EP1248685B1 - Verfahren zur herstellung eines mikrostrukturierten oberflächenreliefs durch prägen thixotroper schichten und mikrostrukturiertes oberflächenrelief - Google Patents

Verfahren zur herstellung eines mikrostrukturierten oberflächenreliefs durch prägen thixotroper schichten und mikrostrukturiertes oberflächenrelief Download PDF

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EP1248685B1
EP1248685B1 EP01911478A EP01911478A EP1248685B1 EP 1248685 B1 EP1248685 B1 EP 1248685B1 EP 01911478 A EP01911478 A EP 01911478A EP 01911478 A EP01911478 A EP 01911478A EP 1248685 B1 EP1248685 B1 EP 1248685B1
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Prior art keywords
surface relief
microstructured surface
coating composition
producing
thixotropic
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German (de)
English (en)
French (fr)
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EP1248685A2 (de
Inventor
Andreas Gier
Nora Kunze
Martin Mennig
Peter W. Oliveira
Stefan Sepeur
Bruno SCHÄFER
Helmut Schmidt
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Leibniz Institut fuer Neue Materialien Gemeinnuetzige GmbH
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Leibniz Institut fuer Neue Materialien Gemeinnuetzige GmbH
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/12—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by mechanical means
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D1/00—Processes for applying liquids or other fluent materials
    • B05D1/40—Distributing applied liquids or other fluent materials by members moving relatively to surface
    • B05D1/42—Distributing applied liquids or other fluent materials by members moving relatively to surface by non-rotary members

Definitions

  • the present invention relates to a method for producing microstructured Surface reliefs in which the surface relief is embossed with an embossing device embossed thixotropic coating composition applied to a substrate is provided with this microstructured surface relief substrates as well as the Use of these substrates.
  • Surface relief structures are used for various fields of application. In the foreground are decorative applications, for example on metal, plastic, cardboard or stone. In addition, applications for the production of non-slip floor coverings, shoe soles, refined textiles, structured soundproofing panels or electrical cables are mentioned. In addition to screen printing processes, printing processes with structured rollers or casting processes are used to create relief structures with dimensions in the mm range. For technical reasons, thixotropic, structurally or highly viscous lacquers are used, additives known from the prior art being used for thixotroping. These can also be fine-scale inorganic powders such as SiO 2 or CaCO 3 . Thixotropic lacquer and binder systems can also be used to produce stochastic surface relief structures using spray processes with the addition of relatively coarse-grained particles that determine the structural geometry.
  • embossing Roll embossing processes
  • stamping thixotropic lacquers reactive stamping.
  • the embossing roller is hot stamped into a thermoplastic substrate which is over the Glass transition point is heated, pressed. Then the structure is through rapid cooling fixed after the roller was pulled out.
  • This process also uses small, rigid stamps Production of very fine structures in the ⁇ m and 100 nm range for electronic Applications examined. Disadvantages here are inaccuracies that are caused are used by the high thermal expansion coefficient thermoplastic polymers and the high restoring forces as a result are very small Radii of curvature that also round off edges when cooling rapidly to lead.
  • WO-A-95/31413 describes a process for the production of structured inorganic layers where a coating composition that is available is by hydrolysis and polycondensation of hydrolyzable silanes and optionally adding fine-scale fillers, applied to a substrate and e.g. is structured with an embossing stamp.
  • the coating composition is structured while the die is in the coating composition located. Thixotropic coating compositions will not described.
  • WO-A-93/06508 discloses optical elements with an embossed surface structure, where the embossed surface is made of a transparent composite material consists.
  • the structuring can also be done here by means of an embossing stamp and the composition is cured before removing the stamp.
  • Thixotropic coatings are also not mentioned.
  • the invention has for its object a method for producing To provide microstructures with dimensions in the lower ⁇ m to nm range, that on the one hand the high demands on impression accuracy, which are in this dimension range are necessary, guaranteed and on the other hand shorter manufacturing times allows.
  • the object of the invention is surprisingly achieved by a method for Production of a microstructured surface relief solved, in which one Substrate applies a coating composition that is thixotropic or that obtained thixotropic properties with a Embossing device the surface relief in the applied thixotropic coating composition embosses and the coating composition Removing the embossing device hardens.
  • the coating composition can be applied in any conventional manner become. All common wet chemical coating processes can be used be used. Examples are spin coating, (electro) dip coating, Knife coating, spraying, spraying, pouring, brushing, flood coating, film casting, Knife casting, slot coating, meniscus coating, curtain coating, roller application or Common printing processes, such as screen printing or flexoprint. Are preferred continuous coating processes such as flat spraying, flexoprinting, Roller application or wet chemical film coating techniques.
  • the amount of applied coating composition is chosen so that the desired layer thickness is achieved. For example, it works in such a way that the embossing process layer thicknesses in the range of 0.5 to 50 microns, preferably 0.8 to 10 microns, particularly preferably 1 to 5 microns can be obtained.
