Patent Application
20080081181
The object of the present invention was, therefore, to provide a coating (A) that has the required combination of the four properties, namely a high real component n of the complex refractive index, as small an imaginary component k of the refractive index as possible, as low a surface roughness as possible and as high a scratch resistance as possible. In particular, it was an object of the present invention to provide a coating (A) that is characterised in that the coating (A) has a real component n of the refractive index of at least 1.70, an imaginary component k of the refractive index of not more than 0.016, a surface roughness, as the Ra value, of less than 20 nm, and a scratch resistance of less than or equal to 0.75 μm scratch depth.
It has now been found, surprisingly, that the object according to the invention is achieved by a coating (A) that is obtainable by the following steps:
The invention therefore provides a coated product containing a substrate (S) and a coating (A) obtainable by the following steps:
Preferably, after step iii) the substrate (S) wetted with the casting solution (A*) is freed wholly or partially of solvent and/or the coating obtained after step iv) is subjected to thermal after-treatment.
The coated product according to the present invention contains a substrate (S) and a coating (A), the coating (A) being characterised in that it has a real component n of the complex refractive index n of at least 1.70, preferably at least 1.80, particularly preferably at least 1.85, an imaginary component k of the complex refractive index of not more than 0.016, preferably not more than 0.008, a surface roughness, as the Ra value, of less than 20 nm, and a scratch resistance of less than or equal to 0.75 μm, preferably less than or equal to 0.7 μm, particularly preferably less than or equal to 0.65 μm, scratch depth.
The properties of the coating (A) of the coated product were determined as follows: The real component n and the imaginary component k of the complex refractive index were measured at a wavelength of from 400 to 410 nm (i.e. in the wavelength range of blue laser). The surface roughness was measured as the Ra value by means of AFM (atomic force microscopy). For determining the scratch resistance, a diamond needle with a tip radius of 50 μm was moved over the coating at a rate of advance of 1.5 cm/s and with an applied weight of 40 g, and the resulting scratch depth was measured. Details of the respective measuring methods are given in the section relating to the production and testing of the coated products.
The coating A is obtainable from the casting solution A*, the casting solution A* being applied to a substrate (S) or to an information and storage layer (B) and crosslinked.
The casting solution A* according to the invention contains the following components:
Within the scope of the present invention, nanoparticles are understood as being particles that have a mean particle size (d50) of less than 100 nm, preferably from 0.5 to 50 nm, particularly preferably from 1 to 40 nm, very particularly preferably from 5 to 30 nm. Preferred nanoparticles additionally have a d90 value of less than 200 nm, in particular less than 100 nm, particularly preferably less than 40 nm, very particularly preferably less than 30 nm. The nanoparticles are preferably in monodisperse form in the suspension. The mean particle size d50 is the diameter above and below which in each case 50 wt. % of the particles lie. The d90 value is the diameter below which 90 wt. % of the particles lie. Laser light scattering or, preferably, the use of analytical ultracentrifugation (AUC) are suitable for determining the particle size and demonstrating monodispersity. AUC is known to the person skilled in the art, as described, for example, in “Particle Characterization”, Part. Part. Syst. Charact., 1995, 12, 148-157.
For the preparation of component A1 (a suspension containing nanoparticles and a mixture of water and at least one organic solvent), aqueous suspensions of nanoparticles of Al2O3, ZrO2, ZnO, Y2O3, SnO2, SiO2, CeO2, Ta2O5, Si3N4, Nb2O5, NbO2, HfO2 or TiO2 are suitable, an aqueous suspension of CeO2 nanoparticles being particularly suitable. Particularly preferably, the aqueous suspensions of the nanoparticles contain one or more acids, preferably carboxylic acids RC(O)OH wherein R═H, C1- to C18-alkyl, which may optionally be substituted by halogen, preferably by chlorine and/or bromine, or C5- to C6-cycloalkyl, C6- to C20-aryl or C7- to C12-aralkyl, each of which may optionally be substituted by C1- to C4-alkyl and/or by halogen, preferably chlorine, bromine. R is preferably methyl, ethyl, propyl or phenyl and particularly preferably is ethyl. The nanoparticle suspension may also contain as the acid mineral acid, such as, for example, nitric acid, hydrochloric acid or sulfuric acid. The aqueous suspensions of the nanoparticles preferably contain from 0.5 to 10 parts by weight, particularly preferably from 1 to 5 parts by weight, of acid, based on the sum of the parts by weight of acid and water. For example, the nanoparticle suspensions NanoCeria® CeO2-ACT (an aqueous suspension of CeO2 nanoparticles stabilised with acetic acid, pH value=3.0) and CeO2—NIT (an aqueous suspension of CeO2 nanoparticles stabilised with nitric acid, pH value=1.5) from Nyacol NanoTechn., Inc., USA are suitable.
