable examples are the reaction products of ethylene glycol, propylene glycol, glycerol, trimethylolethane or trimethylolpropane, pentaerythritol with ethylene oxide, propylene oxide or butylene oxide or mixtures thereof.
  • the alcohols mentioned may themselves also be "dual-functional", ie thus also have unsaturated double bonds and hydroxyl groups, the double bond eg by partial esterification with acrylic acid or reaction with di- or polyisocyanates and further reaction - as described above - with hydroxy-functional double bond carriers
  • the molecular weight (Mn) of the polyols is about 50 to 5000 g / mol (number average molecular weight, Mn, as determined by GPC), in particular from 150 to 2500 g /
  • Such polyols are known to the person skilled in the art and are commercially available.
  • the polyol is characterized by an OH functionality of 1 to 6, preferably 1.5 to 5, more preferably 1.7 to 4, particularly preferably 1.8 to 3.5 and most preferably 2.
  • the unsaturated urethane acrylate (component C) differs from the isocyanate-functional urethane acrylate in that it does not carry free NCO groups.
  • the unsaturated urethane acrylates used according to the invention are, like the isocyanate-functional urethane acrylates, composed of a polyfunctional isocyanate, wherein in the case of the unsaturated urethane acrylates all of the isocyanate groups are reacted with a hydroxy-functional acrylate or methacrylate.
  • the same compounds which are stated above for the isocyanate-functional urethane acrylates are suitable in principle.
  • the polyfunctional isocyanates for the unsaturated urethane acrylates are selected from the aliphatic polyfunctional isocyanates. In other words, therefore, an unsaturated aliphatic urethane acrylate is preferred as component C). These compounds are particularly preferred because they improve the flexibility of the composition used in the invention after curing.
  • the unsaturated urethane acrylate has a proportion of OH Groups on.
  • the OH functionality is generally low and may be, for example, 0.01 to 1, preferably 0.05 to 0.8, more preferably 0.08 to 0.6, most preferably 0.09 to 0.5 and in particular 0.1. These OH groups are also available for reaction with NCO groups. More preferably, the unsaturated urethane acrylate has an average molecular weight of from 200 to 3,000, especially from 300 to 2,000.
  • the double bond functionality of the unsaturated urethane acrylate can vary over a wide range.
  • the double bond functionality is preferably 1 to 6, preferably 2 to 5, more preferably 2.5 to 4.
  • the double bond functionality is defined here as the statistical average number of double bonds per molecule of the unsaturated urethane acrylate.
  • the (meth) acrylate component (component D) may be selected from aliphatic and / or aromatic methacrylates.
  • Useful alkyl (meth) acrylates are, for example, linear or branched monofunctional unsaturated (meth) acrylates of non-tertiary alkyl alcohols whose alkyl groups have 4 to 14 and in particular 4 to 12 carbon atoms.
  • Examples of such lower alkyl acrylates are n-butyl, n-pentyl, n-hexyl, cyclohexyl, isoheptyl, n-nonyl, n-decyl, isohexyl, isobornyl, 2-ethyloctyl, isooctyl, 2-ethylhexyl, tetrahydrofurfuryl, ethoxyethoxyethyl, phenoxyethyl, cyclo Trimethylolpropane, 3,3,5-trimethylcyclohexyl, t-butylcyclohexyl, t-butyl acrylates and methacrylates.
  • Preferred alkyl acrylates are isooctyl acrylate, 2-ethylhexyl acrylate, 2-ethyloctyl acrylate, n-butyl acrylate, tetrahydrofurfuryl acrylate, isobornyl acrylate, ethoxyethoxyethyl acrylate, phenoxyethyl acrylate, 3,3,5-trimethylcyclohexyl acrylate and cyclohexyl acrylate.
  • the component E is selected from the group comprising UV initiators, thermally activatable initiators and redox initiators.
  • photoactivatable initiators for example, benzoin ethers may be used, such as benzoin methyl ether, benzoin isopropyl ether, substituted benzoin ethers such as anisoin methyl ether, acetophenones such as 2,2-diethoxyacetophenone, substituted acetophenones such as 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone and 1-phenyl 2-hydroxy-2-methyl-1-propanone, substituted alpha-ketols such as 2-methyl-2-hydroxypropiophenone, aromatic sulphonyl chlorides and photoactive oximes such as 1-phenyl-1, 1-propanedione-2- (0-ethoxycarbonyl) oxime.
  • Suitable thermally activatable initiators are organic peroxides, such as di-tert-butyl peroxide, benzoyl peroxide and lauryl peroxide, and also 2,2'-azobis (isobutyronitrile).
  • the amounts used of the aforementioned initiators are known in principle to the person skilled in the art and amount to for example, about 0.01 to 8 wt .-%, in particular 0.5 to 5 wt .-%, preferably Ibis 3 wt .-%.
  • composition may still contain conventional additives.
  • suitable fillers, stabilizers, in particular UV stabilizers, fungicides, dyes, pigments, polymerization catalysts, plasticizers and solvents are suitable for this purpose.
  • a polymerization catalyst for example, known isocyanate addition catalysts can be used, such as. B triethylamine, 1,4-diazabicyclo [2.2.2] octane, tin dioctoate, dibutyltin dilaurate or bismuth octoate.
  • the radically crosslinkable resin contains the components in the following amounts, wherein the data in% by weight add up to 100% by weight:
  • the initiator for free-radical crosslinking of the resin is selected from: UV-activatable initiators, thermally activatable initiators, redox initiators and a combination of at least two thereof.
  • benzoin ethers may be used, such as benzoin methyl ether, benzoin isopropyl ether, substituted benzoin ethers such as anisoin methyl ether, acetophenones such as 2,2-diethoxyacetophenone, substituted acetophenones such as 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone and 1-phenyl 2-hydroxy-2-methyl-1-propanone, substituted alpha-ketols such as 2-methyl-2-hydroxypropiophenone, aromatic sulphonyl chlorides and photoactive oximes such as 1-phenyl-1, 1-propanedione-2- (0-ethoxycarbonyl) oxime.
  • benzoin ethers such as benzoin methyl ether, benzoin isopropyl ether, substituted benzoin ethers such as anisoin methyl ether, acetophenones such as 2,2-diethoxyacetophenone, substituted
  • Suitable thermally activatable initiators are organic peroxides, such as di-tert-butyl peroxide, benzoyl peroxide and lauryl peroxide, and also 2,2'-azobis (isobutyronitrile).
  • the polyurethane resin may be a thermoplastic polyurethane resin which is first melted during printing and then cooled below its melting point again.
  • the thermoplastic polyurethane resin preferably has a melting range determined according to DIN EN ISO 11357-3: 2013-04 by means of DSC, Differential Scanning Calorimetry; from> 20 ° C to ⁇ 240 ° C, preferably> 40 ° C to ⁇ 220 ° C, more preferably> 70 ° C to ⁇ 200 ° C, to, a Shore A hardness according to DIN ISO 7619-1 of> 40 bis and ⁇ 85 Shore D, preferably> 50 Shore A to ⁇ 80 Shore D, more preferably> 60 Shore A to ⁇ 75 Shore D, and a melt volume rate (MVR) according to ISO 1133 (190 ° C, 10 kg) of> 25 to ⁇ 200, preferably> 30 to ⁇ 150, more preferably> 35 to ⁇ 100 cm 3/10 min.
  • MVR melt volume rate
  • thermoplastic polyurethane resin preferably with a melting range determined according to DIN EN ISO 11357-3: 2013-04 by means of DSC, Differential Scanning Calorimetry; from> 20 ° C to ⁇ 240 ° C, or preferably> 40 ° C to ⁇ 220 ° C, more preferably> 70 ° C to ⁇ 200 ° C is also called fusible polymer below.
  • the material is subjected to the following temperature cycle: 1 minute at minus 60 ° C, then heating to 240 ° C at 20 Kelvin / minute, then cooling to minus 60 ° C at 5 Kelvin / minute, then 1 minute at minus 60 ° C, then heating to 240 ° C at 20 Kelvin / minute.
  • the polyurethane resin in particular the meltable polymer, is preferably a thermoplastic elastomer and has a melting temperature (DSC, differential scanning calorimetry, heating at a rate of 5 K / min.) Of> 70 ° C. to ⁇ 200 ° C. and / or an amount the complex viscosity ⁇ ⁇ * ⁇ (determined by viscometry measurement in the melt with a plate / plate - Oszillationsscherviskosimeter at 20 ° C above the melting temperature and a shear rate of 1 / s) of> 10 Pas to ⁇ 1000000 Pas.
  • DSC differential scanning calorimetry, heating at a rate of 5 K / min.
