Antisoiling coatings for antireflective surfaces and methods of preparation

专利摘要:
The present invention relates to anti-stain coatings for antireflective surfaces, in particular for external surfaces of anti-reflective film laminates, wherein the anti-stain coatings are represented by fluorinated siloxanes, preferably represented by formula (I) Fluorinated siloxane prepared by applying a coating composition of at least about 1000 fluorinated silanes. Formula I R f- [R 1 -SiY 3-x R 2 x ] y In the above formula, R f is a monovalent or divalent polyfluoropolyether group, R 1 is a divalent alkylene group, arylene group or a mixture thereof, R 2 is a lower alkyl group, Y is a halide, lower alkoxy group or lower acyloxy group, x is 0 or 1, y is 1 or 2.
公开号:KR20010034441A
申请号:KR1020007008219
申请日:1998-06-11
公开日:2001-04-25
发明作者:인비에쥬디스엠；펠리라이트마크제이
申请人:스프레이그 로버트 월터；미네소타 마이닝 앤드 매뉴팩춰링 캄파니；
IPC主号:

专利说明:

Anti-reflective coating for anti-reflective surfaces and method for manufacturing same {ANTISOILING COATINGS FOR ANTIREFLECTIVE SURFACES AND METHODS OF PREPARATION}
The glass surface has, for example, about 4% surface reflectance. With the aid of special coatings such as metal oxides, such surface reflectance can be reduced to less than about 0.5% average integrated intensity in the spectral visible region 450-650 nm. The coating can be a multi-layer dielectric material deposited to a submicron thickness that is arranged to produce constructive or destructive interference of light waves of different wavelengths. In the visible region the antireflective material typically consists of three or four layers, two of which consist of different materials, ie alternating high and low index materials. The design of such materials typically uses layers with optical wavelengths of 1/4 wavelength and 1/2 wavelength.
Antireflective (AR) film laminates made by vacuum deposition (eg, vacuum sputtering) of thin metal oxide films on substrates made of plastic, particularly flexible plastics or glass, are particularly useful for display devices in electronic equipment. These metal oxide films are relatively porous and consist of a group of particles that form a relatively coarse profile, which helps to reduce glare and reflection. If such a material is conductive, it also helps to reduce electrostatic discharge and electromagnetic emissions. Thus, the most important use of such coatings is to provide contrast enhancing and antireflective properties to improve the readability of display devices such as computer monitors.
Antireflective coatings of vacuum deposited (eg sputtered) metal oxides are generally durable and uniform. In addition, since the optical properties of such a coating are controllable, the coating may be highly desirable. However, these coatings also have very high surface energy and refractive index. The high surface energy of the vacuum deposited (eg sputtered) metal oxide surface tends to contaminate the surface by organic impurities (from sources such as fingerprints). The presence of surface contaminants is a significant source of sensitivity to the antireflectivity properties of metal oxide coatings. In addition, because of the high refractive index, surface contamination is very noticeable to the end user.
Unfortunately, high surface energy makes it difficult to clean vacuum deposited (eg sputtered) metal oxide surfaces without the use of environmentally undesirable solvent-based cleaners. In addition, the removal of surface contaminants can adversely affect the antireflective properties of the surface if the cleaning process leaves the residue behind. Therefore, it is necessary to have a protective coating on the antireflective surface that is relatively durable, more resistant to contamination, and easier to clean than the antireflective surface itself.
Numerous attempts have been made to provide anti-reflective properties on anti-reflective surfaces. This is accomplished by providing anti-reflective properties to the anti-reflective coating itself or by providing an anti-stain coating over the anti-reflective coating. Examples of such anti-stain overcoats are described in the applicant's U.S. Patent Application No. 08 / 902,666 (Felilite et al., Filed Jul. 30, 1997), and Japanese Patent No. 9-127307 (Sony Corporation) and the United States. Patent No. 5,622,784 (Okaue et al.). However, the materials disclosed in the former literature are generally not suitable for continuous coating techniques. The materials disclosed in the latter two documents belong to the general types of compounds used in Comparative Examples B, I, O and P herein and do not sufficiently provide a durable stain resistant coating. E.I. in Wilmington, Delaware. Perfluoroether derivatives such as those sold under the trade name KRYTOX 157 FS (L) from DuPont de Nemours Company are used as lubricants on the surfaces of magnetic media articles and discs, but the derivatives alone in Comparative Example D herein As described, it provides little anti-staining properties when applied to a transparent substrate. Thus, there is still a need today for materials that form durable stain resistant coatings suitable for application to substrates, in particular flexible substrates, by continuous coating techniques.
Transparency of glass or plastic present in the form of porches, windows, lenses, filters, display devices (e.g., display panels) of electronic equipment may be compromised by the glare and reflection of light. For example, to reduce the amount of glare on glass or plastic, the surface typically includes a single layer of metal oxides (eg, silicon dioxide), metal fluorides, metal nitrides, metal sulfides, and the like. This coating acts as an antireflective coating.
Summary of the Invention
The present invention provides a protective coating on an antireflective surface that is relatively durable, more resistant to contamination, and easier to clean than the antireflective surface itself. That is, the present invention provides an antireflective article comprising an antireflective surface and a substrate having an antireflective coating on the surface. The anti-stain coating is at least partially cured (ie, solidified, such as by polymerization and / or crosslinking) and a coating composition comprising at least one fluorinated silane represented by formula (I) Fluorinated siloxane prepared by the application).
R _f- [R ¹ -SiY _3-x R ² _x ] _y
In the above formula,
R _f is a monovalent or divalent polyfluoropolyether group,
R ¹ is a divalent alkylene group, arylene group or mixtures thereof, optionally containing one or more hetero atoms or functional groups, optionally substituted by halides, and containing about 2 to about 16 carbon atoms,
R ² is a lower alkyl group (ie, a (C ₁ -C ₄ ) alkyl group),
Y is a halide, lower alkoxy group (i.e. (C ₁ -C ₄ ) alkoxy group, preferably methoxy or ethoxy group) or lower acyloxy group (i.e. -OC (O) R ³ , where R ³ is ( C ₁ -C ₄ ) alkyl group,
x is 0 or 1,
y is 1 (R _f is _monovalent ) or 2 (R _f is bivalent).
Typically suitable compounds have a molecular weight (number average) of at least about 1000. It is preferable that Y is a lower alkoxy group and R _f is a perfluoropolyether group.
The antireflective surface preferably comprises a metal oxide film having at least one metal oxide, preferably with vacuum deposition (eg, sputter coating) of the metal.
The anti-stain coating preferably has a thickness of at least about 15 mm 3, and preferably at most about 150 mm 3 for a desirable balance in performance regarding stain resistance, durability and antireflection. The antireflective article preferably has a first surface antireflection that differs by less than about 0.5% from that of the same article that does not contain an antistain coating.