Some of the water from these aqueous suspensions is replaced by at least one organic solvent. This partial solvent exchange is carried out by means of distillation or by means of membrane filtration, preferably by means of ultrafiltration, for example according to the “cross-flow” process. Cross-flow ultrafiltration is a form of ultrafiltration on an industrial scale (M. Mulder: Basic Principles of Membrane Technology, Kluwer Acad. Publ., 1996, 1st Edition), in which the solution to be filtered (feed solution) flows tangentially through the membrane. There is used for this solvent exchange preferably at least one solvent selected from the group consisting of alcohols, ketones, diketones, cyclic ethers, glycols, glycol ethers, glycol esters, N-methylpyrrolidone, dimethylformamide, dimethyl sulfoxide, dimethylacetamide and propylene carbonate. Preference is given to the use of a solvent mixture of at least two solvents from the above-mentioned group, a solvent mixture of 1-methoxy-2-propanol and diacetone alcohol particularly preferably being used. Particular preference is given to the use of a solvent mixture of 1-methoxy-2-propanol (MOP) and diacetone alcohol (DAA), preferably in a ratio of from 95:5 to 30:70, particularly preferably from 90:10 to 50:50. Water may be present in the solvent that is used, preferably in an amount of up to 20 wt. %, more preferably in an amount of from 5 to 15 wt. %.
In a further embodiment of the invention, the suspension of the nanoparticles is prepared by solvent exchange in at least one of the above-mentioned organic solvents and then a further solvent is added, this further solvent being selected from the group consisting of alcohols, ketones, diketones, cyclic ethers, such as, for example, tetrahydrofuran or dioxane, glycols, glycol ethers, glycol esters, N-methylpyrrolidone, dimethylformamide, dimethyl sulfoxide, dimethyl-acetamide, solketal, propylene carbonate and alkyl acetate, for example butyl acetate. In this embodiment too, water may be present in the solvent used, preferably in an amount of up to 20 wt. %, more preferably in an amount of from 5 to 15 wt. %.
Preference is given to the use of ultrafiltration membranes made of polyether polysulfone, which preferably have a cut-off of less than 200,000 D, preferably less than 150,000 D, particularly preferably less than 100,000 D. The cut-off of a membrane is defined as follows: molecules of the corresponding size (for example 200,000 D and larger) are retained, while molecules and particles of smaller sizes are able to pass through (“Basic Principles of Membrane Technology”, M. Mulder, Kluwer Academic Publishers, 1996, 1st Edition). Such ultrafiltration membranes retain the nanoparticles even at high flow rates, while the solvent passes through. According to the invention, the solvent exchange takes place by continuous filtration, the water that passes through being replaced by the corresponding amount of solvent or solvent mixture. As an alternative to polymer membranes it is also possible to use ceramics membranes in the process step of solvent exchange.
The process according to the invention is characterised in that the replacement of water by one of the above-mentioned organic solvents or solvent mixtures does not fall below a limiting value of 5 wt. % in the resulting nanoparticle suspension (A1). Preferably, the replacement of water by the organic solvent or solvent mixture is so carried out that the resulting nanoparticle suspension (A1) has a water content of from 5 to 50 wt. %, preferably from 7 to 30 wt. %, particularly preferably from 10 to 20 wt. %. The resulting nanoparticle suspension preferably contains from 1 to 50 wt. %, more preferably from 5 to 40 wt. %, particularly preferably from 15 to 35 wt. % nanoparticles (referred to hereinbelow as the nanoparticle solids fraction).