  • the meltable polymer is a thermoplastic elastomer and has a melting range (determined according to DIN EN ISO 11357-3: 2013-04 by means of DSC, Differential Scanning Calorimetry, from> 20 ° C.
  • melt volume rate (MVR) according to ISO 1133 (10 kg) of 5 to 15, preferably> 6 to ⁇ 12, more preferably> 7 to ⁇ 10 cm 3/10 min and / or a change in the melt volume rate (10 kg) with an increase in this temperature T at 20 ° C of ⁇ 90, preferably ⁇ 70, more preferably ⁇ 50 cm 3/10 min up.
  • the meltable polymer is a thermoplastic elastomer and has a melting range (DSC, Differential Scanning Calorimetry, second heating with heating rate 20 K / min) of 160 to 240 ° C., a Shore D hardness according to DIN ISO 7619-1 of 50 or more, and preferably at a temperature T a melt volume rate (melt volume rate (MVR)) in accordance with ISO 1133 of 5 to 15 cm 3/10 min and a change in the MVR with an increase in this temperature T at 20 ° C of> 90 cm 3/10 min.
  • DSC Differential Scanning Calorimetry, second heating with heating rate 20 K / min
  • the meltable polymer is a thermoplastic elastomer and has a flow temperature (crossing point of E 'and E "in the DMA) of> 80 ° C to ⁇ 180 ° C and a Shore A hardness according to DIN ISO 7619-1 of> 50 Shore a and ⁇ 85 Shore a, and preferably at a temperature T a melt volume rate (melt volume rate (MVR)) in accordance with ISO 1133 of> 5 to ⁇ 15 cm 3/10 min and a change in the MVR with an increase in this temperature T is 20 ° C of> 90 cm 3/10 min.
  • MVR melt volume rate
  • the material is subjected to the following temperature cycle: 1 minute at -60 ° C, then heating to 240 ° C at 20 Kelvin / minute, then cooling to -60 ° C at 5 Kelvin / minute, then 1 minute at minus 60 ° C, then heating to 240 ° C with 20 Kelvin / minute.
  • thermoplastic polyurethane elastomer is obtainable from the reaction of the components: a) at least one organic diisocyanate, b) at least one compound having a number average molecular weight (M n ) of> 500 g / with isocyanate-reactive groups. mol to ⁇ 6000 g / mol and a number average functionality of the total of the components under b) of> 1.8 to ⁇ 2.5, c) at least one chain extender having a molecular weight (Mn) of 60-450 g / mol and a number average Functionality of the entirety of the chain extenders under c) from 1.8 to 2.5.
  • At least one of the at least one organic diisocyanate a) is an aliphatic diisocyanate.
  • only aliphatic diisocyanates are used for the preparation of the polyurethane resins according to the invention.
  • the polyurethane resin prepared according to the invention using exclusively aliphatic diisocyanates is particularly resistant to weathering and color.
  • the weather resistance is determined according to ISO 4892-2.
  • a good weathering resistance is characterized by an unchanged surface and a color change after L * a * b measurement according to the CIELAB model with a change of b ⁇ 10 after 500 h and preferably 1000h weathering.
  • thermoplastic polyurethane elastomer TPU
  • isocyanate component under a): aliphatic diisocyanates, such as ethylene diisocyanate, Tetramethylene diisocyanate, 1,5-pentamethylene diisocyanate, 1,6-hexamethylene diisocyanate, 1,12-dodecane diisocyanate, cycloaliphatic diisocyanates such as isophorone diisocyanate, 1,4-cyclohexane diisocyanate, 1-methyl-2,4-cyclohexane diisocyanate and 1-methyl-2,6-cyclohexane diisocyanate and the corresponding isomer mixtures, 4,4'-dicyclohexylmethane diisocyanate, 2,4'-dicyclohexylmethane diisocyanate and 2,2'-dicyclohexylmethane diisocyan
  • Dicyclohexylmethandiisocyanat and the corresponding isomer mixtures also aromatic diisocyanates such as 2,4-tolylene diisocyanate, mixtures of 2,4-tolylene diisocyanate and 2,6-toluene diisocyanate.
  • aromatic diisocyanates such as 2,4-tolylene diisocyanate, mixtures of 2,4-tolylene diisocyanate and 2,6-toluene diisocyanate.
  • aromatic diisocyanates such as 2,4-tolylene diisocyanate, mixtures of 2,4-tolylene diisocyanate and 2,6-toluene diisocyanate.
  • the diisocyanates mentioned can be used individually or in the form of mixtures with one another. They can also be used together with up to 15 mol% (calculated on the total diisocyanate) of a polyisocyanate, but at most so much polyisocyanate may be added that a still thermoplastically processable product is formed.
  • Examples of polyisocyanates are triphenylmethane-4,4 ', 4 "-triisocyanate and polyphenyl-polymethylene-polyisocyanates.
  • Examples of longer-chain isocyanate-reactive compounds under b) are those having on average at least 1.8 to 3.0 Zerewitinoff-active hydrogen atoms and a number-average molecular weight of 500 to 10,000 g / mol.
  • amino groups containing thiol groups or compounds containing carboxyl groups in particular two to three, preferably two hydroxyl groups having compounds especially those with number average molecular weights Mn from 500 to 6000 g / mol, particularly preferably those having a number average molecular weight Mn from 600 to 4000 g / mol, for example, hydroxyl-containing polyester polyols, polyether polyols, polycaprolactones, polycarbonate polyols and polyester polyamides.
  • Suitable polyester diols can be prepared by reacting one or more alkylene oxides containing 2 to 4 carbon atoms in the alkylene radical with a starter molecule containing two active hydrogen atoms.
  • alkylene oxides which may be mentioned are: ethylene oxide, 1,2-propylene oxide, epichlorohydrin and 1,2-butylene oxide and 2,3-butylene oxide.
  • Preferably used are ethylene oxide, propylene oxide and mixtures of 1,2-propylene oxide and ethylene oxide.
  • the alkylene oxides can be used individually, alternately in succession or as mixtures.
  • Suitable starter molecules are, for example, water, amino alcohols, such as N-alkyldiethanolamines, for example N-methyldiethanolamine and diols, such as ethylene glycol, 1,3- Propylene glycol, 1,4-butanediol and 1,6-hexanediol.
  • Suitable polyether diols are also the hydroxyl-containing polymerization of tetrahydrofuran. It is also possible to use trifunctional polyethers in proportions of from 0 to 30% by weight, based on the bifunctional polyether diols, but at most in such an amount that a product which can still be melt-processed is formed.
  • the substantially linear polyether diols preferably have number average molecular weights n of 500 to 6000 g / mol. They can be used both individually and in the form of mixtures with one another.
  • Suitable polyester diols can be prepared, for example, from dicarboxylic acids having 2 to 12 carbon atoms, preferably 4 to 6 carbon atoms, and polyhydric alcohols.
  • Suitable dicarboxylic acids are, for example: aliphatic dicarboxylic acids such as succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid and sebacic acid, or aromatic dicarboxylic acids such as phthalic acid, isophthalic acid and terephthalic acid.
  • the dicarboxylic acids can be used singly or as mixtures, e.g. in the form of an amber, glutaric and adipic acid mixture.
  • the corresponding dicarboxylic acid derivatives such as carbonic diesters having 1 to 4 carbon atoms in the alcohol radical, carboxylic acid anhydrides or carbonyl chlorides.
  • polyhydric alcohols are glycols having 2 to 10, preferably 2 to 6 carbon atoms, for example: Ethylene glycol, diethylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,10-decanediol, 2,2-dimethyl-1,3-propanediol, 1,3-propanediol or dipropylene glycol.
  • the polyhydric alcohols may be used alone or mixed with each other.
  • esters of carbonic acid with the diols mentioned in particular those having 4 to 6 carbon atoms, such as 1, 4-butanediol or 1,6-hexanediol, condensation products of ⁇ -hydroxycarboxylic acids such as ⁇ -hydroxycaproic acid or polymerization products of lactones, e.g. optionally substituted ⁇ -caprolactone.
  • polyester diols Preferably used as polyester diols are ethanediol polyadipates, 1,4-butanediol polyadipates, ethanediol-1,4-butanediol polyadipates, 1,6-hexanediol neopentyl glycol polyadipates, 1,6-hexanediol-1,4-butanediol polyadipates and polycaprolactones.
  • the polyester diols preferably have number-average molecular weights Mn of 450 to 6000 g / mol and can be used individually or in the form of mixtures with one another.
