RESIN COMPOSITION

Abstract

A resin composition for three dimensional printing at elevated temperatures forming high temperature-resistant materials, the resin composition comprising a heat curable component A having one or more chemical species chosen from the group comprised of monomers and/or oligomers and/or prepolymers of maleimide derivatives according to formula and a light-curable component B having one or more chemical species chosen from the group comprised of (meth)acrylate, (meth)acrylamide, vinyl esters, vinyl ether, vinyl, allyl, alkinyl or styrenic compounds as well as derivatives thereof substituted with at least one molecule from the group from which component A is chosen, wherein the amount of component A ranges from 30 wt % to 95 wt % based on the total weight of components A and B and the amount of the light-curable component B ranges from 5 to 70 wt %, based on the total weight of components A and B.

##STR00001##

Claims

1. A resin composition for three-dimensional printing, the resin composition comprising: a) a heat curable component A having one or more chemical species chosen from the group comprised of monomers and/or oligomers and/or prepolymers of maleimide derivatives according to Formula (I) ##STR00028## as well as isomers thereof, in particular itaconimide, wherein: n is an integer between 1 and 10 R1 represents H, CH3 or CH2, R2 independently represents a linear, branched or cyclic C5-C40 aliphatic or aromatic residue of one or more of the group consisting of phenyl, benzyl, phenethyl, methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, decanyl, dodecanyl, acetic, propanoic, butanoic, pentanoic, undecanoic, dodecanoic, benzoic acid and corresponding esters, alkyl or aromatic esters, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, adamantyl, isobornyl, propenyl, biphenyl, naphthyl, anthracenyl, pyrenyl, bis(methylene)oxy, bis(ethylene)oxy, bis(phenyl)methane, bis(phenyl)ethane, bis(phenyl)propane, bis(phenyl)butane, bis(phenyl)ether, bis(phenyl)thioether, bis(phenyl)amino and bis(phenyl)sulfone, which are optionally substituted with one or more C1-C6 alkyl, C1-C6 alkoxy, C1-C6 thioether, halogen, —NO2, —SO3H, —CF3, —OH, —NH2, —SH, —CN, -isocyanato, -trimethoxysilyl, -triethoxysilyl or a polymerisable group from the substance classes of maleimide and citraconimide compounds and/or isomers thereof, in particular itaconimide, and: b) a light-curable component B having one or more chemical species chosen from the group comprised of (meth)acrylate, (meth)acrylamide, vinyl esters, vinyl ether, vinyl, allyl, alkynyl or styrenic compounds as well as derivatives thereof substituted with at least one molecule from the group from which component A is chosen, wherein the amount of component A ranges from 30 wt % to 95 wt % based on the total weight of components A and B and the amount of the light-curable component B ranges from 5 to 70 wt %, based on the total weight of components A and B characterized in that component A comprises a species of component A with n being an integer from 2 to 10 having an aromatic residue linked to the N-atom of the maleimide ring of Formula I, preferably via a methylene group, in an amount ranging from 20 wt % to 100 wt %, preferably from 30 wt % to 100 wt % and more preferably from 40 wt % to 100 wt %, based on the total weight of component A comprised in the resin composition.

2. The resin composition according to claim 1, characterized in that the amount of component A ranges from 40 wt % to 95 wt %, preferably from 50 wt % to 95 wt %, more preferably from 60 wt % to 95 wt % and even more preferably from 70 wt % to 95 wt % based on the total weight of components A and B and the amount of the light-curable component B ranges from 5 wt % to 60 wt %, preferably from 5 wt % to 50 wt %, more preferably from 5 wt % to 40 wt %, even more preferably from 5 wt % to 30 wt % based on the total weight of components A and B.

3. The resin composition according to claim 1, characterized in that component A further comprises a species of component A with n being an integer from 2 to 10, in which R2 is an aliphatic residue in an amount ranging from 0.5 wt % to 50 wt %, preferably from 3 wt % to 30 wt % and more preferably from 5 wt % to 15 wt %, based on the total weight of component A comprised in the resin composition.

