Liquid radiation-curable formulation, in particular for use in stereolithography

• US 5,461,088 A
• Filed: 08/18/1994
• Issued: 10/24/1995
• Est. Priority Date: 08/26/1993
• Status: Expired due to Term

• Current Assignee: 3D Systems, Inc. (3D Systems Corporation)
• Original Assignee: Ciba-Geigy Corporation (Novartis Ag)
• Inventors: Wolf, Jean-Pierre, Schulthess, Adrian, Hunziker, Max, Steinmann, Bettina
• Primary Examiner(s): Berman, Susan W.
• Application Number:
  US08/292,654
• Time in Patent Office: 432 Days
• Field of Search: 522/137, 522/142, 522/148, 522/172, 522/103, 522/182, 522/138, 522/141, 522/143, 430/269
• US Class Current: 522/103
• CPC Class Codes: B33Y 70/00 Materials specially adapted for additive manufacturing
• CPC Class Codes: G03F 7/0037 Production of three-dimensional images
• CPC Class Codes: G03F 7/0757 Macromolecular compounds containing Si-O, Si-C or Si-N bonds G03F7/0752 takes precedence

Abstract

Liquid radiation-curable formulation, in particular for stereolithography, based on at least one compound that contains free radically polymerisable groups, and at least one photoinitiator suitable for the polymerisation, which formulation additionally contains a polyoxyalkylene-polysiloxane block copolymer that is selected from copolymers of the chemical formulae

R.sup.1 --(OC.sub.c H.sub.2c).sub.d --{[T]--(C.sub.c H.sub.2c O).sub.d-1

--(C_c H_2c)}_g --OR¹ (I) ##STR1## wherein: R¹ is a hydrogen atom or a C₁ -C₈ alkyl group;

R² is a methyl or phenyl group;

[T] is a polysiloxane group [PS] terminated as described in the specification in more detail;

[PS] is the group of formula ##STR2## and [Alk] is an alkylene group of 3 to 10 carbon atoms, as well as novel block copolymers of formulae (I) and (II). The cured formulations have, inter alia, superior impact strength.

Claims

1. A liquid radiation-curable formulation, in particular for use in stereolithography, comprising at least one compound that contains free radically polymerisable groups, and at least one photoinitiator suitable for the polymerisation, which formulation additionally comprises a polyoxy-alkylene-polysiloxane block copolymer which is selected from copolymers of the chemical formulae

View Dependent Claims (2, 3, 4, 5, 6, 7)

2. A formulation according to claim 1, wherein is chosen from alkylene groups of 2 to carbon atoms and divalent hydrocarbon radicals containing not more than 30, preferably not more than 20, carbon atoms, which last mentioned radicals contain at least one six-membered carbon ring which is unsubstituted or carries one or more than one straight-chain or branched C₁ -C₄ alkyl substituent.

3. A formulation according to claim 2, wherein

R¹ is a member selected from hydrogen and C₁ -C₄ alkyl

R² is a methyl group;

[Alk] is a --(CH₂)₃ -- group;

[Alk¹ ] is an alkylene group containing 2 to 10, preferably 2 to 4 carbon atoms;

X is an oxygen atom;

[D] is a divalent hydrocarbon radical selected from radicals of the following formulae;

##STR30## c is a number from 2 to 4;

d is an integer from 5 to 50;

b is an integer from 10 to 50;

m is a number from 2 to 4;

n is an integer from 5 to 20;

e is an integer from 1 to 50, and

f is an integer from 1 to 25.

4. A formulation according to claim 3, wherein

R¹ is a methyl group;

[Alk] and

[Alk¹ ] are each a --(CH₂)₃ -- group;

c is 2;

d if the formulation contains a block copolymer of formula (I) or (II), is an integer from 7 to 25 and, if the formulation contains a block copolymer of formula (Ill), is an integer from 2 to 20;

g is 1;

m is 2, and

n is an integer from 7 to 20.

5. A formulation according to claim 1, wherein the polyoxyalkylene-polysiloxane block copolymer is selected from copolymers of the chemical formulae (I) and (II) and wherein the compounds that contain free radically polymerisable groups are a mixture comprising the following components:

(i) a difunctional monomeric or polymeric acrylate or methacrylate;

(ii) a tri- or polyfunctional acrylate or methacrylate;

(iii) an unsaturated monomer of formula ##STR31## wherein R⁵ is a member selected from hydrogen and methyl, and

R⁶ is a radical of formula ##STR32## wherein R⁷ is a radical selected from the group consisting of tetrahydrofurfuryl, cyclohexyl, 2-phenoxyethyl, benzyl, isobomyl, glycidyl, dicyclopentyl, morpholinoethyl, dimethylaminoethyl and straight-chain and branched C₁ -C₂₀ alkyl radicals, or if R⁵ is a hydrogen atom, R⁶, in additional to the radicals cited above, can also be a radical selected from the group consisting of pyrrolidon-2-yl, imidazonyl, carbazolyl, anthracenyl, phenyl, C₅ -C₈ cycloalkyl, naphthenyl, 2-norbornyl, pyridyl, N-caprolactamyl, formamidyl, acetamidyl and toluolyl.

6. A formulation according to claim 5 comprising as component (i) at least one compound of formula ##STR33## wherein p is 0 or 1,

t is 0 or 1 or, if p is 0, is an integer from 1 to 3,

[Z] is --O--, --S--, --SO₂ -- or --C(R¹⁰)(R¹¹)--,

R¹⁰ and

R¹¹ are each independently of the other a radical selected from hydrogen, --CF₃ and methyl,

R¹⁴ if p is 0, is hydrogen or methyl, and, if p is 1, is hydrogen,

R⁸ if p is 0, is hydrogen and if p is 1, is hydroxyl and

R⁹ is hydrogen or methyl,

as component (ii) a triacrylate or trimethacrylate of formula

7. A formulation according to claim 6, which comprises as component (i) at least two compounds of formula (VI) in which

[Z] in both compounds is a --C(CH₃)₂ -- group, and

p in the formula of one of the two compounds is 0 and in the other is 1,

and component (iii) is selected from 1-vinylpyrrolidone, phenoxyethylacrylate, phenoxyethylmethacrylate and a mixture of at least two of the components.