Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
  • C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
• • 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
  • B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
  • B29C45/0001—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor characterised by the choice of material
• • 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
  • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
  • B29C48/022—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the choice of material
• • 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
  • B29C64/141—Processes of additive manufacturing using only solid materials
  • B29C64/153—Processes of additive manufacturing using only solid materials using layers of powder being selectively joined, e.g. by selective laser sintering or melting
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B33—ADDITIVE MANUFACTURING TECHNOLOGY
  • B33Y—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
  • B33Y70/00—Materials specially adapted for additive manufacturing
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J3/00—Processes of treating or compounding macromolecular substances
  • C08J3/12—Powdering or granulating
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
  • C08K5/0041—Optical brightening agents, organic pigments
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/16—Nitrogen-containing compounds
  • C08K5/34—Heterocyclic compounds having nitrogen in the ring
  • C08K5/3442—Heterocyclic compounds having nitrogen in the ring having two nitrogen atoms in the ring
  • C08K5/3462—Six-membered rings
  • C08K5/3465—Six-membered rings condensed with carbocyclic rings
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/16—Nitrogen-containing compounds
  • C08K5/34—Heterocyclic compounds having nitrogen in the ring
  • C08K5/35—Heterocyclic compounds having nitrogen in the ring having also oxygen in the ring
  • C08K5/357—Six-membered rings
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
  • C08K5/45—Heterocyclic compounds having sulfur in the ring
  • C08K5/46—Heterocyclic compounds having sulfur in the ring with oxygen or nitrogen in the ring
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
  • C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
  • C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
  • C09B67/0097—Dye preparations of special physical nature; Tablets, films, extrusion, microcapsules, sheets, pads, bags with dyes

Definitions

• the present invention relates to a polyamide composition (PZ) containing at least one polyamide (P) and at least one additive (A).
• the present invention also relates to the use of the polyamide composition (PZ) in a selective laser sintering process, in an injection molding process, for the production of moldings and in an extrusion process.
• plastic powders are suitable for use in a selective laser sintering process.
• plastic powder Frequently used as plastic powder are polyamides.
• some of these polyamides show an increased shrinkage or even a delay in selective laser sintering, which makes it difficult to use or further process the components obtained.
• polyamides because of their high chemical resistance and due to their good mechanical properties as a powder coating material for the production of paint-like coatings of metals. The coating takes place here, for example, by vortex sintering process, flame spraying or electrostatic coating process.
• polyamide powders which have a narrow particle size distribution, a round shape and a smooth surface.
• Polyamide powders which fulfill the abovementioned properties are readily fluidisable and therefore particularly suitable for coating processes.
• the object underlying the present invention is therefore to provide a novel polyamide composition.
• the polyamide composition should be particularly suitable for the production of moldings. This object is achieved by a polyamide composition (PZ) which contains at least one polyamide (P) and at least one additive (A), where the at least one additive (A) is selected from compounds of the general formula (I)
• R 1 and R 3 are independently selected from the group consisting of H, C to C 10 alkyl and NR 5 R 6 , wherein R 5 and R 6 are independently selected from the group consisting of H and d- to Cio-alkyl;
• R 2 and R 4 are independently selected from the group consisting of H, C to Cio-alkyl and NR 7 R 8 , wherein independently of one another are selected from the group consisting of H and Cr to Ci 0 alkyl;
• X is N, O + or S + ; wherein the compounds of general formula (I) have a positive charge when X is O + or S + and the compounds of general formula (I) then contain an anion Y " , wherein Y "is selected from the group consisting of hydroxide, chloride, bromide, iodide, sulfate, sulfite, phosphate and phosphite.
• a polyamide composition (PZ) containing at least one polyamide (P) and at least one additive (A) is suitable for use in a selective laser sintering process.
• the molded articles produced with the polyamide composition (PZ) have a significantly reduced or even no distortion.
• the polyamide composition (PZ) according to the invention is suitable for use in the selective laser sintering process, in injection molding processes and in extrusion processes.
• the molded bodies produced have improved color stability.
• the polyamide composition (PZ) when used in a selective laser sintering process, can be reused.
• the polyamide composition (PZ), which has not been melted during selective laser sintering has similarly advantageous sintering properties after several laser sintering cycles as in the first sintering cycle.
• the polyamide composition (PZ) according to the invention is explained in more detail below.
• the polyamide composition (PZ) comprises at least one polyamide (P) and at least one additive (A).
• At least one polyamide (P) is understood to mean both exactly one polyamide (P) and one mixture of two or more polyamides (P).
• At least one additive (A) in the context of the present invention means both exactly one additive (A) and one mixture of two or more additives (A).
• the polyamide composition (PZ) may contain the at least one polyamide (P) and the at least one additive (A) in any desired amounts.
• the polyamide composition (PZ) contains in the range of 95 to 99.9 wt .-% of the at least one polyamide (P) and in the range of 0.1 to 5 wt .-% of the at least one additive (A), based on the Sum of the weight percent of at least one Polyamide (P) and at least one additive (A), preferably based on the total weight of the polyamide composition (PZ).