The present invention also provides an anti-staining coating composition represented by the above formula (I) and comprising at least one fluorinated silane having a number average molecular weight of at least about 1000. It is preferable that this coating composition (as opposed to at least partially cured coating) comprises an unsalted solvent. This unsalted solvent is preferably selected from fluorinated alkanes, alkyl perfluoroalkyl ethers and mixtures thereof. Most preferably the unsalted solvent is an alkyl perfluoroalkyl ether. The coating composition preferably comprises fluorinated silane at a concentration of less than about 2.0% by weight.
The present invention also provides a method of applying a stain resistant coating to a substrate having an antireflective surface. The method is represented by formula (I) above and includes treating the antireflective surface with a coating composition comprising at least one fluorinated silane having a number average molecular weight of at least about 1000. The coating method preferably includes a coating continuous process that can be performed using a continuous roll coater such as, for example, a gravure coater. The gravure coating process preferably includes supplying the coating composition to the doctor blade, moving the coating composition from the doctor blade to the gravure roll, and applying the coating composition from the gravure roll to the antireflective surface of the substrate.
Coated substrates are subjected to ambient conditions (ie, room temperature, pressure and humidity) as long as the silane groups are hydrolyzed and condensation reacts with each other and with the antireflective substrate surface. ) And allowed to dry and at least partially cure. Alternatively, the coated substrate may be heated to a temperature of at least about 100 ° C. to at least partially cure the coating.
The present invention furthermore relates to a transparent substrate having a first surface and a second surface, preferably a flexible organic substrate, an antireflective coating on at least a portion of the first surface, and a polycovalently bonded to silicon via siloxane groups and organic crosslinking groups. An antireflective article comprising an antistain coating comprising a fluoropolyether segment, wherein the polyfluoropolyether segment has a molecular weight of at least about 1000. The organic linker comprises a nitrogen atom and the antistain coating preferably has an atomic ratio of fluorine to nitrogen of about 25 to about 150.
Detailed Description of the Preferred Embodiments
Antireflective coatings are transparent (i.e., light, such as glass, quartz or organic polymer substrates, including polymethyl methacrylate, polystyrene, polyvinyl chloride, polyethylene, polypropylene, polycarbonates, polyimides and polyesters, especially polyethylene terephthalates). Permeable) and one or more layers of material disposed on the substrate. The simplest antireflective coating is a single layer of transparent material having a refractive index less than the refractive index of the substrate on which the coating is disposed. The multilayer antireflective coating includes two or more layers of dielectric material on the substrate, wherein the one or more layers have a refractive index that is greater than the refractive index of the substrate. Multilayer antireflective coatings are often referred to as antireflective (AR) film laminates. Such AR film laminates can be purchased, for example, from Viratec Thin Films Incorporated in Paribold, Minnesota.
Multilayer AR coatings (ie AR film laminates) are generally deposited by thermal evaporation, sputtering or other vacuum deposition methods. Such multilayer coatings are described, for example, in International Application Publication No. WO 96/31343 (Southwell Technologies, Inc.), U.S. Patent No. 5,091,244 (Bzonard), 5,105,310 (Dick Kay), 5,147,125 (Austin) 5,270,858 (Dick Kay), 5,372,874 (Dick Kay et al.), 5,407,733 (Dick Kay), 5,450,238 (Bezonad et al.) And 5,579,162 (Bezonad et al.). The last patent describes anti-stain coatings on flexible plastics, wherein the anti-stain coatings of the present invention are particularly useful for such flexible plastics.
Antireflective surfaces can be provided by a wide variety of conventional materials. The antireflective surface is preferably provided by a thin metal oxide film, more preferably by a sputter coated thin metal oxide film. As used herein, "metal oxide" includes oxides of alloys as well as oxides of single metals (metalloids). Preferred metal oxides include silicon oxides, which can deplete oxygen (ie, the amount of oxygen in the oxide is less than the stoichiometric amount). The metal oxide film on the outermost surface preferably comprises silicon oxide (SiO _x , where x is 2 or less), but other suitable materials include tin, titanium, niobium, zinc, zirconium, tantalum, yttrium, aluminum, cerium Oxides of tungsten, bismuth and indium and mixtures thereof. Specific examples include SnO ₂ , TiO ₂ , Nb ₂ O ₅ , ZnO, ZrO ₂ , Ta ₂ O ₅ , Y ₂ O ₃ , Al ₂ O ₃ , CeO ₂ , WO ₃ , Bi ₂ O ₅ , In ₂ O ₃ and ITO (indium tin oxide) is mentioned. Sputter coated metal oxide films are preferred over thermally evaporated films because these sputter coated films have higher density, hardness, smoothness and stability than thermally evaporated films. Such sputter-coated metal oxide films are relatively porous and consist of a group of particles having a diameter of about 5 nm to about 30 nm, as measured by atomic force microscopy, but the film is mechanical and electrical of the film. And sufficient impermeability to water and gases that can change optical properties.
Suitable substrates include glass and transparent thermoplastics such as poly (meth) acrylates, polycarbonates, polystyrenes, styrene copolymers (eg acrylonitrile-butadiene-styrene copolymers and acrylonitrile-styrene copolymers) , Cellulose esters, in particular cellulose acetate and cellulose acetate-butyrate copolymers, polyvinyl chloride, polyolefins (e.g. polyethylene and polypropylene), polyimides, polyphenyleneoxides, and polyesters, especially polyethylene terephthalates. The term “poly (meth) acrylate (or acrylic)” refers to cast acrylic sheeting, elongated acrylic, poly (methylmethacrylate) (“PMMA”), poly (methacrylate), poly (etaacrylate) And methylmethacrylate-ethylacrylate copolymers and the like, which are usually mentioned. However, the thickness of the substrate can vary, typically from about 0.1 mm to about 1 mm in thickness for flexible organic films. In addition, the organic polymer substrate may be a laminate of two or more different thermoplastic materials attached together, with or without an adhesive layer between the layers. Organic polymer substrates can be prepared by a variety of different methods. For example, the thermoplastic material can be extruded and cut into predetermined dimensions. The thermoplastic may be mold molded to form the desired shape and dimensions. In addition, the thermoplastic material can be cell molded and then heated and stretched to form an organic polymeric substrate.
The substrate to which the antireflective coating is applied may comprise a primed surface. The primer treated surface can be formed by application of a chemical primer layer, such as an acrylic layer, or by chemical etching, electron beam irradiation, corona treatment, plasma etching, or coextrusion of an adhesion promotion layer. Such primer treated substrates are commercially available. For example, polyethylene terephthalate substrates primed with aqueous acrylic latex are available under the trade names ICI 454 and ICI 617 from Imperial Chemical Industries Films, Hopewell, North Carolina.
