# US 11,999,865 B2 · UV curable composition for use in 3D printing

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- Number: US 11,999,865 B2
- Document ID: US11999865B2
- Status: Granted
- Kind: B2
- Application number: 17/279,369
- Filed: 2019-09-20
- Published: 2021-12-23
- Granted: 2024-06-04
- Earliest claimed: 2018-09-24
- Assignees: BASF SE
- Applicants: BASF SE
- Inventors: Giovanni D'Andola; Andre Fuchs; Edouard Loisel; Dagmar Pascale Kunsmann-Keitel; Erhard Guenther
- Web page: https://patentgrep.com/patent/US11999865B2

## CPC

- C09D 11/101: Inks specially adapted for printing processes involving curing by wave energy or particle radiation, e.g. with UV-curing following the printing
- C09D 139/04: Homopolymers or copolymers of monomers containing heterocyclic rings having nitrogen as ring member
- B29C 64/124: using layers of liquid which are selectively solidified
- B33Y 10/00: Processes of additive manufacturing
- B33Y 70/00: Materials specially adapted for additive manufacturing
- B33Y 80/00: Products made by additive manufacturing
- C09D 11/102: containing macromolecular compounds obtained by reactions other than those only involving unsaturated carbon-to-carbon bonds
- B29K 2039/00: Use of polymers with unsaturated aliphatic radicals and with a nitrogen or a heterocyclic ring containing nitrogen in a side chain or derivatives thereof as moulding material
- B29K 2995/0077: Yield strength; Tensile strength
- B29K 2995/0089: Impact strength or toughness
- C09D: COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR (cosmetics A61K; processes for applying liquids or other fluent materials to surfaces, in general, B05D; staining wood B27K5/02; glazes or vitreous enamels C03C; natural resins, French polish, drying-oils, driers, turpentine, per se, C09F; polishing compositions other than French polish, ski waxes C09G; adhesives or use of materials as adhesives C09J; materials for sealing or packing joints or covers C09K3/10; materials for stopping leaks C09K3/12; processes for the electrolytic or electrophoretic production of coatings C25D)
- B29C: SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING (making preforms B29B11/00; making laminated products by combining previously unconnected layers which become one product whose layers will remain together B32B37/00 - B32B41/00)
- 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
- B29K: INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR {MOULDS, } REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS

## Abstract

The present invention relates to photocurable compositions, comprising (A1) a N-vinyloxazolidinone of formula (I), wherein R1, R2, R3 and R4 are independently of each other a hydrogen atom or an organic group having not more than 10 carbon atoms, (A2) optionally one, or more second reactive diluents, (B) one, or more oligomers, and (C) a photoinitiator (C), wherein the amount of component (A1) is 5 to 70% by weight based on the amount of components (A1), (A2) and (B), wherein the viscosity of said photocurable composition is in the range 10 to 3000 mPa·s, preferably 10 to 1500 mPa·s at 30° C. The compositions, from which cured three-dimensional shaped articles having balanced mechanical properties combining stiffness with high toughness can be made, are particularly suitable for the production of three-dimensional articles by stereolithography and photopolymer jetting.

## Claims

### Claim 1

A method for producing a three-dimensional article, comprising
a) providing the photocurable composition,
b) exposing the photocurable composition to actinic radiation to form a cured crossection,
c) repeating steps (a) and (b) to build up a three-dimensional article;
wherein the photocurable composition, comprises
(A1) a N-vinyloxazolidinone of formula
wherein
R1, R2, R3 and R4 are independently of each other a hydrogen atom or an organic group having not more than 10 carbon atoms,
(A2) optionally one, or more second reactive diluents,
(B) one, or more oligomers, and
(C) a photoinitiator (C), wherein the amount of component (A1) is 5 to 70% by weight based on the amount of components (A1), (A2) and (B).

### Claim 2 (depends on 1)

The method according to claim 1, wherein the amount of components (A1) and (A2) is 30 to 70% by weight, and the amount of component (B) is 70 to 30% by weight, based on the amount of components (A1), (A2) and (B).

### Claim 3 (depends on 1)

The method according to claim 1, wherein and least two of R1 to R4 n formula I are a hydrogen atom.

