Stereolithography using vinyl ether based polymers
First Claim
1. In a process for forming a three-dimensional object from a liquid polymer precursor comprising repeatedly exposing the surface of a bath of said precursor to a beam of actinic light to solidify successive layers of said precursor the improvement comprising employing as said liquid polymer precursor a mixture of(a) at least one vinyl ether oligomer having the formula
whereR'"'"' and R" are H or an alkyl group having 1 to 10 carbon atomsA is a moiety from at least one of the group consisting of urethanes, phenols, polyesters, polyethers, and polysiloxanes and has a molecular weight of about 400 to 10,000Z is a moiety from a saturated aliphatic or cyclo aliphatic hydrocarbon or a polyalkylene ether and has a molecular weight of about 28 to 250n is an integer from 2 to 6;
CR'"'"'--OZ).sub.n --A
(b) at least one vinyl ether monomer having the formula
space="preserve" listing-type="equation">(R'"'"'CH═
CR"--O--Z).sub.n --B whereR'"'"' and R" are H or an alkyl group having 1 to 10 carbon atomsZ is a moiety from a saturated aliphatic or cyclo aliphatic hydrocarbon or a poly alkylene ether and has a molecular weight of about 28 to 250n is an integer from 1 to 4B is from at least one of the group consisting of aliphatic and aromatic hydrocarbons, esters, and ethers and has a molecular weight of about 60 to 400;
and(c) a cationic photoinitiator.
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Abstract
Polymer precursor formulations suitable for stereolithography may be prepared from compositions containing (a) a vinyl ether oligomer, and (b) mono and/or multifunctional vinyl ether monomers.
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Citations
36 Claims
- 1. In a process for forming a three-dimensional object from a liquid polymer precursor comprising repeatedly exposing the surface of a bath of said precursor to a beam of actinic light to solidify successive layers of said precursor the improvement comprising employing as said liquid polymer precursor a mixture of
(a) at least one vinyl ether oligomer having the formula - space="preserve" listing-type="equation">(R'"'"'CH═
CR'"'"'--OZ).sub.n --A
where R'"'"' and R" are H or an alkyl group having 1 to 10 carbon atoms A is a moiety from at least one of the group consisting of urethanes, phenols, polyesters, polyethers, and polysiloxanes and has a molecular weight of about 400 to 10,000 Z is a moiety from a saturated aliphatic or cyclo aliphatic hydrocarbon or a polyalkylene ether and has a molecular weight of about 28 to 250 n is an integer from 2 to 6; (b) at least one vinyl ether monomer having the formula
space="preserve" listing-type="equation">(R'"'"'CH═
CR"--O--Z).sub.n --Bwhere R'"'"' and R" are H or an alkyl group having 1 to 10 carbon atoms Z is a moiety from a saturated aliphatic or cyclo aliphatic hydrocarbon or a poly alkylene ether and has a molecular weight of about 28 to 250 n is an integer from 1 to 4 B is from at least one of the group consisting of aliphatic and aromatic hydrocarbons, esters, and ethers and has a molecular weight of about 60 to 400; and (c) a cationic photoinitiator. - View Dependent Claims (2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36)
- 9. The process of claim 1 wherein said vinyl ether oligomers of (a) are derived from a polyester obtained by reacting
(a) a dicarboxylic acid having the formula ##STR7## where X and Y are divalent radicals having a molecular weight of about 28 to 500 and selected from the group consisting of alkylene, arylene, aralkylene, and cycloalkylene radicals m has an average value of about 1 to 100; -
(b) with a hydroxy monovinyl ether having the formula
space="preserve" listing-type="equation">R'"'"'CH═
CR"OZOHwhere R'"'"' and R" are monovalent radicals selected from the group consisting of H and alkyl groups having 1-10 carbon atoms Z is a divalent radical having a molecular weight of about 28 to 250 and selected from the group consisting of alkylene, cycloalkylene, or polyalkylene ether radicals.
- 10. The process of claim 1 wherein said vinyl ether oligomers of (a) are derived from a polysiloxane defined as
- space="preserve" listing-type="equation">(R'"'"'CH═
CR"--O--Z--).sub.n --A'"'"'
where R'"'"', R", and Z are as defined above N is an integer from 2 to 8 A'"'"' is a polysiloxane having n Si--H groups and a molecular weight of 140 to 5,000. - space="preserve" listing-type="equation">(R'"'"'CH═
- space="preserve" listing-type="equation">(R'"'"'CH═
CR"--O--Z--O--).sub.n --A"
- ,α
'"'"' diradical derived from 1,4-dimethylcyclohexane and M1 is alkylene with 2 to 4 carbon atoms.
- space="preserve" listing-type="equation">M.sub.2 --(--OZ--OCR"═
CHR'"'"').sub.n
- space="preserve" listing-type="equation">M.sub.3 --(--OZ--OCR"--CHR'"'"').sub.n
- ,α
'"'"' diradical derived from 1,4-dimethylcyclohexane.
Specification