In addition, the substrate can include an adhesion enhancing coating to enhance adhesion between the antireflective coating and the substrate. Such adhesion enhancing coatings are commercially available. Preferred adhesion-enhancing coatings are those described in the applicant's U.S. Patent Application, filed Jan. 27, 1998, Agent No. 53252 USA 8A, entitled "Adhesion-Enhancing Coating for Optically Functional Materials and Methods of Preparation." have. Adhesion enhancing coatings are particularly preferred for use on flexible organic polymer substrates. In addition to enhancing the adhesion of the anti-reflective coating to the primer-treated or untreated organic polymer substrate, the adhesion-enhancing coating also provides the plasticity of the anti-reflective coating so that the adhesion-enhancing coating more closely mimics the hardness of the AR coating on glass. Improved durability can provide improved durability to antireflective coatings on flexible organic polymer substrates. Typically cured adhesive reinforcement coatings have a coating thickness of at least about 1 micron, preferably at least about 2 microns. The adhesion enhancing coating can be any thickness, but is typically about 50 microns or less, preferably about 25 microns or less, more preferably 10 microns or less, and most preferably about 4 microns or less.
Preferred adhesion enhancing coatings described in the applicant's US patent application (filed Jan. 27, 1998, Agent No. 53252 USA 8A) include an organic matrix and inorganic oxide particles dispersed in the matrix. Such adhesion enhancing coatings are prepared from precursor compositions comprising a ceramer composition and optionally one or more solvents. The ceramic composition comprises substantially non-aggregated colloidal inorganic oxide particles dispersed in the curable organic binder composition. The ceramer composition has a refractive index of about 1.40 to about 1.65 when measured with a conventional refractometer using conventional measurement procedures, such as ASTM D1747-94 ("Standard Test Method for Refractive Index of Viscous Materials"). It is preferable. The curable organic binder composition may include various monomers, oligomers, and / or polymers capable of forming a cured matrix for inorganic oxide particles. The ceramic composition preferably comprises an inorganic colloidal indenter comprising an ethylenically unsaturated monomer, any organic functional silane monomer coupling agent and at least silica. Alternative ceramer compositions include inorganic colloidal particles comprising an organic functional silane monomer coupling agent and at least silane. The organic polymer substrate may be coated with an adhesion enhancing coating, then at least partially cured, and an antireflective coating applied onto the adhesion enhancing coating.
The present invention relates to an antireflective surface, in particular an antireflective film, preferably an antireflective metal oxide film (preferably having at least one metal oxide), more preferably sputter-coated, on the outer surface or top of the antireflective film stack. An antistain coating is provided on any surface having an antireflective metal oxide film (preferably comprising silicon oxide). The anti-stain coating of the present invention allows the surface to be more resistant to contamination, such as for example by sebum of fingerprints. In addition, stain resistant coatings make the surface easier to clean by dry wipe or water cleaning. In addition, the anti-stain coating can withstand several cleaning processes. In addition, the anti-stain coating is relatively easy to apply, and it destroys little or no optical properties of the surface to which the anti-stain coating is applied, especially the anti-reflective surface of the film laminate. That is, the anti-stain coating of the present invention does not significantly increase the reflectance of the film laminate.
Articles of the invention are glass or organic polymer substrates, optionally anti-reflective coatings, preferably multilayers, optionally having a primer-treated surface coated with any adhesion enhancing coating. Film laminates, and the anti-stain coating of the present invention. The substrate is preferably flexible so that the finished article can be stored in roll form.
On the opposite surface of the substrate there is preferably a layer of an adhesive and a liner on the adhesive. The adhesive can be selected from a wide range of pressure sensitive adhesives, as described in the applicant's U.S. patent application (filed Jan. 27, 1998, Agent No. 53892 USA 8A). Particularly useful adhesives include (a) 50 to 90% by weight of n-butyl acrylate and (b) 2-hydroxy ethyl acrylate, 2-hydroxy ethyl methacrylate, hydroxy propyl acrylate monomer or mixtures thereof 10 There is a water-resistant pressure-sensitive adhesive comprising-50% by weight. Such water resistant emulsion pressure sensitive adhesives have a haze of less than 2%, a opacity of less than 20%, and a transmittance of at least about 95% in the visible spectrum of 380-720 nm after the wet laminate process. Water-resistant emulsion pressure-sensitive adhesives are alkyl acrylate monomer (preferably 0 to 50% by weight), polar monomer (preferably 0 to 5% by weight), ethylenically unsaturated free radical polymerizable monomer (0 to 50% by weight) Preferably a%) or a mixture thereof, optionally containing a copolymerizable monomer. Other optional components of the water resistant emulsion pressure sensitive adhesive include multifunctional crosslinkers. If present, these crosslinkers are present in amounts ranging from 0% by weight to about 10% by weight.
Antistain coatings of the present invention include fluorinated siloxane films containing organic groups optionally containing heteroatoms and / or functional groups (ie, fluorine-containing organic polysiloxane films with Si—O—Si bonds). Polyfluoropolyether segments are bonded to silicon atoms via organic linking groups. Unlike the preferred anti-stain coatings of the applicant's US patent application Ser. No. 08 / 902,664 (filed Jul. 30, 1997), the coatings of the present invention typically do not have self-assembling. In addition, the coatings of the present invention are typically not monolayers of materials that are covalently attached to oligomeric materials adsorbed to a monolayer.
The overall coating thickness is determined from reconciling the need for a thin coating that maintains the antireflective properties of the AR substrate with the need for a thick coating to enhance anti-staining properties and durability. It is advantageous for the coating compositions of the present invention to provide dried or cured (or at least partially cured) coatings that are relatively thin but may have desirable stain resistant properties and durability. Typically, the overall coating thickness of the anti-stain coating of the present invention is at least about 15 mm 3, preferably at least about 20 mm 3, more preferably at least about 50 mm 3. If necessary, thicker coatings can be obtained, but the coating thickness is preferably about 500 kPa or less, more preferably about 300 kPa or less, and most preferably about 150 kPa or less.
The anti-stain coating of the present invention can be applied to the antireflective surface (or a portion thereof) of a transparent substrate (ie, AR substrate) in a variety of techniques. The antireflective surface is preferably treated with a coating composition (typically a solution) comprising fluorine substituted silanes (ie, fluorinated silanes). As used herein, "silane" includes acyloxy substituted silanes, halo substituted silanes and alkoxy substituted silanes. Although it is possible to treat all surfaces or only part of one surface of the substrate, it is advantageous to coat only the top surface (ie antireflective surface) of the AR substrate.
The fluorinated silane preferably belongs to the following formula (I).
