COMPOSITION FOR THREE-DIMENSIONAL PRINTING, A METHOD FOR PREPARATION THEREOF AND USES THEREOF

Abstract

The disclosure concerns a composition for three-dimensional printing, said composition being free from polylactic acid (PLA) and includes the following components:

(a) a polysaccharide comprising a cellulose derivative and/or a lignocellulosic derivative;

(b) a pH regulator selected from at least one of the following: organic acids, inorganic acids, acid generating salts, bases, buffers,

(c) a resin selected from melamine resin and/or phenol resin, and

(d) optionally a rheology modifier selected from water and/or glycerol.

The disclosure also concerns a kit of parts for producing the described composition, a method for three-dimensional printing of the described composition and articles obtainable by said method.

Claims

1. A composition for three-dimensional printing, said composition being free from polylactic acid (PLA) and comprising the following components: (a) a polysaccharide comprising a cellulose derivative and/or a lignocellulosic derivative; (b) a pH regulator selected from at least one of the following: organic acids, inorganic acids, acid generating salts, buffers, acidic polymers, bases, (c) a resin selected from melamine resin and/or phenol resin, and (d) optionally a rheology modifier selected from water and/or glycerol.

2. A composition according to claim 1, which comprises: (d) a rheology modifier selected from water and/or glycerol, thereby forming a paste.

3. A composition according to claim 1, which does not comprise: (d) a rheology modifier selected from water and/or glycerol, thereby forming a powder.

4. A composition according to any one of claims 1-3, wherein the at least one polysaccharide comprising a cellulose derivative and/or a lignocellulosic derivative is selected from at least one of the following: wood fibres, sander dust, sawing dust, lignocellulosic fibres, lignocellulosic paste, lignocellulosic powder, cellulose powder, cellulose paste, cellulose fibres, regenerated cellulose, lignocellulosic composite.

5. A composition according to any one of the preceding claims, wherein the at least one polysaccharide comprising a cellulose derivative and/or a lignocellulosic derivative is selected from at least one of the following: wood fibres, bamboo fibres, sander dust, sawing fibres.

6. A composition according to any one of the preceding claims, wherein the pH regulator is an organic acid.

7. A composition according to any one of claims 1-5, wherein the pH regulator is selected from at least one of the following: formic acid, oxalic acid, ammonium sulphate.

8. A composition according to any one of the preceding claims, wherein the resin comprises or consists of melamine urea formaldehyde and/or melamine formaldehyde

9. A composition according to any one of the preceding claims, further comprising at least one of the following components: (e) a binder selected from at least one of the following: starch, lignin, protein, (f) a filler selected from at least one of the following: fibrous filler, organic filler, inorganic filler, silica, colour pigment, (g) a functionality carrier selected from at least one of the following: metallic particles, carbon, glass particles, caprolactam, (h) a further rheology modifier selected from at least one of the following: acrylic polymers, alginates, gums derived from cellulose, cellulose fibres, polyethylene, a derivative of any of the foregoing.

10. A composition according to claim 9, wherein the organic filler is selected from at least one of the following: cellulose fibres, algenite, cork, latex, wax, shellac, gum arabic.

11. A composition according to claim 9, wherein the inorganic filler is selected from at least one of the following: kaolin, ground glass, glass fibres, carbon fibres, carbonate fibres, tubes, concrete powder.

12. A composition according to any one of the preceding claims, wherein the amount of the components based on the total amount of the composition is: from 10 wt % to 87 wt % of the polysaccharide comprising a cellulose derivative and/or lignocellulose derivative, from 0.1 wt % t 10 wt % of the pH regulator, from 5 wt % to 70 wt % of the resin and binder, from 1 wt % to 10 wt % of the filler, 0.1 to 10 wt % of the functionality carrier, water, glycerol and/or binder present in an amount up to 100 wt %.