  • the chain extenders under c) have an average of 1.8 to 3.0 Zerewitino ff-active hydrogen atoms and have a molecular weight of 60 to 450 g / mol. By these is meant, in addition to amino groups, thiol groups or carboxyl-containing compounds, those having two to three, preferably two hydroxyl groups.
  • the chain extenders used are preferably aliphatic diols having 2 to 14 carbon atoms, for example ethanediol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol,
  • 2,3-butanediol 1,5-pentanediol, 1,6-hexanediol, diethylene glycol and dipropylene glycol.
  • diesters of terephthalic acid with glycols of 2 to 4 carbon atoms e.g. Terephthalic acid bis-ethylene glycol or terephthalic acid bis-l, 4-butanediol, hydroxyalkylene ethers of hydroquinone, e.g. 1,4-di (b-hydroxyethyl) hydroquinone, ethoxylated bisphenols, e.g.
  • 1,4-di (b-hydroxyethyl) bisphenol A (cyclo) aliphatic diamines such as isophoronediamine, ethylenediamine, 1,2-propylenediamine, 1,3-propylenediamine, N-methyl-propylene-1,3-diamine, N , N'-dimethylethylenediamine and aromatic diamines, such as 2,4-toluenediamine, 2,6-toluenediamine, 3,5-diethyl-2,4-toluenediamine or 3,5-diethyl-2,6-toluenediamine or primary mono-, di-, tri- or tetraalkyl-substituted 4,4'-diaminodiphenylmethanes.
  • aliphatic diamines such as isophoronediamine, ethylenediamine, 1,2-propylenediamine, 1,3-propylenediamine, N-methyl-propylene-1,3-diamine, N ,
  • Ethanediol, 1,4-butanediol, 1,6-hexanediol, 1,4-di (.beta.-hydroxyethyl) -hydroquinone or .alpha. are particularly preferred as chain extenders
  • 1,4-di ( ⁇ -hydroxyethyl) bisphenol A used. It is also possible to use mixtures of the abovementioned chain extenders. In addition, smaller amounts of triols can be added.
  • Compounds which are monounsaturated with respect to isocyanates can be used under f) in proportions of up to 2% by weight, based on TPU, as so-called chain terminators.
  • Suitable are e.g. Monoamines such as butyl and dibutylamine, octylamine, stearylamine, N-methylstearylamine, pyrrolidine, piperidine or cyclohexylamine, monoalcohols such as butanol, 2-ethylhexanol, octanol, dodecanol, stearyl alcohol, the various amyl alcohols, cyclohexanol and ethylene glycol monomethyl ether.
  • the isocyanate-reactive substances should preferably be selected so that their number-average functionality does not significantly exceed two if thermoplastically processable polyurethane elastomers are to be produced. If compounds with higher functionality are used, compounds with a functionality ⁇ 2 should reduce the overall functionality accordingly.
  • the relative amounts of the isocyanate groups and isocyanate-reactive groups are preferably selected such that the ratio is 0.9: 1 to 1.2: 1, preferably 0.95: 1 to 1.1: 1.
  • thermoplastic polyurethane elastomers used according to the invention may contain as auxiliary and / or additives up to a maximum of 50% by weight, based on the total amount of TPU, of the customary auxiliaries and additives.
  • auxiliaries and additives are catalysts, antiblocking agents, inhibitors, pigments, dyes, flame retardants, stabilizers against aging and weathering, against hydrolysis, light, heat and discoloration, plasticizers, lubricants and mold release agents, fungistatic and bacteriostatic substances, Reinforcing agents and inorganic and / or organic fillers and mixtures thereof.
  • additives examples include lubricants, such as fatty acid esters, their metal soaps, fatty acid amides, fatty acid ester amides and silicone compounds, and reinforcing agents, e.g. fibrous reinforcing materials, such as inorganic fibers, which are produced according to the prior art and may also be treated with a size.
  • lubricants such as fatty acid esters, their metal soaps, fatty acid amides, fatty acid ester amides and silicone compounds
  • reinforcing agents e.g. fibrous reinforcing materials, such as inorganic fibers
  • Suitable catalysts are the tertiary amines known and customary in the art, e.g. Triethylamine, dimethylcyclohexylamine, N-methylmorpholine, ⁇ , ⁇ '-dimethylpiperazine, 2- (dimethylaminoethoxy) ethanol, diazabicyclo [2,2,2] octane and the like and in particular organic metal compounds such as titanic acid esters, iron compounds or tin compounds such as tin diacetate, tin dioctoate, tin dilaurate or the tin dialkyl salts of aliphatic carboxylic acids such as dibutyltin diacetate or dibutyltin dilaurate or the like.
  • Preferred catalysts are organic metal compounds, in particular titanic acid esters, iron and tin compounds.
  • the total amount of catalysts in the TPU used is generally about 0 to 5 wt .-%, preferably 0 to 2 wt .-%, based on the total amount of TPU.
  • the meltable polymer is a thermoplastic elastomer and has a melting range (DSC, differential scanning calorimetry, heating at a heating rate of 5 K / min.) Of> 20 ° C. to ⁇ 100 ° C. and Amount of Complex Viscosity ⁇ ⁇ * ⁇ (determined by viscometry measurement in the melt with a plate / plate oscillation shear viscosimeter at 100 ° C and a shear rate of 1 / s) of> 10 Pas to ⁇ 1000000 Pas.
  • a melting range DSC, differential scanning calorimetry, heating at a heating rate of 5 K / min.
  • Amount of Complex Viscosity ⁇ ⁇ * ⁇ determined by viscometry measurement in the melt with a plate / plate oscillation shear viscosimeter at 100 ° C and a shear rate of 1 / s
  • This thermoplastic elastomer has a melting range of from> 20 ° C to ⁇ 100 ° C, preferably from> 25 ° C to ⁇ 90 ° C, and more preferably from> 30 ° C to ⁇ 80 ° C.
  • the material is subjected to the following temperature cycle: 1 minute at -60 ° C, then heating to 200 ° C at 5 Kelvin / minute, then cooling to -60 ° C at 5 Kelvin / minute, then 1 minute at -60 ° C, then heating to 200 ° C with 5 Kelvin / minute.
  • thermoplastic elastomer also has an amount of complex viscosity ⁇ ⁇
  • the amount of the complex viscosity ⁇ ⁇ * ⁇ describes the ratio of the viscoelastic moduli G '(storage modulus) and G "(loss modulus) to the excitation frequency ⁇ in a dynamic-mechanical material analysis:
  • thermoplastic elastomer is preferably a thermoplastic polyurethane elastomer.
  • the meltable polymer is a thermoplastic polyurethane elastomer obtainable from the reaction of a polyisocyanate component and a polyol component, the polyol component comprising a polyester polyol having a pour point (ASTM D5985) of> 25 ° C.
  • this polyurethane diols of the molecular weight range of> 62 to ⁇ 600 g / mol can be used as a chain extender.
  • This polyisocyanate component may comprise a symmetrical polyisocyanate and / or a nonsymmetric polyisocyanate.
  • symmetrical polyisocyanates are 4,4'-MDI and HDI.
  • non-symmetrical polyisocyanates the steric environment of one NCO group in the molecule is different from the steric environment of another NCO group.
  • An isocyanate group then reacts more rapidly with isocyanate-reactive groups, for example OH groups, while the remaining isocyanate group is less reactive.
  • a consequence of the non-symmetrical structure of the polyisocyanate is that the polyurethanes constructed with these polyisocyanates also have a less straight structure.
  • non-symmetrical polyisocyanates are selected from the group comprising: 2,2,4-trimethyl-hexamethylene diisocyanate, ethylethylene diisocyanate, non-symmetrical isomers of dicyclohexylmethane diisocyanate (H12-MDI), non-symmetrical isomers of 1,4-diisocyanatocyclohexane, non-symmetrical symmetrical isomers of 1,3-diisocyanatocyclohexane, non-symmetrical isomers of 1,2-diisocyanatocyclohexane, non-symmetrical isomers of 1,3-diisocyanatocyclohexane Diisocyanatocyclopentane, non-symmetrical isomers of 1,2-diisocyanatocyclopentane, non-symmetrical isomers of 1,2-diisocyanatocyclobutane, 1-isocyanatomethyl-3-isocyanato-1, 5,
  • This polyol component comprises a polyester polyol having a pour point (No Flow Point, ASTM D5985) of> 25 ° C, preferably> 35 ° C, more preferably> 35 ° C to ⁇ 55 ° C.
  • a measuring vessel is placed in a slow rotation (0.1 rpm) with the sample.
  • a flexibly mounted measuring head dips into the sample and is moved on reaching the pour point by the sudden increase in viscosity from its position, the resulting tilting movement triggers a sensor.