Formula I
R _f- [R ¹ -SiY _3-x R ² _x ] _y
In the above formula,
R _f is a monovalent or divalent polyfluoropolyether group,
The linking group R ¹ optionally contains at least one hetero atom (eg oxygen, nitrogen or sulfur) or functional group (eg carbonyl, amido or sulfonamido) and is optionally substituted by a halogen atom, preferably about 2 Divalent alkylene groups, arylene groups or mixtures thereof containing from about 16 to about 16 carbon atoms (more preferably, from about 3 to 10 carbon atoms),
R ² is a lower alkyl group (ie, a (C ₁ -C ₄ ) alkyl group, preferably a methyl group),
Y is a halide, lower alkoxy group (i.e. (C ₁ -C ₄ ) alkoxy group, preferably methoxy or ethoxy group) or lower acyloxy group (i.e. -OC (O) R ³ , where R ³ is ( C ₁ -C ₄ ) alkyl group,
x is 0 or 1,
y is 1 (R _f is _monovalent ) or 2 (R _f is bivalent).
Typically suitable compounds have a number average molecular weight of at least about 1000, preferably at least about 1500. It is preferable that x = 0 and Y is a lower alkoxy group.
The polyfluoropolyether groups (R _f ) may comprise straight, branched and / or cyclic structures which are saturated or unsaturated and may be substituted by one or more oxygen atoms. R _f is preferably a perfluorinated group (ie all CH bonds are replaced with CF bonds). R _{f is-} (C _n F _2n )-,-(C _n F _2n O)-,-(CF (Z))-,-(CF (Z) O)-,-(CF (Z) C _n F It is preferred to include perfluorinated repeat units selected from the group consisting of _2n O)-,-(C _n F _2n CF (Z) O)-,-(CF ₂ CF (Z) O)-and mixtures thereof. Do. Z in these repeat units is a perfluoroalkyl group, an oxygen substituted perfluoroalkyl group, a perfluoroalkoxy group or an oxygen substituted perfluoroalkoxy group, all of which may be straight, branched or cyclic, and It is preferred to have from 1 to about 9 carbon atoms and 0 to 4 oxygen atoms. Examples of polyfluoropolyethers containing polymer moieties consisting of these repeat units are disclosed in US Pat. No. 5,306,758 (Pellilite et al.). The number of repeating units in the polyfluoropolyether group (R _f ) should be sufficient to form a compound having a number average molecular weight of at least about 1000, preferably to form a polyfluoropolyether group having a number average molecular weight of at least about 1000. It should be enough to be able. For monovalent polyfluoropolyether groups, where y in formula (I) is 1, the terminal groups are (C _n F _{2n + 1} )-, (C _n F _{2n + 1} 0)-, ( X'C _n F _2n O)-or (X'C _n F _{2n + 1} O)-, wherein X 'is, for example, H, Cl or Br. These end groups are preferably perfluorinated. In these repeating units or end groups, n is at least 1, preferably from about 1 to about 4.
The approximate average structure preferred for bivalent perfluoropolyether groups is -CF0 (CF ₂ O) _m (C ₂ F ₄ O) _p CF _2- , -CF (CF ₃ ) O (CF (CF ₃ ) CF ₂ O ) _p CF (CF ₃ )-, -CF ₂ O (C ₂ F ₄ O) _p CF ₂ -and-(CF ₂ ) ₃ O (C ₄ F ₈ O) _p (CF ₂ ) _3- , Wherein the mean value for m is 0 to about 50, and the mean value for p is 0 to 50, provided that both m and p cannot be zero in the same group. Among these, particularly preferred, the average structures are -CF ₂ O (CF ₂ O) _m (C ₂ F ₄ O) _p CF _2- , CF ₂ O (C ₂ F ₄ O) _p CF ₂ -and -CF ( CF ₃ ) O (CF (CF ₃ ) CF ₂ O) _p CF (CF ₃ ) —. Particularly preferred alternative structures for monovalent perfluoropolyether groups are -C ₃ F ₇ O (CF (CF ₃ ) CF ₂ O) _p CF (CF ₃ )-and CF ₃ O (C ₂ F ₄ O) _p CF ₂ −, wherein the average value for p is 0 to about 50. When synthesized, these compounds typically comprise a mixture of polymers. Approximate average structure is the approximate mean of the polymer mixture.
The divalent R ¹ group can be a straight, branched or cyclic structure that can be saturated or unsaturated. R ¹ groups may contain hetero atoms (eg oxygen, nitrogen or sulfur) or functional groups (eg carbonyl, amido or sulfonamido). In addition, the R ¹ group may be substituted by a halogen atom, preferably a fluorine atom, but this is more preferable because it may lead to instability of the compound. The divalent R ¹ group is preferably a hydrocarbon group containing a hetero atom or a functional group, more preferably one or more functional groups, preferably a straight chain hydrocarbon group. Examples of R ¹ groups include —C (O) NH ₂ (CH ₂ ) ₃ —, —CH ₂ O (CH ₂ ) ₃ —, and — (C _n H _2n ) —, where n is from about 2 to About 6. Preferred R ¹ groups are-(CO) NH ₂ (CH ₂ ) _3- .
Compounds of formula (I) suitable for use in preparing the anti-stain coatings of the present invention have a molecular weight (number average) of at least about 1000, preferably at least about 1500. Typically, the molecular weight is about 5000 or less, but this is typically limited by availability, viscosity and ease of curing, preferably up to about 3000 depending on the desired viscosity and cure time properties.
Examples of preferred perfluorinated silanes include the following approximate average structures: XCF ₂ O (CF ₂ O) _m (C ₂ F ₄ O) _p CF ₂ X, C ₃ F ₇ O (CF (CF ₃ ) CF ₂ O) _p CF (CF ₃ ) X, XCF (CF ₃ ) O (CF (CF ₃ ) CF ₂ O) _p CF (CF ₃ ) X, XCF ₂ O (C ₂ F ₄ O) _p CF ₂ X, CF ₃ O (C ₂ F ₄ O) _p CF ₂ X and X (CF ₂ ) ₃ O (C ₄ F ₈ O) _p (CF ₂ ) ₃ X, but are not limited to -X is -R ¹ -SiY _3-x R ² _x as defined above in formula (I) or a nonsilane containing end group [(C _n F _{2n + 1} )-, (C _n F _{2n +} as defined above) _{; 1} O)-, (X'C _n F _2n O)-or (X'C _n F _{2n + 1} O)-, wherein X 'is H, Cl or Br] provided that at least one X per molecule is silane Should be In each of the silanes R ¹ preferably comprises nitrogen. One or more X groups per molecule are C (O) NH (CH ₂ ) ₃ Si (OR) ₃ , where R is methyl, ethyl or mixtures thereof, and other non-silanes are OCF ₃ or OC ₃ F ₇ Is preferably. The values of m and p in these approximate average structures can vary as long as the number average molecular weight of the material is at least about 1000. The mean value of m is within about 1 to about 50, and the mean value of p is preferably about 4 to about 40. Because these average structures are polymeric materials, such compounds exist as a mixture, suitable for use in synthesis. In addition, these mixtures may comprise perfluoropolyether chains containing no functional groups (inert fluids) or at least two end groups (branched chain structures) as a result of the method used for their synthesis. Typically a mixture of polymeric materials containing less than 10% by weight of an unfunctionalized polymer (eg, no silane group) can be used. It is also possible to use mixtures of any of the compounds listed in each of formula (I).
