WO2023117656A1 - Composition durcissable et son utilisation - Google Patents

Composition durcissable et son utilisation Download PDF

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Publication number
WO2023117656A1
WO2023117656A1 PCT/EP2022/086026 EP2022086026W WO2023117656A1 WO 2023117656 A1 WO2023117656 A1 WO 2023117656A1 EP 2022086026 W EP2022086026 W EP 2022086026W WO 2023117656 A1 WO2023117656 A1 WO 2023117656A1
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Prior art keywords
meth
thiol
acrylate
weight
composition according
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PCT/EP2022/086026
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German (de)
English (en)
Inventor
Zhihao Tian
Xuan Zhang
René HENSEL
Eduard Arzt
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Leibniz-Institut Für Neue Materialien Gemeinnützige Gmbh
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Publication of WO2023117656A1 publication Critical patent/WO2023117656A1/fr

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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • 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
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y70/00—Materials specially adapted for additive manufacturing
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • 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
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/0037—Production of three-dimensional images
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • 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
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/0275—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with dithiol or polysulfide compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • 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
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/20—Exposure; Apparatus therefor
    • G03F7/2051—Exposure without an original mask, e.g. using a programmed deflection of a point source, by scanning, by drawing with a light beam, using an addressed light or corpuscular source
    • G03F7/2053—Exposure without an original mask, e.g. using a programmed deflection of a point source, by scanning, by drawing with a light beam, using an addressed light or corpuscular source using a laser

Definitions

  • the invention relates to a curable composition, in particular for the direct printing of elastic, complex microstructures and metamaterials by means of two-photon lithography.
  • Two-photon lithography is a technology that enables the production of three-dimensional structures through local polymerization. As a result, the simple production of complex structures is also possible.
  • IP-S two-photon lithography deform plastically
  • IP-DIP IP-DIP
  • the modulus of elasticity is also not adjustable with it.
  • silicone lacquers such as IP-PDMS are elastic, they only allow a low resolution (greater than 10 pm) and form fidelity.
  • the object of the invention is to specify a composition for two-photon lithography which allows high resolution and shape fidelity. This allows complex elastic microstructures to be printed directly.
  • a curable composition for two-photon lithography which comprises the following components: a) at least one oligomer having at least 2 (meth)acrylate groups; b) at least one photoinitiator; c) at least one crosslinker; d) optionally at least one stabilizer; e) optionally at least one thiol compound.
  • a (meth)acrylate group is understood as meaning a methacrylate group or acrylate group, with an acrylate group being preferred.
  • the oligomer has at least 2 (meth)acrylate groups, preferably exactly 2 (meth)acrylate groups.
  • the oligomer segment can be derived from different polymers. These can be, for example, olefins, polyethers, poly(meth)acrylates such as poly(meth)acrylamide, poly(meth)acrylic acid, polyHPMA or polyHEMA, polyethylene glycol (PEG), polyvinyl alcohol (PVA), polyurethane (PU), polyvinylpyrrolidone (PVP) , polyamides , poly ( amidoamine ) ( PAMAM ) , polyesters, polylactides , polyglycolic acid ( PGA ) or poly ( lactide-co-glycolide) ( PLGA ) , polyanhydrides , poly ( ortho ) esters, polyacetals , poloxamers (block copolymers of Ethylene oxide (PEG) and propylene oxide (PPG)) such as PEG-Co
  • oligomer segment derived from polyurethanes which is modified with (meth)acrylate groups is preferred.
  • the oligomer can also include other comonomers such as esters, ethers or alkyl groups.
  • the (meth)acrylate groups are preferably arranged at least at the ends of the oligomer chain, in particular via esterification with diols having 2 to 5 carbon atoms.
  • the oligomer preferably has a molecular weight of less than 20000 g/mol, in particular less than 10000 g/mol, preferably between 1000 g/mol and 20000 g/mol, in particular between 1000 g/mol and 10000 g/mol, very particularly between 2000 g/mol mol and 7000 g/mol .
  • the oligomer preferably the urethane (meth) acrylate oligomer is preferably in a proportion of 30 to 99 wt. -% in the composition, preferably 40 to 99 wt. -%, in particular 49.5 to 99% by weight. % .
  • the composition includes at least one photoinitiator.