  • polyester polyols which may have such a pour point are reaction products of phthalic acid, phthalic anhydride or symmetrical ⁇ , ⁇ -C t- to ci-dicarboxylic acids with one or more C 2 to C 10 diols. They preferably have a number average molecular weight M n of> 400 g / mol to ⁇ 6000 g / mol.
  • Suitable diols are in particular monoethylene glycol, 1,4-butanediol, 1,6-hexanediol and neopentyl glycol.
  • Preferred polyester polyols are given below with indication of their acid and diol components: adipic acid + monoethylene glycol; Adipic acid + monoethylene glycol + 1,4-butanediol; Adipic acid + 1,4-butanediol; Adipic acid + 1,6-hexanediol + neopentyl glycol; Adipic acid + 1,6-hexanediol; Adipic acid + 1,4-butanediol + 1,6-hexanediol; Phthalic acid (anhydride) + monoethylene glycol + trimethylolpropane; Phthalic acid (anhydride) + monoethylene glycol.
  • Preferred polyurethanes are obtained from a mixture containing IPDI and HDI as a polyisocyanate component and a polyol component containing a previously mentioned preferred polyester polyol. Particularly preferred is the combination of a mixture containing IPDI and HDI as the polyisocyanate component with a polyester polyol of adipic acid + 1,4-butanediol + 1,6-hexanediol to build up the polyurethanes. It is further preferred that these polyester polyols have an OH number (DIN 53240) of> 25 to ⁇ 170 mg KOH / g and / or a viscosity (75 ° C, DIN 51550) of> 50 to ⁇ 5000 mPas.
  • a polyurethane obtainable from the reaction of a polyisocyanate component and a polyol component wherein the polyisocyanate component comprises an HDI and IPDI and wherein the polyol component comprises a polyester polyol resulting from the reaction of a reaction mixture comprising adipic acid and 1,6-hexanediol and 1,4-butanediol with a molar ratio of these diols of> 1: 4 to ⁇ 4: 1 is available and which has a number average molecular weight M n (GPC, against polystyrene standards) of> 4000 g / mol to ⁇ 6000 g / mol having.
  • M n number average molecular weight
  • Such a polyurethane may have an amount of complex viscosity ⁇ ⁇ ⁇ (determined by melt viscometry measurement with a plate / plate oscillation viscosimeter according to ISO 6721-10 at 100 ° C and a shear rate of 1 / s) of> 4000 Pas to ⁇ 160000 Pas have.
  • a suitable polyurethane is a substantially linear polyester polyurethane having terminal hydroxyl groups, as described in EP 0192946 A1, prepared by reacting a) polyester diols of over 600 molecular weight and optionally b) diols in the molecular weight range of 62 to 600 g / mol as a chain extender with c) aliphatic diisocyanates while maintaining an equivalent ratio of hydroxyl groups of components a) and b) to isocyanate groups of component c) of 1: 0.9 to 1: 0.999, wherein the component a) to at least 80 wt .-% of Polyester diols of the molecular weight range 4000 to 6000 based on (i) adipic acid and (ii) mixtures of 1,4-dihydroxybutane and 1,6-dihydroxyhexane in the molar ratio of the diols of 4: 1 to 1: 4.
  • component a) consists of 100% of a polyester diol of the molecular weight range 4000 to 6000, in the preparation thereof as diol mixture a mixture of 1,4-dihydroxybutane and 1,6-dihydroxyhexane in a molar ratio of 7: 3 to 1: 2 has been used.
  • the component c) contains IPDI and further HDI.
  • polyesterpolyurethane it is further preferred that in the preparation thereof as component b) alkanediols selected from the group consisting of: 1,2-dihydroxyethane, 1,3-dihydroxypropane, 1,4-dihydroxybutane, 1,5-dihydroxypentane, 1,6-dihydroxyhexane or a Combination of at least two thereof, in an amount of up to 200 hydroxyl equivalent percent, based on the component a), have been used.
  • alkanediols selected from the group consisting of: 1,2-dihydroxyethane, 1,3-dihydroxypropane, 1,4-dihydroxybutane, 1,5-dihydroxypentane, 1,6-dihydroxyhexane or a Combination of at least two thereof, in an amount of up to 200 hydroxyl equivalent percent, based on the component a), have been used.
  • thermoplastic elastomer after heating to 100 ° C and cooling to 20 ° C at a cooling rate of 4 ° C / min in a temperature range of 25 ° C to 40 ° C for> 1 minute (preferably> 1 minute to ⁇ 30 minutes, more preferably> 10 minutes to ⁇ 15 minutes), a storage modulus G '(determined at the prevailing temperature with a plate / plate oscillation viscosimeter according to ISO 6721-10 at a shear rate of 1 / s) of> 100 kPa to ⁇ 1 MPa and after cooling to 20 ° C and storage for 20 minutes a storage modulus G '(determined at 20 ° C with a plate / plate oscillating viscometer according to ISO 6721-10 at a shear rate of 1 / s) of> 10 MPa.
  • the second object portion can be produced, for example, by a method selected from casting, injection molding, deep drawing, foaming, machining, weaving, braiding, laying, knitting, folding, thermoforming, extruding, or a combination of at least two of these methods.
  • the material of the second object portion may be selected from plastics, metals, ceramics, vitreous materials, wood, stone, leather, paper, nature and synthetic fibers, composites, preferably polycarbonate and polyurethane, or combination materials thereof.
  • the material of the second object section of thermoplastically processable plastic formulations based on polyamides, polyurethanes, polyesters, polyimides, Polyetherkethonen, polycarbonates, poly (meth) acrylates, polyolefins, polyvinyl chloride, polyoxymethylene and / or crosslinked materials based on polyepoxides, polyurethanes, polysilicones , Polyacrylates, polyesters and mixtures thereof and copolymers.
  • the second object section substantially forms the support structure of the object and the first object section essentially forms the functional structure of the object.
  • a semifinished product of sufficient mechanical load capacity suitable for several applications is used as the second object section, which can be customized by means of 3D printing.
  • Exemplary applications for such a method is the combination of conventional orthopedic insoles, preferably based on polyurethane foam, with orthopedically active elements, such as support elements, applied by means of 3D printing, in particular FFF pressure.
  • the desired functionality produced by means of 3D printing typically has a higher mechanical strength and hardness (Shore A) than the foundation ground, and is connected to it in such a way that it can not be removed without destroying the foundation ground.
  • Another exemplary application for such a method is the printing of individualized studs on a TPU or PU resin based sole body to achieve individualized support or bottom handle properties according to the foot shape / body shape of the wearer.
  • the thus produced 3D printed supplements of the sole body can have both a greater and a smaller mechanical strength and hardness (Shore A) than the sole basic body.
  • damping structural elements are preferably TPU based and adapted to the load and shape needs of the wearer.
  • the structural elements are preferably designed as spatial grids. The strength and hardness of these damping structural body is typically less than that of the prefabricated protector shell.
  • individualized handles on an existing handle blank is preferably based on PU, PC or TPU materials and may be formed as a foam or as a solid solid.
  • the 3D printed individualized handle is preferably manufactured on the basis of PU or TPU.
  • a further exemplary application for such a method is the printing of emblems, surface patterns or haptics by means of 3D printing process, preferably via FFF or reactive LAM (Liquid Additive Manufacturing) on a preferably textile or leather-like, three-dimensional shape as a replacement for common screen printing.
  • a further embodiment of the method according to the invention is therefore one in which the functional structure of the object forming the first object section as haptic surface, emblem, handle, geometric pattern, lettering, image, pictogram, survey, sole, profile, button, plate, hook, lotus surface , Shark skin surface, female and / or male Velcro surface, adhesive layer, paint, conductor, magnetic surface, stopper, studs or damping body is formed.
  • the material of the second object section forming the support structure may have a higher flexural rigidity in accordance with DIN EN ISO 178 2013-09 than the first object section forming the functional structure of the object.
