IP Library Granted Patent US 10,843,401
Granted Patent B2
US 10,843,401 · App. 14/070,053 · Granted Nov 24, 2020

Fuse molded three dimensional article and a method for making the same

Inventor: Marcus Greger (Amsterdam, NL)
Assignee: Kraton Polymers U.S. LLC
B29C64/118B29C67/0055B29C70/68C08L53/00B29K2025/08B29K2096/04B29K2105/0085B29K2867/00B29K2875/00B29K2995/007B33Y10/00B33Y70/00Y10T428/24983
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Quick Facts
Patent No.
US 10,843,401
App. No.
14/070,053
Granted
Nov 24, 2020
Kind
B2
Abstract

A fuse molded modeling three dimensional article having areas of dissimilar or different hardness is described, wherein one of said areas is hard and is plastic, metal, glass, wood, concrete, rock, or mixtures thereof, and another of said areas is a less hard area comprising a controlled distribution hydrogenated styrenic block copolymer composition. Although the metal, glass, wood, concrete, and rock are not fuse moldable material, the plastic and the controlled distribution hydrogenated styrenic block copolymer composition are. Thus the scope of the invention is meant to include articles where only one area or layer of the article is fuse molded, or wherein both the hard area/layer and the soft area/layer is formed via a fuse molded technique.

Claims (65)

1. A fuse molded modeling three dimensional article having areas of dissimilar or different hardness,

wherein the areas of dissimilar or different hardness are fuse deposition molded;

wherein one of said fuse deposition molded area is hard, and another of said fuse deposition molded areas is a flexible material that is less hard;

wherein the hard area comprises a thermoplastic selected from acrylonitrile-butadiene-styrene, polylactic acid, polyamide, polyphenylsulfone, polycarbonate, polyethylene, polypropylene, polyethylene/acrylonitrile-butadiene-styrene, polycarbonate/acrylonitrile-butadiene-styrene, methylmethacrylate/acrylonitrile-butadiene-styrene, polyetherimide, and mixtures thereof;

wherein the flexible material consists essentially of a block copolymer composition, and 15 to 60 wt. % of a polyester, copolyester, polyurethane, or a mixture of two or more of these, or 15 wt. % of high impact polystyrene;

wherein said block copolymer composition comprises:

20 to 85 wt % of a controlled distribution hydrogenated styrene-ethylene butadiene-styrene block copolymer based on the total weight of the composition;

up to 30 wt % of a functionalized controlled distribution hydrogenated styrene-ethylene butadiene-styrene block copolymer having maleic anhydride grafted onto a mid block of the styrene-ethylene butadiene-styrene block copolymer; and

wherein the flexible material has

a melt flow rate of less than 28 dg/min according to ASTM D1238 at 230° C. and 2.16 kg, and

a peel strength of at least about 60N/25 mm in 180° initial adhesion test on the thermoplastic, according to JIS K6854;

wherein said thermoplastic is supplied as flexible filaments, sticks, or pellets initially in solid form to an extrusion head of a 3-D printer, where the thermoplastic is melted and deposited, forming the hard area;

wherein the flexible material has a Shore A hardness of from greater than 80 to about 95;

wherein said flexible material is not a temporary supporting material, wherein said flexible material is fuse molded on the hard area comprising the thermoplastic by deposition using the 3-D printer, and said flexible material is supplied as a flexible filament, sticks, or pellets initially in solid form to an extrusion head of the 3-D printer, and

wherein the three dimensional article is made without a mold using the 3-D printer.

2. The fuse molded modeling three dimensional article of claim 1 , wherein said controlled distribution hydrogenated styrene-ethylene butadiene-styrene block copolymer is in a range of 40 to 85 wt. %.

3. The fuse molded modeling three dimensional article of claim 1 , wherein the flexible material consist essentially of the block copolymer composition, and thermoplastic elastomer ii a copolyester.

4. The fuse molded modeling three dimensional article of claim 1 ,

wherein the flexible material consist essentially of the block copolymer composition, and a copolyester; and

wherein said thermoplastic forming said hard area is acrylonitrile-butadiene-styrene, polylactic acid, polyamide, polyphenylsulfone, polycarbonate, polyethylene, polypropylene, polyethylene/acrylonitrile-butadiene-styrene, polycarbonate/acrylonitrile-butadiene-styrene, methylmethacrylate/acrylonitrile-butadiene-styrene, or polyetherimide.