13. A composition according to any one of the preceding claims, which is biodegradable.

14. A kit of parts for providing a composition according to any one of the preceding claims, wherein said kit of parts comprises: (i) a first component comprising a pH regulator as defined in any one of the preceding claims, (ii) a second component comprising a resin as defined in any one of the preceding claims, wherein said first component and/or said component further comprise(s): a polysaccharide as defined in any one of the preceding claims, and optionally one or more of the following: a binder as defined in any one of the preceding claims; a filler as defined in any one of the preceding claims, a functionality carrier as defined in any one of the preceding claims, a further rheology modifier as defined in any one of the preceding claims.

15. A kit of parts according to claim 14, wherein the first component and/or the second component further comprise a rheology modifier selected from water and/or glycerol thereby providing said first component as a first paste and/or said second component as a second paste.

16. A kit of parts according to claim 14 or 15, wherein: said first component is provided as a powder, and said second component further comprises a rheology modifier selected from water and/or glycerol thereby providing said second component as a paste.

17. A kit of parts according to claim 14 or 15, wherein: said first component further comprises the rheology modifier selected from water and/or glycerol thereby providing said first component as a paste, and said second component is provided as a powder.

18. A method for three-dimensional printing of a paste according to any one of claim 2 or 4-13, said method comprising the steps of. (a) combining the first component and the second component according to any one of claims 15-17 into a paste, or adding water and/or glycerol to the powder composition according to any one of claim 3-11 or 13 thereby providing a paste, (b) optionally adding a component according to any one of claims 9-11 to said paste, and (c) producing at least one layer comprising the paste, (d) optionally combining several of said at least one layer, and (e) curing said at least one layer.

19. A method according to claim 18, wherein said at least one layer is produced using extrusion.

20. A method for three-dimensional printing of a powder composition according to any one of claim 3-11 or 13, said method comprising the steps of: (a) providing a layer comprising or consisting of a powder composition as defined in any one of claim 3-11 or 13, (b) adding a rheology modifier selected from water and/or glycerol and/or a further rheology modifier as defined in claim 9 to said layer, (c) optionally repeating steps (a) and (b), and (d) curing.

21. A method according to any one of claims 18-20, wherein one or more of the steps take place at room temperature.

22. A method according to any one of claims 18-21, wherein said method does not involve polylactic acid.

23. A method according to any one of claims 18-22, which does not involve supply of heat and/or energy.

24. A method according to any one of claims 18-22, which does not involve heating and/or cooling.

25. An article obtainable by the method according to any one of claims 18-22.

26. An article according to claim 23, which is at least one of the following: headphone, prosthetic device, mold, decorative object, temporary object, furniture, wearables, biodegradable objects, facades, implants, toys, skis, construction parts, walls, composite material.

27. An article according to claim 23 or 24 having sound isolating properties.

28. Use of an article according to any one of claims 23-25 in recycling.

29. Use according to claim 26, wherein said article is crushed, shredded and/or melted.

30. Use according to claim 26 or 27, wherein said article is a raw material for making a composition according to any one of claims 1-13.

Description

EXAMPLES

[0196] Materials

[0197] Preparation of materials for 3D printing.

[0198] List of material:

TABLE-US-00001 Name Suppliers Specification Kaolin BASF AVG. PARTICLE SIZE 2.5 m-5 m Arbocel J. Rettenmeier Wood meal & Sne GmbH MAX PARTICLE SIZE 80 m Corn starch Cargill AVG. PARTICLE SIZE 20 m Sander dust European MDF MAX PARTICLE SIZE plant 150 m Sodium Algenate Sigma Aldrich CAS Number: 9005-38-3 Prefere ExpL-3089 Dynea melamine urea resin containing more than 20 wt % melamine and having a molar ratio formalde- hyde:amino groups of 0.9:1 or less Micronised wax Lubrizol Melting point >100 C. Formic acid 85 wt % in water Oxalic acid Powder Glycerol Sigma Aldrich 86 wt % in water Elotex Akzo-Nobel Caprolactam Wood fibres MDF plant Cellulose Fibres 10% paste

[0199] In this document wt % refers to % by weight based in the total weight.