  • the coating composition can be thixotropic even before application or after application to the substrate it is pretreated to be thixotropic Attained properties.
  • a coating composition is preferably used which only after application to the substrate by appropriate Pretreatment becomes thixotropic.
  • the thixotropy is one Property of certain viscous compositions whose viscosity Action of mechanical forces (shear stress, shear stress, etc.) decreases.
  • Thixotropic systems in the narrower sense differ of pseudoplastic systems in that the change in viscosity with them there is a certain time delay (hysteresis). Because of this are Thixotropic systems according to the invention preferred, although also pseudoplastic Systems with good results can be used and therefore by the here terms used "thixotropy” and "thixotropic” are included.
  • Thixotropic compositions are familiar to the person skilled in the art. It is him too Measures such as the addition of thixotropic agents or viscosity regulators, known, which lead to thixotropic compositions.
  • the applied coating composition is pretreated so that sets the thixotropic behavior.
  • Application Thixotropic coating composition pretreated after application e.g. to reinforce the thixotropic behavior.
  • a non-thixotropic coating composition must be selected so that it can acquire the thixotropic property through pretreatment.
  • Pretreatment here is in particular a thermal treatment or Understood radiation treatment of the applied coating composition, which can also be used in combination. If necessary but also a simple evaporation of the solvent (flashing off) are sufficient to achieve a thixotropic behavior.
  • the ventilation can also be one precede the above pretreatments. Examples of usable Radiation types are IR radiation, UV radiation, electron radiation and / or Laser radiation.
  • the pretreatment preferably consists of a thermal one Treatment. For this the coated substrate, e.g. in an oven, over one warmed up for a certain period of time.
  • the temperature ranges used or the intensity of the Radiation and the pretreatment time from each other and especially from the Coating composition e.g. the type of coating composition, the additives used and the type and amount of the used Solvent, from.
  • the applied Coating compositions thixotropic. It is important to ensure that still there is no curing of the coating composition.
  • the corresponding Parameters are known to the person skilled in the art, or he can easily use them determine routine attempts.
  • the parameters of the pretreatment e.g. the temperature, preferably so chosen that the solvent residues present in the layer largely be driven out, but that it is not yet to harden the coating composition, e.g. about cross-linking reactions. This is especially in The presence of thermostars is important. With thermal treatment it will coated substrate e.g. at temperatures in the range of 60 to 180 ° C, preferred 80 to 120 ° C over a period of e.g. Warmed for 30 s to 10 min. Especially the pretreatment is preferably carried out so that for the applied Coating composition a viscosity of 30 Pa s to 30,000 Pa s, preferably 30 Pa s to 1000 Pa s, particularly preferably 30 Pa s - 100 Pa s, achieved becomes. This also applies to non-pretreated coating compositions preferred areas.
  • the pretreated layer may e.g. both Organic coating compositions listed below modified inorganic polycondensates or precursors thereof to form a gel act.
  • the microstructured surface relief is embossed using a conventional one Embosser. It can e.g. around a stamp or a roller act, the use of rollers is preferred. For special cases, e.g. Rigid stamps are also suitable.
  • the roller can e.g. a hand roller or one machine embossing roller.
  • the negative is on the embossing device Image (negative master) of the microstructure to be embossed a positive master is won.
  • the structure of the master can be flexible or be rigid.
  • Typical contact pressures are in the range of 0.1 to 100 MPa, depending on, for example, the structural geometry and the degree of crosslinking of the coating film.
  • Typical roller speeds are in the range from 0.6 m / min to 60 m / min.
  • the hardening becomes the usual in coating technology Hardening processes understood that lead to essentially none (Permanent) deformation of the hardened layer is more possible. Here you will find in Depending on the type of coating composition e.g. a Crosslinking, compaction or glazing, condensation or drying instead of.
  • the hardening or fixation of the embossed surface relief should be within 1 minute, better within 30 s and preferably within 3 s Demoulding, that is to say after the embossing device has been removed. If necessary, the hardened layer can also be subjected to thermal aftertreatment be glazed in the organic components leaving a pure inorganic matrix are burned out.
  • the hardening is in particular in the form of a thermal hardening, a hardening by radiation or a combination thereof.
  • known radiation curing methods used. Examples of usable Radiation types have been listed above for pretreatment. Prefers radiation curing takes place by means of UV radiation or electron beams. In each The fixation should be for maximum possible networking, densification or Condensation of the coating.
  • the surface relief structure is independent of any existing one random surface roughness a defined pattern of surveys and Indentations in the surface layer.
  • the pattern formed can be stochastic or periodic, but it can also be a certain desired pattern represent.
  • a microstructured surface profile has dimensions in the ⁇ mouth / or nm range, with dimensions being the dimensions of the Depressions or increases (amplitude height) or the distances (period) between them is understood.