• the polyamide composition (PZ) particularly preferably contains in the range from 97.5 to 99.5% by weight of the at least one polyamide (P) and in the range from 0.5 to 2.5% by weight of the at least one additive (A ), in each case based on the sum of the weight percentages of the at least one polyamide (P) and the at least one additive (A), preferably based on the total weight of the polyamide composition (PZ).
• the polyamide composition (PZ) contains in the range of 99 to 99.5 weight percent of the at least one polyamide (P) and in the range of 0.5 to 1 weight percent of the at least one additive (A), respectively based on the sum of the percentages by weight of the at least one polyamide (P) and the at least one additive (A), preferably based on the total weight of the polyamide composition (PZ).
• the present invention thus also provides a polyamide composition (PZ) in which the polyamide composition (PZ) is in the range from 95 to 99.9% by weight of the at least one polyamide (P) and in the range from 0.1 to 5% by weight. % of the at least one additive (A), in each case based on the sum of the percentages by weight of the at least one polyamide (P) and of the at least one additive (A).
• the polyamide composition (PZ) may be in any form.
• the polyamide composition (PZ) is present as a powder.
• the polyamide composition (PZ) is present as a powder having a particle size in the range from 1 to 200 ⁇ m, more preferably in the range from 10 to 150 ⁇ m, and most preferably in the range from 20 to 120 ⁇ m.
• the present invention thus also provides a polyamide composition (PZ) in which the polyamide composition (PZ) is present as a powder having a particle size in the range from 1 to 200 ⁇ m.
• the polyamide composition (PZ) has a D10 value in the range of 10 to 30 ⁇
• the polyamide composition (PZ) particularly preferably has a D10 value in the range from 10 to 30 ⁇ m
• D10 value in this context means the particle size at which 10% by volume of the particles, based on the total volume of the particles, is less than or equal to the D10 value and 90% by volume of the particles Particles, based on the total volume of the particles, are greater than the D10 value.
• D50 value is understood as meaning the particle size, in which 50% by volume of the particles, based on the total volume of the particles, is smaller or equal are D50 value and 50% by volume of the particles, based on the total volume of the particles, are greater than the D50 value.
• the "D90 value” is understood to mean the particle size at which 90% by volume of the particles, based on the total volume of the particles, are less than or equal to the D90 value and 10% by volume of the particles on the total volume of particles are greater than the D90 value.
• the polyamide composition (PZ) is suspended by means of compressed air or in a solvent such as water or ethanol, and the suspension is measured.
• the D10, D50 and D90 values are determined by means of laser diffraction using a Mastersizer 2000 from Malvern, the evaluation being carried out using Mie theory and Fraunhofer approximation.
• the polyamide composition (PZ) can contain, in addition to the at least one polyamide (P) and the at least one additive (A), further additives (wA).
• the polyamide composition (PZ) may, for example, in the range of 0.1 to 60 wt .-% further additives (wA), based on the total weight of the polyamide composition (PZ).
• the polyamide composition (PZ) preferably contains in the range from 0.25 to 40% by weight of further additives (wA), particularly preferably in the range from 0.3 to 30% by weight, in each case based on the total weight of the polyamide composition (PZ).
• the present invention thus also provides a polyamide composition (PZ) in which the polyamide composition (PZ) in the range from 0.1 to 60 wt .-% further additives (wA), based on the total weight of the polyamide composition (PZ). It goes without saying that if the polyamide composition (PZ) contains further additives (wA), the weight percent of the at least one polyamide (P) contained in the polyamide composition (PZ) correspondingly reduce, so that the sum of the wt .-% of the at least one polyamide (P), the at least one additive (A) and the other additives (wA) add to 100%.
• the polyamide composition contains, for example, in the range from 35 to 99.8% by weight of the at least one polyamide (P), in the range from 0.1 to 5% by weight of the at least one additive (A) and in the range of 0.1 to 60 wt .-% of the further additives (wA), each based on the sum of the weight percent of the at least one polyamide (P), the at least one additive (A) and further additives (wA), preferably based on the total weight of the polyamide composition (PZ).
• the polyamide composition contains, for example, in the range from 35 to 99.8% by weight of the at least one polyamide (P), in the range from 0.1 to 5% by weight of the at least one additive (A) and in the range of 0.1 to 60 wt .-% of the further additives (wA), each based on the sum of the weight percent of the at least one polyamide (P), the at least one additive (A) and further additives (wA), preferably based on the total weight of the polyamide composition
• the polyamide composition (PZ) preferably contains in the range from 57.5 to 99.0% by weight of the at least one polyamide (P), in the range from 0.5 to 2.5% by weight of the at least one additive (A). and in the range from 0.25 to 40% by weight of the further additives (wA), in each case based on the sum of the percentages by weight of the at least one polyamide (P), of the at least one additive (A) and of the further additives (wA), preferably based on the total weight of the polyamide composition (PZ).