4. The resin composition according to claim 1, characterized in that component A comprises a species of component A with n being 1, in which R2 independently represents a linear, branched or cyclic C5-C40 aliphatic or aromatic residue of one or more of the group consisting of phenyl, benzyl, phenethyl, methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, decanyl, dodecanyl, acetic, propanoic, butanoic, pentanoic, undecanoic, dodecanoic, benzoic acid and corresponding esters, alkyl or aromatic esters, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, adamantyl, isobornyl, propenyl, biphenyl, naphthyl, anthracenyl, pyrenyl, (methylene)oxy, (ethylene)oxy, which are optionally substituted with one or more C1-C6 alkyl, C1-C6 alkoxy, C1-C6 thioether, halogen, —NO2, —SO3H, —CF3, —OH, —NH2, —SH, —CN, -isocyanato, -trimethoxysilyl or -triethoxysilyl, in an amount ranging from 0.5 wt % to 30 wt %, preferably from 1 wt % to 20 wt % and more preferably from 5 wt % to 20 wt %, based on the total weight of component A comprised in the resin composition.

5. The resin composition according to claim 1, characterized in that component A comprises one or more of the group consisting of N-phenylmaleimide, 2,6-xylylmaleimide, N,N′-m-phenylenebismaleimide, N,N′-(4-methyl-m-phenylene)-bismaleimide, 4,4′-diphenylmethanebismaleimide, m-xylylenebismaleimide, 1,3-bis(citraconimidomethyl)benzene, 1,6-bismaleimido-(trimethyl)hexane (isomeric mixture of 2,2,4- and 2,4,4-trimethyl) and/or oligomers and/or prepolymers thereof.

6. The resin composition according to claim 1, characterized in that the composition comprises toughness modifiers selected from the group consisting of thermoplastic resins, in particular polyethylene oxide and polypropylene oxide, reactive rubbers, in particular maleimido-terminated butadiene-acrylonitrile copolymer and/or monomers comprising reactive maleimide- or citraconimide groups with flexible linkers, in particular long aliphatic chains and/or ethylene glycol spacers, monomers such as Q-BOND (a bismaleimide 36 carbon cycloaliphatic branched structure) and/or MIA (an oligomeric polyether bismaleimide, poly(oxybutylene)-di(2-maleimidoacetate), oligomers and/or prepolymers thereof.

7. The resin composition according to claim 1, characterized in that component B comprises a multifunctional (meth)acrylate and/or a mixture of mono- and multifunctional (meth)acrylates, in particular methyl-, ethyl-, 2-hydroxyethyl, butyl-, benzyl-, tetrahydrofurfuryl- or isobornyl(meth)acrylate, 1,4-butanedioldi(meth)acrylate, 1,6-hexanedioldi(meth)acrylate, 1,10-decanedioldi(meth)acrylate or 1,12-dodecanedioldi-(meth)acrylate, 2-(2-biphenyloxy)-ethyl(meth)acrylate, bisphenol-A-di(meth)acrylate, ethoxy- or propoxylated bisphenol-A-di(meth)acrylate (e.g. 2-[4-(2-(meth)acryloyloxyethoxyethoxy)phenyl]-2-[4-(2-(meth)acryloyloxyethoxy)phenyl]-propane) or 2,2-bis[4-(2-(meth)acryloxypropoxy)phenyl]propane, 1,6-bis-[2-(meth)-acryloyloxyethoxycarbonylamino]-2,2,4-trimethylhexane, pentaerythrittetra(meth)acrylate, tricyclodecanedimethanol di(meth)acrylate, di-, tri- or tetraethylenglycol-di(meth)acrylate and/or trimethylolpropantri(meth)acrylate.

