Radiation-curable composition containing mercapto-functional polyorganosiloxanes for additive-manufacturing technology

Patent metadata

Field	Value
Publication number	US-11267968-B2
Application number	US-201916967544-A
Country	US
Kind code	B2
Filing date	Jan 29, 2019
Priority date	Feb 5, 2018
Publication date	Mar 8, 2022
Grant date	Mar 8, 2022

Abstract

The invention relates to a radiation-curable silicone composition for additive-manufacturing technology comprising mercapto-functional polyorganosiloxane(s) as Component A, organosiloxane(s) with at least two aliphatic unsaturated carbon-carbon moieties as Component B, photo-initiator(s) as Component C for initiating a curing reaction between Component A and Component B, dye(s) as Component D, and at least one of the following as Component E: solvent being able to dissolve the dye(s); and/or surfactant(s) being able to dissolve the dye(s).

First claim

What is claimed is:

1. A radiation-curable silicone composition for additive-manufacturing technology, the radiation-curable silicone composition comprising:
mercapto-functional polyorganosiloxane(s) as Component A,
organosiloxane(s) with at least two aliphatic unsaturated carbon-carbon moieties as Component B;
photo initiator(s) as Component C for initiating a curing reaction between Component A and Component B;
dye(s) as Component D; and
surfactant(s) as Component E, wherein the selected surfactant(s) is able to dissolve the dye(s).

2. The radiation-curable silicone composition of claim 1 , wherein the dye is characterized by the following features alone or in combination:
solubility: at least 0.5 wt. % at 50° C. in polyethylene glycol with an Mn of 400 g/mol;
having a light absorption maximum in the range of 460 to 600 nm;
comprising a perylene moiety;
color: red, orange or yellow;
amount: being present from 0.001 to 1 wt. % with respect to the weight of the whole radiation-curable composition.

3. The radiation-curable silicone composition of claim 1 , wherein the mercapto-functional polyorganosiloxane is characterized by the following features alone or in combination:
fraction of (mercaptoalkyl)methylsiloxane units: 7-100 mol-%;
being characterized by the following formula:
[(CH 3 ) 2 RSiO 1/2 ] w [(CH 3 ) 3 SiO 1/2 ] x [(CH 3 ) 2 SiO] y [R(CH 3 )SiO] z ,

with w being 0 to 0.1, x being 0 to 0.1 and w+x being 0.01 to 0.1; y being 0 to 0.93, z being 0.07 to 0.99, wherein each R is independently selected from a mercapto C 1 -C 10 hydrocarbyl group;
molecular weight (Mn): 500 to 20,000 g/mol;
viscosity: 10 to 1,000 mPa*s at 23° C.;
amount: being present in the composition of 0.5 to 50 wt. % with respect to the weight of the whole radiation-curable composition.

4. The radiation-curable silicone composition according of claim 1 , the surfactant is selected from the group consisting of:
a non-ionic surface-active substance according to the formula:
R 1 —O—[CH 2 CH 2 O] n —[R 2 O] m —R 3 ,

wherein:
R 1 is an aromatic or aliphatic, linear or branched hydrocarbon group having at least 8 carbon atoms,
R 2 represents an alkylene having 3 carbon atoms,
R 3 represents hydrogen or a C1-C3 alkyl group,
n is an integer selected from 0 to 40,
m is an integer selected from 0 to 40, and
n+m is at least 2;

a Si-containing surfactant according to the formula:

wherein:
each R is independently selected from a monovalent hydrocarbyl radical with 1 to 22 C-atoms,
R 1 is a divalent hydrocarbylene radical 1 to 26 C-atoms,
each R 2 is independently hydrogen or a lower hydroxyalkyl radical,
R 3 is hydrogen or a monovalent hydrocarbyl radical with 1 to 22 C-atoms,
n and b are independently an integer greater than or equal to zero, and
m and a are independently an integer greater than or equal to one; and