If the solvent exchange of the nanoparticle suspension at the membrane cell is carried out for longer, so that a water content of less than 5 wt. % results, particle aggregation occurs, so that the resulting coating does not meet the conditions of monodispersity and high transparency. If, on the other hand, the water content in the organically based nanoparticle suspension is greater than 50 wt. %, the binders that are to be used in a subsequent step may no longer be dissolved in the water-containing suspension to give a clear solution, so that in both these cases, that is to say with agglomerated nanoparticles or with binders that have not dissolved to give a clear solution, the resulting coatings do not fulfil the simultaneous requirement for a high refractive index n and high transparency.
As binders (A2) there may be used both non-reactive, thermally drying thermoplastics, for example polymethyl methacrylate (Elvacite®, Tennants) or polyvinyl acetate (Mowilith 300, Synthomer), and reactive monomer components which, after coating, may be reacted by a chemical reaction or by means of a photochemical reaction to give highly crosslinked polymer matrices. For example, crosslinking is effected by means of UV radiation. Crosslinking by means of UV radiation is particularly preferred in view of increased scratch resistance. The reactive components are preferably UV-crosslinkable acrylate systems, as are described, for example, in P. G. Garratt in “Strahlenhärtung” 1996, C. Vincentz Vlg., Hanover. The binder (A2) is preferably selected from at least one of the group consisting of polyvinyl acetate, polymethyl methacrylate, polyurethane and acrylate. The binder (A2) is particularly preferably selected from at least one of the group consisting of hexanediol diacrylate (HDDA), tripropylene glycol diacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate (DPHA), ditrimethylolpropane tetraacrylate (DTMPTTA), tris-(2-hydroxyethyl)-isocyanurate triacrylate, pentaerythritol triacrylate, tris-(2-hydroxyethyl)-isocyanurate triacrylate and hexanediol diacrylate (HDDA).
The components used as further additives (A3) in the casting solution are preferably at least one additive selected from the group of the photoinitiators and thermoinitiators. Based on the sum of the parts by weight of the components of the casting solution, up to 3 parts by weight of additives (A3) are used, preferably from 0.05 to 1 part by weight, particularly preferably from 0.1 to 0.5 part by weight. Typical photoinitiators (UV initiators) are α-hydroxy ketones (Irgacure® 184, Ciba) or monoacylphosphines (Darocure® TPO, Ciba). The amount of energy (energy of the UV radiation) required to initiate the UV polymerisation is in the range of approximately from 0.5 to 4 J/cm2, particularly preferably in the range from 2.0 to 3.0 J/cm2 of coated surface. Also suitable as further additives are so-called coating additives, as are supplied, for example, by Byk/Altana (46483 Wesel, Germany) under the names BYK, for example BYR 344®.
The casting solution A* for the high refractive index coatings according to the invention is prepared by dissolving at least one binder (A2) and optionally further additives (A3) in an organic solvent or solvent mixture, which may contain water. The resulting solution (referred to hereinbelow as the binder solution) is mixed with component A1 and optionally filtered and degassed. In a preferred embodiment, component A1 contains the same organic solvent or solvent mixture as the binder solution.
The casting solution A* preferably has the following composition:
The casting solution A* generally has a solids content of from 10 to 50 wt. %, preferably from 14 to 28 wt. %. The solids content of the casting solution A* is the sum of components A2, A3 and the nanoparticle solids fraction. The ratio of binder (A2) to nanoparticle solids fraction in the casting solution is preferably from 40:60 to 7:93, particularly preferably the ratio is from 26:74 to 12:88.