5. An additive-process method for making a three dimensional article, comprising:

providing a solid feedstock of a first plastic material to at least one extrusion head of a 3-D printer,

melting said solid feedstock of the first plastic material in said at least one extrusion head,

depositing layers of said first plastic material on to a platform to form a portion of a three dimensional article,

providing a solid second feedstock of a second plastic material to said at least one extrusion head, wherein said solid second feedstock of the second plastic material is less hard has a dissimilar hardness compared to said solid feedstock of the first plastic material,

melting said solid feedstock of the second plastic material in said at least one extrusion head, and

depositing layers of said second plastic material on to said portion of said three dimensional article comprising the first plastic material, thereby forming the three dimensional article having layers or areas of dissimilar or different hardness, wherein the first plastic material consists essentially of a thermoplastic selected from acrylonitrile-butadiene-styrene, polylactic acid, polyamide, polyphenylsulfone, polycarbonate, polyethylene, polypropylene, polyethylene/acrylonitrile-butadiene-styrene, polycarbonate/acrylonitrile-butadiene-styrene, methylmethacrylate/acrylonitrile-butadiene-styrene, polyetherimide, and mixtures thereof;

wherein the second plastic material consists essentially of:

a) a controlled distribution hydrogenated styrenic block copolymer composition comprising:

20 to 85 wt % of a controlled distribution hydrogenated styrene-ethylene butadiene-styrene block copolymer based on the total weight of the composition, and

up to 30 wt % of a functionalized controlled distribution hydrogenated styrene-ethylene butadiene-styrene block copolymer of maleic anhydride grafted onto a mid block of the styrene-ethylene butadiene-styrene, and

b) 15 to 60 wt % of a polyester, copolyester, or polyurethane, or a mixture of two or more of these, or high impact polystyrene; and wherein,

the second plastic material has a melt flow rate of less than 28 dg/min according to ASTM D1238 at 230° C. and 2.16 kg, and a peel strength of at least about 60N/25 mm in 1800 initial adhesion test on the first plastic material according to JIS K6854;

wherein the first plastic material is supplied as a-flexible filaments, sticks, or pellets initially in solid form to the at least one extrusion head of the 3-D printer;

wherein the second plastic material has a Shore A hardness of from greater than 80 to about 95;

and wherein the three dimensional article is made without a mold using the 3-D printer.

6. The additive-process method according to claim 5 , wherein said solid feedstock of the first plastic material consists essentially of methylmethacrylate/acrylonitrile-butadiene-styrene.

7. The additive-process method according to claim 5 , wherein said solid feedstock of the first plastic material consists essentially of acrylonitrile-butadiene-styrene.

8. The additive-process method according to claim 5 , wherein said solid feedstock of the first plastic material consists essentially of polycarbonate.

9. The additive-process method according to claim 5 , wherein said solid feedstock of the first plastic material consists essentially of polycarbonate/acrylonitrile-butadiene-styrene.

10. An additive-process method for making a three dimensional article, comprising

providing a portion of a three dimensional solid article comprising a thermoplastic selected from acrylonitrile-butadiene-styrene, polylactic acid, polyamide, polyphenylsulfone, polycarbonate, polyethylene, polypropylene, polyethylene/acrylonitrile-butadiene-styrene, polycarbonate/acrylonitrile-butadiene-styrene, methylmethacrylate/acrylonitrile-butadiene-styrene, polyetherimide, and mixtures thereof,

providing a solid feedstock consisting essentially of 15 to 60 wt. % of a polyester, copolyester, or polyurethane, or a mixture of two or more of these, or 15 wt. % of high impact polystyrene; and a controlled distribution hydrogenated styrenic block copolymer composition as a flexible filament, sticks, or pellets initially in solid form to at least one extrusion head of a 3-D printer, wherein the controlled distribution hydrogenated styrenic block copolymer composition comprises:

20 to 85 wt % of a controlled distribution hydrogenated styrene-ethylene butadiene-styrene block copolymer based on the total weight of the composition, and

up to 30 wt % of a functionalized controlled distribution hydrogenated styrene-ethylene butadiene-styrene block copolymer of maleic anhydride grafted onto a mid block of the styrene-ethylene butadiene-styrene;

melting said solid feedstock in said at least one extrusion head, and

depositing layers of said molten feedstock on to said portion of a three dimensional solid article,

thereby forming a three dimensional article having areas of dissimilar hardness;

wherein the solid feedstock has a lesser hardness than the thermoplastic

wherein the flexible material has

a peel strength of at least about 60N/25 mm in 180° initial adhesion test on the thermoplastic according to JIS K6854,

a melt flow rate of less than 28 dg/min according to ASTM D1238 at 230° C. and 2.16 kg, and

a Shore A hardness of from greater than 80 to about 95; and

wherein the three dimensional article is made using the 3-D printer in a 3-D fused deposition printing process without a mold.