Example 1

[0200] Water (71.1 g), glycerol (13.4 g), formic acid (65.9 g), were mixed by Rodelys RS 300 stirrer at 250 rpm. Corn starch (184.7 g), kaolin (164.7 g) were added slowly (over 30 min) and simultaneously into the mix under stirring of 180 rpm to provide a first homogenous paste composition. In this document, rpm intends revolutions per minute.

[0201] Water (87,5 g) was added to Prefere ExpL-3089 (312 g) synthetic binder from Dynea under stirring of 300 rpm). Micronised wax (2.5 g) and Arbocel (43.3 g) were stirred in the mix, at 130 rpm to provide a second homogenous paste composition.

Example 2.

[0202] Water (104 g), oxalic acid (29 g), were mixed by Rodelys RS 300 stirrer at 250 rpm. Wood fibres (150), sander dust (97.7 g) were added slowly (over 30 min) and simultaneously into the mix under stirring of 180 rpm to provide a first homogenous paste composition.

[0203] Water (100 g) was added to Prefere ExpL-3089 (170 g) under stirring of 300 rpm. Caprolactam (2 g) and Arbocel (89.5 g) were stirred in the mix, at 130 rpm. Corn starch (37g) was added to provide a second homogenous paste composition.

Example 3.

[0204] Water (60 g), formic acid (15 g), were mixed by Rodelys RS 300 stirrer at 250 rpm. Arbocel (130 g) and kaolin (130 g) were added slowly (over 30 min) and simultaneously into the mix under stirring of 180 rpm to provide a first homogenous paste composition.

[0205] Water (100 g) was added Prefere ExpL-3089 (100 g) under stirring of 300 rpm and cellulose fibres (10 g) were added. Elotex (95 g) and Arbocel (130 g) were stirred in the mix, at 130 rpm to provide a second homogenous paste composition.

Example 4.

[0206] Sander dust (320 g) was mixed with wood-fibres (64 g), corn starch (31 g) Prefere ExpL-3d 3089 (120 g) and ammonium sulphate (14 g) to form -a powder mixture for 3D printing.

[0207] Printing/Extruding Procedure

[0208] The pastes of Examples 1-3 were tested for three-dimensional printing as follows.

[0209] The first homogenous paste and the second homogenous paste were mixed in 50:50 (w/w) ratio in inline mixer at pressure of 2-5.5 bar, through a nozzle of 0.5-6 mm to be extruded into objects.

[0210] Objects with layer height from 2-7 mm and layer width of 2-7 mm, at speed of 3.5 s /cm were extruded. The layers were dried just after extrusion.

[0211] The dried objects were immersed into cold for 24 h and warm water (60 C.) for 4 hours.

[0212] There was no change in appearance or formation observed.

[0213] It was possible to drill a hole in the object, polish it, coat it and paint it.

Example 5.

[0214] The powder mixture of Example 4 above was laid on the powder bed in Electro Optical Systems powder printer and with printer-head sprayed water between the layers. As a result, an object comprising layers was formed. The object was dried at room temperature for 24 hours. It was concluded that the powder mixture could be used in three-dimensional printing.

Example 6

[0215] Water (104 g), oxalic acid (29 g), were mixed by Rodelys RS 300 stirrer at 250 rpm. Wood fibres (150), sander dust from spruce panels (92.0 g) were added slowly (over 30 min) and simultaneously into the mix under stirring of 180 rpm to provide a first homogenous paste composition.

[0216] Water (101,7 g) was added to Prefere ExpL-3089 (174 g) under stirring of 300 rpm. Caprolactam (2 g) and Arbocel (89.5 g) were stirred in the mix, at 130 rpm. Corn starch (37g) was added to provide a second homogenous paste composition.

