Granted Patent B2

US 12,612,511 · App. 17/639,606 · Granted Apr 28, 2026

Inventors: David McCann (Geleen, NL); Joanna Marguier (Geleen, NL); Sebastian Hörold (Geleen, NL)

Assignee: Stratasys, Inc.

C08K5/5313B29C64/118B29C64/153B33Y10/00B33Y70/00B33Y70/10C08K3/016C08K3/22C08K3/32C08K3/40C08K7/14B29K2077/00B29K2105/0026B29K2105/06B29K2995/0016C08K2003/2227C08K2003/321C08K2003/328C08K5/0066C08L2201/02

Abstract

Claims (60)

1 . A thermoplastic mass usable for 3D printing comprising:

(A) 55 to 80% by weight of component A;

(B) 13% by weight of component B;

(C) 7% by weight of component C;

(D) 10 to 25% by weight of component D; and

(E) 0.1 to 1% by weight of component E;

wherein component A comprises a polyamide;

wherein component B comprises a non-halogenated organic flame retardant selected from the group consisting of a dialkylphosphinic salt of the formula (I), a diphosphinic salt of the formula (II), or a combination thereof,

in which

R 1 and R 2 are identical or different and are C 1 -C 6 -alkyl, linear or branched or H; R 3 is C 1 -C 10 -alkylene, linear or branched, C 6 -C 10 -arylene, C 7 -C 20 -alkylarylene, or C 7 -C 20 -arylalkylene;

M is selected from the group consisting of Sb, Sn, Ge, Fe, Zr, Ce, Bi, Sr, Mn, Li, Na, K, and a protonated nitrogen base;

m is from 1 to 4;

n is from 1 to 4; and

x is from 1 to 4;

wherein component C comprises a particulate inorganic flame retardant selected from the group consisting of particulate zinc phosphate complex, Al(OH)O, zinc oxide/phosphate complex, basic zinc phosphate complex, calcium zinc molybdate complex, and mixtures of two or more thereof;

wherein component D comprises a reinforcing or filler material;

wherein component E comprises at least one aromatic di- or tricarboxylic ester/amide; and at least one stabilizer having a CAS number selected from the group consisting of 119345-01-6, 2082-79-3, 6683-19-8, 32509-66-3, 90498-90-1, 40601-76-1, 27676-62-6, 10191-41-0, 10081-67-1, 181314-48-7, 143925-92-2, 31570-04-4, 26741-53-7, 693-36-7, 2500-88-1, 1843-05-6, 25973-55-1, 05.11.3896, 147-75-9, 3864-99-1, 2440-22-4, 155633-54-8, 70321-86-7, 2725-22-6, 147315-50-2, 14516-71-3, 2403-88-5411, 52829-07-9, 167078-06-0 (24860-22-8), 124172-53-8, 65447-77-0, 71878-19-8 (70624-18-9), 82451-48-7, 106990-43-6, and combinations thereof;

wherein the thermoplastic mass is in the form of a spooled filament used for 3D printing;

wherein the thermoplastic mass has a surface flammability ≤25 and not less than 8; and

wherein the thermoplastic mass has a specific optical density ≤165 and not less than 94.

2 . The thermoplastic mass of claim 1 , wherein component A comprises PA6/6.6, PA6, PA6.6, PA4.6, PA12, PA6.10, PA6T/66, PA6T/6, PA6T, PA4T, PAST, PA10T, copolymers of two or more thereof, or blends of two or more thereof.

3 . The thermoplastic mass of claim 2 , wherein component A is recycled.

4 . The thermoplastic mass of claim 1 , wherein component C comprises Al(OH)O.

5 . The thermoplastic mass of claim 1 , wherein component D comprises:

(a) a reinforcing fiber material;

(b) a filler material; or

(c) a combination of (a) and (b).

6 . The thermoplastic mass of claim 5 , wherein the reinforcing fiber material possesses a mean fiber length and/or a mean fiber diameter, wherein the mean fiber length is less than or equal to 10 mm; and/or

the mean fiber diameter is from 1 to 20 μm.

7 . The thermoplastic mass of claim 1 , comprising:

(A) 59.4% by weight of component A;

(B) 13% by weight of component B;

(C) 7% by weight of component C;

(D) 20% by weight of component D; and

(E) 0.6% by weight of component E.

8 . The thermoplastic mass of claim 1 , comprising:

(A) 55 to 78.9% by weight of at least one polyamide (PA) component selected from the group consisting of PA6/6.6, PA6, PA6.6, PA4.6, PA12, PA6.10, PA6T/66, PA6T/6, PA6T, PA4T, PAST, PA10T, copolymers of two or more thereof, and blends of two or more thereof;

(B) 13% by weight of at least one phosphinate-based flame retardant selected from the group consisting of a dialkylphosphinic salt of the formula (I), a diphosphinic salt of the formula (II), or a combination thereof,

in which

R 1 and R 2 are identical or different and are C 1 -C 6 -alkyl, linear or branched or H; R 3 is C 1 -C 10 -alkylene, linear or branched, C 6 -C 10 -arylene, C 7 -C 20 -alkylarylene, or C 7 -C 20 -arylalkylene;

M is selected from the group consisting of Sb, Sn, Ge, Fe, Zr, Ce, Bi, Sr, Mn, Li, Na, K, and a protonated nitrogen base;

m is from 1 to 4;

n is from 1 to 4; and

x is from 1 to 4;

(C) 7% by weight of the particulate inorganic flame retardant;

(D) 10 to 25% by weight of at least one reinforcing or filler material; and

(E) 0.1 to 1% by weight of at least one aromatic di- or tricarboxylic ester/amide; and

at least one stabilizer having a CAS number selected from the group consisting of 119345-01-6, 2082-79-3, 6683-19-8, 32509-66-3, 90498-90-1, 40601-76-1, 27676-62-6, 10191-41-0, 10081-67-1, 181314-48-7, 143925-92-2, 31570-04-4, 26741-53-7, 693-36-7, 2500-88-1, 1843-05-6, 25973-55-1, 05.11.3896, 147-75-9, 3864-99-1, 2440-22-4, 155633-54-8, 70321-86-7, 2725-22-6, 147315-50-2, 14516-71-3, 2403-88-5411, 52829 07-9, 167078-06-0 (24860-22-8), 124172-53-8, 65447-77-0, 71878-19-8 (70624-18-9), 82451-48-7, 106990-43-6, and combinations thereof.

9 . A 3D printing filament comprising a thermoplastic mass of claim 1 , wherein the 3D printing filament has a diameter in the range of from 0.5 to 5 mm.

10 . A method of preparing a three-dimensionally shaped product by means of 3D printing, said method comprising the steps of:

(i) providing the thermoplastic mass of claim 1 ;

(ii) heating defined parts of the thermoplastic mass of step (i) above the glass transition temperature to obtain a plastic mass;

(iii) preparing the three-dimensionally shaped product from the plastic mass of step (iii) (ii); and

(iv) cooling the plastic mass of step (iii) to obtain a solid product.

11 . A method of preparing a three-dimensionally shaped product by means of 3D printing, comprising the steps of:

(i) providing the thermoplastic mass of claim 1 ;

(ii) extruding and thereby heating the filament to obtain a plastic mass at an outlet die of the extruder;

(iii) adding the plastic mass from the outlet die of the extruder to the desired three-dimensional shape of the product;

(iv) cooling the plastic mass of step (iii) to obtain a solid part of the product; and

(v) continuing steps (i) to (iv) until the three-dimensionally shaped product is obtained.

Assignments (6)

Continuity (1)

References Cited (68)