Compounds of formula (I) can be synthesized by standard techniques, for example, perfluoropolyether esters that are purchased or readily synthesized are 3-aminopropyl, according to US Pat. No. 3,810,874 (Mitsch et al.). It may be combined with functionalized alkoxysilanes such as alkoxysilanes. A variation of this method is described in the examples. Such materials may or may not need to be purified prior to use in the stain resistant composition.
While not intending to be bound by theory by the present inventors, the compound of formula (I) reacts with the substrate surface to form a siloxane coating having strong interaction with the antireflective surface, for example through the formation of a covalent bond. It is thought to be. In this context, the "siloxane" is bound to a polyfluoropolyether segment (in this case, such as R _f in formula (I)), preferably the perfluoropolyether segment optionally contains a hetero atom or a functional group. It means a -Si-O-Si- bond is bonded to the silicon atom through an organic crosslinking group (in the present specification, such as R ¹ in the formula (I)). In cured coatings (at least partially cured coatings), the polyfluoropolyether segments preferably have a number average molecular weight of at least about 1000. In a particularly preferred embodiment, the R ¹ group comprises a nitrogen atom (such as in an amido group) and the atomic ratio of fluorine to nitrogen in the coating is in the range of about 25 to about 150. In addition, a coating made with a coating composition comprising a compound of formula (I) may include unreacted or non-condensed silanol groups.
In order to make a durable coating, sufficient water must be present to cause the formation of an interaction between the fluorinated siloxane coating and the antireflective surface. The interaction is said to be formed as a result of hydrolysis of the silane end groups, for example into residues present in the coating composition or adsorbed on the substrate surface, and then condensation of the formed silanol groups on or to the antireflective surface. I think. Subsequently, in addition to the formation of Si-O-Si bonds, it is also believed that M-O-Si bonds are also formed, where M represents the base metal (as used herein includes a metalloid). Typically, when the coating process is carried out at room temperature under an atmosphere with a relative humidity of about 30% to about 55%, sufficient water must be present to prepare the durable coating.
It is preferred that the anti-stain coating composition of the present invention comprise at least one solvent. The solvent (s) used in the stain resistant coating composition are substantially inert (i.e., non-reactive with substantially fluorinated silane), aprotic, and disperse or dissolve (preferably, substantially fluorinated silane) Complete dissolution). Examples of suitable solvents include, but are not limited to, fluorinated hydrocarbons, in particular fluorine substituted alkanes, ethers, especially alkyl perfluoroalkyl ethers, and hydrochlorofluoro alkanes and ethers. The solvent (s) is preferably non-chlorinated and nonflammable. Mixtures of these solvents can be used. Particularly preferred solvents include alkyl perfluoroalkyl ethers such as methyl perfluorobutyl ether and ethyl perfluorobutyl ether because of the good balance of solubilization properties and flammability.
In addition, the coating compositions of the present invention containing a predetermined solvent or mixture of these solvents and fluorinated silanes may include additives such as HCl scavengers, catalysts and odor blockers, provided that these additives are fluorinated silanes. Should not react with The catalyst can be any of the catalysts typically used to cure reactive organic silanes by hydrolysis and condensation. Examples of suitable catalysts for use in thermally cured systems include alkyl tin esters such as dibutyltin diacetate, titanate esters such as tetraisopropyl titanate, inorganic acids, alkylsulfonic acids, carboxylic acids, halogenated carboxylic acids Or acids such as alkylsulfonic acids, fluorinated sulfonamides or sulfonimides, and bases such as trialkalamines. Examples of suitable catalysts for use in UV cured or electron beam cured systems include iodine compounds and sulfonium compounds, such as those disclosed in US patent application Ser. No. 08 / 815,029 (March 14, 1997). have.
It is desirable to clean the AR substrates extremely cleanly before applying the stain resistant coating to achieve optimum coating properties, particularly durability. That is, the AR surface of the substrate to be coated must be substantially free of organic contamination before coating. The cleaning technique depends on the type of substrate, such as ultrasonic cleaning techniques performed in a solvent bath (eg ethanol / chloroform), gas phase discharge techniques such as air corona treatment, detergents and / or hot water (eg , About 48 ° C. to about 67 ° C.), or combinations of these techniques.
A wide range of coating methods such as spray coating, knife coating, dip coating, meniscus coating, flow coating, roll coating and the like can be used to apply the anti-stain coating composition of the present invention. To coat hard substrates, dip coating, spray coating and meniscus coating are typically used. To coat the flexible substrate, a wide variety of conventional roll coating techniques such as squeeze coating, kiss coating, gravure coating and the like can be used. A preferred coating method for applying the coating composition of the present invention to a web or flexible substrate is a continuous process as can be carried out using gravure coating. Since relatively high volatility solvents are preferably included in the anti-stain coating compositions of the present invention, more preferred gravure coating methods for applying the anti-stain coating compositions include methods using a two roll laminate design. In this roll configuration arrangement, the lower roll is a soft roll and the upper roll is a gravure roll. The web is supported by a soft roll. The coating solution is metered and transferred through the pump means to the doctor blade which acts as a reservoir. As the gravure roll rotates, the gravure roll comes in direct contact with the coating solution. The amount of solution deposited on the gravure roll is determined by the total carrying capacity of the cells imprinted on the gravure roll. The gravure roll moves the coating solution directly onto the antireflective surface of the substrate. That is, the coating composition is applied directly onto the surface of the substrate using a gravure roll, and the oppositely positioned soft rolls provide a uniform pressure from the back side of the substrate to form a relatively thin anti-stain coating.
The stain resistant coating composition is relatively diluent, which typically comprises less than about 2.0 weight percent of fluorinated silane, more preferably less than about 0.5 weight percent of fluorinated silane, most preferably less than about 0.3 weight percent Solution. The substrate to be coated may typically be contacted with a coating composition (typically a coating solution) at room temperature (typically from about 20 ° C to about 25 ° C).
Typically, after applying the anti-staining coating composition to the AR substrate, the solvent used may be evaporated or removed, and the dried composition may be at least partially cured to impart mechanical stability. This can be done in one or multiple steps. Typically, the drying and curing steps are performed by leaving the coated substrate in a damp environment (eg, an atmosphere having a relative humidity of about 30% to about 55% at room temperature) or by thermal energy, infrared radiation, ultraviolet radiation, electron beam radiation or By applying visible radiation. The longer the time to leave the coated substrate is, the greater the degree of cure is typically. Although not preferred, the method may also require a gloss step or solvent cleaning step after application of the anti-stain coating composition to remove excess material that may adversely affect the antireflective properties of the coating.