• the polyamide composition (PZ) contains in the range of 69 to 99.2 weight percent of the at least one polyamide (P), in the range of 0.5 to 1 weight percent of the at least one additive (A) and in the Range of 0.3 to 30 wt .-% of the further additives (wA), in each case based on the sum of the weight percent of the at least one polyamide (P), the at least one additive (A) and the other additives (wA), preferably based on the total weight of the polyamide composition (PZ).
• the weight% of the at least one polyamide (P) contained in the polyamide composition (PZ), of the at least one additive (A) and of the further additives (wA) optionally present usually add up to 100%.
• Suitable further additives (wA) are known to those skilled in the art.
• the further additives (wA) are selected from the group consisting of stabilizers, dyes, pigments, fillers, reinforcing agents, impact modifiers and plasticizers.
• the present invention thus also provides a polyamide composition (PZ) which comprises further additives (wA), the other additives (wA) being selected from the group consisting of stabilizers, Dyes, pigments, fillers, reinforcing agents, impact modifiers and plasticizers.
• Suitable stabilizers are, for example, phenol, talc, alkaline earth silicates, sterically hindered phenols, phosphites and alkaline earth glycerophosphates.
• Suitable dyes and pigments are, for example, transition metal oxides or nigrosines.
• Suitable fillers are, for example, glass beads, glass fibers, kaolin, wollastonite, muscovite, phlogopite, carbon fibers, carbon nanotubes and chalk.
• Suitable impact modifiers are, for example, polymers based on ethylene-propylene (EPM) or ethylene-propylene-diene (EPDM) rubbers or thermoplastic urethanes, and ionomers or styrene-based rubbers.
• EPM ethylene-propylene
• EPDM ethylene-propylene-diene
• Suitable polyamides (P) generally have a viscosity number of from 70 to 350 ml / g, preferably from 70 to 240 ml / g.
• the determination of the viscosity number is carried out according to the invention from a 0.5 wt .-% solution of the polyamide (P) in 96 wt .-% sulfuric acid at 25 ° C according to ISO 307th
• polyamides (P) semicrystalline polyamides are preferred. Suitable polyamides (P) have a weight-average molecular weight (M w ) in the range from 500 to 2,000,000 g / mol, preferably in the range from 5,000 to 500,000 g / mol and particularly preferably in the range from 10,000 to 100,000 g / mol, up. The weight average molecular weight (M w ) is determined according to ASTM D4001.
• polyamides (P) for example, polyamides (P) are suitable, which are derived from lactams with 7 to 13 ring members.
• polyamides (P) polyamides (P) are also suitable, which are obtained by reacting dicarboxylic acids with diamines.
• polyamides (P) derived from lactams include polyamides derived from polycaprolactam, polycapryl lactam and / or polylaurolactam.
• polyamides (P) are obtainable from ⁇ -aminoalkylnitriles.
• Preferred ⁇ -aminoalkyl nitrile is aminocapronitrile, which leads to polyamide 6.
• dinitriles can be reacted with diamine.
• Adiponitrile and hexamethylenediamine are preferred, the polymerization of which leads to polyamide 66.
• the Polymerization of nitriles occurs in the presence of water and is also referred to as direct polymerization.
• dicarboxylic acid alkanes aliphatic dicarboxylic acids
• aromatic dicarboxylic acids are suitable.
• adipic acid, azelaic acid, sebacic acid, dodecanedioic acid and also terephthalic acid and / or isophthalic acid may be mentioned here as dicarboxylic acids.
• Suitable diamines are, for example, alkanediamines having 4 to 36 carbon atoms, preferably alkanediamines having 6 to 12 carbon atoms, in particular alkanediamines having 6 to 8 carbon atoms and aromatic diamines, for example m-xylylenediamine, di (4-aminophenyl) methane, di- (4 -aminocyclohexyl) methane, 2,2-di- (4-aminophenyl) -propane and 2,2-di- (4-aminocyclohexyl) -propane and 1, 5-diamino-2-methyl-pentane.
• Preferred polyamides (P) are polyhexamethylene adipamide, polyhexamethylene sebacamide and polycaprolactam and copolyamide 6/66, in particular with a content of 5 to 95% by weight of caprolactam units.
• polyamides (P) which are obtainable by copolymerization of two or more of the monomers mentioned above and below, or mixtures of several polyamides (P), the mixing ratio being arbitrary. Particularly preferred mixtures are mixtures of polyamide 66 with other polyamides (P), in particular copolyamide 6/66.
• Suitable polyamides (P) are thus aliphatic, partially aromatic or aromatic polyamides (P).
• aliphatic polyamides means that the polyamides (P) are exclusively composed of aliphatic monomers
• partially aromatic polyamides means that the polyamides (P) are composed of both aliphatic and aromatic monomers.