### Claim 4 (depends on 1)

The method according to claim 1, wherein the N-vinyloxazolidinone of formula I is selected from a compound, wherein R1, R2, R3 and R4 are a hydrogen atom, a compound, wherein R1 is a C1-C4alkyl group, and R2, R3 and R4 are a hydrogen atom, and a compound, wherein 1 and R2 are a hydrogen atom and R3 and R4 are a C1-C4alkyl group, and mixtures thereof.

### Claim 5 (depends on 1)

The method according to claim 1, wherein the oligomer (B) is selected from the group consisting of polyester acrylates, polyether acrylates, epoxy acrylates and urethane acrylates.

### Claim 6 (depends on 1)

The method according to claim 1, wherein the oligomer (B) is obtained by reacting
(B1) a hydroxyalkylacrylate, or hydroxyalkylmethacrylate,
(B2) an aliphatic diisocyanate, an aliphatic polyisocyanate, a cycloaliphatic diisocyanate, a cycloaliphatic polyisocyanate, an aromatic diisocyanate, or an aromatic polyisocyanate, or mixtures thereof,
(B3) a polyester polyol, which is derived from aliphatic dicarboxylic acids and aliphatic diols, and
(B4) optionally a secondary polyol.

### Claim 7 (depends on 6)

The method according to claim 6, wherein component (B1) is selected from the group consisting of 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2- or 3-hydroxypropyl acrylate, 2- or 3-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, and 4-hydroxybutyl acrylate, component (B2) is selected from the group consisting of 4,4′-, 2,4′- and/or 2,2′-methylenedicyclohexyl diisocyanate (H12MDI), isophorone diisocyanates (IPDI) and tolylene 2,4- and/or 2,6-diisocyanate (TDI) and the polyester polyol (B3) is derived from adipic acid and ethylene glycol and 1,4-butanediol ((poly(ethylene 1,4-butylene adipate) diol, PEBA).

### Claim 8 (depends on 5)

The method according to claim 5, wherein the oligomer (B) is obtained by reacting a polyalkylene glycol with a lactone of formula
at least one cycloaliphatic or asymmetric aliphatic diisocyanate and an hydroxyalkyl(meth)acrylate, or by reacting a lactone of formula (B) with at least one cycloaliphatic or asymmetric aliphatic diisocyanate and an hydroxyalkyl(meth)acrylate, wherein R113 is a divalent alkylene radical having 1 to 12 carbon atoms and which is optionally be substituted by C1-C4alkyl groups and/or interrupted by one or more oxygen atoms.

### Claim 9 (depends on 8)

The method according to claim 8, wherein the oligomer (B) is obtained by reacting c-caprolactone, 4,4′-, 2,4′- and/or 2,2′-methylenedicyclohexyl diisocyanate and hydroxyethylacrylate.

### Claim 10 (depends on 5)

The method according to claim 5, wherein the oligomer (B) is obtained by reacting aliphatic, aromatic, or cyclic diisocyanates with hydroxyalkyl(meth)acrylate.

### Claim 11 (depends on 1)

The method according to claim 1, wherein the photoinitiator (C) is selected from acylphosphine oxide compounds, benzophenone compounds, alpha-aminoketone compounds, phenylglyoxylate compounds, oxime ester compounds, mixtures thereof and mixtures with alpha-hydroxy ketone compounds, or alpha-alkoxyketone compounds.