  • additional ones can also be Superstructures are integrated, e.g. save special information can. Examples of this are light-directing or holographic structures and optical data storage.
  • micro-structured reliefs e.g.
  • the Microstructured surface reliefs generally have structures Dimensions below 800 ⁇ m, preferably below 500 ⁇ m, particularly preferably below 200 ⁇ m. Even with even smaller dimensions under 30 ⁇ m and even in Nanometer range below 1 ⁇ m and even below 100 nm will give good results achieved.
  • the coating composition used according to the invention can be applied to any any substrate can be applied.
  • examples of this are metal, glass, ceramics, Paper, plastic, textiles or natural materials such as Wood.
  • metal substrates e.g. Called copper, aluminum, brass, iron and zinc.
  • plastic substrates are polycarbonate, polymethyl methacrylate, Polyacrylates, polyethylene terephthalate.
  • the substrate can be in any form e.g. as a plate or foil.
  • surface-treated ones are also suitable Substrates for the production of microstructured surfaces, e.g. painted or metallized surfaces.
  • the coating compositions can be chosen so that opaque or transparent, electrically conductive, photoconductive or insulating coatings can be obtained. Are preferred, especially for optical applications, transparent coatings.
  • the coatings can also be colored.
  • the coating compositions can e.g. are in the form of gels, sols, dispersions or solutions.
  • the applied one Coating composition before the embossing process as a gel.
  • the coating composition is applied as a sol to the substrate and converted into the gel by the pretreatment, the thixotropic behavior is obtained.
  • the gel formation comes e.g. by solvent withdrawal and / or Condensation processes.
  • Coating compositions can be conventional Coating systems based on organic polymers or glass or ceramic-forming compounds as binders or matrix-forming components act if the coating compositions are thixotropic or by pretreatment can achieve thixotropic behavior.
  • Can as a binder the organic polymers known to the person skilled in the art are used.
  • the coating compositions further contain with organic polymers as binders, preferably still nanoscale inorganic solid particles so that coatings are formed from a polymer layer compounded with nanoparticles.
  • polymers are any known plastics such.
  • polyacrylic acid polymethacrylic acid
  • Polyacrylates polymethacrylates, polymethacrylates, polyolefins, polystyrene, polyamides, polyimides
  • Polyvinyl compounds such as polyvinyl chloride, polyvinyl alcohol, polyvinyl butyral, Polyvinyl acetate and corresponding copolymers, e.g. B. poly (ethylene vinyl acetate), Polyester, e.g. B. polyethylene terephthalate or polydiallyl phthalate, polyarylates, Polycarbonates, polyethers, e.g. B. polyoxymethylene, polyethylene oxide or Polyphenylene oxide, polyether ketones, polysulfones, polyepoxides and fluoropolymers, e.g. B. polytetrafluoroethylene.
  • Coating compositions based on glass- or ceramic-forming compounds can be coating compositions based on inorganic solid particles, preferably nanoscale inorganic solid particles, or hydrolyzable starting compounds, in particular metal alkoxides or alkoxysilanes.
  • inorganic solid particles preferably nanoscale inorganic solid particles, or hydrolyzable starting compounds, in particular metal alkoxides or alkoxysilanes.
  • nanoscale inorganic solid particles and of hydrolyzable starting compounds are given below.
  • Particularly good results are obtained with coating compositions based on organically modified inorganic polycondensates (ormocers, nanomers, etc.), for example polyorganosiloxanes, or their precursors. Accordingly, the use of such coating compositions is particularly preferred.
  • organically modified inorganic polycondensates or precursors thereof contain organic radicals with functional groups via which crosslinking is possible and / or if they are in the form of so-called inorganic-organic nanocomposite materials.
  • Coating compositions based on organically modified inorganic polycondensates which are suitable for the present invention are described, for example, in DE 19613645, WO 92/21729 and WO 98/51747, to which reference is made. These components are explained in detail below.
  • the production of the organically modified inorganic polycondensates or Precursors of this take place in particular by hydrolysis and condensation of hydrolyzable starting compounds according to the prior art known sol-gel process.
  • Prehydrolyzates in particular are among precursors and / or pre-condensates with a lower degree of condensation Roger that.
  • the hydrolyzable starting compounds are Element compounds with hydrolyzable groups, at least a part these compounds also include non-hydrolyzable groups, or oligomers from that.
  • organic polymers In addition, mixtures of organic monomers, oligomers and / or polymers of the usual type can be used with the organic polymers.
  • the organically modified inorganic polycondensates or their precursors used hydrolyzable starting compounds it is in particular connections of at least one element M from the Main groups III to V and / or the subgroups II to IV of the periodic table of the elements.
  • They are preferably hydrolyzable compounds of Si, Al, B, Sn, Ti, Zr, V or Zn, in particular those of Si, Al, Ti or Zr, or Mixtures of two or more of these elements.