• aromatic polyamides means that the polyamides (P) are composed exclusively of aromatic monomers.
• PA 46 tetramethylenediamine, adipic acid
• PA 66 hexamethylenediamine, adipic acid
• PA 69 hexamethylene diamine, azelaic acid
• PA 610 hexamethylenediamine, sebacic acid
• PA 612 hexamethylenediamine, decanedicarboxylic acid
• PA 613 hexamethylenediamine, undecanedicarboxylic acid
• PA 1212 1, 12-dodecanediamine, decanedicarboxylic acid
• PA 1313 1, 13-diaminotridecane, undecanedicarboxylic acid
• PA 6T hexamethylenediamine, terephthalic acid
• PA MXD6 m-xylyenediamine, adipic acid
• PA 6I hexamethylenediamine, isophthalic acid
• PA 6-3-T trimethylhexamethylenediamine, terephthalic acid
• PA 6 / 6T (see PA 6 and PA 6T)
• PA 6/66 (see PA 6 and PA 66)
• PA 6/12 see PA 6 and PA 12
• PA 66/6/610 see PA 66, PA 6 and PA 610)
• PA 6I / 6T see PA 61 and PA 6T
• PA PA PACM 12 diaminodicyclohexylmethane, laurolactam
• PA 6I / 6T / PACM such as PA 6I / 6T and diaminodicyclohexylmethane
• PA 12 / MACMI laurolactam dimethyldiaminodicyclohexylmethane, isophthalic acid
• PA 12 / MACMT laurolactam dimethyldiaminodicyclohexylmethane, terephthalic acid
• the present invention thus also provides a polyamide composition (PZ) in which the at least one polyamide (P) is selected from the group consisting of PA 4, PA 6, PA 7, PA 8, PA 9, PA 1 1, PA 12 , PA 46, PA 66, PA 69, PA 510, PA 610, PA 612, PA 613, PA 1212, PA 1313, PA 6T. PA MXD6.
• the at least one polyamide (P) is selected from the group consisting of polyamide 6 (PA 6), polyamide 66 (PA 66), polyamide 6/66 (PA 6/66), polyamide 66/6 (PA 66/6) , Polyamide 610 (PA 610), Polyamide 6 / 6T (PA 6 / 6T), Polyamide 12 (PA12) and Polyamide 1212 (PA1212).
• Particularly preferred polyamide (P) are polyamide 6 (PA 6) and / or polyamide 66 (PA 66), polyamide 6 (PA 6) being particularly preferred.
• the present invention thus also provides a polyamide composition (PZ) in which the at least one polyamide (P) is selected from the group consisting of polyamide 6 (PA 6), polyamide 66 (PA 66), polyamide 6/66 (PA 6 / 66), polyamide 66/6 (PA 66/6), polyamide 610 (PA 610), polyamide 6 / 6T (PA 6 / 6T), polyamide 12 (PA12) and polyamide 1212 (PA1212).
• PZ polyamide composition in which the at least one polyamide (P) is selected from the group consisting of polyamide 6 (PA 6), polyamide 66 (PA 66), polyamide 6/66 (PA 6 / 66), polyamide 66/6 (PA 66/6), polyamide 610 (PA 610), polyamide 6 / 6T (PA 6 / 6T), polyamide 12 (PA12) and polyamide 1212 (PA1212).
• the at least one additive (A) is selected from compounds of the general formula (I) in which
• R 1 and R 3 are independently selected from the group consisting of
• R 5 and R are independently selected from the group consisting of H and d- to Ci 0 alkyl;
• R 2 and R 4 are independently selected from the group consisting of
• R 7 and R 8 are independently selected from the group consisting of H and Cr to Ci 0 alkyl;
• X is N, O + or S + ; wherein the compounds of general formula (I) have a positive charge when X is O + or S + and the compounds of general formula (I) then contain an anion Y " , wherein
• Y is selected from the group consisting of hydroxide, chloride, bromide, iodide, sulfate, sulfite, phosphate and phosphite It will be apparent to those skilled in the art that when the compounds of general formula (I) have a positive charge, that in the formula (I) anion " generally compensates for the positive charge. This means, for example, when the compound of the general formula (I) has a positive charge and the anion Y "is chloride, the positive charge of the general formula (I) and the negative charge of the anion Y " balance each other.
• the anion Y is, for example, phosphate
• the anion carries a triply negative charge
• One of the charges balances the positive charge of the compound of general formula (I)
• the remainder Both of the negative charges balance the positive charges of other compounds of general formula (I), as known to those skilled in the art.
• R 1 and R 3 are independently selected from the group consisting of
• R and R are independently selected from the group consisting of
• R 7 and R 8 are independently selected from the group consisting of H and C 1 to C 5 alkyl
• N or S + means; wherein the compounds of general formula (I) have a positive charge when XS + means and the compounds of general formula (I) then contain an anion Y " , wherein Y "is selected from the group consisting of hydroxide, chloride, bromide, iodide.
