Polymerizable materials based on dimerizable benzaldehyde derivatives

Patent metadata

Field	Value
Publication number	US-10875949-B2
Application number	US-201916549163-A
Country	US
Kind code	B2
Filing date	Aug 23, 2019
Priority date	Sep 11, 2018
Publication date	Dec 29, 2020
Grant date	Dec 29, 2020

Abstract

The present invention relates to polymerizable and photochemically crosslinkable compositions which contain at least one polymerizable benzaldehyde derivative according to general formula I

and which are suitable as materials for technical and medical applications, for example in surgery or ophthalmology, and in particular as dental materials.

First claim

The invention claimed is:

1. A method of manufacturing a medical-technical material for the production of medical devices, implants for auditory prostheses, cartilage or bone replacement parts, as a material for ophthalmology, or for the production of intraocular lenses comprising
stereolithographically processing a composition comprising
a) 0.1 to 50 wt.-% of at least one benzaldehyde derivative of Formula I,

in which
R 1 is hydrogen, a branched or unbranched, saturated or unsaturated C 1 -C 14 alkyl group which can be interrupted by O or S, a C 6 -C 14 aryl group or a C 4 -C 14 heteroaryl group which can contain N, O or S, wherein the alkyl, aryl or heteroaryl groups can be substituted with thioether, amino, alkoxy or alkyl groups with 1 to 14 carbon atoms or C 6 -C 14 aryl groups and wherein the substituents can be bridged to each other,
R 2-5 in each case independently of each other are hydrogen, an NH 2 group, a branched or unbranched, saturated or unsaturated thioether, amino, alkoxy or alkyl group with 1 to 14 carbon atoms, a branched or unbranched, saturated or unsaturated C 7 -C 15 arylalkoxy group, benzyloxy group (Ph-CH 2 —O—), or a C 6 -C 14 aryl group which can be bound via O or S, wherein R 2-3 can be bridged to each other and R 2 and/or R 4 is/are —X—SP-PG,
X is dispensed with or is —O—, —CO—O— or —O—CO—,
SP is a linear or branched C 1 -C 6 alkylene group, wherein the alkylene group can be interrupted by O, S, —CO—O—, —O—CO— and/or phenylene,
PG is a polymerizable group,
R 6-7 in each case independently of each other are hydrogen or a C 1 -C 10 alkyl group which can be branched or unbranched, saturated or unsaturated,
b) 30 to 99 wt.-% of at least one further monofunctional radically or cationically polymerizable monomer,
c) 0 to 20 wt.-% of at least one multifunctional radically or cationically polymerizable monomer,
d) 0.001 to 5.0 wt.-% of at least one photoinitiator,
e) 0 to 5.0 wt.-% additive(s),
in each case relative to the total mass of the material,
wherein said composition does neither contain further 1,3-dienes nor dienophiles,

into the medical-technical material and
curing the medical-technical material during or after the stereolithographically processing step,
wherein the curing is effected in two stages, the first stage comprising irradiation of the material with visible light and the second stage irradiation of the material with UV-A light.

2. The method of manufacturing according to claim 1 , wherein the variables of Formula I have the following meanings:
R 1 is hydrogen or C 1 -C 4 alkyl group,
R 2-5 in each case independently of each other are hydrogen or a C 1 -C 4 alkoxy or C 1 -C 4 alkyl group, wherein R 2 and/or R 4 is/are —X—SP-PG,
X is —O—,
SP is a linear C 2 -C 6 alkylene group, wherein the alkylene group can be interrupted by O, —CO—O— and/or phenylene, C 2 -C 4 alkylene group or —CH 2 -Ph-CO—O—CH 2 CH 2 —,
PG is a cationically or radically polymerizable group, a (meth)acrylate group or an acrylamide group,
R 6-7 are both hydrogen or R 6 =C 1 -C 10 alkyl and R 7 =H.

3. The method of manufacturing according to claim 1 , wherein the variables of Formula I have the following meanings:
R 1 is hydrogen or —CH 3 ,
R 2-3 in each case independently of each other are hydrogen, —CH 3 or —OCH 3 , wherein R 2 or R 4 is —X—SP-PG,
X is —O—,
SP is a linear C 2 -C 6 alkylene group, wherein the alkylene group can be interrupted by O, —CO—O— and/or phenylene, a C 2 -C 4 alkylene group or —CH 2 −Ph-CO—O—CH 2 CH 2 —,
PG is a cationically or radically polymerizable group, a (meth)acrylate group or an acrylamide group,
R 6-7 in each case are hydrogen.