  • other hydrolyzable compounds can also be used can, especially those of elements of main groups I and II of Periodic table (e.g. Na, K, Ca and Mg) and the subgroups V to VIII of the Periodic table (e.g.
  • hydrolyzable compounds of Lanthanides can be used. Preferably they just do it but no more than 40 and in particular no more than 20 of the compounds mentioned Mol% of the total hydrolyzable monomeric compounds used.
  • highly reactive hydrolyzable compounds e.g. aluminum compounds
  • complexing agents that have a spontaneous precipitation of the corresponding hydrolysates after adding water prevent. Suitable complexing agents are mentioned in WO 92/21729 reactive hydrolyzable compounds can be used.
  • the at least one non-hydrolyzable Group are preferably hydrolyzable organosilanes or oligomers of it used. Accordingly, organosilanes that can be used in the following explained in more detail.
  • organosilanes that can be used in the following explained in more detail.
  • Corresponding hydrolyzable starting compounds of others The above-mentioned elements are derived analogously from those listed below hydrolyzable and non-hydrolyzable residues, where appropriate the different valence of the elements must be taken into account. This too In addition to the hydrolyzable groups, compounds preferably contain only one non-hydrolyzable group.
  • a preferred coating composition accordingly preferably comprises a polycondensate or precursors obtainable, for example, by the sol-gel process, based on one or more silanes of the general formula R a -Si-X (4-a) (I), in which the radicals R are identical or are different and represent non-hydrolyzable groups, the radicals X are identical or different and mean hydrolyzable groups or hydroxyl groups and a is 1, 2 or 3, or an oligomer derived therefrom.
  • the value a is preferably 1.
  • the hydrolyzable groups X which can be identical or different, are, for example, hydrogen or halogen (F, Cl, Br or I), alkoxy (preferably C 1-6 alkoxy, such as methoxy, ethoxy) , n-propoxy, i-propoxy and butoxy), aryloxy (preferably C 6-10 aryloxy such as phenoxy), acyloxy (preferably C 1-6 acyloxy such as acetoxy or propionyloxy), alkylcarbonyl (preferably C 2- 7- alkylcarbonyl, such as acetyl), amino, monoalkylamino or dialkylamino, preferably having 1 to 12, in particular 1 to 6, carbon atoms.
  • Preferred hydrolyzable radicals are halogen, alkoxy groups and acyloxy groups. Particularly preferred hydrolyzable radicals are C 1-4 alkoxy groups, especially methoxy and ethoxy.
  • non-hydrolyzable radicals R the same or different can be non-hydrolyzable radicals R with a functional Group via which crosslinking is possible or non-hydrolyzable residues R act without a functional group.
  • the non-hydrolyzable radical R without a functional group is, for example, alkyl (preferably C 1-8 -alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, s-butyl and t-butyl, pentyl, hexyl, octyl or cyclohexyl ), Aryl (preferably C 6-10 aryl, such as phenyl and naphthyl) and corresponding alkylaryls and arylalkyls.
  • the radicals R and X may optionally have one or more customary substituents, such as halogen or alkoxy.
  • functional groups via which crosslinking is possible are, for example, the epoxy, hydroxy, ether, amino, monoalkylamino, dialkylamino, optionally substituted anilino, amide, carboxy, vinyl, allyl, alkynyl -, acrylic, acryloxy, methacrylic, methacryloxy, mercapto, cyano, alkoxy, isocyanato, aldehyde, alkylcarbonyl, acid anhydride and phosphoric acid groups.
  • These functional groups are bonded to the silicon atom via alkylene, alkenylene or arylene bridge groups, which can be interrupted by oxygen or -NH groups.
  • non-hydrolyzable radicals R with vinyl or alkynyl group are C 2-6 alkenyl, such as vinyl, 1-propenyl, 2-propenyl and butenyl and C 2-6 alkynyl, such as acetylenyl and propargyl.
  • the bridging groups mentioned and any substituents present, such as in the case of the alkylamino groups, are derived, for example, from the alkyl, alkenyl or aryl radicals mentioned above.
  • the radical R can also have more than one functional group.
  • non-hydrolyzable radicals R with functional groups via which crosslinking is possible are a glycidyl or a glycidyloxy (C 1-20 ) alkylene radical, such as ⁇ -glycidytoxyethyl, ⁇ -glycidyloxypropyl, ⁇ -glycidyloxybutyl, ⁇ -glycidyloxypentyl, ⁇ -glycidyloxyhexyl, and 2- (3,4-epoxycyclohexyl) ethyl, a (meth) acryloxy (C 1-6 ) alkylene radical, where (C 1-6 ) alkylene, for example for methylene, Ethylene, propylene or butylene, and a 3-isocyanatopropyl radical.
