Coloured curable composition for additive manufacturing processes, 3-dim composite article and use thereof

Patent metadata

Field	Value
Publication number	US-11583373-B2
Application number	US-201716327111-A
Country	US
Kind code	B2
Filing date	Aug 14, 2017
Priority date	Aug 25, 2016
Publication date	Feb 21, 2023
Grant date	Feb 21, 2023

Abstract

The invention relates to a coloured curable composition for use in an additive manufacturing process, the composition comprising a curable resin composition comprising radiation curable components, a photo initiator, a dye composition comprising a dye D1 and a dye D2, dye D1 having a light absorption maximum within a wave length range from 400 to 530 nm, dye D2 showing a light absorption maximum within a wave length range from 540 to 650 nm. The invention also relates to a 3-dim composite article obtained by processing the curable composition in an additive manufacturing process.

First claim

What is claimed is:

1. A coloured curable composition for use in an additive manufacturing process, the composition comprising:
a curable resin composition comprising radiation curable components,
a photo initiator,
a dye composition comprising a dye D1 and a dye D2,
dye D1 having a light absorption maximum within a wave length range from 400 to 530 nm,
dye D2 showing a light absorption maximum within a wave length range from 540 to 650 nm.

2. The coloured curable composition of claim 1 , wherein either dye D1 or dye D2 or dye D1 and dye D2 have an additional light absorption within a wave length range from 300 to 400 nm with an intensity being at least 20% compared to the intensity of the light absorption of the respective dye(s) within a wave length range from 400 to 650 nm.

3. The curable composition of claim 1 , being characterized by one or more of the following features:
viscosity: less than 200 mPa*s at 23° C.;
light absorption in the range from 400 to 650 nm: more than 90% for a path length of 5 mm;
light transmission: less than 25% for a path length of 1 mm;
colour impression: deeply coloured for a path length of 1 mm or more;
pH value if the curable composition is brought in contact with wet pH sensitive paper: 6-8;
optionally combustible within a temperature range from 600 to 900° C. without residues.

4. The curable composition of claim 1 , the photo initiator being characterized by one or more of the following features:
showing a light absorption band within a wave length range from 300 to 450 nm;
solubility in curable composition: at least 2 g/l at 23° C.

5. The curable composition of claim 1 , dye D1 being characterized by one or more of the following features:
molecular weight: from 50 to 1,000 g/mol;
solubility in the curable composition: at least 0.1 g/l at 23° C.;
comprising an anthraquinone moiety, azo moiety, naphthoquinolinedione moiety, isoquinoline moiety or xanthenone moiety.

6. The curable composition of claim 1 , dye D2 being characterized by one or more of the following features:
molecular weight: from 50 to 1,000 g/mol;
light absorption within a wave length range from 300 to 400 nm with an intensity being at least 20% compared to the intensity of the light absorption within a wave length range from 540 to 650 nm;
solubility in the curable composition: at least 0.05 g/l at 23° C.;
comprising an anthraquinone moiety, azo moiety, phenoxazine moiety, or triphenylmethane moiety.

7. The curable composition of claim 1 , the radiation curable component(s) comprising a backbone and reactive groups being attached to the backbone, the radiation curable component(s) being characterized by one or more of the following features (chemical):
bearing one or more (meth)acrylate moieties as reactive groups;
bearing aromatic, aliphatic, or aromatic-aliphatic moieties in the backbone;
optionally bearing one or more urethane moieties in the backbone;
optionally bearing one or more hydroxyl groups in the backbone.

8. The curable composition of claim 1 , the ratio of dye D1 to dye D2 in the curable composition being from 0.1:1 to 3:1 with respect to weight.

9. The curable composition of claim 1 comprising one or more of the following component(s):
high boiling additive(s), preferably having a boiling point above 100° C. in an amount from 1 to 20 wt. % with respect to the weight of the whole composition;
stabilizer(s), preferably in an amount from 0.001 to 1 wt. % with respect to the weight of the whole composition.

10. The curable composition of claim 1 , not comprising one or more of the following component(s):
filler(s) in an amount of more than 1 wt. %;
inorganic pigment(s) in an amount of more than 1 wt. %;
component(s) comprising elements other than C, H, O, N, S, P, Hal in an amount of more than 1 wt. %;

wt. % with respect to the weight of the whole composition.

11. The curable composition of claim 1 , comprising:
radiation curable component(s) from 50 to 98 wt. %,
photo initiator from 0.5 to 10 wt. %,
dye D1 from 0.01 to 1 wt. %,
dye D2 from 0.01 to 1 wt. %,
high boiling additive from 0 to 20 wt. %,
wt. % with respect to the weight of the whole composition.

12. The curable composition of claim 1 , comprising:
radiation curable components comprising a (meth)acrylate moiety and being present in an amount from 50 to 96 wt. %,
photo initiator comprising a phosphine oxide moiety and being present in an amount from 0.5 to 10 wt. %,
dye D1 comprising an anthraquinone moiety and being present in an amount from 0.01 to 1 wt. %,
dye D2 comprising an anthraquinone moiety and being present in an amount from 0.01 to 1 wt. %,
high boiling additive having a molecular weight from 100 to 500 g/mol and being present in an amount from 1 to 15 wt. %,
the curable composition not comprising
filler(s) in an amount of more than 1 wt. %,
inorganic pigment(s) in an amount of more than 1 wt. %,
component(s) comprising elements other than C, H, O, N, S, P, Hal in an amount of more than 1 wt. %,
wt. % with respect to the weight of the whole composition.

13. A process of producing a 3-dim article, the process comprising the step of processing the curable composition of claim 1 , by an additive manufacturing technique.

14. A 3-dim composite article obtained or obtainable of claim 1 , the article being characterized by one or more of the following features:
light transmission: less than 20% for a path length of 1 mm;
colour impression: black at a layer thickness of 2 mm or more;
hue h°: below 30 determined for a path length of 5 mm in transmission mode according to the CIELCh colour system;
chroma C*: less than 20 determined for a path length of 5 mm in transmission mode according to the CIELCh colour system;
combustible within a temperature range of 800 to 950° C. without residues.

15. A process of producing a 3-dim cast article, the process comprising:
processing the curable composition of claim 1 , in an additive manufacturing process to obtain a 3-dim composite article,
embedding the 3-dim composite article in an investment material,
replacing the material of the 3-dim composite article by a casting material to obtain a 3-dim cast article embedded in the investment material,
removing the investment material from the 3-dim cast article.

16. The composition of claim 1 , wherein dye D1 is present in an amount from 0.04 to 0.1 wt. % and dye D2 is present in an amount from 0.02 to 0.1 wt. %, each wt. % with respect to the weight of the whole composition.

Assignees

• 3M Innovative Properties Company

Inventors

• Raia Gioacchino
• Eckert Adrian S
• Korten Malte
• Goetzinger Martin

Classifications

• B33Y70/00

  Materials specially adapted for additive manufacturing · CPC title

• C08K5/08

  Quinones · CPC title

• C08K5/0041

  Optical brightening agents, organic pigments · CPC title

• A61C7/14

  Brackets (A61C7/28 takes precedence); Fixing brackets to teeth · CPC title

• B33Y10/00

  Processes of additive manufacturing · CPC title