  • the second object section forming the support structure can be formed as a plate, framework structure, multi-face plate, solid, hollow body, foam, textile fabric or injection-molded blank.
  • a third or also further object sections can furthermore be applied, wherein the third and / or the further object sections are preferably produced by means of a 3D printing method.
  • the third and / or the further object sections are preferably produced by means of a 3D printing method.
  • the 3-dimensional object can be partially or completely provided with a coating after the 3D printing process, wherein the coating covers in particular the transition between the first and second object section.
  • the material transition can be laminated optically.
  • the coating may, for example, be selected from a coating, a metallic coating, a hydrophobing, a hydrophilization, a paint, an adhesive, a wax, a silicone oil, a shrink film, a film, a woven fabric or combinations thereof.
  • 3D printing methods for the method according to the invention.
  • 3D printing processes are generally used, with which three-dimensional surfaces can also be specifically modified (XYZ methods for FFF / LAM).
  • Suitable means for this are printheads for thermoplastics or reactive compositions, inkjet heads with a suitable droplet throw, powder method and the use of confocal laser for curing targeted at a point in a three-dimensional volume on a given surface.
  • Suitable methods are, for example, selected from Fused Filament Fabrication (FFF), Ink Jet Printing, Photopolymer Jetting, Stereo Lithography, Selective Laser Sintering, Digital Light Processing-based Additive Manufacturing System, Continuous Liquid Interface Production, Selective Laser Melting, Binder Jetting based additive manufacturing, Multijet Fusion based additive manufacturing, High Speed Sintering Process and Laminated Object Modeling or combinations of at least two of them.
  • FFF Fused Filament Fabrication
  • Ink Jet Printing Photopolymer Jetting
  • Stereo Lithography Stereo Lithography
  • Selective Laser Sintering Digital Light Processing-based Additive Manufacturing System
  • Continuous Liquid Interface Production Selective Laser Melting
  • Binder Jetting based additive manufacturing Multijet Fusion based additive manufacturing
  • High Speed Sintering Process High Speed Sintering Process
  • fused filament fabrication means a manufacturing process in the field of additive manufacturing, with which a workpiece
  • the plastic can be used with or without further additives, such as fibers FFF machines belong to the machine class of 3D printers
  • This process is based on the liquefaction of a wire-shaped plastic or wax material by heating.
  • the material is solidified by extrusion with a freely movable heating nozzle with respect to a production plane, where either the production plane can be fixed and the nozzle is freely movable or a nozzle is fixed and a substrate table (with a production level) can be moved or both elements, nozzle un d manufacturing levels, are movable.
  • the speed with which the substrate and the nozzle are movable relative to each other is preferably in a range of 1 to 100 mm / s.
  • the layer thickness is depending on the application in a range of 0.025 and 1.25 mm, the exit diameter of the material jet (Düsenauslass scrmesser) from the nozzle is typically at least 0.05 mm.
  • the individual layers combine to form a complex part.
  • the structure of a body is carried out by repeating regularly, one row at a time working plane (formation of a layer) and then the working plane "stacking" is shifted upwards (forming at least one further layer on the first layer), so that a form is formed in layers
  • the basic principle is also used when printing with reactive 1K or 2K polyurethane systems.
  • the nozzle is preferably in the SD printing process at a distance over the second object portion (when the first layer is applied) or driven over already applied layers, the 0.3 times to 1 times, preferably the 0.3 times to 0.9 times such.
  • This correlation between the sub-nozzle distance (substrate is either the plane base plate or an already applied layer) and nozzle outlet diameter ensures that the material is pressed onto the substrate with some pressure, thus creating better adhesion between the layers of the resulting surface portion.
  • Another object of the present invention relates to a 3-dimensional object, which is produced or produced by a method according to the invention.
  • the invention additionally relates to the use of a 3D printing method for producing a functionally-individualized 3-dimensional object comprising at least a first and a second object section, wherein the first object section is functionally individualized by means of a 3D printing method and generated directly on the second object section not generated by a 3D printing process.
  • the first object section preferably contains or consists of a polyurethane resin.
  • the composition of the polyurethane resin is preferably selected from the group of polyurethane resins previously described for the process according to the invention.
  • the invention relates to a method for producing a 3-dimensional object comprising at least a first and a second object section, wherein the first object section is generated directly on the second object section by means of a 3D printing method which does not generate via a 3D printing method is, characterized in that the first object section generated by means of a 3D printing process contains or consists of a polyurethane resin.
  • the invention relates to a method according to embodiment 1, characterized in that the polyurethane resin is supplied to the 3D printing process as a reactive resin mixture and cured, wherein the curing takes place in particular during and / or after printing, preferably after printing.
  • the invention relates to a method according to embodiment 1, characterized in that the polyurethane resin is a thermoplastic polyurethane resin, which is first melted during printing and then cooled below its melting point, wherein the thermoplastic polyurethane resin preferably determined a melting range according to DIN EN ISO 11357-3: 2013-04 by DSC, Differential Scanning Calorimetry; from> 20 ° C to ⁇ 240 ° C, and preferably a Shore A hardness according to DIN ISO 7619-1 of> 40 to and ⁇ 85 Shore D, and preferably a melt volume rate (MVR) according to ISO 1133 (190 ° C, 10 kg) having> 25 to ⁇ 200 cm 3/10 min.
  • the polyurethane resin is a thermoplastic polyurethane resin, which is first melted during printing and then cooled below its melting point
  • the thermoplastic polyurethane resin preferably determined a melting range according to DIN EN ISO 11357-3: 2013-04 by DSC, Differential Scanning Calorimetry; from> 20 °
  • the invention relates to a method according to one of the preceding embodiments, characterized in that the second object section by a method selected from casting, injection molding, deep drawing, foaming, machining, weaving, braiding, laying, knitting, folding, thermoforming, Extrusion or a combination of at least two of these methods is generated.
  • the invention relates to a method according to one of the preceding embodiments, characterized in that the material of the second object section is selected from plastics, metals, ceramics, vitreous materials, wood, stone, leather, paper, nature and synthetic fibers, composites , preferably of polycarbonate, polyurethane, polyamide, polyimide or combination materials of these.
  • the invention relates to a method according to one of the preceding embodiments, characterized in that the material of the second object section is selected from thermoplastically processable plastic formulations based on polyamides, polyurethanes, polyesters, polyimides, Polyetherkethonen, polycarbonates, poly (meth) acrylates , Polyolefins, polyvinyl chloride, polyoxymethylene and / or crosslinked materials based on polyepoxides, polyurethanes, polysilicones, polyacrylates, polyesters and mixtures thereof and copolymers.