  • a glycidyl or a glycidyloxy (C 1-20 ) alkylene radical such as ⁇ -glycidytoxyethyl,
  • silanes are ⁇ -glycidyloxypropyltrimethoxysilane (GPTS), ⁇ -glycidyloxypropyltriethoxysilane (GPTES), 3-isocyanatopropyltriethoxysilane, 3-isocyanatopropyldimethylchlorosilane, 3-aminopropyltrimethoxysilane (APTS), 3-aminopropyltriethoxysilane, N- (2-aminoethyl) -3-aminoproyltrimethoxysilane, N- [N '- (2'-aminoethyl) -2-aminoethyl] -3-aminopropyltrimethoxysilane, hydroxymethyltriethoxysilane, Bis- (hydroxyethyl) -3-aminopropyltriethoxysilane, N-hydroxyethyl-N-methylaminopropyltrie
  • the functional groups mentioned above via which crosslinking is possible is, it is in particular polymerizable and / or polycondensable Groups, under polycondensation reactions also polyaddition reactions be understood. If used, the functional groups are preferred selected so that via optionally catalyzed polymerization, addition or cross-linking reactions can be carried out.
  • Functional group can be chosen, which with itself the above can perform the reactions mentioned.
  • Examples of such functional Groups are epoxy-containing groups and reactive carbon-carbon multiple bonds (especially double bonds). Concrete and preferred Examples of such functional groups are glycidoxy and above (Meth) acryloxy radicals. It can also be a functional group, which can enter into corresponding reactions with other functional groups (so-called corresponding functional groups). Then there will be hydrolyzable starting compounds are used, both functional groups contain or mixtures that the respective corresponding functional Groups included. Is only one in the polycondensate or in the preliminary stage contain functional group, the corresponding corresponding functional group in the crosslinking agent which may then be used are located.
  • Examples of corresponding functional group pairs are vinyl / SH, Epoxy / amine, epoxy / alcohol, epoxy / carboxylic acid derivatives, methacryloxy / amine, Allyl / amine, amine / carboxylic acid, amine / isocyanate, isocyanate / alcohol or Isocyanate / phenol. When using isocyanates, these are preferred in Form of blocked isocyanates used.
  • organically modified inorganic Polycondensates or precursors thereof based on hydrolyzable starting compounds used at least a part of the used hydrolyzable compounds are the hydrolyzable compounds discussed above Compounds with at least one non-hydrolyzable residue with a functional group through which networking is possible.
  • Prefers contain at least 50 mol%, particularly preferably at least 80 mol% and very particularly preferably 100 mol% of the hydrolyzable used Starting compounds with at least one non-hydrolyzable residue functional group through which crosslinking is possible.
  • ⁇ -glycidyloxypropyltrimethoxysilane GPTS
  • ⁇ -glycidyloxypropyltriethoxysilane are particularly preferred (GPTES)
  • organically modified inorganic polycondensates or precursors thereof can be used which at least partially have organic radicals which are substituted with fluorine.
  • hydrolyzable silicon compounds can be used with at least one non-hydrolyzable radical which has 2 to 30 fluorine atoms bonded to carbon atoms, which are preferably separated from Si by at least two atoms.
  • hydrolyzable groups z. B. those are used as indicated in formula (I) for X.
  • fluorinated silane results in the corresponding coating being additionally given hydrophobic and oleophobic properties.
  • silanes are described in detail in DE 4118184. These fluorinated silanes are preferably used when rigid punches are used. The proportion of fluorinated silanes is preferably 0.5 to 2% by weight, based on the total organically modified inorganic polycondensate used.
  • the organically modified inorganic condensates also partially hydrolyzable starting compounds are used which have no non-hydrolyzable groups.
  • the usable hydrolyzable groups and the usable elements M is based on referenced above. Are particularly preferred for this Alkoxides of Si, Zr and Ti used.
  • Such coating compositions based on hydrolyzable compounds with non-hydrolyzable groups and hydrolyzable compounds without non-hydrolyzable groups are e.g. in WO 95/31413 (DE 4417405) to which reference is hereby made. With these coating compositions, the surface relief can thermal aftertreatment to a glass-like or ceramic microstructure be compressed.
  • inorganic-organic nanocomposites are used. These are, in particular, composites based on the hydrolyzable starting compounds listed above, at least some of which have non-hydrolyzable groups, and nanoscale inorganic solid particles or composites based on nanoscale inorganic solid particles modified with organic surface groups.
  • These inorganic-organic nanocomposites of the former case can be obtained by simply mixing the organically modified inorganic polycondensates or precursors obtained from the hydrolyzable starting compounds with the nanoscale inorganic solid particles.
  • the hydrolysis and condensation of the hydrolyzable starting compounds can, however, also preferably take place in the presence of the solid particles.
  • nanocomposites are produced by compounding soluble organic polymers with the nanoscale particles.