If thermal energy is used to dry and / or harden the stain resistant coating, the conditions should be chosen so that the coating can be at least partially cured. This typically includes a drying or curing step performed at a temperature that does not break the integrity of the article (eg, the temperature at which the substrate does not melt). The temperature is preferably about 100 ° C. or higher, more preferably about 120 ° C. or higher, and typically below the melting temperature of the substrate. The time required to dry and / or at least partially cure the coating composition is preferably about 1 minute or more, more preferably about 2 minutes or more. For enhanced performance, the coating composition can typically be cured substantially completely. The degree of sufficient curing can be determined by the ink test and / or wear test described herein. Even when partially or fully cured, suitable coatings are coatings that produce dewetting and droplet forming or at least very thin continuous lines of the ink that can be easily removed with a dry cloth as described in the ink test. Preferred coatings are coatings that produce such properties even after wear, as described in the wear test.
Electron beam radiation can be used at an energy level of about 0.1 Mrad to about 10 Mrad, preferably at an energy level of about 1 Mrad to about 10 Mrad. Ultraviolet radiation means nonparticulate radiation with a wavelength within about 200 nm to about 400 nm, preferably between about 250 nm and about 400 nm. By visible radiation is meant nonparticulate radiation having a wavelength within about 400 nm to about 650 nm, preferably between about 400 nm and about 550 nm. UV and visible light curing is preferred because when these UV or visible light is used as an energy source to cure the composition, even if it damages the thermoplastic, the damage is very small.
Anti-stain coatings of the present invention, typically about 15 mm 3 or more thick, provide significant resistance to staining by conventional organic contaminants such as fingerprints and solvent-based inks. In other words, the anti-stain coating of the present invention exhibits much less tendency to be stained, for example by fingerprints, than that of AR substrates which do not contain this anti-stain coating. Accumulated fingerprints can be easily removed from the anti-stain coating of the present invention by dry wiping or water cleaning. Such contamination is not easily removed from the untreated substrate, in which case a solvent based cleaner should be used.
Stain protection properties can be demonstrated by using an ink challenge test as disclosed in Example 1 of US Pat. No. 5,382,639 (More, et al.). In this test the ink is applied from the permanent marking pen to the surface of the coated substrate. This coating preferably results in dewetting and droplet formation (ie, discontinuous lines) or at least very thin continuous lines of the ink that can be easily cleaned by dry tissue. That is, it is desirable that the ink be formed as droplets as small discrete droplets that can be easily wiped off by a dry tissue to leave little or no traces of residue and cause little or no change in the antireflection of the substrate. . It is desirable that this ink immune test can be repeated several times with little or no loss of initial performance. For example, the ink immune test can be repeated five or more times with no performance impairment (ie, no impairment of anti-staining properties as measured by the ink's dewetting and droplet formation). In contrast, untreated samples are water soluble to permanent ink, which can typically be removed only by a solvent assisted cleaning step. Preferred coatings are coatings which, as described in the abrasion test, result in dewetting and droplet formation of the ink or at least very thin continuous lines, which can be easily wiped off with a dry tissue even after wear. Typically, the harsher the wear conditions the coating can tolerate, the more durable and more desirable the coating becomes.
Importantly, the anti-stain coating of the present invention having a thickness of about 150 mm or less has little effect on the reflective properties of the AR substrate as compared to AR substrates that do not include this anti-stain coating. Thus, the anti-stain coating of the present invention does not substantially change the antireflection of the antireflective article to which it is coated. For example, on a sample coated only on a part of the surface with the anti-stain coating of the present invention having a thickness of about 150 mm 3 or less, the boundary between the coated area and the uncoated area is hardly detected by the naked eye.
Surface reflectance measurements as used herein are reported as first surface reflectance (%) as the average of integration over the visible spectrum (450-650 nm). The first surface reflectance is the result of interference patterns originating from the laminate, any adhesion enhancing coating, any primer layer, and the substrate, while the second surface reflectance is from the backside of the substrate.
The lower the first surface reflectance (%) value, the less the tendency of the antireflective surface to create a mirror image. Typically, the reflectance measurements of the coated substrates of the present invention show little change (ie, substantially no change) compared to the uncoated control. The difference (increase or decrease) between the first surface reflectance measurement after treatment and the first surface reflectance measurement before treatment is about 0.5% (this is a simple difference between% reflectance, i.e. a difference of less than about 0.5% of units, Less than 1%), more preferably less than about 0.2%, even more preferably less than about 0.1%, most preferably less than about 0.05%, wherein the treatment is performed by treating the antireflective surface with methyl perfluoro Coating using a # 6 wire wound rod with a 0.1% by weight solution of fluorinated silane according to the invention dissolved in butyl ether, evaporating the solvent, and curing the coating at 120 ° C. For speculum reflection of about 0.5% or less, it becomes difficult to see the reflected image. Antireflective surfaces having a first surface reflectance of at least about 1.5% and typically up to about 4.0% are generally considered to be of low quality for optical applications.
Experimental Example
The advantages of the invention are illustrated by the following examples. However, the specific materials and amounts thereof recited in these examples, as well as other conditions and details, should be construed as broadly applicable in the art and should not be construed as inappropriately limiting the invention.
matter
Methyl perfluorobutyl ether was purchased from 3M Chemicals of 3M Company, St. Paul, Minn. Under the trade name HFE-7100. Alkoxysilanes 3-aminopropyltrimethoxysilane and 3-aminopropyltriethoxysilane were purchased from Aldrich Chemical Company, Milwaukee, WI, while 3-aminopropylmethyldiethoxysilane was located in Tulitown, Pennsylvania. It was purchased from Gelist Incorporated. Fluorinated Silanes C ₇ F ₁₅ CH ₂ OCH ₂ CH ₂ CH ₂ SiCl ₃ and C ₇ F ₁₅ CH ₂ OCH ₂ CH ₂ CH ₂ Si (OC ₂ H ₅ ) ₃ are disclosed in US Pat. No. 5,274,159 (such as Felite). As described in the prepared in Example 1 and Example 5. C ₇ F ₁₅ CONHCH ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₃ was prepared in Example 9 as described in US Pat. No. 5,274,159 (Fellirite et al.). C ₂ F ₅ OC ₂ F ₄ OCF ₂ CONHCH ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₃ was prepared in Example 17 as described in US Pat. No. 5,274,159 (Pellilite et al.).