### Claim 12 (depends on 1)

The method according to claim 1, wherein the photoinitiator (C) is a compound of the formula
wherein
R50 is unsubstituted cyclohexyl, cyclopentyl, phenyl, naphthyl or biphenylyl; or is cyclohexyl, cyclopentyl, phenyl, naphthyl or biphenylyl substituted by one or more halogen, C1-C12alkyl, C1-C12alkoxy, C1-C12alkylthio or by NR53R54 ; or R50 is unsubstituted C1-C20alkyl or is C1-C20alkyl which is substituted by one or more halogen, C1-C12-alkoxy, C1-C12alkylthio, NR53R54 or by —(CO)—O—C1-C24alkyl;
R51 is unsubstituted cyclohexyl, cyclopentyl, phenyl, naphthyl or biphenylyl; or is cyclohexyl, cyclopentyl, phenyl, naphthyl or biphenylyl substituted by one or more halogen, C1-C12alkyl, C1-C12-alkoxy, C1-C12alkylthio or by NR53R54; or R51 is —(CO)R′52; or R51 is C1-C12-alkyl which is unsubstituted or substituted by one or more halogen, C1-C12-alkoxy, C1-C12alkylthio, or by NR53R54;
R52 and R′52 independently of each other are unsubstituted cyclohexyl, cyclopentyl, phenyl, naphthyl or biphenylyl, or are cyclohexyl, cyclopentyl, phenyl, naphthyl or biphenylyl substituted by one or more halogen, C1-C4alkyl or C1-C4alkoxy; or R52 is a 5- or 6-membered heterocyclic ring comprising an S atom or N atom;
R53 and R54 independently of one another are hydrogen, unsubstituted C1-C12alkyl or C1-C12alkyl substituted by one or more OH or SH wherein the alkyl chain optionally is interrupted by one to four oxygen atoms; or R53 and R54 independently of one another are C2-C12-alkenyl, cyclopentyl, cyclohexyl, benzyl or phenyl, or the photoinitiator (C) is a mixture of a compound of the formula (XII) and a compound of the formula
wherein
R29 is hydrogen or C1-C18 alkoxy;
R30 is hydrogen, C1-C18 alkyl, C1-C12 hydroxyalkyl,C1-C18 alkoxy, OCH2CH2—OR34, morpholino, S—C1-C18 alkyl, a group —HC═CH2, —C(CH3)═CH2,
D, E and f are 1-3;
c is 2-10;
G1 and G2 independently of one another are end groups of the polymeric structure;
R34 is hydrogen,
R31 is hydroxy, C1-C16alkoxy, morpholino, dimethylamino or —O(CH2CH2O)g-C1-C16alkyl;
g is 1-20;
R32 and R33 independently of one another are hydrogen, C1-C6alkyl, C1-C16alkoxy or —O(CH2CH2O)g-C1-C16alkyl; or are unsubstituted phenyl or benzyl; or phenyl or benzyl substituted by C1-C12-alkyl; or R32 and R33 together with the carbon atom to which they are attached form a cyclohexyl ring;
R35 is hydrogen, OR36 or NR37R38;
R36 is hydrogen, C1-C12alkyl which optionally is interrupted by one or more non-consecutive O-atoms and which uninterrupted or interrupted C1-C12alkyl optionally is substituted by one or more OH, or R36 is
R37 and R38 independently of each other are hydrogen or C1-C12alkyl which is unsubstituted or is substituted by one or more OH;
R39 is C1-C12alkylene which optionally is interrupted by one or more non-consecutive O—(CO)—NH—C1-C12alkylene—NH—(CO)— or
with the proviso that R31, R32 and R33 not all together are C1-C16alkoxy or —O(CH2CH20)g-C1-C16alkyl, or the photoinitiator is a mixture of different compounds of the formula (XII), or the photoinitiator is a mixture of compounds of the formula (XII) and (XI).

### Claim 13 (depends on 1)

The method according to claim 1, comprising a vat photopolymerization, wherein the photocurable composition according to claim 1 in step b) is cured directly onto a translated or rotated substrate, and the irradiation is patterned via stereolithography, holography, or digital light projection (DLP).

### Claim 14 (depends on 1)

The method according to claim 1, comprising
a) applying a layer of the photocurable composition onto a surface;
b) exposing the layer imagewise to actinic radiation to form an imaged cured cross-section;
c) applying a second layer of the photocurable composition onto the previously exposed imaged cross-section;
d) exposing the layer from step (c) imagewise to actinic radiation to form an additional imaged cross-section, wherein the radiation causes curing of the second layer in the exposed areas and adhesion to the previously exposed cross-section; and
e) repeating steps (c) and (d) in order to build up a three-dimensional article.

### Claim 15 (depends on 1)

A three-dimensional article produced by the method according to claim 1.

### Claim 16 (depends on 15)

The three-dimensional article according to claim 15 having an Izod impact strength (unnotched) of greater than 45 kJ/m2 and/or an E modulus of greater than 1750 MPa.

### Claim 17 (depends on 1)

The method according to claim 1, wherein the viscosity of said photocurable composition is in the range 10 to 1500 mPa·s at 30 ° C.

### Claim 18 (depends on 1)

The method according to claim 1, wherein the amount of components (A1) and (A2) in the photocurable composition is 50 to 70% by weight, and the amount of component (B) in the photocurable composition is 50 to 30% by weight based on the amount of components (A1), (A2) and (B).

### Claim 19 (depends on 1)

The method according to claim 1, wherein the viscosity of the photocurable composition is in the range of 10 to 3000 mPa·s.