Radiation curable composition for additive manufacturing processes

Patent metadata

Field	Value
Publication number	US-11597830-B2
Application number	US-201816624806-A
Country	US
Kind code	B2
Filing date	May 21, 2018
Priority date	Jun 20, 2017
Publication date	Mar 7, 2023
Grant date	Mar 7, 2023

Abstract

The invention relates to a radiation curable composition for additive-manufacturing processes, the composition comprising (meth)acrylate component(s) not comprising an urethane moiety having a molecular weight Mw of at least 1,000 as Component A1, photo initiator as Component B, red, yellow or orange dye or combination thereof as Component C, blue dye having a light absorption band in the range of 350 to 420 nm as Component D, and optionally stabilizer as Component E. The invention further relates to a process of producing an elastomeric 3-dim article from the radiation curable composition in an additive-manufacturing process and the obtained elastomeric 3-dim article.

First claim

The invention claimed is:

1. A radiation curable composition for additive-manufacturing processes, the composition comprising:
a (meth)acrylate component(s) not comprising a urethane moiety moiety as Component A1,
the (meth)acrylate component(s) comprising a polyether backbone to which (meth)acrylate moieties are attached and the (meth)acrylate component(s) characterized by a molecular weight Mw of at least 1,000 g/mol;

photo initiator as Component B;
a red dye, a yellow dye, an orange dye, or combination thereof as Component C, the red dye, the yellow dye, and the orange dye comprising a perylene moiety;
a blue dye as Component D,
the blue dye comprising a terephthalate moiety, and
the blue dye characterized by having a light absorption band in the range of 350 to 420 nm; and

optionally stabilizer as Component E.

2. The radiation curable composition according to claim 1 , the composition being characterized by the following features alone or in combination:
viscosity: less than 200 Pa*s at 23° C.;
pH value: 6 to 8;
light transmission: at least 40% for a path length of 1 mm using light having a wave length of 500 nm;
radiation curable with light having a wavelength in the range of 350 to 420 nm;
appearance: transparent;
color: red, yellow or orange.

3. The radiation curable composition according to claim 1 , the (meth)acrylate component(s) being characterized by the following features alone or in combination:
comprising at least 2 (meth)acrylate moieties;
molecular weight (Mw): from 1,000 to 20,000 g/mol;
viscosity: from 0.1 to 100 Pa*s at 23° C.

4. The radiation curable composition according to claim 1 , the red, orange or yellow dye being characterized by the following features alone or in combination:
solubility: soluble in triethylenglycoldi(meth)acrylate at 23° C.;
having a light absorption band in the range of 460 to 600 nm.

5. The radiation curable according to claim 1 , the blue dye being characterized by the following features alone or in combination:
solubility: soluble in triethylenglycoldi(meth)acrylate at 23° C.

6. The radiation curable composition according to claim 1 , the composition comprising in addition (meth)acrylate component(s) comprising an urethane moiety as Component A2, wherein Component A1 is present in a higher amount compared to Component A2.

7. A process of producing an elastomeric 3-dim article, the process comprising the step of processing the radiation curable composition described in claim 1 in an additive-manufacturing process comprising a radiation curing step using light with a wave length in the range from 350 to 420 nm.

8. The process of claim 7 , the elastomeric 3-dim article having the shape of an orthodontic or dental article, the dental article having the shape of a dental impression.

9. An elastomeric 3-dim article comprising the radiation curable composition as described in claim 1 in its cured state.

10. The elastomeric 3-dim article of claim 9 being characterized by the following features alone or in combination:
Tensile strength: from 0.5 to 50 MPa according to ISO/DIN 53504 (2015-8);
Elongation at break: from 10 to 1000% according to ISO/DIN 53504 (2015-8);
Shore hardness A: from 30 to 90 according to ISO/DIN 53505 (2000-8);
Light transmission: at least 50% for a path length of 1 mm at using light having a wave length in the range of 450 to 600 nm
Water contact angle: ≤100°;
Not sticky to surfaces of cured (meth)acrylates;
Color: red, orange or yellow.

11. A process of curing a radiation curable Composition II, the process comprising the steps of:
a) providing a radiation curable Composition I, the radiation curable Composition I being the radiation curable composition as described in claim 1 , b) processing the radiation curable Composition I in an additive-manufacturing process using radiation for curing the Composition I to obtain a transparent elastomeric 3-dim article having an outer side and an inner side, c) placing the radiation curable Composition II on the inner side of the transparent elastomeric 3-dim article, d) light curing the radiation curable Composition II from the outer side of the transparent elastomeric 3-dim article
the radiation curable Composition II being different from the radiation curable Composition I, the radiation curable Composition II comprising (meth)acrylate moieties, photo-initiator(s) and optionally filler(s).

12. The process of claim 11 , wherein the curing in step b) and step d) is done at different wave lengths.

13. The process of claim 11 ,
the radiation curing step b) being done at a wave length in the range from 350 to 420 nm,
the radiation curing step d) being done at a wave length in the range from 430 to 500 nm.

14. The process of claim 11 , the radiation curable Composition II being selected from a dental cement, a dental adhesive, or a dental composite material.

15. A kit of parts comprising:
a radiation curable Composition I, the radiation curable Composition I being the radiation curable composition as described in claim 1 , and
a radiation curable Composition II being different in its chemical composition from the radiation curable Composition I and being radiation curable within a wavelength in the range of 430 to 500 nm.

Assignees

• 3M Innovative Properties Company

Inventors

• Zech Joachim
• Grupp Hendrik
• Korten Malte
• Paehl Ralf
• Blees Dietmar
• Raia Gioacchino

Classifications

• B33Y80/00

  Products made by additive manufacturing · CPC title

• C08K5/005

  Stabilisers against oxidation, heat, light, ozone · CPC title

• C08K5/0041

  Optical brightening agents, organic pigments · CPC title

• C08L33/10 Primary

  Homopolymers or copolymers of methacrylic acid esters · CPC title

• B33Y10/00

  Processes of additive manufacturing · CPC title