• the present invention therefore also provides a polyamide composition (PZ) in which the substituents of the compounds of the general formula (I) have the following meaning:
• R 1 and R 3 are independently selected from the group consisting of H and C 1 to C 5 alkyl
• R 2 and R 4 are independently selected from the group consisting of C 1 to C 5 alkyl and NR 7 R 8 , wherein independently of one another are selected from the group consisting of H and Cr to C 5 alkyl;
• X is N or S + , wherein the compounds of general formula (I) have a positive charge when XS + means and the compounds of general formula (I) then contain an anion Y " , wherein
• Y is selected from the group consisting of hydroxide, chloride, bromide and iodide
• hydroxide OH under chloride CI " , under bromide Br “ , under iodide, under sulfate S0 4 2 “ , with sulfite S0 3 2 “ , under phosphate P0 4 3” and under phosphite P0 3 3 " understood.
• C 1 -C 10 -alkyl denotes saturated and unsaturated, preferably saturated, hydrocarbons having a free valency (radical) and from 1 to 10 carbon atoms.
• the hydrocarbons may be linear or cyclic, preferably linear. It is also possible that they contain a cyclic and a linear component. Examples of such alkyl groups are methyl, ethyl, N-propyl, N-butyl, hexyl and cyclohexyl. Corresponding statements also apply to C 1 to C 1 alkyl.
• the at least one additive (A) is selected from the group consisting of compounds of formula (II) and the formula
• the compound of formula (II) is a dye, also referred to as methylene blue.
• Other names are ⁇ , ⁇ , ⁇ ', ⁇ '-tetramethylenethionine chloride and Basic Blue 9 (Color Index 52015, CAS numbers 61-73-4 and 122965-43-9 (hydrate)).
• the compound of formula (III) is a dye, also referred to as neutral red.
• Neutral red is also known under the name 3-amino-7-dimethylamino-2-methylphenazine hydrochloride or toluene red (Color Index 50040, CAS number 553-24-2).
• the at least one additive is therefore selected from the group consisting of neutral red and methylene blue.
• the present invention therefore also provides a polyamide composition (PZ) in which the at least one additive (A) contained is selected from the group consisting of neutral red and methylene blue.
• the polyamide composition (PZ) can be prepared by all methods known to those skilled in the art.
• It is preferably prepared by compounding or by precipitation.
• the at least one polyamide (P), the at least one additive (A) and optionally the further additives (wA) can be compounded in an extruder and then extruded from this, optionally followed by strand granulation.
• the at least one polyamide (P), the at least one additive (A) and optionally the further additives (wA) can be ground to obtain the polyamide composition (PZ) in the form of a powder.
• Methods for grinding the polyamide composition (PZ) are known to those skilled in the art.
• the polyamide composition (PZ) can be placed in a mill and ground.
• Suitable mills are all mills known to the person skilled in the art, for example classifier mills, counter-jet mills, hammer mills, ball mills, vibrating mills and rotor mills.
• Grinding in the mill can likewise be carried out by all methods known to the person skilled in the art, for example the grinding can take place under inert gas and / or under cooling with liquid nitrogen. Cooling under liquid nitrogen is preferred.
• the temperature during grinding is arbitrary.
• the milling is carried out at temperatures of liquid nitrogen, for example at a temperature in the range of -210 ° C to -195 ° C.
• the at least one polyamide (P) is usually mixed with a solvent (LM) and the at least one polyamide (P) is dissolved, if appropriate, with heating in the solvent (LM) to obtain a polyamide solution ( PL).
• the polyamide (P) can be partially or completely dissolved in the solvent (LM).
• the polyamide (P) is completely dissolved in the solvent (LM).
• a polyamide solution (PL) is preferably obtained which contains the at least one polyamide (P) completely dissolved in the solvent (LM).
• the at least one additive (A) and optionally the further additives (wA) are added to the mixture of the at least one polyamide (P) and the solvent (LM).
• the time of addition of the at least one additive (A) and optionally the other additives (wA) is irrelevant. However, the addition generally takes place before the precipitation of the polyamide composition (PZ).
• the at least one additive (A) and optionally the further additives (wA) can be added to the solvent (LM) before the at least one polyamide (P) is mixed with the solvent (LM). It is also possible, the at least one additive (A) and optionally the other additives (wA) to the mixture of the at least one polyamide (P) and the solvent (LM) before the at least one polyamide (P) is dissolved in the solvent (LM). It is likewise possible to add the at least one additive (A) and optionally the further additives (wA) to the polyamide solution (PL).
• the polyamide solution (PL) contains the at least one additive (A) usually dissolved.
• the at least one additive (A) may be completely dissolved in the polyamide solution (PL), it is also possible that the at least one additive A) is partially dissolved in the polyamide solution (PL).
• the at least one additive (A) is completely dissolved in the polyamide solution (PL).