Perfluoropolyether esters
CH ₃ O ₂ CCF ₂ O (CF ₂ O) _m (C ₂ F ₄ O) _p CF ₂ CO ₂ CH ₃ (<m> and <p> = about 9 to 11, where <> means an average value ) Purchased commercially available under the trade name FOMBLIN Z-DEAL from Osmont USA, Morristown, New Jersey. Fluorinated Poly (ethyleneoxide) Ester CH ₃ O ₂ CCF ₂ O (C ₂ F ₄ O) _n CF ₂ CO ₂ CH ₃ (F-PEO) and CF ₃ O (C ₂ F ₄ O) _n CF ₂ CO ₂ CH ₃ (F-MPEG) was obtained in Example 2 (polyethylene glycol diacetate and polyethylene glycol monomethyl ether acetate as starting materials, respectively) as described in US Pat. No. 5,488,142 (Paul et al.), While fluorinated Poly (tetramethylene oxide) ester (F-PTMO) CH ₃ O ₂ C (CF ₂ ) ₃ O (C ₄ F ₈ O) _n (CF ₂ ) ₃ CO ₂ CH ₃ is disclosed in US Pat. No. 5,488,142 (Paul et al. Was obtained in Example 1 as described above. The average functionality of the materials under the trade names F-PEO and F-PTMO diesters was generally less than 2 ester groups per molecule, which means that these materials also contained monoesters (e.g. -OCF ₃ as the other end group). It contains various amounts of those having) and inert perfluoropolyether chains (eg those having no functional groups at all). The value of average ester functionality as measured by fluorine-19 NMR analysis is expressed in% in the relevant examples. Perfluorinated monocarboxylic acids (C ₃ F ₇ O (CF (CF ₃ ) CF ₂ O) _n CF (CF ₃ ) CO ₂ H, <n> = about 10) and difunctional methyl ester (CH ₃ O ₂ CCF (CF ₃ ) O (CF (CF ₃ ) CF ₂ O) _n CF (CF ₃ ) CO ₂ CH ₃ , <n> = approximately 10) is EI Dupont de Nemours in Wilmington, Delaware. A commercially available one was purchased from the company under the registered trademark KRYTOX (perfluorinated monocarboxylic acid is more specifically referred to as KRYTOX 157 FS (L)). Typically, the carboxylic acid is treated with thionyl chloride to convert to acid chloride followed by methanol hydrolysis to produce methyl ester before conversion to silane.
For Examples 1-30 and Comparative Example A, the perfluoropolyether esters were treated with a predetermined 3-aminopropylalkoxysilane as taught in Table 1, line 6 of US Pat. No. 3,810,874 (Mitsch et al.). Thereby converting to an alkoxysilane functional derivative. This exothermic reaction is readily performed at room temperature simply by mixing the starting materials. The course of the reaction was monitored by infrared analysis until the ester carbonyl band disappeared at about 1790 cm ⁻¹ and replaced with the amide carbonyl absorption band at about 1715 cm ⁻¹ . For example, when methyl ester is combined with ethoxysilane, exchange may occur such that the product formed may contain methoxysilane groups and ethoxysilane groups. For Examples 1-30 and Comparative Example A, the product was used without further purification or byproduct alcohol.
materials
The substrate coated in the examples below is a polyester film having a thickness of about 4-7 mils (0.1-0.18 mm) coated with an acrylate latex-based primer layer, trademarked from Imperial Chemicals Industries Films, Hopewell, Virginia. A commercially available product was purchased as ICI 617. The substrate is also an NALC0 2327 silica sol (ammonium ion stabilized dispersion (40% solids) of colloidal silica particles having a pH of 9.3 and an average particle diameter of 20 nm, purchased from Nacol Chemical Company, Chicago, Illinois). 1195 g, 118 g of N, N-dimethyl acrylamide, 120 g of 3- (trimethoxysilyl) propyl methacrylate coupling agent, 761 g of pentaerythritol triacrylate (all three raw materials are based in Milwaukee, WI) Purchased from Aldrich Chemical Company, Inc.). This ceramer composition is combined with isopropanol and a photoinitiator (4 parts of ceramer, 21 parts of isopropanol and 0.14 parts of IRGACURE 184 photoinitiator (purchased from Ciba-Geigy, Hodon, NY), and the applicant's US patent application ( A method analogous to that described in Example 1 of Agent No. 54252 USA 8A, filed Jan. 27, 1998, except that the polyester substrate ICI 617, primed with a gravure coater, was 70 to 90 feet / minute (21 to Coating on one surface of the substrate, with the exception of coating at a rate of 28 meters per minute). Prior to reaching the curing step, the coated film was dried to 67 ° C. in a forced air oven to remove isopropanol solvent, and the dried coating was then subjected to a pair of fusion “H” ultraviolet lamps (Model MC-6RQN, MD) (Fusion UV Curing Inc., Rockville). The adhesion enhancing coating formed was about 3 microns thick. Such coating compositions may be coated in a variety of ways, with or without continuous coating techniques and may be cured in a variety of ways, as described in the Applicant's US Patent Application (Attorney No. 53252 USA 8A, filed Jan. 27, 1998). You can.
In addition, the substrate was further coated with a conductive antireflective four layer coating laminate consisting of ITO and sputter coated silicon dioxide (SiO _x , where x is about 2 or less) on the adhesion enhancing coating. The bottom layer (ie, the layer of the multilayer film laminated directly onto the adhesion enhancing coating) contained ITO and the top layer of the film laminate comprised silicon dioxide. This anti-reflective coating laminate was purchased commercially under the trade name CARC from Cortols Performance Films, Kano Park, Calif.
Way
Coating method of antistain composition
In the case of Examples 32-48, the antifouling composition was applied on the antireflective substrate prepared as described above. The stain resistant coating composition was coated by the gravure coating method. A gear pump (commercially available from Parker Hannipin Corporation, Sanford, NC) under the trade name ZENITH was used to transfer the stain resistant composition to the doctor blade, where the doctor blade was used to draw the coating composition. It serves as a reservoir for contact with the beer roll. The gravure roll moves the coating solution directly onto the antireflective surface of the substrate. The doctor blade was made from cold rolled spring steel with a thickness of 0.025 cm. The coating speed was about 1.5-7.6 meters / minute, the oven temperature was about 106-177 ° C., and the pump flow rate was about 3-35 cm ³ / min. In particular, the coating conditions are described in the specific examples described later. Rubber rolls purchased from FR Gross Incorporated, Stowe, Ohio, supported the web as it passed through the coater.
Gravure purchased from Pharmaco, New Jersey, New Jersey, with the trade name G8, theoretical capacity of 4.6 x 10 ⁹ μm ³ / in ² (which can apply a wet phase coating thickness of 0.28 mil (7.1 micron)) A roll (ROTO-FLOW Quad) was used in Examples 32-41. The brand name is G4 and the theoretical capacity is 2.8 × 10 ⁹ μm ³ / in ² (which can be applied with a wet phase coating thickness of 0.17 mil (4.3 microns)), likewise gravure rolls purchased from Pharmaco. Used at 48.