The layer thickness of the coating A is from 50 nm to 10,000 nm, preferably from 100 nm to 2000 nm, particularly preferably from 150 nm to 900 nm. The layer thickness may be adjusted by the solids content of the casting solution, in particular in the case of the spin coating process. If high layer thicknesses of the coating are desired, a higher solids content of the casting solution is used; if thinner coatings are desired, a low solids content of the casting solution is used.
The substrate (S) is at least one member selected from the group consisting of glass, quartz, silicon and organic polymer. The organic polymer used is preferably polycarbonate, polymethacrylate, polyester, cycloolefin polymer, epoxy resin and UV-curable resin. The substrate is preferably a substrate that contains polycarbonate, in particular highly transparent substrate sheets containing the polycarbonate types Makrolon® DP1-1265 or OD 2015. The molecular weight Mw of the grades DP1-1265 and OD 2015 are in the range 17 000 to 22 000 g/mol. The substrate (S) may exhibit spiral grooves, indentations and/or raised portions.
The invention therefore also provides a coated product which has a layer sequence (S)-(A) or (A)-(S)-(A).
The coated product according to the invention may contain as further layers an information and storage layer. The information and storage layer is composed of at least one selected from the group of the metals, semiconductor materials, dielectric materials, metal chalcogenides or organic dyes.
There is used as metal in particular Ag, Al, Au and/or Cu.
There is used as semiconductor material in particular silicon.
There is used as dielectric material in particular phase change material, particularly preferably SiO, SiN, SiH, Si, ZnO and ZnS.
The further layers B may be applied to the substrate, or to the underlying layer, by means of sputtering processes, for example.
The invention therefore also provides a coated product which has a layer sequence
The coated product according to the invention may be used in the production of optical data storage means. The present invention accordingly further provides optical data storage means containing a coating A and a substrate B.
The casting solution A* is optionally treated with ultrasound for up to 5 minutes, preferably for from 10 to 60 seconds, and/or filtered through a filter, preferably with a 0.2 μm membrane (e.g. RC membrane, Sartorius). Ultrasonic treatment can be applied to destroy nanoparticle agglomerates if present.
The casting solution is applied to the surface of the substrate or to the surface of the information and storage layer. After removal of excess casting solution, preferably by spinning, a residue of the casting solution remains on the substrate, the thickness of which residue is dependent on the solids content of the casting solution and, in the case of spin coating, on the spin conditions. Some or all of the solvent contained in the casting solution may optionally be removed, preferably by thermal treatment. Subsequent crosslinking of the casting solution, or of the residue, is carried out by thermal methods (for example using hot air) or photochemical methods (for example UV light). Photochemical crosslinking may be carried out on a UV exposure apparatus, for example: To this end, the coated substrate is placed on a conveyor belt, which is moved past the UV light source (Hg lamp, 80 W) at a speed of about 1 m/minute. This process may also be repeated in order to influence the radiation energy per cm2. A radiation energy of at least 1 J/cm2, preferably from 2 to 10 J/cm2, is preferred. The coated substrate may then be subjected to thermal after-treatment, preferably with hot air, for example for from 5 to 30 minutes at from 60° C. to 120° C.
The invention accordingly further provides a process for the production of a coated product, comprising the following steps:
Ceria CeO2-ACT®:aqueous suspension of CeO2:20 wt. % CeO2 nanoparticles in 77 wt. % water and 3 wt. % acetic acid, pH value of the suspension: 3.0, particle size of the suspended CeO2 nanoparticles: 10-20 nm, spec. weight: 1.22 g/ml, viscosity: 10 mPa·s, manufacturer: Nyacol Inc., Ashland, Mass., USA.
Binder: dipentaerythritol penta-/hexa-acrylate (DPHA, Aldrich).
UV photoinitiator: Irgacure® 184 (1-hydroxy-cyclohexyl phenyl ketone), Ciba Specialty Chemicals Inc., Basle, Switzerland.
Quartz glass specimen holder of dimensions 25×25×1 mm from Heraeus, SUP1 quality, ident. no. 09679597.
CD substrate of polycarbonate (Makrolon® OD2015, Bayer MaterialScience AG, Leverkusen, Germany) produced by injection-moulding against a blank matrix; diameter: 120 mm, thickness: 1.2 mm.