  • the invention is not subject to any relevant restrictions in the choice of the free-radical and/or cationic photoinitiator used. It is easily possible for a person skilled in the art to choose a suitable photoinitiator on the basis of knowledge of the present technological field. It has been shown that when choosing the free-radical photoinitiator or several free-radical photoinitiators, those of the Norrish type I and/or Norrish type II are of particular advantage. These photoinitiator types differ in manner their initiation of the photochemical processes. Photoinitiators of Norrish type II are preferred.
  • the Norrish type I free radical photoinitiator decomposes with alpha cleavage of the bond between the carbonyl function and the alkyl group to form free radicals.
  • the radicals formed interact with the monomers to be polymerized, which initiates the polymerization.
  • Photoinitiators of Norrish type I are basically unimolecular photoinitiators and can be based on benzyl ketones, monomeric hydroxy ketones, polymeric hydroxy ketones, alpha-amino ketones, acylphosphine oxides and metallocenes. This list is not exhaustive.
  • Norrish type I photoinitiators 2-Hydroxy-1- ⁇ 4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]-phenyl ⁇ -2-methyl-propane-1 -one (Irgacure 127) , 1-Hydroxycyclohexyl-phenyl-ketone (Irgacure 184, Doublecure 184) , Phenylbis 2 , 4 , 6-trimethylenezoylphosphine oxide (Irgacure 819) , 2-Benzyl-2-dimethylamino-l- ( 4-morpholino- phenyl ) -butanone-1 (Irgacure 369) , 2 , 4 , 6-trimethylbenzoyl-diphenyl-phosphine oxide (Doublecure TPO, Genocure LTM) , 2-dimethylamino-2-( 4-methyl-benzyl ) -1-( 4-
  • Norrish type II photoinitiators 2-ethylhexyl 4-methylaminobenzoate (Genocure EHA), ethyl 4-dimethylaminobenzoate, isopropyl ithioxanthone (Genocure ITX), benzophenone, 4-phenylbenzophenone (Genocure PBZ ) , 4,4'-bis(diethylamino)benzophenone (doublecure EMK) .
  • Type II photoinitiators are typically bimolecular photoinitiators and can be used with or without an additional synergist.
  • a corresponding synergist is present in particular in the form of acrylated or non-acrylated tertiary amines or alkoxylated acrylate monomers.
  • Particularly suitable amines are trimethylamine, dimethylethanolamine, methyldiethanolamine and/or acrylated amines and alkoxylated acrylate monomers such as diethylene glycol diacrylate.
  • the photoinitiator is preferably used in a proportion of 0.5 to 5% by weight.
  • the photoinitiator must be suitable for two-photon lithography.
  • the composition also includes at least one crosslinker.
  • This is a compound which, in particular, comprises at least 3 (meth)acrylate groups.
  • the at least one crosslinker has at least 3, preferably at least 4, (meth)acrylate groups.
  • Particularly preferred are 3, 4, 5, 6, 7, 8, 9 or 10 (meth)acrylate groups, preferably 3, 4, 5, 6, 7, 8 (meth)acrylate groups, particularly preferably 3, 4, 5 or 6 (meth)acrylate groups, in particular 3 or 4 (meth)acrylate groups, very particularly 4 (meth)acrylate groups .
  • Crosslinkers based on (poly)ethylene glycol (PEG), polyols, alditols, polyvinyl alcohol (PVA), polyurethane (PU), polyvinylpyrrolidone (PVP), polyamides, poly(amidoamine) (PAMAM), polyesters, polylactides, polyglycolic acid ( PGA) or poly(lactide-co-glycolide) (PLGA), polyanhydrides, poly(ortho)ester, polyacetals, poloxamers (block copolymers of ethylene oxide (PEG) and propylene oxide (PPG)) such as PEG-Co-PPG-Co-PEG) , (poly)glycerol.
  • PEG polyethylene glycol
  • PVA polyvinyl alcohol
  • PU polyurethane
  • PVP polyvinylpyrrolidone
  • PAMAM polyamides
  • PAMAM poly(amidoamine)
  • polyesters polylactides, polyglycoli
  • Crosslinkers based on polyols are preferred.
  • Suitable crosslinkers with at least three (meth)acrylate groups are glycerol triacrylate; TMPTMA, trimethylolpropane trimethacrylate; TMPTA, trimethylolpropane tri(meth)acrylate; DTMPTA; Ditrimethylolpropanetetra(meth)acrylate; DiPENTA, dipentaerythritol penta(meth)acrylate; or DPEHA, dipentaerythritol hexa(meth)acrylate.