• the further additives (wA) may be partially or completely dissolved in the polyamide solution (PL). It is also possible that they are suspended in the polyamide solution (PL). If the other additives (wA) are suspended in the polyamide solution (PL), the polyamide solution (PL), the dispersant (continuous phase) and the other additives (wA) form the disperse phase. It goes without saying that it is also possible for part of the further additives (wA) to be present dissolved in the polyamide solution (PL) and for another part of the further additives (wA) to be suspended in the polyamide solution (PL).
• the polyamide composition (PZ) from the polyamide solution (PL) containing the at least one additive (A) and optionally further additives (wA) are precipitated.
• the precipitation can be carried out by all methods known to the person skilled in the art.
• the polyamide composition (PZ) may be precipitated by cooling the polyamide solution (PL) containing the at least one additive (A) and optionally the other additives (wA), the solvent (LM) from the polyamide solution (PL). , which is distilled off the at least one additive (A) and optionally further additives (wA), or a precipitant (FM) to the polyamide solution (PL), the at least one additive (A) and optionally the other additives (wA) contains, is given.
• the polyamide composition (PZ) is precipitated by cooling the polyamide solution (PL) containing the at least one additive (A).
• solvent As solvent (LM) exactly one solvent can be used. It is also possible to use two or more solvents as the solvent (LM). Suitable solvents (LM) are for example selected from the group consisting of alcohols, lactams and ketones. Preferably, the solvent (LM) is selected from the group consisting of alcohols and lactams. According to the invention, lactam is generally understood to mean cyclic amides which contain 3 to 12 carbon atoms, preferably 4 to 6 carbon atoms, in the ring.
• Suitable lactams are, for example, selected from the group consisting of propio-3-lactam ( ⁇ -lactam, ⁇ -propiolactam), butyro-4-lactam ( ⁇ -lactam, ⁇ -butyrolactam), 2-piperidinone, ( ⁇ -lactam, ⁇ -Valerolactam), hexano-6-lactam ( ⁇ -lactam; ⁇ -caprolactam), heptano-7-lactam ( ⁇ -lactam; ⁇ -heptanolactam), octano-8-lactam ( ⁇ -lactam; ⁇ -octanolactam), nonano -9-lactam ( ⁇ -lactam; ⁇ -nonanolactam), decano-10-lactam ( ⁇ -decanolactam), undecano-1 1-lactam ( ⁇ -undecanolactam) and dodecano-12-lactam ( ⁇ -dodecan
• the lactams may be unsubstituted or at least monosubstituted. In the event that at least monosubstituted lactams are used, these may carry on the nitrogen atom and / or on the carbon atoms of the ring one, two or more substituents which are independently selected from the group consisting of C 1 -C 10 -alkyl, C 5 - to C 6 -cycloalkyl and C 5 - to C 0 -aryl.
• Cio-alkyl substituents for example, methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl and tert-butyl are suitable.
• a suitable C 5 - to C 6 -cycloalkyl substituent is, for example, cyclohexyl.
• Preferred C 5 to Cio-aryl substituents are phenyl and anthranyl.
• Unsubstituted lactams are preferably used, with ⁇ -lactam ( ⁇ -butyrolactam), ⁇ -lactam ( ⁇ -valerolactam) and ⁇ -lactam ( ⁇ -caprolactam) being preferred. Particularly preferred are ⁇ -lactam ( ⁇ -valerolactam) and ⁇ -lactam ( ⁇ -caprolactam), with ⁇ -caprolactam being particularly preferred.
• the solvent (LM) preferably contains at least 20% by weight of lactam, more preferably at least 25% by weight of lactam, more preferably at least 30% by weight of lactam and most preferably at least 40% by weight of lactam, based in each case on Total weight of the solvent (LM).
• the solvent (LM) is lactam.
• the solvent (LM) contain less than 80% by weight of water, more preferably less than 75% by weight of water, more preferably less than 70% by weight of water, and most preferably less than 60% by weight .-% water, each based on the total weight of the solvent (LM).
• the lower limit of the water content of the solvent (LM) is generally in the range of 0 to 0.5 wt .-%, preferably in the range of 0 to 0.3 wt .-%, particularly preferably in the range of 0 to 0.1 wt .-%, in each case based on the total weight of Lösunasstoffs (LM).
• the at least one polyamide (P) can be dissolved at any temperature in the solvent (LM).
• the at least one polyamide (P) is dissolved with heating in the solvent (LM).
• the dissolution temperature is in the range of 80 to 200 ° C, preferably in the range of 90 to 190 ° C, and more preferably in the range of 120 to 180 ° C.
• the polyamide solution (PL) containing the at least one additive (A) and optionally the other additives (wA) are cooled by all methods known in the art.
• the polyamide solution (PL) containing the at least one additive (A) and optionally the other additives (wA) can be cooled to any desired temperature.