Component S-3 is component S-2 which has been coated with a reflective layer of 20 nm Ag. This reflective layer was applied by means of a sputtering process.
The following components were used as organic solvents in the examples:
1-methoxy-2-propanol (MOP), manufacturer: Aldrich
diacetone alcohol (DAA), manufacturer: Aldrich.
The refractive index n and the imaginary component of the refractive index k (also referred to hereinbelow as the absorption constant k) of the coatings were obtained from the transmission and reflection spectra. To this end, about 100-300 nm thick films of the coating were applied by spin coating from dilute solution to quartz glass carriers. The transmission and reflection spectrum of this layer structure was measured by means of a spectrometer from STEAG ETA-Optik, CD-Measurement System ETA-RT and then the layer thickness and the spectral progression of n and k were adapted to the measured transmission and reflection spectra. This is effected using the internal software of the spectrometer and additionally requires the n and k data of the quartz glass substrate, which were determined previously in a blank measurement. k is related to the decay constant α of the light intensity as follows:
λ is the wavelength of the light.
The surface roughness was determined as the Ra value by means of atomic force microscopy (AFM) in tapping mode (in accordance with ASTM E-42.14 STM/AFM).
In order to determine the scratch resistance, scratches are made in the radial direction, from inside to outside, using a diamond needle with a tip radius of 50 μm, at a rate of advance of 1.5 cm/s and with an applied weight of 40 g. The scratch depth is measured using an Alpha Step 500 step profiler from Tencor and is a measure of the scratch resistance. The smaller the value, the more scratch resistant the corresponding substrate.
The water content is determined by the method of Karl Fischer.
A membrane module from PALL (Centramate OS070C12) with a UF membrane cassette (PES, MW 100,000) was used for the cross-flow ultrafiltration (UF). Permeation took place at a pressure of 2.5 bar, the water-containing permeate being discarded and the decreasing retentate being replaced by the alcoholic solvent mixture 1-methoxy-2-propanol (MOP)/diacetone alcohol (DAA) (MOP/DAA ratio=85/15). 6.5 litres of component A.0 were used. As is shown in the table below, the filtration was ended after three cycles of different lengths, and there were thus obtained nanoparticle suspensions in a mixture of organic solvent and water (components A1-1, A1-2, A1-3) that differ in terms of their water content.
1)determined by means of Karl Fischer titration
2)contains 3 wt. % acetic acid
Solutions A and B were combined, then treated again with ultrasound for 30 seconds and filtered over a 0.2 μm filter (Minisart RC membrane). The calculated composition of the casting solution (component A*-1) is as follows:
Composition and properties of component A*-1 (casting solution): see Table 3.
Solutions A and B were combined, then treated again with ultrasound for 30 seconds and filtered over a 0.2 μm filter (Minisart RC membrane). The calculated composition of the casting solution (component A*-2) is as follows: Composition and properties of component A*-2 (casting solution): see Table 3.
1)solvent mixture of MOP and DAA in the ratio MOP/DAA = 85/15
Composition and properties of components A*-3 to A*-5: see Table 3.
Solutions A and B were combined and then treated again with ultrasound for 30 seconds. The resulting cloudy suspension (component A*-6) could not be filtered over a 0.2 μm filter (Minisart RC membrane).
Composition and properties of component A*-6 (casting solution): see Table 3.
1)The nanoparticle solids fraction (here CeO2) resulting from component A.1
2)The indicated solids content of each casting solution is the sum of A.2 + A.3 + nanoparticle solids fraction (CeO2).
Component S-1 was loaded with about 0.5 ml of component A*-1. Coating was carried out with a spin coater under the following conditions:
speed of rotation: 10,000 rpm, 10 seconds.
The coating was crosslinked with a Hg lamp at 5.5 J/cm and then tempered for 10 minutes at 80° C.
In order to determine the scratch resistance, the casting solution was applied by spin coating to component S-2.