  • TMPTMA trimethylolpropane trimethacrylate
  • TMPTA trimethylolpropane tri(meth)acrylate
  • DTMPTA Ditrimethylolpropanetetra(meth)acrylate
  • DiPENTA dipentaerythritol penta(meth)acrylate
  • DPEHA dipentaerythritol hexa(meth)acrylate.
  • the at least one crosslinker preferably has a molecular weight of less than 2000 g/mol, in particular less than 1000 g/mol, preferably between 100 g/mol and 2000 g/mol, very particularly between 200 g/mol and 1000 g/mol.
  • the crosslinking agent is preferably used in a proportion of 0.5 to 50% by weight, preferably 5 to 50% by weight, particularly preferably 5 to 40% by weight. A higher proportion of crosslinker increases the modulus of elasticity.
  • a ratio of at least 1.01:1 is preferred.
  • the acrylate groups of the crosslinker are therefore preferably present in excess.
  • the composition optionally includes at least one stabilizer.
  • stabilizers can be the stabilizers known for (meth)acrylates. If thiol compounds are present, the stabilizers can influence the polymerization by the thiol-ene reaction.
  • At least one stabilizer is preferably a compound based on phosphorus (III), preferably based on triphenyl phosphite.
  • the composition optionally comprises at least one other stabilizer, preferably based on phenols or di- or trihydroxybenzenes, such as catechol, hydroquinone, reorcinol, pyrogallol, butylated hydroxytoluene (BHT), methoxyhydroquinone (MEHQ).
  • at least one other stabilizer preferably based on phenols or di- or trihydroxybenzenes, such as catechol, hydroquinone, reorcinol, pyrogallol, butylated hydroxytoluene (BHT), methoxyhydroquinone (MEHQ).
  • the stabilizers can increase the durability of the composition since they prevent the reaction between (meth)acrylate groups and thiols.
  • the composition optionally includes at least one thiol compound.
  • a connection with at least two is preferred thiol groups.
  • the thiol compound leads to a significant
  • the thiol compound is not further restricted in its chemical structure and preferably includes aromatic and aliphatic thiols and combinations thereof.
  • the at least one thiol compound is preferably selected from the group consisting of ester-based thiols, polyethers with reactive thiol groups, polythioethers, polythioetheracetals, polythioetherthioacetals, polysulfides, thiol-terminated urethanes, thiol derivatives of isocyanurates and glycoluril and combinations thereof.
  • ester-based thiols based on 2-mercaptoacetic acid examples include trimethylolpropane trimercaptoacetate, pentaerythritol tetramercaptoacetate and glycol dimercaptoacetate, which are available from Bruno Bock under the brand names ThiocureTM TMPMA, PETMA and GDMA.
  • ester-based thiols include trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptobutylate), glycol di(3-mercaptopropionate), and tris[2-(3-mercaptopropionyloxy)ethyl ] isocyanurate, which are available under the brand names ThiocureTM TMPMP, PETMP, GDMP and TEMPIC from Bruno Bock.
  • thioethers examples include DMDO (1,8-dimercapto-3,6-dioxaoctane) available from Arkema S.A. , DMDS ( Dimercaptodiethylsulfide ) and DMPT ( 2 , 3- Di((2-mercaptoethyl)thio)-1-propanethiol) both available from Bruno Bock.
  • DMDO 1,8-dimercapto-3,6-dioxaoctane
  • DMDS Dimercaptodiethylsulfide
  • DMPT 2 , 3- Di((2-mercaptoethyl)thio)-1-propanethiol
  • thiol compounds having at least 2 thiol groups, preferably at least 3, in particular at least 4 thiol groups.
  • Thiol compounds having 2, 3, 4, 5, 6, 7, 8 thiol groups, in particular 2, 3, 4, 5, 6 thiol groups, particularly preferably 2, 3, 4, 5 thiol groups, very particularly 4 thiol groups, are particularly preferred.
  • thiol compounds with 3 or 4 groups contribute to the additional crosslinking of the (meth)acrylate.
  • the at least one thiol compound preferably has a molecular weight of less than 2000 g/mol, in particular less than 1000 g/mol, preferably between 100 g/mol and 2000 g/mol, very particularly between 200 g/mol and 1000 g/mol.
  • the at least one thiol compound is preferably used in a proportion of 0 to 20% by weight, preferably 0 to 10% by weight.
  • At least one thiol compound When at least one thiol compound is added, it is preferably added in a proportion of 0.1 to 20% by weight, more preferably 2 to 20% by weight, particularly 2 to 10% by weight.