• the polyamide solution (PL), which contains the at least one additive (A) and optionally the other additives (wA) to a temperature in the range of 20 to 80 ° C, particularly preferably in the range of 20 to 75 ° C, cooled ,
• the temperature at which the polyamide solution (PL) containing the at least one additive (A) and optionally the other additives (wA) is cooled is below the temperature at which the polyamide (P ) is dissolved in the solvent (LM).
• the polyamide solution (PL) may be stirred during the cooling, for example produce fine particles of the polyamide composition (PZ).
• the polyamide composition (PZ) contains the at least one polyamide (P) and the at least one additive (A) and optionally further additives (wA).
• the polyamide composition (PZ) may contain the at least one polyamide (P) in addition to the at least one additive (A) and optionally further additives (wA). It is likewise possible for the at least one polyamide (P) to be at least partially coated with the at least one additive (A) and, if appropriate, the further additives (wA).
• the polyamide (P) is first dissolved in the solvent (LM) to obtain a solution.
• the dissolution can be carried out by all methods known to those skilled in the art, for example as described above, although preferably the at least one additive (A) is not added.
• the polyamide (P) is precipitated from the solution and dried to obtain a powder of Polyamide (P). Suitable for precipitation are all methods known to the person skilled in the art, for example those described above for the polyamide solution (PL).
• the obtained powder of the polyamide (P) is then contacted with a solution of the at least one additive (A) and then dried to obtain the sintering powder (SP).
• Suitable solvents in the solution of the at least one additive (A) are all solvents known to those skilled in the art which dissolve the at least one additive (A) and which preferably poorly or not at all dissolve the polyamide (P), for example water and / or alcohols .
• the polyamide composition (PZ) according to the invention can be used for the production of moldings.
• the present invention thus also relates to the use of the polyamide composition (PZ) according to the invention for the production of moldings.
• the shaped bodies can be produced by all methods known to the person skilled in the art. For example, by a selective laser sintering process, an injection molding process or by an extrusion process. These methods are known to those skilled in the art.
• the present invention thus also relates to the use of the polyamide composition (PZ) according to the invention in an injection molding process.
• the present invention furthermore relates to the use of the polyamide composition (PZ) according to the invention in an extrusion process.
• the polyamide composition (PZ) according to the invention can be used in any extrusion process known to the person skilled in the art. For example, for the production of semi-finished products, films or blow molding.
• the present invention therefore also relates to the use of the polyamide composition (PZ) according to the invention in a blow molding process.
• the present invention furthermore relates to the use of the polyamide composition (PZ) according to the invention in an extrusion process for the production of semi-finished products.
• the present invention furthermore relates to the use of the polyamide composition (PZ) according to the invention in a film extrusion process.
• the present invention furthermore relates to the use of the polyamide composition (PZ) according to the invention in a selective laser sintering process.
• a first layer of a sinterable powder is arranged in a powder bed and exposed locally and briefly with a laser beam.
• a laser beam In this case, only the part of the sinterable powder which has been exposed by the laser beam, selectively melted (selective laser sintering).
• the molten sinterable powder flows into one another and thus forms a homogeneous melt in the exposed area.
• the area cools down again and the sinterable powder solidifies again.
• the powder bed is lowered by the layer thickness of the first layer, a second layer of the sinterable powder applied, selectively exposed to the laser and melted.
• the upper second layer of the sinterable powder connects to the lower first layer, and in addition the particles of the sinterable powder within the second layer combine with one another by melting.
• the application of the sinterable powder and the melting of the sinterable powder three-dimensional molded bodies can be produced.
• By the selective exposure of certain points with the laser beam it is possible to produce molded bodies which, for example, also have cavities.
• An additional support material is not necessary because the unmelted sinterable powder itself acts as a support material.
• Suitable sinterable powders in selective laser sintering are all powders known to those skilled in the art which can be melted by exposure to a laser.
• the polyamide composition (PZ) is used as the sinterable powder in selective laser sintering.
• the polyamide composition (PZ) is then used as a sintering powder, which may also be referred to as a sinterable powder.
• the present invention therefore also relates to the use of the polyamide composition (PZ) according to the invention as a sintering powder.
• Suitable lasers for selective laser sintering are known to the person skilled in the art and, for example, fiber lasers, Nd: YAG lasers (neodymium-doped yttrium aluminum garnet lasers) and carbon dioxide lasers.
• the sinterable powder is the polyamide composition (PZ) according to the invention
• the sintering window (W) is used as “sintered window” in the context of the present invention (W S P) "of the polyamide composition (PZ).
• the sinterable powder is the at least one polyamide (P) contained in the polyamide composition (PZ)
• the sintering window (W) is referred to as the "sintered window (W P )" of the at least one polyamide (P) in the context of the present invention.
• the sintering window (W) of a sinterable powder can be determined, for example, by differential scanning calorimetry (DSC).
• the temperature of a sample in this case a sample of the sinterable powder, and the temperature of a reference are changed linearly with time.
• the sample and the reference are supplied with heat or removed therefrom. It determines the amount of heat Q necessary to keep the sample at the same temperature as the reference.
