# US 5,705,316 A · Vinyl ether compounds having additional functional groups other than vinyl ether groups and the use thereof in the formulation of curable compositions

> Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt

- Number: US 5,705,316 A
- Document ID: US5705316A
- Status: Granted
- Kind: A
- Application number: 08/555,821
- Filed: 1995-11-09
- Granted: 1998-01-06
- Earliest claimed: 1993-09-16
- Assignees: Ciba Specialty Chemicals Corporation
- Inventors: Bettina Steinmann; Adrian Schulthess; Max Hunziker
- Web page: https://patentgrep.com/patent/US5705316A

## CPC

- C08F 16/26: Monomers containing oxygen atoms in addition to the ether oxygen
- B33Y 10/00: Processes of additive manufacturing
- B33Y 70/00: Materials specially adapted for additive manufacturing
- C07C 271/28: to a carbon atom of a non-condensed six-membered aromatic ring
- C07C 271/38: with the nitrogen atom of at least one of the carbamate groups bound to a carbon atom of a six-membered aromatic ring
- C07D 303/24: with polyhydroxy compounds
- C07D 303/40: by ester radicals
- G03F 7/0037: {Production of three-dimensional images}
- G03F 7/027: Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds (G03F7/075 takes precedence)
- G03F 7/029: Inorganic compounds; Onium compounds; Organic compounds having hetero atoms other than oxygen, nitrogen or sulfur
- C07C 2603/68: Dicyclopentadienes; Hydrogenated dicyclopentadienes
- C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- B33Y: ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- C07C: ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07D: HETEROCYCLIC COMPOUNDS (macromolecular compounds C08)
- G03F: PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR; (phototypographic composing devices B41B; photosensitive materials or processes for photographic purposes G03C; electrophotography, sensitive layers or processes therefor G03G)

## Abstract

The invention relates to compounds having at least one vinyl ether group which also contain in the molecule at least one further functional group selected from acrylate, methacrylate, epoxy, alkenyl, cycloalkenyl and vinylaryl groups, to compositions, especially for stereolithography, comprising those vinyl ether compounds, and to a method of producing three-dimensional objects using those compositions.

## Claims

### Claim 1

A method of producing three-dimensional objects from a composition comprising a compound of the formula
›H.sub.2 C.dbd.CH--O!--.sub.z A,
the symbols used in that formula and in the formulae below having the following definitions:
A is a z-valent radical selected from the radicals of the following formulae (1), (2), (3)
and (4) ##STR57## ›D! is a group of the formula ##STR58## ›E! is a C.sub.1 - or a C.sub.2 -alkylene group; R.sup.0 is a hydrogen atom or a methyl group;
R.sup.1 is a z-valent radical selected from aliphatic, cycloaliphatic, aromatic, aliphatic-aromatic and aliphatic-cycloaliphatic hydrocarbon radicals and polyoxyalkylene radicals;
R.sup.2 is a radical selected from the radicals of the formulae ##STR59## R.sup.4 is a group selected from the groups of the formulae ##STR60## R.sup.5 is a group selected from the groups of the formulae ##STR61## R.sup.6 is a (2.z)-valent organic group which, together with the carbon atoms C.sup..alpha. and C.sup..beta. of each of the z groups of the formula ##STR62## in a radical of formula (2), forms a cycloaliphatic ring having at least 5 carbon atoms;
R.sup.14 and
R.sup.15 are each a hydrogen atom or, when ›E! is a C.sub.2 alkylene group, are each a hydrogen atom or together form a methylene group;
i is an integer from 0 to 20;
m is an integer from 1 to 20;
s is an integer from 2 to 10;
t is an integer from 0 to 10;
u in the individual units of the formula ##STR63## in formula (5) are independently of one another an integer from 1 to 20; v is an integer from 0 to 4;
x and
y are independently of one another an integer from 2 to 20, and
z is the number 1 or 2,
a photoinitiator and, optionally, at least one other polymerizable compound different from the vinylether compound of formula ›H.sub.2 C.dbd.CH--O!--.sub.z A, which method comprises a step in which the surface of a layer of the composition is irradiated over its entire surface or in a predetermined pattern with an UV/VIS light source, so that in the irradiated regions a layer of the desired thickness is solidified, and then a fresh layer of the composition is formed on the solidified layer, and that fresh layer is likewise irradiated over its entire surface or in a predetermined pattern, and as a result of the repeated coating and irradiation there are obtained three-dimensional objects consisting of a number of solidified layers adhering one to another.

### Claim 2 (depends on 1)

A method according to claim 1 including the polymerisable component having the formula ##STR64## wherein R.sup.1, R.sup.2, R.sup.6, x and z are as defined in claim 1.