Example 7

[0217] Water (104 g), oxalic acid (29 g), were mixed by Rodelys RS 300 stirrer at 250 rpm. Wood 30 fibres (150), sander dust from amino resin bonded spruce MDF boards (97.7 g) were added slowly (over 30 min) and simultaneously into the mix under stirring of 180 rpm to provide the first homogenous paste composition.

[0218] Water (100 g) was added to Prefere ExpL-3089 (170 g) under stirring of 300 rpm. Caprolactam (2 g) and Arbocel (89.5 g) were stirred in the mix, at 130 rpm. Corn starch (37g) was added to provide a second homogenous paste composition.

Example 8

[0219] Water (109 g), oxalic acid (30.5 g), were mixed by Rodelys RS 300 stirrer at 250 rpm. Wood fibres (150 g), sawing dust from amino resin bonded pine particle board (87.2 g) were added slowly (over 30 min) and simultaneously into the mix under stirring of 180 rpm to provide a first homogenous paste composition.

[0220] Water (100 g) was added to Prefere ExpL-3089 (174 g) under stirring of 300 rpm. Caprolactam (2 g) and Arbocel (89.5 g) were stirred in the mix, at 130 rpm. Corn starch (37g) was added to provide a second homogenous paste composition.

Example 9

[0221] Water (106 g), oxalic acid (31.5 g), were mixed by Rodelys RS 300 stirrer at 250 rpm. Wood fibres (150), bamboo fibres (85 g) were added slowly (over 30 min) and simultaneously into the mix under stirring of 180 rpm to provide a first homogenous paste composition.

[0222] Water (100 g) was added to Prefere ExpL-3089 (179.2 g) under stirring of 300 rpm.

[0223] Caprolactam (2 g) and Arbocel (89.5 g) were stirred in the mix, at 130 rpm. Corn starch (37 g) was added to provide second homogenous paste composition.

Example 10

[0224] The mixture from example 7 where the first composition was prepared by mixing Water (104 g) and oxalic acid (29 g) by Rodelys RS 300 stirrer at 250 rpm, and later added wood fibres (150), sander dust from amino resin bonded spruce MDF boards (97.7 g) over 30 min into the existing mix under stirring of 180 rpm to provide the homogenous paste 30 composition.

[0225] The second composition was prepared by mixing Prefere ExpL-3089 (170 g) into water (100 g) under stirring of 300 rpm. Caprolactam (2 g) and Arbocel (89.5 g) were stirred in the mix, at 130 rpm. Corn starch (37 g) was added to provide second homogenous paste composition.

[0226] The first and the second composition were transferred into separate plastic patronsand were joined with Y-joint. Y-joint was connected to the Archimedes screw. Pressure was applied on the top of the patrons, and the two compositions were mixed in site prior to extrusion through nozzle of size of 75 mm. In this document, mm refers to millimetres. 5 The layers that we extruded were in the size of ca 75 mm. The mixture was flowing at the point of extrusion, but as soon as it was laid on the extrusion surface, the mixture was stiff and if became hard on touch within a few seconds.

Example 11

[0227] In yet another example water (90 g), formic acid (19 g), were mixed by Rodelys RS 300 stirrer at 250 rpm. Wood fibres (150), sander dust from spruce panels (92.0 g) were added slowly (over 30 min) and simultaneously into the mix under stirring of 180 rpm to provide the first homogenous paste composition.

[0228] Water (101.7 g) was added Prefere ExpL-3089 (174 g) under stirring of 300 rpm. Caprolactam (2 g) and Arbocel (89.5 g) were stirred in the mix, at 130 rpm. Corn starch (37g) was added to provide second homogenous paste composition. The first and the second composition was transferred into separate plastic patrons, and we joined with Y-joint. Y-joint was connected to the Archimedes screw. Pressure was applied on the top of the patrons, and the two compositions were mixed in site prior to extrusion through nozzle with a diameter of 0.4 mm.

[0229] Layer of size achieve of 0.5 mm (width)0.5 mm (height) was extruded, and it was cured by the extrusion of the next layer.