a polyether carbosilane accordingly to the formula:
Q-P—(OC n H 2n ) x -OT,

wherein:
Q is for (R) 3 —Si— or (R) 3 —Si—(R′—Si(R) 2 ) a —R′—Si(R″) 2 —,
each R is independently selected from an aliphatic C 1 -C 18 , a cycloaliphatic C 6 -C 12 , and an aromatic C 6 -C 12 hydrocarbon radical, which can optionally be substituted by halogen atoms,
R′ is a C 1 -C 14 alkylene group,
R″ is R in the case of a≠0, or
R″ is R or R 3 SiR′ in the case of a=0, and
a is an integer selected from 0-2;
P is a C 2 -C 18 alkylene group or A-R″′,
wherein:
A is a C 2 -C 18 alkylene group, and
R′″ is selected from —NHC(O)—, —NHC(O)—(CH 2 ) n−1 —, —NHC(O)C(O)—, —NHC(O)(CH 2 ) v C(O)—, —OC(O)—, —OC(O)—(CH 2 ) n−1 —, —OC(O)C(O)—, —OC(O)(CH 2 ) v C(O)—, —OCH 2 CH(OH)CH 2 OC(O)(CH 2 ) n−1 —, and —OCH 2 CH(OH)CH 2 OC(O)(CH 2 ) v C(O)—;
v is an integer selected from 1-12;
T is H, a C 1 -C 4 alkyl radical, or a C 1 -C 4 acyl radical;
x is an integer selected from 1 to 200, and
n is an integer selected from 1 to 6.

5. The radiation-curable silicone composition of claim 1 , wherein the organosiloxane(s) with at least two aliphatic unsaturated carbon-carbon moieties is characterized by the following features alone or in combination:
structure:

wherein R independently represent a non-substituted or substituted, monovalent hydrocarbon group with 1 to about 6 C atoms and wherein n is in the range of 3 to 10,000
viscosity: 1 to 90,000 mPa*s at 23° C.;
amount: being present from 10 to 98 wt. % with respect to the weight of the whole radiation-curable composition.

6. The radiation-curable silicone composition of claim 1 , the organosiloxane(s) with at least two aliphatic unsaturated carbon-carbon moieties comprising a QM resin containing vinyl groups, which is further characterized by the following features alone or in combination:
concentration of unsaturated moieties: at least 0.15 mmol/g;
viscosity: 500 to 90,000 mPa*s at 23° C.;
amount: being present from 10 to 98 wt. % with respect to the weight of the whole radiation-curable composition.

7. The radiation-curable silicone composition of claim 1 , comprising:
an organosiloxane(s) with at least two aliphatic unsaturated carbon-carbon moieties characterized by the following features alone or in combination:
structure:

wherein R independently represent a non-substituted or substituted, monovalent hydrocarbon group with 1 to about 6 C atoms and wherein n is in the range of 3 to 10,000;

viscosity: 1 to 90,000 mPa*s at 23° C.;
amount: being present from 10 to 98 wt. % with respect to the weight of the whole radiation-curable composition; and

an organosiloxane(s) with at least two aliphatic unsaturated carbon-carbon moieties comprising a QM resin containing vinyl groups characterized by the following features alone or in combination:
concentration of unsaturated moieties: at least 0.15 mmol/g;
viscosity: 500 to 90,000 mPa*s at 23° C.;
amount: being present from 10 to 98 wt. % with respect to the weight of the whole radiation-curable composition.

8. The radiation-curable silicone composition of claim 1 , comprising in addition either of the following components alone or in combination:
filler(s) as Component F in an amount of 0.5 to 60 wt. %,
stabilizer(s) as Component G in an amount of 0.001 to 1 wt. %,
wt. % with respect to the whole radiation-curable composition.

9. The radiation-curable silicone composition of claim 1 , wherein:
Component A:
being present in an amount of 0.5 to 50 wt. %,
comprising 7 to 100 mol-% (mercaptoalkyl)methylsiloxane units;

organosiloxane(s) with at least two aliphatic unsaturated carbon-carbon moieties as Component B:
being present in an amount of 10 to 98 wt. %,
having a viscosity of 1 to 90,000 mPa*s,

Component C:
being present in an amount of 0.01 to 5 wt. %,
having a light absorption band in the range of 300 to 450 nm,

Component D:
being present in an amount of 0.001 to 1 wt. %,
having a light absorption maximum in the range of 460 to 600 nm,
having a solubility of less than 1 g in 100 g water at 23° C.,

Component E:
being present in an amount of 0.1 to 15 wt. %,

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

10. A process for producing a cured 3-dim article, the process comprising:
providing a radiation-curable silicone composition of claim 1 , and
curing the radiation-cur

Assignees

• 3M Innovative Properties Co

Inventors

• Osswald Peter
• Hoffmann Henning
• Grupp Hendrick
• Zech Joachim
• Oberpertinger Daniel
• Korten Malte
• Schechner Gallus

Classifications

• B33Y70/00

  Materials specially adapted for additive manufacturing · CPC title

• C08G77/28

  sulfur-containing groups · CPC title

• B29K2083/00

  Use of polymers having silicon, with or without sulfur, nitrogen, oxygen, or carbon only, in the main chain, as moulding material · CPC title

• C08G77/20

  containing silicon bound to unsaturated aliphatic groups · CPC title

• B29C64/129

  characterised by the energy source therefor, e.g. by global irradiation combined with a mask · CPC title