### Claim 3 (depends on 1)

A method according to claim 1 wherein
R.sup.1 is a z-valent radical selected from
a) aliphatic radicals having from 2 to 20 carbon atoms,
b) cycloaliphatic and aromatic radicals each having from 6 to 14 carbon atoms,
c) aliphatic-aromatic and aliphatic-cycloaliphatic radicals each having from 7 to 25 carbon atoms, and
d) polyoxyalkylene radicals of the formulae R.sup.7 --›OC.sub.g H.sub.2g !.sub.n -- and --(C.sub.g H.sub.2g)--›OC.sub.g H.sub.2g !.sub.n-1 -- wherein
R.sup.7 is an alkyl group having from 1 to 8 carbon atoms,
g is a number from 1 to 8 corresponding to the average number of carbon atoms of an alkylene unit of the polyoxyalkylene radical and
n is an integer from 2 to 20,
and the radical R.sup.1 is unsubstituted or in addition may have one or more substituents which
in the case of an aliphatic radical R.sup.1 are selected from C.sub.1 -C.sub.4 alkoxy and halogen substituents; and
in the case of other types of radical R.sup.l are selected from C.sub.1 -C.sub.4 alkyl, C.sub.1 -C.sub.4 alkoxy and halogen substituents.

### Claim 4 (depends on 3)

A method according to claim 3 wherein
R.sup.1 is a radical selected from the radicals of the formulae ##STR65## R and R.sup.3 are independently of one another a hydrogen atom or methyl and
f is an integer from 2 to 20.

### Claim 5 (depends on 4)

A method according to claim 4 wherein
R.sup.l is a radical selected from the radicals of the formulae ##STR66## and phenyl; R.sup.4 is a group selected from the groups of the formulae ##STR67## R.sup.5 is a group selected from the groups of the formulae ##STR68## and R and
R.sup.3 are both either a hydrogen atom or methyl; and
k is an integer from 2 to 10, and the index
m has an upper limit of 10.

### Claim 6 (depends on 5)

A method according to claim 5 wherein
R.sup.1 is a radical selected from an alkylene radical having from 2 to 4 carbon atoms, a phenyl radical and a radical of the formula ##STR69## R.sup.4 is a group of the formula ##STR70## and R.sup.5 is a group selected from the groups of the formulae ##STR71##

### Claim 7 (depends on 1)

A method according to claim 1 wherein
R.sup.6 is an organic group having from 3 to 50 carbon atoms.

### Claim 8 (depends on 7)

A method according to claim 7 wherein
z is 1 and
R.sup.6 together with the carbon atoms C.sup..alpha. and C.sup..beta. of the group of formula (6) forms a cycloalkyl radical having from 5 to 7 ring carbon atoms to which a further cycloalkyl radical having from 5 to 7 ring carbon atoms may have been fused.

### Claim 9 (depends on 8)

A method according to claim 8 wherein
R.sup.6 together with the carbon atoms C.sup..alpha. and C.sup..beta. of the group of formula (6) forms a cyclopentyl or cyclohexyl radical.

### Claim 10 (depends on 7)

A method according to claim 7 wherein
R.sup.6 is a group of the formula R.sup.8 --›G!--R.sup.9 wherein
R.sup.8 together with the carbon atoms C.sup..alpha. and C.sup..beta. of a group of formula (6) forms a cycloalkyl radical having from 5 to 7 ring carbon atoms to which a further cycloalkyl radical having from 5 to 7 ring carbon atoms may have been fused;
R.sup.9 either likewise forms, together with the carbon atoms C.sup..alpha. and C.sup..beta. of a further group of formula (6), a cycloalkyl radical having from 5 to 7 ring carbon atoms to which a further cycloalkyl radical having from 5 to 7 ring carbon atoms may have been fused, or is a cycloalkyl radical having from 5 to 7 ring carbon atoms to which a further cycloalkyl radical having from 5 to 7 ring carbon atoms may have been fused;
›G! is a structural unit selected from a single bond and the groups of the formulae ##STR72## and h is an integer from 1 to 6, especially from 2 to 4.

### Claim 11 (depends on 10)

A method according to claim 10 having the formula ##STR73## wherein one of the radicals R.sup.10 and R.sup.13 is a group of the formula H.sub.2 C.dbd.CH--O--(CH.sub.2).sub.x --O-- and the other is a group of the formula R.sup.2 O-- and, likewise, one of the radicals R.sup.11 and R.sup.12 is a group of the formula H.sub.2 C.dbd.CH--O--(CH.sub.2).sub.x --O-- and the other is a group of the formula R.sup.2 O--, and x and h are each independently of the other an integer from 2 to 4.

### Claim 12 (depends on 1)

A method according to claim 1 wherein ##STR74##

### Claim 13 (depends on 1)

A method according to claim 1 wherein
A is a radical of formula (3) or (4), and
s is an integer from 2 to 4,
t is an integer from 0 to 2,
u is the number 1,
v is the number 0 or 1, and
x and
are each an integer from 2 to 10.

### Claim 14 (depends on 1)

A method according to claim 1 wherein
A is a radical of formula (4),
R.sup.14 and
R.sup.15 are each a hydrogen atom and
z is the number 1.

### Claim 15 (depends on 1)

A method according to claim 1 wherein the composition for producing the three-dimensional objects comprises at least one other polymerizable compound different from the vinylether compound of formula ›H.sub.2 C.dbd.CH--O!.sub.z A.

### Claim 16 (depends on 15)

A method according to claim 15 wherein the polymerisable component has the formula ##STR75##