The spin coating conditions were as follows:
metering of component A*-1 at 50 rpm, distribution of component A*-1 at 10 rpm over a period of 60 seconds, removal of component A*-1 by spinning at 3000 rpm for a period of 15 seconds.
The coating was crosslinked with a Hg lamp at 5.5 J/cm2 and then tempered for 10 minutes at 80° C.
The spin coating conditions were as follows:
metering of component A*-1 at 50 rpm, distribution of component A*-1 at 10 rpm over a period of 60 seconds, removal of component A*-1 by spinning at 3000 rpm for a period of 15 seconds.
The coating was crosslinked with a Hg lamp at 5.5 J/cm2 and then tempered for 10 minutes at 80° C.
One component S-1 in each case was loaded with about 0.5 ml of a component selected from the group of A*-2 to A*-5. Coating was carried out with a spin coater under the following conditions:
speed of rotation: 10,000 rpm, 10 seconds.
The coating was crosslinked with a Hg lamp at 5.5 J/cm2 and then tempered for 10 minutes at 80° C.
In order to determine the scratch resistance, the casting solution was applied by spin coating to component S-2.
The spin coating conditions were as follows:
metering of component A*-2 at 50 rpm, distribution of component A*-2 at 10 rpm over a period of 60 seconds, removal of component A*-2 by spinning at 3000 rpm for a period of 15 seconds.
The coating was crosslinked with a Hg lamp at 5.5 J/cm2 and then tempered for 10 minutes at 80° C.
Component S-1 was loaded with about 0.5 ml of component A*-6. Coating was carried out with a spin coater under the following conditions:
speed of rotation: 10,000 rpm, 10 seconds.
The coating was crosslinked with a Hg lamp at 5.5 J/cm2 and then tempered for 10 minutes at 80° C.
For comparison with the corresponding coated products, the uncoated substrate S-2 was tested in respect of scratch resistance, with the following result:
For comparison with the corresponding coated products, the uncoated substrate S-3 was tested in respect of scratch resistance, with the following result:
When the aqueous nanoparticle suspension is converted into a suspension of a mixture of water and organic solvent (Example 1), a further, significant reduction in the amount of water to markedly less than 10 wt. % requires an over proportional increase in the permeation time, because the permeation of solvent from the increasingly more pasty retentate takes place increasingly more slowly. “Pasty retentate” hereby means the retentate becomes highly viscous and permeation speed is strongly reduced.
Comparison Example 5 (see also Table 3) shows that a casting solution A*-6 having a water content of 5.1 wt. % is already cloudy. The fact that this casting solution A*-6 is already thixotropic in consistency also has an adverse effect on the process step of coating. As has been shown by means of Comparison Example 8, it is not possible to prepare a high refractive index coating that has the high transparency required according to the invention from the cloudy casting solution A*-6 (Comparison Example 8).
The casting solutions prepared in Comparison Examples 4a to 4c have a water content of 30 wt. % and above. Although these casting solutions A*-3 to A*-5 are still transparent, the coatings obtained therefrom are cloudy (Comparison Examples 7a-2 to 7a-4, see also Table 4).
The object according to the invention may be achieved with casting solutions A*-1 and A*-2 (Examples 2 and 3) having a water content of 10.5 and 24.4 wt. %, respectively. The resulting coatings (see Examples 6 and 7) fulfil all the requirements according to the invention. The coating obtained from casting solution A*-2 is particularly advantageous because the resulting coating has a very low absorption constant k of 0.003 (see Example 7a)
As will be seen by comparing the scratch resistance measurements of Comparison Examples 9 and 10 with the scratch resistance measurement of the substrates coated according to the invention (Examples 6b, 6c, 7b), the coating according to the invention markedly increases the scratch resistance of the substrate.
Although the invention has been described in detail in the foregoing for the purpose of illustration, it is to be understood that such detail is solely for that purpose and that variations may be made therein by those skilled in the art without departing from the spirit and scope of the invention except as it may be limited by the claims.
| Number | Date | Country | Kind |
|---|---|---|---|
| 102006046160.6 | Sep 2006 | DE | national |