  • the nanoscale inorganic solid particles can consist of any inorganic materials, but in particular they consist of metals or metal compounds such as (optionally hydrated) oxides such as ZnO, CdO, SiO 2 , TiO 2 , ZrO 2 , CeO 2 , SnO 2 , Al 2 O 3 , In 2 O 3 , La 2 O 3 , Fe 2 O 3 , Cu 2 O, Ta 2 O 5 , Nb 2 O 5 , V 2 O 5 , MoO 3 or WO 3 ; Chalcogenides such as sulfides (e.g.
  • CdS, ZnS, PbS and Ag 2 S selenides (e.g. GaSe, CdSe and ZnSe) and tellurides (e.g. ZnTe or CdTe), halides such as AgCl, AgBr, Agl, CuCl, CuBr, Cdl 2 and Pbl 2 ; Carbides such as CdC 2 or SiC; Arsenides such as AlAs, GaAs and GeAs; Antimonides such as InSb; Nitrides such as BN, AIN, Si 3 N 4 and Ti 3 N 4 ; Phosphides such as GaP, InP, Zn 3 P 2 and Cd 3 P 2 ; Phosphates, silicates, zirconates, aluminates, stannates and the corresponding mixed oxides (e.g.
  • metal-tin oxides such as indium-tin oxide (ITO), antimony-tin oxide (ATO), fluorine-doped tin oxide (FTO), Zn- doped Al 2 O 3 , luminescent pigments with Y- or Eu-containing compounds, or mixed oxides with a perovskite structure such as BaTiO 3 and PbTiO 3 ).
  • ITO indium-tin oxide
  • ATO antimony-tin oxide
  • FTO fluorine-doped tin oxide
  • Zn- doped Al 2 O 3 luminescent pigments with Y- or Eu-containing compounds
  • luminescent pigments with Y- or Eu-containing compounds or mixed oxides with a perovskite structure such as BaTiO 3 and PbTiO 3
  • a type of nanoscale inorganic solid particles or a mixture of different nanoscale inorganic solid particles can be used.
  • the nanoscale inorganic solid particles are preferably an oxide, hydrated oxide, nitride or carbide of Si, Al, B, Zn, Cd, Ti, Zr, Ce, Sn, In, La, Fe, Cu, Ta, Nb, V, Mo or W, particularly preferably of Si, Al, B, Ti and Zr.
  • Oxides or oxide hydrates are particularly preferably used.
  • Preferred nanoscale inorganic solid particles are SiO 2 , Al 2 O 3 , ITO, ATO, AlOOH, ZrO 2 and TiO 2 , such as boehmite and colloidal SiO 2 .
  • Particularly preferred nanoscale SiO 2 particles are commercially available silica products, for example silica sols such as the Levasile®, silica sols from Bayer AG, or pyrogenic silicas, for example the Aerosil products from Degussa.
  • the nanoscale inorganic solid particles generally have a particle size in the range from 1 to 300 nm or 1 to 100 nm, preferably 2 to 50 nm and particularly preferably 5 to 20 nm.
  • This material can be used in the form of a powder, but is preferably in the form of a, in particular acidic or alkaline, stabilized sols are used.
  • the nanoscale inorganic solid particles can be used in an amount of up to 50% by weight, based on the solid components of the coating composition. In general, the content of nanoscale inorganic solid particles is in the range from 1 to 40, preferably 1 to 30, particularly preferably 1 to 15% by weight.
  • the inorganic-organic nanocomposites can be composites Basis of nanoscale modified with organic surface groups act inorganic solid particles.
  • modifying the surface of nanoscale solid particles are known in the art Methods as e.g. is described in WO 93/21127 (DE 4212633).
  • Nanoscale inorganic solid particles are preferably used here, those with polymerizable and / or polycondensable organic surface groups or such surface groups are provided that one of the matrix have a similar chemical structure or polarity.
  • Such polymerizable and / or polycondensable nanoparticles and their production are e.g. in the WO 98/51747 (DE 19746885).
  • nanoscale inorganic Solid particles can, in principle, be carried out in two different ways become, namely on the one hand by surface modification of already produced nanoscale inorganic solid particles and on the other Production of these inorganic nanoscale solid particles using of one or more compounds which are polymerizable via such and / or polycondensable groupings. These two ways will be explained in more detail in the above-mentioned patent application.
  • organic polymerizable and / or polycondensable surface groups can be any groups known to the person skilled in the art which a polymerization or polycondensation are accessible. It is here in particular to the functional groups already mentioned above, via which networking is possible.
  • Surface groups that have a (meth) acrylic, allyl, vinyl or epoxy group have, with (meth) acrylic and epoxy groups being particularly preferred.
  • at the polycondensing groups would e.g. Isocyanate, alkoxy, hydroxy, To name carboxy and amino groups, with the help of urethane, ether, ester and Amide bonds between the nanoscale particles can be obtained.