  • thermoplastically processable plastic formulations based on polyamides, polyurethanes, polyesters, polyimides, Polyetherkethonen, polycarbonates, poly (meth) acrylates , Polyolefins, polyvinyl chloride, polyoxymethylene and / or crosslinked materials based on polyepoxides, polyurethanes, polysilicones, polyacrylates, polyesters and mixtures thereof and cop
  • the invention relates to a method according to one of the preceding embodiments, characterized in that the second object section essentially forms the support structure of the object and the first object section essentially forms the functional structure of the object.
  • the invention relates to a method according to embodiment 7, characterized in that the material of the second object section forming the support structure has a higher bending stiffness according to DIN EN ISO 178 2013-09 than the first object section forming the functional structure of the object.
  • the invention relates to a method according to one of the embodiments 7 or 8, characterized in that the support structure forming the second object portion as a plate, scaffold structure, Multistegplatte, solid, hollow body, foam, textile fabric or injection molded blank is formed.
  • the invention relates to a method according to one of the embodiments 7 to 9, characterized in that the first object section forming the functional structure of the object as a haptic surface, emblem, handle, geometric pattern, lettering, image, pictogram, elevation, sole, Profile, button, plate, hook, lotus surface, sharkskin surface, female and / or male Velcro surface, adhesive layer, paint, conductor, magnetic surface, stopper, studs and / or damping body is formed.
  • the invention relates to a method according to one of the preceding embodiments, characterized in that a third or further object sections are applied, wherein the third and / or the further object sections are preferably produced by means of a 3D printing method.
  • the invention relates to a method according to one of the preceding embodiments, characterized in that the 3-dimensional object is partially or completely provided with a coating after the 3D printing process, the coating in particular the transition between the first and second object section covers.
  • the invention relates to a method according to embodiment 12, characterized in that the coating is selected from a coating, a metallic coating, a hydrophobing, a hydrophilization, a paint, an adhesive, a wax, a silicone oil, a shrink film, a film, a fabric or combinations of these.
  • the invention relates to a method according to one of the preceding embodiments, characterized in that the 3D printing method is selected from fused filament fabrication (FFF), LAM (liquid additive manufacturing), ink-jet printing, photopolymer Jetting, Stereo Lithography, Selective Laser Sintering, Digital Light Processing based Additive Manufacturing System, Continuous Liquid Interface Production, Selective Laser Melting, Binder Jetting based Additive Manufacturing, Multijet Fusion based Additive Manufacturing, High Speed Sintering Process and Laminated Object Modeling.
  • the invention relates to a 3-dimensional object manufactured or manufacturable by a method according to one of embodiments 1 to 14.
  • the polyurethane resin prepared by a process according to the invention, in particular according to any of embodiments 1 to 14, using exclusively aliphatic diisocyanates is particularly weathering and color resistant.
  • the weather resistance is determined according to ISO 4892-2.
  • a good weathering resistance is characterized by an unchanged surface and a color change after L * a * b measurement according to the CIELAB model with a change of b ⁇ 10 after 500 h and preferably 1000h weathering.
  • the invention relates to the use of a 3D printing method for producing a functional-individualized 3-dimensional object comprising at least a first and a second object section, wherein the first object section is functionally individualized by means of a 3D printing method and is generated directly on the second object section, which is not generated via a 3D printing method.
  • FIG. 1 shows a second object section in the form of a screen before the application of a first and further object sections by means of 3D printing
  • FIG. 2 shows the screen from FIG. 1 after application of a first and the further object sections by means of 3D printing
  • FIG. 3 shows the sieve of FIG. 2 from the opposite perspective
  • FIG. 4 shows the screen of FIG. 1 after application of a first and the further object sections by means of 3D printing of a different configuration than in FIG. 2, FIG.
  • Fig. 6 shows another embodiment of a mattress with a 3D printing applied
  • FIG. 8 shows a shoe sole with successively applied further object sections in the form of studs.
  • FIG. 1 shows a hemispherical screen 1 produced as a second object section in a three-dimensional view obliquely from above by means of a conventional production method, ie not via 3D printing, wherein the fabric of the screen 1 is not completely shown for the sake of clarity.
  • Fig. 2 shows the screen 1 of FIG. 1 from the opposite side and after the application of a first object section 2, and two further object sections 3, 4 by means of inventive method via 3D printing.
  • the first object portion 2 is formed by an annular portion which is printed on the outside of the screen 1 in its central region. Starting from this annular section 2, the object section 3 serving to reinforce the screen 1 and divided into four strip-shaped sections 3a, 3b, 3c, 3d (FIG.
  • Fig. 3 shows the screen 1 of Fig. 2 in part from a mirrored in the plane of the paper of Fig. 2 perspective, the underlying part of the screen 1 is not shown for the sake of clarity.
  • FIG. 4 shows a second embodiment produced according to the invention.
  • This is in turn a screen 1, which is designed with a differently designed reinforcement in the form of a applied on the inside of the screen 1 flat object portion 6.
  • the planar object section 6 has substantially the same bending radius as the screen 1 and is provided at its upper edge region with semicircular recesses 7 and within its surface with circular recesses 8. In its center is a central opening. 9
  • a third embodiment generated by the method according to the invention is shown in a perspective view obliquely from above.
  • a second object section 10 in the form of a conventionally produced cold foam mattress of polyurethane foam in two surface sections of one of the main surfaces of the cold foam mattress 10 by means of the method according to the invention, ie via 3D printing, with a first and third object section 11, 12 surface-modified.
  • the first object section 11 is used in the use of the mattress of the individual support of a person, such as a patient, in the head and neck area.
  • the third object section 12 serves for lateral stabilization of the patient in order to hold the latter in a predetermined position.
  • FIG. 6 shows a fourth embodiment produced by the method according to the invention in a perspective view obliquely from above.
  • a second object section 20 is formed by a mattress, but in contrast to the embodiment shown in FIG. 5, only in one surface section has a surface modification in the form of a first object section 21 applied by means of the method according to the invention via 3D printing.
  • the first object section 11 is used in the use of the mattress of the individual support of a person in the head and neck area.
  • FIGS. 7 and 8 show two different methods according to the invention for producing studs on the underside of a sole 30 of a sports shoe.
  • the sole 30 is made in a conventional manner and represents the second object section 30, whereas the cleats are thereupon produced via 3D printing and represent the first, third and further object sections 31a-g.
  • the marks X1.7 indicate the positions for the cleats 31a-g.
  • the cleats 31a-g are created synchronously in that an application head 32 of the 3D printer each applies a first layer of the cleats 31a-g before the second and subsequent layers are applied until the desired cleat height is achieved.
  • the cleats 31a-g are successively formed by the application head 32 of the 3D printer first finishing the cleats 31a with the first cleats before the second cleat 31b and the further cleats 31c-g are produced.