  • the molar ratio of the total (meth)acrylate groups of oligomer and crosslinker to the thiol groups of the thiol compound is preferably 10:1 to 1:2, preferably 5:1 to 1:1.5.
  • the crosslinking of the (meth)acrylate groups in the presence of the at least one thiol compound becomes a step-growth polymerization (thiol-ene reaction). This reduces structure shrinkage and reduces reaction volume, increasing resolution.
  • the thiol compound reduces the influence of atmospheric oxygen on the curable composition.
  • the addition of the thiol lowers the modulus of elasticity of the cured composition. It may be necessary to adjust the proportion of the other components, in particular the crosslinking agent.
  • the composition a) comprises 30 to 99% by weight of at least one oligomer, preferably
  • Urethane (meth)acrylate oligomer, with at least 2 (meth)acrylate groups b) 0.5 to 5% by weight of at least one photoinitiator; c) 0.5 to 50% by weight of at least one crosslinker; d) 0 to 1% by weight of at least one stabilizer; e) 0 to 20% by weight of at least one thiol compound.
  • composition a) comprises 30 to 94.5% by weight of at least one oligomer, preferably
  • the composition a) comprises 30 to 98.9% by weight of at least one oligomer, preferably
  • Urethane (meth)acrylate oligomer, with at least 2 (meth)acrylate groups b) 0.5 to 5% by weight of at least one photoinitiator; c) 0.5 to 50% by weight of at least one crosslinker; d) 0 to 1% by weight of at least one stabilizer; e) 0.1 to 20% by weight of at least one thiol compound.
  • composition a) comprises 30 to 98.9% by weight of at least one oligomer, preferably
  • Urethane (meth)acrylate oligomer, with at least 2 (meth)acrylate groups b) 0.5 to 5% by weight of at least one photoinitiator; c) 0.5 to 50% by weight of at least one crosslinker; d) 0 to 1% by weight of at least one stabilizer; e) 0.1 to 20% by weight of at least one thiol compound.
  • the composition comprises a) 30 to 97% by weight of at least one urethane (meth)acrylate oligomer having at least 2 (meth)acrylate groups; b) 0.5 to 5% by weight of at least one photoinitiator; c) 0.5 to 50% by weight of at least one crosslinker; d) 0 to 1% by weight of at least one stabilizer; e) 2 to 20% by weight of at least one thiol compound, preferably 2 to 10% by weight
  • the at least one oligomer, preferably urethane (meth)acrylate oligomer has two (meth)acrylate groups
  • the at least one crosslinker has at least three (meth)acrylate groups
  • the at least one thiol compound if present, at least three thiol groups, preferably the at least one oligomer, preferably urethane (meth)acrylate oligomer, has two (meth)acrylate groups.
  • composition according to the invention preferably does not comprise any solvents, particularly preferably no further components.
  • the invention also relates to the use of the composition according to the invention in two-photon lithography.
  • the invention also relates to a method for producing three-dimensional structures, comprising the following steps: a) providing a composition according to the invention; b) Selective polymerization by two-photon lithography:
  • the structures produced are preferably elastic structures.
  • the simple possibility of varying the modulus of elasticity over a large range also enables the simple production of multilayer structures.
  • the method is carried out at least twice in succession with at least two different compositions, at least one composition being a composition according to the invention, so that a structure with at least two regions with different moduli of elasticity is obtained.
  • a first structure can be produced, which in a second step is then at least partially coated with a material having a different, preferably lower, modulus of elasticity.
  • a material having a different, preferably lower, modulus of elasticity This makes it possible to produce soft shell structures.
  • the composition according to the invention allows the modulus of elasticity to be easily adjusted over a wide range.
  • the invention also relates to a three-dimensional structure produced with the composition according to the invention.
  • composition according to the invention is particularly suitable for producing structures with reversible deformation, for example for mechanical metamaterials.
  • the structures produced can in particular have adhesive properties, particularly dry-adhesive properties, and can have switchable adhesion, for example.
  • the manufactured structures can also be used for grippers or similar tools, especially when handling small objects.
  • the modulus of elasticity of the structure obtained can be varied, for example in a range from 4 to 140 MPa, in particular by adding crosslinking agents and optionally the thiol compound.
  • the resolution of the two-photon lithography can be significantly improved, in particular the vertical resolution.
  • the vertical resolution is preferably below 10 pm, in particular below 5 pm, very particularly below 1 pm. Even vertical resolutions below 800 nm can be achieved.
  • composition according to the invention has a particularly low shrinkage of less than 1% during crosslinking. This guarantees high dimensional stability and low residual stresses in the structures produced.