8. The resin composition according to claim 1, characterized in that the resin composition comprises at least one photoinitiator suitable for radical polymerization upon light excitation, preferably light excitation within the wavelength spectrum of 150 nm to 580 nm, more preferably between 300 nm to 500 nm, preferably in amounts of 0.01 wt % to 10 wt %, preferably 0.1 wt % to 7 wt %, more preferably 0.2 wt % to 5 wt % based on the weight of components A and B.

9. The resin composition according to claim 8, characterized in that the at least one photoinitiator is, alone or in combination with each other, 2-hydroxy-2-methylpropiophenone, 1-hydroxycyclohexyl phenyl ketone, methyl phenyl glyoxylates, 2-benzyl-2-(dimethylamino)-4′-morpholinobutyrophenone, [1-(4-phenylsulfanylbenzoyl)heptylideneamino]benzoate, [1-[9-ethyl-6-(2-methylbenzoyl)carbazol-3-yl]ethylideneamino] acetate, bis (cyclopentadienyl) bis [2,6-difluoro-3-(1-pyrryl) phenyl] titanium, acyl- or bisacyl-phosphine oxide-based initiators, in particular 2,4,6-trimethylbenzoyldiphenylphosphine oxide (TPO), ethyl-(2,4,6-trimethylbenzoyl)phenyl phosphinate (TPO-L), phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide (BAPO), ethyl (3-benzoyl-2,4,6-trimethylbenzoyl)phenyl phosphinate, acyl-, bisacyl- or tetraacylgermanes, in particular bis(4-methoxybenzoyl)diethylgermane (BMDG), acyl-, bisacyl- or tetraacylsilanes, acyl-, bisacyl- or tetraacylstannanes, benzophenones, in particular benzophenone, 4-methyl benzophenone and/or 4,4′-bis(diethylamino)benzophenone, benzoin, diketones, in particular 9,10-phenanthrenequinone, 1-phenyl-propane-1,2-dione, diacetyl or 4,4′-dichlorobenzil and/or derivatives thereof, thioxanthones, in particular 2,4-diethyl-9H-thioxanthen-9-one.

10. The resin composition according to claim 1, characterized in that the resin composition comprises one and/or more initiators for radical polymerisation, in particular thermal initiators, preferably azo compounds, more preferably 2,2′ azobis(isobutyronitrile) and/or azobis-(4-cyanovaleric acid)) and/or peroxides (e.g. dibenzoyl peroxide, dilauroyl peroxide, dicumyl peroxide, tert-butylperbenzoate, di-(tert-butyl)-peroxide) and/or 1,1,2,2-tetraphenyl-1,2-ethanediol.

11. The resin composition according to claim 1, characterized in that the resin composition comprises at least one polymerisation inhibitor, preferably an inhibitor selected from the group consisting of hydroquinones, benzoquinones and/or phenothiazines.

12. The resin composition according to claim 9, characterized in that photoinitiators, thermal initiators and/or polymerization inhibitors are additionally functionalized with a polymerisable functional group, which can undergo copolymerisation either with component A or component B.

13. The resin composition according to claim 1, characterized in that component A further comprises a comonomer and/or cooligomer and/or coprepolymer, which is able to copolymerize with component A as well as with derivatives thereof, in particular a comonomer and/or cooligomer and/or coprepolymer selected from the group of alkenylphenol, alkenylphenyl ether, alkenylphenol ether, polyamine, aminophenol, amino acid hydrazine, cyanate ester, diallyl phthalate, triallyl isocyanurate, triallyl cyanurate, vinylic and/or styrenic functional groups.

14. The resin composition according to claim 1, characterized in that the resin composition comprises at least one catalyst for the thermal curing of component A, the catalyst preferably being selected from the group consisting of tertiary amines, in particular (1,4-diazabicyclo[2.2.2]octane) (DABCO) and triethylamine, phosphines, triphenyl phosphonate, imidazoles, in particular 2-methyl-1-vinyl imidazole, organic acids and/or peroxides.