Landscapes

  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Physics & Mathematics (AREA)
  • Mechanical Engineering (AREA)
  • Optics & Photonics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

L'invention concerne un procédé pour fabriquer un objet tridimensionnel comportant au moins une première et une deuxième partie d'objet. La première partie d'objet est produite au moyen d'un procédé d'impression 3D directement sur la deuxième partie d'objet qui n'a pas été produite par l'intermédiaire d'un procédé d'impression 3D. Le procédé selon l'invention est caractérisé en ce que la première partie d'objet produite au moyen d'un procédé d'impression 3D contient une résine polyuréthane ou est constituée de celle-ci. L'invention concerne également un objet tridimensionnel qui est fabriqué ou peut être fabriqué selon le procédé cité ci-dessus, ainsi que l'utilisation d'un procédé d'impression 3D pour la production d'un objet tridimensionnel individualisé du point de vue fonctionnel comportant au moins une première et une deuxième partie d'objet, la première partie d'objet étant individualisée du point de vue fonctionnel au moyen d'un procédé d'impression 3D et étant produite directement sur la deuxième partie d'objet qui n'est pas produite par l'intermédiaire d'un procédé d'impression 3D.
PCT/EP2018/071477 2017-08-09 2018-08-08 Procédé pour fabriquer un objet tridimensionnel présentant une partie d'objet individualisée et produite par l'intermédiaire d'une impression 3d WO2019030267A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP17185442.5 2017-08-09
EP17185442 2017-08-09

Publications (1)

Publication Number Publication Date
WO2019030267A1 true WO2019030267A1 (fr) 2019-02-14

Family

ID=59581752

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2018/071477 WO2019030267A1 (fr) 2017-08-09 2018-08-08 Procédé pour fabriquer un objet tridimensionnel présentant une partie d'objet individualisée et produite par l'intermédiaire d'une impression 3d

Country Status (1)

Country Link
WO (1) WO2019030267A1 (fr)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021076946A1 (fr) * 2019-10-16 2021-04-22 Avery Dennison Retail Information Services, Llc Procédés et systèmes de fabrication additive pour fixer des embellissements à des matériaux et articles associés
WO2021094271A1 (fr) 2019-11-14 2021-05-20 Covestro Intellectual Property Gmbh & Co. Kg Procédé pour revêtir un substrat avec une imprimante à jet d'encre du type goutte à la demande
WO2021094273A1 (fr) 2019-11-14 2021-05-20 Covestro Intellectual Property Gmbh & Co. Kg Procédé de revêtement d'un substrat avec une imprimante à jet d'encre goutte à la demande
US11724458B2 (en) 2016-12-06 2023-08-15 Hochland Se Manufacture of three dimensional objects from thermosets
US12036738B2 (en) 2023-06-01 2024-07-16 Chromatic 3D Materials, Inc. Manufacture of three dimensional objects from thermosets