  • the polymerizable / polycondensable In principle, surface groups are provided in two ways. Will one Surface modification of already produced nanoscale particles, all (preferably low molecular weight) compounds are suitable for this purpose, which on the one hand have one or more groups that are on the surface of the nanoscale solid particles present (functional) groups (such as for example OH groups in the case of oxides) react or at least can interact, and on the other hand at least one polymerizable / polycondensable Have group.
  • all (preferably low molecular weight) compounds are suitable for this purpose, which on the one hand have one or more groups that are on the surface of the nanoscale solid particles present (functional) groups (such as for example OH groups in the case of oxides) react or at least can interact, and on the other hand at least one polymerizable / polycondensable Have group.
  • functional groups such as for example OH groups in the case of oxides
  • ⁇ -diketones or ⁇ -carbonylcarboxylic acids with polymerizable double bonds, ethylenically unsaturated alcohols and amines, epoxies and the like.
  • particular preference as such compounds are especially in the case of oxidic particles - hydrolytically condensable silanes with at least (and preferably) a non-hydrolyzable residue via which crosslinking is possible.
  • the groups R 2 are preferably identical and selected from halogen atoms, C 1-4 alkoxy groups (eg methoxy, ethoxy, n-propoxy, i-propoxy and butoxy), C 6-10 aryloxy groups (eg phenoxy), C 1-4 Acyloxy groups (e.g. acetoxy and propionyloxy) and C 2-10 alkylcarbonyl groups (e.g. acetyl).
  • Particularly preferred radicals R 2 are C 1-4 alkoxy groups and in particular methoxy and ethoxy.
  • silanes of the general formula (II) are (meth) acryloyloxyalkyltrialkoxysilanes such as, for example, 3-methacryloyloxypropyltri (m) ethoxysilane and glycidyloxyalkyltrialkoxysilanes such as for example 3-glycidyloxypropyltri (m) ethoxysilane.
  • Due to the inorganic-organic hybrid character the gels are much more flexible than pure ones made from metal alkoxides inorganic gels, but more stable than solvent-free organic monomer / oligomer layers. This also applies to inorganic-organic composites without nanoparticles, however, the thixotropic character is due to the composition with inorganic Nanoparticles promoted.
  • the coating composition is before the embossing process as a thixotropic gel Solvent removal and largely complete condensation of the existing Inorganically condensable groups were obtained, so that the degree of condensation the inorganic matrix is very high or substantially complete.
  • the subsequent hardening then causes organic crosslinking of the gel existing organic residues with functional groups via which one Crosslinking is possible (polymerization and / or polycondensation).
  • the coating composition may optionally contain spacers.
  • Spacers are understood to mean organic compounds which preferably contain at least two functional groups which, with the components of the coating composition, in particular with the functional groups of the polycondensates, via which crosslinking is possible, or the polymerizable and / or polycondensable groups of the nanoscale inorganic solid particles, can interact and thereby, for example, bring about a flexibilization of the layer.
  • the spacers preferably have at least 4 CH 2 groups in front of the organofunctional group, calculated from the group attached to the surface; a CH 2 group can also be replaced by an -O-, -NH or -CONH group.
  • Organic compounds such as phenols
  • the most commonly used connections for this purpose are bisphenol A, (4-hydroxyphenyl) adamantane, hexafluorobisphenol A, 2,2-bis (4-hydroxyphenyl) perfluoropropane, 9,9-bis (4-hydroxyphenyl) fluorenone, 1,2-bis-3- (hydroxyphenoxy) ethane, 4,4'-hydroxy-octafluorobiphenyl and tetraphenolethane.
  • compositions based on (meth) acrylate Components that can be used as spacers are bisphenol A bisacrylate, bisphenol A-bis methacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, neopentylglycol dimethacrylate, Neopentyl glycol diacrylate, diethylene glycol diacrylate, diethylene glycol dimethacrylate, Triethylene glycol diacrylate, diethylene glycol dimethacrylate, Tetraethylene glycol diacrylate, tetraethylene glycol dimethacrylate, polyethylene glycol diacrylate, Polyethylene glycol dimethacrylate, 2,2,3,3-tetrafluoro-1,4-butanediol diacrylate and dimethacrylate, 1,1,5,5-tetrahydroperfluoropentyl-1,5-diacrylate and dimethacrylate, Hexafluorobisphenol A diacrylate and dimethacrylate
  • Polar spacers can also be used, including organic ones Compounds with at least two functional groups (epoxy, (meth) acrylic, Mercapto, vinyl, etc.) at the ends of the molecules, which are due to the Incorporation of aromatic or heteroaromatic groups (such as phenyl, benzyl, etc.) and heteroatoms (such as O, S, N, etc.) have polar properties and a Interaction with the components of the coating composition can enter into.
  • aromatic or heteroaromatic groups such as phenyl, benzyl, etc.
  • heteroatoms such as O, S, N, etc.