15. The resin composition according to claim 1, characterized in that the resin composition at room temperature (20° C.) has a viscosity >5 Pa*s, preferably >50 Pa*s.

16. The use of a resin composition according to claim 1, characterized in that the composition is subjected to a light-induced structuring step followed by a heat-induced curing step.

17. The use of a resin composition according to claim 16, characterized in that the light-induced structuring step is carried out at elevated processing temperatures of the resin composition, preferably at a temperature between 40° C. and 150° C., more preferably between 60° C. and 120° C., even more preferably between 70° C. and 110° C.

18. The use of a resin composition according to claim 17, characterized in that a layer of the resin composition is formed on a carrier, preferably by means of a recoater blade, the resin composition preferably having a viscosity at said processing temperature of 0.01 to 40 Pa*s, preferably of 0.1 to 25 Pa*s

19. The use of a resin composition according to claim 16, characterized in that the light-induced structuring step is performed for building a shaped body by 3D printing, wherein layers of said shaped body are formed one after the other and one on top of each other by each forming a material layer of predetermined thickness of the resin composition between a transparent or at least partially transparent carrier, such as a plate, a carrier film or a bottom of a vat, and a mechanically adjustable construction platform, or the shaped body at least partially formed on the construction platform, and wherein the so defined material layer is cured in a position-selective manner, in particular by irradiation through the transparent or at least partially transparent carrier, to provide the desired shape of the shaped body layer.

20. An item produced by subjecting the resin composition according to claim 1 to a light-induced structuring step followed by a heat-induced curing step.

21. An item according to claim 20, characterized in that the item has a heat deflection temperature (HDT(B)) ranging from 250° C. to 360° C., a storage modulus of >1 GPa up to temperatures in the range from 250° C. to 360° C., a glass transition temperature ranging from 250° C. to 360° C. and a flexural modulus at room temperature (20° C.) of >3 GPa.

Description

BRIEF DESCRIPTION OF THE FIGURES

[0097] FIG. 1 shows a schematic configuration of a high temperature additive manufacturing device used for curing the curable compositions according to the present invention by means of a 3D printing process,

[0098] FIG. 2 represents a schematic example for the network formation via a first light curing step and subsequent heat-induced curing step (i.e. thermal post-processing),

[0099] FIG. 3 shows 3D-parts printed from formulation DM1 (cone filter, post-processed; fan duct, green part),

[0100] FIG. 4 shows the data retrieved from the viscosity measurements of the curable formulations according to the Comparative Example 1 and Examples 1 and 2 at varying temperatures and

[0101] FIG. 5 shows the data retrieved from the DMA measurements (storage modulus G′) of the printed and post-cured polymers according to the Comparative Example 1 and Examples 1 and 2.

[0102] In FIG. 1, reference numeral 1 denotes a material support, on which a material layer 11 is arranged. Spaced from the material support 1, a construction platform 8 is arranged, which is height-adjustable in the z direction and is tiltably mounted about the axis 4. Between the build platform 8 and the material support 1, some material layers 11 are already constructed. The material support 1 is translationally movable along the x-direction perpendicular to the z-direction.

[0103] Furthermore, a material introduction device 3 is provided which comprises a first recoater blade 5 and a second recoater blade 6. The first recoater blade 5 is height adjustable by means of a recoater motor 10 in the z direction and the second recoater blade 6 has a spring 7 which holds the second recoater blade 6 in abutment with the material support 1 in the z direction. Between the two recoater blades 5 and 6 a material reservoir 2 is formed, which can be supplied by means of a conveyor 9 with the inventive resin composition.

[0104] In the phase of the method shown in FIG. 1, the material support 1 is in the second position. The construction platform 8 is lowered in the direction of the material support 1, so that a new material layer 11 of the inventive resin composition can be formed by the material layer 11 and is irradiated selectively on the material support 1 by means of a radiation source, not shown, from below through the material support 1 and thereby structured and solidified. The material layer 11 was applied during the movement of the material support 1 in the second position by the first recoater blade 5.