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2901774A1 (de) 1979-01-18 1980-07-24 Elastogran Gmbh Rieselfaehiges, mikrobenbestaendiges farbstoff- und/oder hilfsmittelkonzentrat auf basis eines polyurethan-elastomeren und verfahren zu seiner herstellung
EP0192946A1 (fr) 1985-01-25 1986-09-03 Bayer Ag Polyesterpolyuréthanes contenant des groupes hydroxy terminaux et leur utilisation comme adhésif ou pour la préparation d'adhésifs
EP1002818B1 (fr) 1998-11-20 2004-12-29 Bayer MaterialScience AG Acrylates d'uréthane, procédé pour leur préparation et leur utilisation
WO2014015033A2 (fr) * 2012-07-19 2014-01-23 Nike International Ltd. Impression directe sur tissu
DE202017103049U1 (de) * 2017-05-19 2017-06-27 Isotech Holding Corporation Llc Schuhschaft mit dreidimensionalen Ziermustern aus Polyurethan sowie Schuh mit dem derartigen Schuhschaft

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2901774A1 (de) 1979-01-18 1980-07-24 Elastogran Gmbh Rieselfaehiges, mikrobenbestaendiges farbstoff- und/oder hilfsmittelkonzentrat auf basis eines polyurethan-elastomeren und verfahren zu seiner herstellung
EP0192946A1 (fr) 1985-01-25 1986-09-03 Bayer Ag Polyesterpolyuréthanes contenant des groupes hydroxy terminaux et leur utilisation comme adhésif ou pour la préparation d'adhésifs
EP1002818B1 (fr) 1998-11-20 2004-12-29 Bayer MaterialScience AG Acrylates d'uréthane, procédé pour leur préparation et leur utilisation
WO2014015033A2 (fr) * 2012-07-19 2014-01-23 Nike International Ltd. Impression directe sur tissu
DE202017103049U1 (de) * 2017-05-19 2017-06-27 Isotech Holding Corporation Llc Schuhschaft mit dreidimensionalen Ziermustern aus Polyurethan sowie Schuh mit dem derartigen Schuhschaft

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
J.H. SAUNDERS; K.C. FRISCH: "Polyurethane", vol. XVI, part 1 und 2 1962, VERLAG INTERSCIENCE PUBLISHERS, article "High Polymers"
KIYOSHI SHIMAMURA; SOSHU KIRIHARA; JUN AKEDO; TATSUKI OHJI; MAKIO NAITO: "A fabrication methodology for dual-material engineering structures using ultrasonic additive manufacturing", vol. 240, 18 August 2016, JOHN WILEY & SONS, pages: 46 ff
R. GÄCHTER; H. MÜLLER: "dem Taschenbuch für Kunststoff- Additive", 1990, HANSER VERLAG
THE INTERNATIONAL JOURNAL OF ADVANCED MANUFACTURING TECHNOLOGY, vol. 70, no. 1-4, January 2014 (2014-01-01), pages 277 - 284

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11724458B2 (en) 2016-12-06 2023-08-15 Hochland Se Manufacture of three dimensional objects from thermosets
WO2021076946A1 (fr) * 2019-10-16 2021-04-22 Avery Dennison Retail Information Services, Llc Procédés et systèmes de fabrication additive pour fixer des embellissements à des matériaux et articles associés
CN114786922A (zh) * 2019-10-16 2022-07-22 艾利丹尼森零售信息服务有限公司 用于在材料及关联单品上附接缀饰的增材制造方法和系统
WO2021094271A1 (fr) 2019-11-14 2021-05-20 Covestro Intellectual Property Gmbh & Co. Kg Procédé pour revêtir un substrat avec une imprimante à jet d'encre du type goutte à la demande
WO2021094273A1 (fr) 2019-11-14 2021-05-20 Covestro Intellectual Property Gmbh & Co. Kg Procédé de revêtement d'un substrat avec une imprimante à jet d'encre goutte à la demande
US12018163B2 (en) 2019-11-14 2024-06-25 Covestro Intellectual Property Gmbh & Co. Kg Method for coating a substrate with a drop-on-demand printer
US12036738B2 (en) 2023-06-01 2024-07-16 Chromatic 3D Materials, Inc. Manufacture of three dimensional objects from thermosets

Similar Documents

Publication Publication Date Title
EP3515255B1 (fr) Objet composite comprenant un corps et une mousse et procédé pour sa fabrication
WO2019030267A1 (fr) Procédé pour fabriquer un objet tridimensionnel présentant une partie d'objet individualisée et produite par l'intermédiaire d'une impression 3d
EP3532272B1 (fr) Procédé de traitement d'au moins une partie de la surface d'un objet imprimé en 3d
EP1338614B1 (fr) Procédé de production des elastomères de polyuréthane thermoplastiques, mous, facilement démoulables et à retrait minime
DE69923210T3 (de) Zellulares kunststoffmaterial
DE102005039933A1 (de) Verfahren zur Herstellung von thermoplastisch verarbeitbaren Polyurethanen
WO2018095967A1 (fr) Procédé pour fabriquer un objet au moins en partie recouvert
EP3083735B1 (fr) Polyuréthane thermoplastique pour applications d'étanchéité
DE102006021734A1 (de) Aliphatische, sinterfähige, thermoplastische Polyurethanformmassen mit verbessertem Ausblühverhalten
DE10103424A1 (de) Verfahren zur Herstellung von Polyisocyanat-Polyadditionsprodukten mittels Plattenreaktor
DE19800287A1 (de) Aliphatische sinterfähige thermoplastische Polyurethanformmassen mit reduzierter mechanischer Festigkeit
EP3615613B1 (fr) Procédé de fabrication additive à l'aide d'un mélange de reconstituant thermoplastique
EP3448676B1 (fr) Systeme sandwich elastomere et elements composites en metal
DE10022848A1 (de) Formkörper aus thermoplastischen Polyurethanen mit reduziertem Fogging
EP3544793A1 (fr) Procédé et système de fabrication d'un objet par construction par couches au moyen d'un procédé de poinçonnage
EP3772519A1 (fr) Procédé de production de polymères de polyuréthane thermoplastiquement façonnables
EP3562648B1 (fr) Procédé de fabrication additive d'un objet comprenant un matériau stratifié avec des couches différentes
EP3615334B1 (fr) Procédé de fabrication additive à partir de plusieurs polyuréthanes thermoplastiques
EP0452775B1 (fr) Elastomères thermoplastiques de polyuréthane-polyurée ayant une résistance élevée à la chaleur
WO2018224456A1 (fr) Biens de consommation à courte durée de vie à base de polyuréthanes thermoplastiques
DE19706452C2 (de) Verwendung von Fettsäuren zur Herstellung von thermoplastischen Polyisocyanat-Polyadditionsprodukten
EP3727858B1 (fr) Procédé d'impression tridimensionnelle en deux phases
EP0854158B1 (fr) Polyuréthanes thermoplastiques ayant des agents de démoulage incorporés
EP1078944B1 (fr) Procédé de preparation de fibres de polyurethane thermoplastique
DE19858906A1 (de) Antibackmittel enthaltendes Kunststoffelastomeres und Verfahren zu dessen Herstellung

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 18748937

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 18748937

Country of ref document: EP

Kind code of ref document: A1