• the reference value used is the quantity of heat Q R supplied or discharged to the reference.
• the measurement provides a DSC diagram in which the amount of heat Q, which is supplied to the sample and discharged from it, is plotted as a function of the temperature T.
• a heating run is first carried out during the measurement, that is, the sample and the reference are heated linearly.
• an additional amount of heat Q must be supplied to keep the sample at the same temperature as the reference.
• a peak is then observed, the so-called AufschmelzDeak.
• a cooling run K is usually measured.
• the sample and the reference are cooled linearly, so heat is dissipated from the sample and the reference.
• a larger amount of heat Q must be dissipated to keep the sample at the same temperature as the reference, since heat is released during crystallization or solidification.
• a peak the so-called crystallization peak, is then observed in the opposite direction to the melting peak.
• Such a DSC diagram with a heating run (H) and a cooling run (K) is shown by way of example in FIG.
• the onset temperature of the melting (T M onset ) and the onset temperature of the crystallization (T c onset ) can be determined.
• T M onset To determine the onset temperature of the reflow (T M onset ), a tangent is applied to the baseline of the heating run (H), which runs at the temperatures below the melting peak. A second tangent is applied to the first inflection point of the reflow peak, which at temperatures below the temperature is at the maximum of the reflow peak. The two tangents are extrapolated to intersect. The vertical extrapolation of the point of intersection to the temperature axis indicates the onset temperature of the melting (T M onset ). To determine the onset temperature of the crystallization (T c onset ), a tangent is applied to the baseline of the cooling run (K), which runs at the temperatures above the Knstallisationspeaks.
• a second tangent is applied at the inflection point of the crackling peak, which at temperatures above the temperature is at the minimum of the crackling peak.
• the two tangents are extrapolated to intersect.
• the vertical extrapolation of the point of intersection to the temperature axis indicates the onset temperature of the crystallization (T c onset ).
• the sintering window (W) results from the difference between the onset temperature of the melting (T M onset ) and the onset temperature of the crystallization (T c onset ). The following applies: onset onset
• the terms "sintering window (W)", “size of the sintering window (W)” and “difference between the onset temperature of the Melting (T M onset ) and the onset temperature of crystallization (T c onset ) "the same meaning and are used synonymously.
• the determination of the sintering window (W S P) of the polyamide composition (PZ) and the determination of the sintering window (W P ) of the at least one polyamide (P) are carried out as described above.
• the polyamide composition (PZ) is then used as a sample for determining the sintering window (W S P) of the polyamide composition (PZ); for determining the sintering window (W P ) of the at least one polyamide (P), the at least one polyamide (P) is used as a sample used.
• Table 1 indicates whether the sintered powder has been prepared by precipitation or by grinding.
• the components shown in Table 1 were in the ratio shown in Table 1 in a twin-screw extruder (ZSK 40) at a speed of 200 U / min, a cylinder temperature of 240 ° C and a throughput of 50 kg / h compounded with a subsequent strand granulation.
• the granules thus obtained were cryogenically ground to obtain the sintered powder (SP).
• the polyamide (P) in the amounts shown in Table 1 at a temperature ramp of 2 hours at 120 ° C, 2 hours at 160 ° C and 0.5 hours at 175 ° C in a solvent consisting of 40 wt .-% caprolactam and 60 wt .-% water, in each case based on the total weight of the solvent, dissolved and then precipitated by cooling. After washing with water and drying, the polyamide (P) was obtained as a powder. Subsequently, the thus obtained powder of the polyamide (P) was contacted with a solution of the additive (A) using the polyamide (P) and the additive (A) in the ratio shown in Table 1. As the solvent in the solution of the additive (A), water was used. After drying, the sintered powder (SP) was obtained.
• the onset temperature of the melting (T M °) and the onset temperature of the crystallization (T c onset ) of the sintering powder were determined as described for FIG. From this, the sintering window (W) was determined.
• the sintering powders were introduced with a layer thickness of 0.1 mm into the installation space at the temperature indicated in Table 2. Subsequently, the sintering powder was exposed to a laser at the laser power indicated in Table 2 and the specified dot pitch, with the speed of the laser above the sample during exposure being at the value indicated in Table 2.
• the dot pitch is also referred to as laser track pitch or track pitch. In selective laser sintering, scanning is usually done in stripes. The dot spacing indicates the distance between the centers of the stripes, ie between the two centers of the laser beam of two stripes. Table 2
• the sintered rod with the concave side was placed on a planar surface. Subsequently, the distance (a m ) between the planar surface and the upper edge of the center of the sintering rod was determined. In addition, the thickness (d m ) in the middle of the sintering bar was determined. The delay in% is then determined according to the following formula:
• V 100 - (a m -d m ) / d m
• the dimension of the sintered rods was usually 80 mm in length, 10 mm in width and 4 mm in thickness.
• Table 3 shows the results of sintering window (W) and draft measurement.

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