  • composition according to the invention is particularly suitable for miniaturized mechanical metamaterials, switchable adhesion structures, microrobotics, sensors, mechanical logic circuits, programmable materials or micro-electronic-mechanical systems.
  • Structures can also be produced on surfaces. These can be, for example, haptic surfaces that are non-linearly deforming for perception.
  • a further application is the production of optical materials, which can also be elastic, such as deformable lenses or optical crystals, and the optical materials produced using the method, such as deformable lenses or optical crystals.
  • range information always includes all - not mentioned - intermediate values and all conceivable sub-intervals.
  • 6 further printed structures with a 25x objective; a, b) columns for mechanical tests with composition A.4 (a) and B.8 (b) ; c) gecko printed with B.3; d) Isotruss cell with a frame thickness of 6.5 gm with composition A.8 with 4% by weight thiol; e) Chiral metamaterial with a structure thickness of 31 gm with composition A.8; f) octet truss with 3x3x3 cells with a frame thickness of 4 gm with composition A.8;
  • FIG. 7 shows examples of printed structures with a 63x objective and composition A.8 with 4% by weight PETMP; a) Eiffel Tower; b) Enlargement of a) ; c) octet truss with 3x3x3 cells and a frame thickness of 1.6 gm; d) Isotruss with 3x3x3 cells and a frame thickness of 2.2 gm;
  • FIG. 11 Switchable adhesion of the structure from FIG. 10 in different steps a) to f);
  • Fig. 14 The figure shows the manufacture of a multi-layer structure.
  • a first step a) a three-dimensional structure is produced; b) this structure is coated with a further composition in a second step.
  • Figure 1 shows chemical structures including urethane acrylate oligomer (CN9002, Sartomer, USA, molecular weight Mw 5450 g/mol, density: D: 1.04 g/ml), photoinitiator (4,4'-bis(diethylamino)benzophenone , EMK Rahn AG, Switzerland, molecular weight Mw 324.4 g/mol, sensitive at 390 nm), crosslinker di(trimethylolpropane) tetraacrylate (DTMPTA, Sigma-Aldrich, USA, Mw 466.52 g/mol, D 1.101 g /ml) , thiol monomer pentarythritoltetrakis (3-mercaptopropionate) (PETMP, Mw 488, 66 g/mol, D 1.28 g/mol) , 2 stabilizers triphenyl phosphite (TPP, Mw 310.28 g/mol, D 1, 18 g/ml
  • FIG. 2 shows the change in the modulus of elasticity as the acrylate monomer DTMPTA is varied.
  • Table 1 shows the compositions used.
  • the acrylate ratio in Table 1 represents the molar ratio of the acrylate groups in the acrylate monomer to the oligomer.
  • FIG. 3 shows mechanical measurements of the samples from Table 2 with variation of the acrylate monomer DTMPTA after addition of the stabilizers TPP and PYR (each 5.875 mmol/L).
  • the acrylate ratio in Table 2 represents the molar ratio of the acrylate groups in the acrylate monomer to the oligomer.
  • the addition of thiol improved the resolution and shrinkage behavior.
  • the compositions tested are shown in Table 3.
  • the addition of thiol lowers the modulus of elasticity from 21 MPa to 3.9 MPa (measurements in FIG. 4).
  • the acrylate ratio in Table 3 represents the molar ratio of the acrylate groups in the acrylate monomer to the oligomer.
  • the thiol ratio in Table 3 is the molar ratio of acrylate groups to thiol groups.
  • Figures 5 and 6 show the improvement in resolution by the addition of thiol with a 25x objective.
  • the structures in Figure 5 were all made with the same parameters.
  • FIG. 7 shows structures which were produced with a 63x objective.
  • a) and b) show a manufactured Eiffel Tower with structures with a vertical resolution of 800 nm.
  • C) and d) show isotruss structures with different frame thicknesses of 1.6 pm and 2.2 pm. This shows the beneficial influence of the crosslinker.
  • FIG. 8 shows a structure for switchable adhesion by twisting produced with the composition according to the invention.
  • Figure 9 shows the dependency of the peel force (adhesive force) and the compression of the structure of Figure 8.
  • FIG. 10 shows an example of a structure with switchable adhesion, in particular for triggering detachment.
  • FIG. 11 shows a sequence of recordings for the switchable detachment by the structure from FIG. 10.
  • the structure is moved downwards onto the object.
  • the structure contacts the object.
  • the object is lifted and transported a little to the right (c).