  • the inorganic-organic nanocomposites can optionally also contain organic polymers, which may have functional groups Have networking. Examples include the examples given above Coating composition based on organic polymers.
  • the coating composition may contain further additives which are described in the technology usually added depending on the purpose and desired properties become.
  • Specific examples are thixotropic agents, crosslinking agents, solvents, e.g. high-boiling solvents, organic and inorganic color pigments, also in the nanoscale range, metal colloids, e.g. as a carrier more optical Functions, dyes, UV absorbers, lubricants, leveling agents, wetting agents, adhesion promoters and starter.
  • the starter can be used for thermally or photochemically induced crosslinking.
  • it can be a thermally activated radical starter, such as a peroxide or an azo compound thermal polymerization, e.g. of methacryloxy groups initiated.
  • a thermally activated radical starter such as a peroxide or an azo compound thermal polymerization, e.g. of methacryloxy groups initiated.
  • the organic crosslinking over actinic radiation e.g. B. UV or laser light or electron beams.
  • the crosslinking of double bonds is usually carried out under UV radiation.
  • radical photo starters that can be used are Irgacure® 184 (1-hydroxycyclohexylphenyl ketone), Irgacure® 500 (1-hydroxycyclohexylphenyl ketone, Benzophenone) and other photoinitiators available from Ciba-Geigy of the Irgacure® type; Darocur® 1173, 1116, 1398, 1174 and 1020 (available from Merck); Benzophenone, 2-chlorothioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, Benzoin, 4,4'-dimethoxybenzoin, benzoin ethyl ether, benzoin isopropyl ether, Benzil dimethyl ketal, 1,1,1-trichloroacetophenone, diethoxyacetophenone and dibenzosuberon.
  • radical thermal starters examples include organic peroxides in the form of diacyl peroxides, peroxydicarbonates, alkyl peresters, alkyl peroxides, perketals, ketone peroxides and alkyl hydroperoxides and azo compounds.
  • Dibenzoyl peroxide, tert-butyl perbenzoate and azobisisobutyronitrile should be mentioned as specific examples.
  • An example of a cationic photo starter is Cyracure® UVI-6974, while a preferred cationic thermal starter is 1-methylimidazole.
  • starters are preferred in the usual amounts known to the person skilled in the art 0.01 - 5 wt .-%, in particular 0.1 - 2 wt .-%, based on the total solids content the coating composition used.
  • the starter can be dispensed with entirely, e.g. in the case of electron beam or laser curing.
  • Crosslinking agents which can be used are those which are conventional in the prior art Compounds with at least two functional groups are used. Of course, the functional groups should be chosen so that one Crosslinking of the coating composition can take place.
  • the substrates obtainable by the process according to the invention with Microstructured surface relief can be advantageous for the production of optical or electronic microstructures are used.
  • Areas of application are optical components such as microlenses and microlens arrays, Fresnel lenses, microfresnel lenses and arrays, light control systems, optical Waveguides and waveguide components, optical gratings, diffraction gratings, Holograms, data storage, digital, optically readable storage, anti-reflective structures (Moth eyes), light traps for photovoltaic applications, labeling, embossed Antiglare layers, microreactors, microtiter plates, relief structures on aero and hydrodynamic surfaces and surfaces with a special feel, transparent, electrically conductive relief structures, optical reliefs on PC or PMMA sheets, security marks, reflective layers for Traffic signs, stochastic microstructures with fractal substructures (Lotus leaf structures) and embossed resist structures for structuring semiconductor materials.

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  • Engineering & Computer Science (AREA)
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  • Application Of Or Painting With Fluid Materials (AREA)
  • Laminated Bodies (AREA)
  • Moulds For Moulding Plastics Or The Like (AREA)
  • Viewfinders (AREA)
  • Paints Or Removers (AREA)
  • Shaping Of Tube Ends By Bending Or Straightening (AREA)
EP01911478A 2000-01-13 2001-01-12 Verfahren zur herstellung eines mikrostrukturierten oberflächenreliefs durch prägen thixotroper schichten und mikrostrukturiertes oberflächenrelief Expired - Lifetime EP1248685B1 (de)

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PCT/EP2001/000333 WO2001051220A2 (de) 2000-01-13 2001-01-12 Verfahren zur herstellung eines mikrostrukturierten oberflächenreliefs durch prägen thixotroper schichten

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WO2001051220A2 (de) 2001-07-19
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JP5279159B2 (ja) 2013-09-04
KR100737554B1 (ko) 2007-07-10
WO2001051220A3 (de) 2002-02-21
CN1176756C (zh) 2004-11-24
DE10001135A1 (de) 2001-07-19
US6855371B2 (en) 2005-02-15
CN1395512A (zh) 2003-02-05
JP2003527231A (ja) 2003-09-16
EP1248685A2 (de) 2002-10-16
DE50103534D1 (de) 2004-10-14
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