Use of moulding compounds based on blends of san-copolymers and polyamide for 3D printing

Patent metadata

Field	Value
Publication number	US-10619061-B2
Application number	US-201716084330-A
Country	US
Kind code	B2
Filing date	Mar 16, 2017
Priority date	Mar 17, 2016
Publication date	Apr 14, 2020
Grant date	Apr 14, 2020

Abstract

The invention relates to the use of a thermoplastic moulding compound for 3D Printing, made of a mixture of the following components A-E: A: 35-60 wt. % impact resistant modified polymer A comprising: 30-95 wt. % SAN-copolymer and 5-70 wt. % ABS-graft copolymer; B: 33-58 wt. % aliphatic polyamide B; C: 1-10 wt. % SANMSA-terpolymer C as a compatibilizing agent; D: 0.01-5 wt. % processing agent D; and E: 0-30 wt. % other additives E.

First claim

The invention claimed is:

1. A method of producing a three-dimensional object by 3D printing, comprising the steps of:
providing a thermoplastic molding composition consisting of a mixture of the components A to E:
A: 35 to 60 wt % of at least one impact-modified polymer A, consisting of the components a and b:
a: 30 to 95 wt % of at least one styrene-acrylonitrile copolymer a having an average molar mass Mw of 150 000 to 350 000 g/mol, obtained by polymerization of:
a1: 18 to 35 wt % of acrylonitrile (AN), and
a2: 82 to 65 wt % of styrene (S); and

b: 5 to 70 wt % of at least one graft copolymer b as impact modifier, with
b1: 45 to 85 wt % of a graft base b1, obtained by polymerization of:
 b11: 80 to 100 wt % of 1,3-butadiene, and
 b12: 0 to 20 wt % of styrene; and
b2: 15 to 55 wt % of a graft b2, obtained by polymerization of:
 b21: 70 to 90 wt % of styrene; and
 b22: 10 to 30 wt % of acrylonitrile;

B: 33 to 58 wt % of at least one polyamide B selected from the following: polyamide 6 (polycaprolactam), polyamide 6,6 (polyhexamethyleneadipamide), polyamide 4,6 (polytetramethyleneadipamide), polyamide 5,10 (polypentamethyleneadipamide), polyamide 6,10 (polyhexamethylenesebacamide), polyamide 7 (polyenantholactam), polyamide 11 (polyundecanolactam), and polyamide 12 (polydodecanolactam);
C: 1 to 10 wt % of at least one compatibilizer C based on a styrene-acrylonitrile-maleic anhydride terpolymer obtained by polymerization of:
C1: 72 to 84.5 wt % of styrene;
C2: 15 to 27.5 wt % of acrylonitrile; and
C3: 0.5 to 5 wt % of maleic anhydride;

D: 0.01 to 5 wt % of one or more auxiliaries selected from the following: stabilizers, oxidation retarders, agents against thermal decomposition and decomposition by ultraviolet light, lubricants and mold release agents, processing assistants, and plasticizers; and
E: 0 to 30 wt % of one or more further additives E;
where the sum of the components A, B, C, D, and, if present, E makes 100 wt %;

fluidizing the thermoplastic molding composition;
extruding the thermoplastic molding composition;
applying a plurality of layers of the thermoplastic molding composition to a base or to a preceding layer of the thermoplastic molding composition; and
consolidating the thermoplastic molding composition to produce the three-dimensional object.

2. A method of claim 1 , wherein the viscosity (measured to ISO 11443:2014) of the molding composition at shear rates of 1 to 10 1/s and at temperatures of 250° C. is not more than 1×10 5 Pa*s and the melt volume rate (MVR, measured to ISO 1133-1:2011 at 240° C. and 10 kg load) of the molding composition is more than 15 ml/10 min.

3. A method of claim 1 , wherein component B is polyamide 6.

4. A method of claim 1 , wherein the thermoplastic molding composition consists of:
35 to 50 wt % of component A,
40 to 58 wt % of component B,
1 to 10 wt % of component C,
0.01 to 5 wt % of component D, and
0 to 20 wt % of component E.

5. A method of claim 1 , wherein the thermoplastic molding composition consists of:
35 to 50 wt % of component A,
45 to 58 wt % of component B,
1 to 10 wt % of component C,
0.01 to 5 wt % of component D, and
0 to 10 wt % of component E.

6. A method of claim 1 , wherein the thermoplastic molding composition consists of:
40 to 50 wt % of component A,
45 to 55 wt % of component B,
2 to 6 wt % of component C,
0.05 to 3 wt % of component D, and
0 to 10 wt % of component E.

7. A method of claim 1 , wherein in the impact-modified polymer A, the fraction of component a is 30 to 60 wt % and the fraction of the graft copolymer b used as impact modifier is 70 to 40 wt %.

8. A method of claim 1 , wherein at least one graft copolymer b is used with:
50 to 80 wt % of a graft base b1 obtained by polymerization of:
b11: 100 wt % of butadiene; and

20 to 50 wt % of a graft b2 obtained by polymerization of:
b21: 70 to 90 wt % of styrene, and
b22: 10 to 30 wt % of acrylonitrile.

9. A method of claim 1 , wherein the particle size (d 50 ) of the graft copolymer b is at least 80 nm and at most 1 μm.

10. A method of claim 1 , wherein the three-dimensional object are bridges.

11. A method of claim 7 , wherein in the impact-modified polymer A, the fraction of component a is 40 to 60 wt %, and the fraction of the graft copolymer b used as impact modifier is 60 to 40 wt %.

12. A method of claim 8 , wherein the at least one graft copolymer b is used with:
50 to 80 wt % of a graft base b1 obtained by polymerization of:
b11: 100 wt % of butadiene; and

20 to 50 wt % of a graft b2 obtained by polymerization of:
b21: 72.5 to 85 wt % of styrene, and
b22: 15 to 27.5 wt % of acrylonitrile.

13. A method of claim 9 , wherein the particle size (d 50 ) of the graft copolymer b is 100 nm to 600 nm.

Assignees

• Ineos Styrolution Group Gmbh

Inventors

• Baumann Stephanie
• Eisentraeger Frank
• Meiners Josef
• Niessner Norbert
• Schmidt Hans-Werner

Classifications

• C09D11/107

  from unsaturated acids or derivatives thereof · CPC title

• C08L2205/035

  containing four or more polymers in a blend · CPC title

• C08L2205/025

  containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure · CPC title

• C09D11/102

  containing macromolecular compounds obtained by reactions other than those only involving unsaturated carbon-to-carbon bonds · CPC title

• C08L25/12 Primary

  with unsaturated nitriles · CPC title