11. An additive-process method for making a three dimensional article, comprising

providing a portion of a three dimensional solid article of a flexible material consisting essentially of 15 to 60 wt. % of a polyester, copolyester, or polyurethane, or a mixture of two or more of these, or 15 wt. % of high impact polystyrene and a controlled distribution hydrogenated styrenic block copolymer composition comprising:

20 to 85 wt % of a controlled distribution hydrogenated styrene-ethylene butadiene-styrene block copolymer based on the total weight of the composition,

up to 30 wt % of a functionalized controlled distribution hydrogenated styrene-ethylene butadiene-styrene block copolymer of maleic anhydride grafted onto a mid block of the styrene-ethylene butadiene-styrene;

providing a solid plastic feedstock as a flexible filament, sticks, or pellets initially in solid form to at least one extrusion head of a 3-D printer, said solid plastic feedstock comprising a thermoplastic selected from acrylonitrile-butadiene-styrene, polylactic acid, polyamide, polyphenylsulfone, polycarbonate, polyethylene, polypropylene, polyethylene/acrylonitrile-butadiene-styrene, polycarbonate/acrylonitrile-butadiene-styrene, methylmethacrylate/acrylonitrile-butadiene-styrene, polyetherimide, and mixtures thereof;

wherein the flexible material has a lesser hardness than the solid plastic feedstock;

melting said solid plastic feedstock in said at least one extrusion head, and

depositing layers of said molten plastic feedstock onto said portion of a three dimensional solid article, thereby forming a three dimensional article having areas of dissimilar hardness; and

wherein the dimensional article is made without a mold using the 3-D printer in a 3-D fused deposition printing process,

wherein the flexible material has a melt flow rate of less than 28 dg/min according to ASTM D1238 at 230° C. and 2.16 kg, a peel strength of at least about 60N/25 mm in 180° initial adhesion test on the thermoplastic according to JIS K6854; and a Shore A hardness of from greater than 80 to about 95.

12. The additive-process method of claim 11 , wherein said solid plastic feedstock is acrylonitrile-butadiene-styrene.

Assignments (10)
RELEASE OF SECURITY INTEREST IN PATENTS Recorded Jul 24, 2024
From: GOLDMAN SACHS BANK USA, AS COLLATERAL AGENT
To: KRATON CHEMICAL, LLC; KRATON CORPORATION
Reel/Frame 068671/0836 →
CORRECTIVE ASSIGNMENT TO CORRECT THE PATENT NO. 8837224 TO PATENT NO. 7737224 PREVIOUSLY RECORDED AT REEL: 037448 FRAME: 0453. ASSIGNOR(S) HEREBY CONFIRMS THE ASSIGNMENT. Recorded Jun 11, 2022
From: KRATON POLYMERS U.S. LLC; ARIZONA CHEMICAL COMPANY, LLC
To: BANK OF AMERICA, N.A.
Reel/Frame 060344/0919 →
SECURITY INTEREST Recorded Mar 18, 2022
From: KRATON CHEMICAL, LLC; KRATON POLYMERS LLC; KRATON POLYMERS U.S. LLC
To: GOLDMAN SACHS BANK USA, AS COLLATERAL AGENT
Reel/Frame 059525/0804 →
SECURITY INTEREST Recorded Mar 18, 2022
From: KRATON CHEMICAL, LLC; KRATON POLYMERS LLC; KRATON POLYMERS U.S. LLC
To: GOLDMAN SACHS BANK USA, AS COLLATERAL AGENT
Reel/Frame 059864/0455 →
RELEASE OF SECURITY INTEREST Recorded Mar 16, 2022
From: BANK OF AMERICA, N.A.
To: KRATON POLYMERS U.S. LLC; KRATON CHEMICAL, LLC F/K/A ARIZONA CHEMICAL COMPANY, LLC; KRATON POLYMERS LLC; KRATON CORPORATION; KRATON CHEMICAL B.V.
Reel/Frame 059910/0017 →
RELEASE OF SECURITY INTEREST Recorded Mar 15, 2022
From: CREDIT SUISSE AG, CAYMAN ISLANDS BRANCH, AS COLLATERAL AGENT
To: KRATON POLYMERS U.S. LLC
Reel/Frame 059366/0611 →
SECURITY INTEREST Recorded Apr 16, 2020
From: KRATON POLYMERS U.S. LLC; KRATON CHEMICAL, LLC F/K/A ARIZONA CHEMICAL COMPANY, LLC; KRATON POLYMERS LLC; KRATON CORPORATION
To: BANK OF AMERICA, N.A.
Reel/Frame 053020/0101 →
PATENT SECURITY AGREEMENT Recorded Jan 7, 2016
From: KRATON POLYMERS U.S. LLC
To: CREDIT SUISSE AG, CAYMAN ISLANDS BRANCH, AS COLLATERAL AGENT
Reel/Frame 037457/0843 →
CORRECTIVE ASSIGNMENT TO CORRECT THE PATENT NUMBER 8837224 TO PATENT NUMBER 7737224 PREVIOUSLY RECORDED AT REEL: 037448 FRAME: 0453. ASSIGNOR(S) HEREBY CONFIRMS THE SECURITY INTEREST. Recorded Jan 6, 2016
From: KRATON POLYMERS U.S. LLC; ARIZONA CHEMICAL COMPANY, LLC
To: BANK OF AMERICA, N.A.
Reel/Frame 037448/0453 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Dec 3, 2013
From: GREGER, MARCUS; KRATON POLYMERS US LLC
To: KRATON POLYMERS U.S. LLC
Reel/Frame 031703/0907 →