4. The method of manufacturing according to claim 1 , wherein the variables of Formula I have the following meanings:
R 1 is hydrogen,
R 2-3 in each case independently of each other are hydrogen or —CH 3 , wherein R 2 or R 4 is —X—SP-PG,
X is —O—,
SP is a linear C 2 -C 4 alkylene group, wherein the alkylene group can be interrupted by O, —CO—O— and/or phenylene, a C 2 alkylene group or —CH 2 -Ph-CO—O—CH 2 CH 2 —,
PG is a radically polymerizable group, a (meth)acrylate group or an acrylamide group,
R 6-7 in each case are hydrogen.

5. The method of manufacturing according to claim 1 , in which PG is a radically polymerizable group, which is selected from a vinyl, (meth)acrylate or (meth)acrylamide group.

6. The method of manufacturing according to claim 1 , in which PG is a cationically polymerizable group, which is selected from an epoxy, oxetane or vinyl ether group.

7. The method of manufacturing according to claim 1 , wherein in the at least one polymerizable additional monomer is selected from methyl acrylate (MA), ethyl acrylate (EA), methyl methacrylate (MMA), butyl methacrylate (BMA), tetrahydrofurfuryl methacrylate (THEMA), isobornyl methacrylate (IBOMA) or a mixture thereof.

8. The method of manufacturing according to claim 1 , wherein the photoinitiator (d) comprises at least one initiator for the polymerization by UV-A light and at least one initiator for the polymerization by visible light.

9. The method of manufacturing according to claim 1 , wherein the composition additionally contains at least one inorganic filler.

10. A method of manufacturing or repairing extraorally dental braces, corrective splints or templates for correcting malocclusions comprising
stereolithographically processing a composition comprising
a) 0.1 to 50 wt.-% of at least one benzaldehyde derivative of Formula I,

in which
R 1 is hydrogen, a branched or unbranched, saturated or unsaturated C 1 -C 14 alkyl group which can be interrupted by O or S, a C 6 -C 14 aryl group or a C 4 -C 14 heteroaryl group which can contain N, O or S, wherein the alkyl, aryl or heteroaryl groups can be substituted with thioether, amino, alkoxy or alkyl groups with 1 to 14 carbon atoms or C 6 -C 14 aryl groups and wherein the substituents can be bridged to each other,
R 2-5 in each case independently of each other are hydrogen, an NH 2 group, a branched or unbranched, saturated or unsaturated thioether, amino, alkoxy or alkyl group with 1 to 14 carbon atoms, a branched or unbranched, saturated or unsaturated C 7 -C 15 arylalkoxy group, benzyloxy group (Ph-CH 2 −O—), or a C 6 -C 14 aryl group which can be bound via O or S, wherein R 2-5 can be bridged to each other and R 2 and/or R 4 is/are —X—SP-PG,
X is dispensed with or is —O—, —CO—O— or —O—CO—,
SP is a linear or branched C 1 -C 6 alkylene group, wherein the alkylene group can be interrupted by O, S, —CO—O—, —O—CO— and/or phenylene,
PG is a polymerizable group,
R 6-7 in each case independently of each other are hydrogen or a C 1 -C 10 alkyl group which can be branched or unbranched, saturated or unsaturated,
b) 30 to 99 wt.-% of at least one further monofunctional radically or cationically polymerizable monomer,
c) 0 to 20 wt.-% of at least one multifunctional radically or cationically polymerizable monomer,
d) 0.001 to 5.0 wt.-% of at least one initiator, in particular photoinitiator,
e) 0 to 5.0 wt.-% additive(s),
in each case relative to the total mass of the material,
wherein said composition does neither contain further 1,3-dienes nor dienophiles,
into a medical device, implant for auditory prostheses, cartilage or bon

Assignees

• Ivoclar Vivadent Ag

Inventors

• Moszner Norbert
• Hendrik John
• Lamparth Iris
• Barner-Kowollik Christopher
• Krappitz Tim
• Feist Florian

Classifications

• C08F2800/10

  as molar percentages · CPC title

• C07C69/76

  Esters of carboxylic acids having a carboxyl group bound to a carbon atom of a six-membered aromatic ring · CPC title

• C08F220/18

  with acrylic or methacrylic acids · CPC title

• C08F220/14 Primary

  Methyl esters {, e.g. methyl (meth)acrylate} · CPC title

• A61L2430/06

  for cartilage reconstruction, e.g. meniscus · CPC title