  • the object is put down again. Further compression compresses the structure (e).
  • the compression is so great that the flexible upper part of the structure folds inwards and reduces adhesion so that the structure can be detached from the object. Through re-expansion and decompression, the structure returns to its original shape.
  • FIG. 12 shows the two-photon structuring process schematically (left) and top views during the process (1-3) and the final structure (4).
  • the usual structure is shown on the left.
  • the curable composition photoresist
  • the laser laser
  • the laser is focused on a specific volume (focused laser) via an objective (objective lens). This is where the polymerization takes place.
  • objective lens objective lens
  • FIG. 13 shows results of pressure tests for mechanical characterization in stress-strain diagrams (stress-strain).
  • stress-strain stress-strain diagrams
  • the pronounced hysteresis in the curves in a) and b) indicate strong irreversible deformation of the commercial coating systems.
  • Their moduli of elasticity are a) 1.4 and b) 1.3 GPa.
  • the deformation in c) is almost exclusively reversible, characterized by the very low hysteresis.
  • the modulus of elasticity is 2.3 MPa.
  • d) Increasing the proportion of crosslinker increases the Young's modulus to 70 MPa, but at the same time increases the irreversible deformation.
  • the ratio of the compression carried out to the remaining deformation is 0.2. This is less than the commercial paint systems where this ratio is greater than 0.5.
  • FIG. 14 shows the production of multi-material structures.
  • structures with areas and/or coatings with different moduli of elasticity can be produced in a simple manner.
  • a structure made up of IP-S (Nanoscribe) produced ( Figure 14 a)).
  • This structure is then coated with a different composition (B. 5) using two-photon lithography.
  • the composition according to the invention in particular allows the modulus of elasticity to be varied in a simple manner, so that, for example, structures with a hard core and a soft coating can be produced easily (soft-shell structures).
  • TPP and PYR were each used at a concentration of 5.875 mmol/L.
  • TPP and PYR were each used at a concentration of 5.875 mmol/L.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Optics & Photonics (AREA)
  • Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)

Abstract

L'invention concerne une composition durcissable pour la production de structures par lithographie à deux photons. Ceci est obtenu au moyen d'une composition durcissable pour la lithographie à deux photons comprenant au moins un oligomère de (méth)acrylate d'uréthane ayant au moins deux groupes (méth)acrylate, au moins un photoinitiateur, au moins un agent de réticulation, éventuellement au moins un stabilisant, et éventuellement au moins un composé thiol.
PCT/EP2022/086026 2021-12-23 2022-12-15 Composition durcissable et son utilisation WO2023117656A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102021134562.6A DE102021134562A1 (de) 2021-12-23 2021-12-23 Härtbare Zusammensetzung und ihre Anwendung
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WO2015072532A1 (fr) * 2013-11-15 2015-05-21 富士フイルム株式会社 Composition durcissable, procédé de production d'un film durci, film durci, et dispositif d'affichage
US20170349707A1 (en) * 2014-12-10 2017-12-07 Joanneum Research Forschungsgesellschaft Mbh Poly- or prepolymer composition, or embossing lacquer comprising such a composition and use thereof
WO2021089313A1 (fr) * 2019-11-07 2021-05-14 Basf Se Compositions rinçables à l'eau destinées à être utilisées en impression 3d
US20210388151A1 (en) * 2018-11-05 2021-12-16 Universiteit Gent Acrylate end-capped urethane- or urea-based polymers
EP4049841A1 (fr) * 2021-02-26 2022-08-31 Cubicure GmbH Composition de résine hybride

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WO2012041519A2 (fr) * 2010-10-01 2012-04-05 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Élastomères photoréticulants pour le prototypage rapide
WO2015072532A1 (fr) * 2013-11-15 2015-05-21 富士フイルム株式会社 Composition durcissable, procédé de production d'un film durci, film durci, et dispositif d'affichage
US20170349707A1 (en) * 2014-12-10 2017-12-07 Joanneum Research Forschungsgesellschaft Mbh Poly- or prepolymer composition, or embossing lacquer comprising such a composition and use thereof
US20210388151A1 (en) * 2018-11-05 2021-12-16 Universiteit Gent Acrylate end-capped urethane- or urea-based polymers
WO2021089313A1 (fr) * 2019-11-07 2021-05-14 Basf Se Compositions rinçables à l'eau destinées à être utilisées en impression 3d
EP4049841A1 (fr) * 2021-02-26 2022-08-31 Cubicure GmbH Composition de résine hybride

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