Ink test
Anti-staining properties were demonstrated by applying ink from a black permanent marking pen commercially available from Sanford Company under the trade name SHARPIE. "Pass" is commercially available under the trade name "KIMWIPE" by Kimberley Clark, Roswell, Georgia, where the ink forms small discrete droplets, leaves no traces of residue and does not cause any change in antireflection properties. It means that it can be wiped by dry tissue. "Through border" indicates that the marked area exhibits partial droplet formation of the ink or no droplet formation of the ink, and the ink can be removed, but extra force is typically applied when scrubbing the worn area with dry KIMWIPE. It means that you need to. "Failed" means that the ink cannot be removed even if the ink wets the substrate and rubs the worn area with dry KIMWIPE. Thus, the failed sample is fully soluble to the permanent pen. One "cycle" of the ink test includes an ink application process / ink wipe (ink / dry wipe cycle).
Abrasion test
The samples were tested for durability by applying a force of 2 kg perpendicular to the surface using a brass plunger of the same structure as specifically described in Figure # 07680606 of Military Speciation MIL-C-48497A. The plunger was equipped with an eraser covered with 12 layers of cheese cloth having an area of about 1 cm ² . The plunger was fixed to the arm reciprocating back and forth a specified number of times. This arm was fixed to the motor which ensures a constant stroke repetition. The instrument was associated with a motor that tracked the number of strokes to operate two strokes per cycle. For example, 100 dry rubs were equal to 50 cycles, and 1000 dry rubs were equal to 500 cycles. In order to "pass" this test, the anti-stain coating should have no visual evidence of coating defects as evidenced by plasticity, flaking, peeling, cracking, and foaming. . The worn areas were then typically subjected to the ink immunity test described above.
Reflectance measurement
Reflectance measurement results for coated and uncoated substrates were obtained from Shimadzu Scientific Instruments, Inc., Columbia, MD, using a spectrometer model UV-3101PC UV-VIS-NIR with MPC-3100 large sample compartment. Obtained using. Measurements were performed through industry recommended procedures as outlined in the Shimadzu UVPC Spectroscopy Instruction Manual, Revision 3.7. Reflectance values were collected over a range of 350 nm to about 800 nm at 12 ° incidence under media scan rate with the slit butterfly set to 5.0 nm and the sampling interval set to "automatic". Reflectance data reported herein is an integrated average reflectance at 450-650 nm. This range is recorded because the human eye is most sensitive to the difference in reflectance in this section of the visible spectrum.
Substrate preparation included taking a sample of 7.5 cm × 12 cm from the center of the substrate and sanding the back side of the substrate with Ultrafine 600 grit abrasive paper of 3M Company. The surface of the sanded substrate was then painted with two coats of KRYLON 1602 ultra flat black spray paint purchased from Surwin-Williams Company, Solohorn, Ohio. The coat of paint was dried at room temperature before applying another coating. Once the coating and drying steps are complete, the samples are typically tested immediately.
Examples 1-6
The perfluoropolyether 3-amidopropylalkoxysilanes described in Table 1 below were used to prepare a 0.1 wt% solution dissolved in methyl perfluorobutyl ether. Using a # 6 wire wound rod (purchased from RD Specialtys, Worcester, NY), each of these solutions was withdrawn and manually spread the coating onto the polyester substrate as described above. The coated sample was left at 120 ° C. for 2 minutes in a forced air oven. After cooling out of the oven, the samples were tested using the SHARPIE black permanent marker ink / dry wipe immune cycle as described above. All samples showed liquid crystal formation of permanent ink as discrete droplets that could be easily removed using only dry wipes. This test repeated a total of five ink / dry wipe cycles with no damage to the droplet formation and removal performance of the ink. In contrast, substrates containing no anti-stain coating on the anti-reflective coating could completely engrave letters, and the ink could not be easily removed by dry wiping.
ExamplePerfluoropolyether estersAlkoxysilaneproduct OneFOMBLIN Z-DEALNH ₂ (CH ₂ ) ₃ Si (OEt) ₃ XCF ₂ O (CF ₂ O) _m (C ₂ F ₄ O) _p CF ₂ XX = CONH (CH ₂ ) ₃ Si (OR) ₃ R = Me, Et; <M> = 10.2, <p> = 9.6 2FOMBLIN Z-DEALNH ₂ (CH ₂ ) ₃ Si (OMe) ₃ XCF ₂ O (CF ₂ O) _m (C ₂ F ₄ O) _p CF ₂ XX = CONH (CH ₂ ) ₃ Si (OMe) ₃ <m> = 10.2, <p> = 9.6 3KRYTOX 157 FS (L) Methyl EsterNH ₂ (CH ₂ ) ₃ Si (OMe) ₃ C ₃ F ₇ O (CF (CF ₃ ) CF ₂ O) _p CF (CF ₃ ) XX = CONH (CH ₂ ) ₃ Si (OMe) ₃ <p> = about 10 4KRYTOX 2 functionalityNH ₂ (CH ₂ ) ₃ SiMe (OEt) ₂ XCF (CF ₃ ) O (CF (CF ₃ ) CF ₂ O) _p CF (CF ₃ ) XX = CONH (CH ₂ ) ₃ SiMe (OR) ₂ R = Me, Et; <P> = approximately 10 5F-PEOMW 1800, 78% FunctionalityNH ₂ (CH ₂ ) ₃ Si (OEt) ₃ XCF ₂ O (C ₂ F ₄ O) _p CF ₂ XX = CONH (CH ₂ ) ₃ Si (OR) ₃ , OCF ₃ R = Me, Et; <P> = approximately 10 6F-MPEGMW 1491NH ₂ (CH ₂ ) ₃ Si (OMe) ₃ CF ₃ O (C ₂ F ₄ O) _p CF ₂ XX = CONH (CH ₂ ) ₃ Si (OMe) ₃ <p> = about 11
Examples 7-14 and Comparative Examples A-G
The compounds listed in Table 2 below were used to prepare 0.25 wt% solutions dissolved in methyl perfluorobutyl ether. Using the coating method described in Examples 1-6 above, each of these solutions was coated onto the substrate as described above. The coated sample was left at 120 ° C. for 2 minutes in a forced air oven and then taken out of the oven and left for 2 days under ambient conditions. Samples were tested using SHARPIE black permanent marker ink / dry wipe immune cycle as described above. The results from this test are listed in Table 3 below.
ExamplePerfluoropolyether estersAlkoxysilaneproduct 7FOMBLIN Z-DEALNH ₂ (CH ₂ ) ₃ SiMe (OEt) ₂ XCF ₂ O (CF ₂ O) _m (C ₂ F ₄ O) _p CF ₂ XX = CONH (CH ₂ ) ₃ SiMe (OR) ₂ R = Me, Et; <M> = 10.2, <p> = 9.6 8F-PTMOMW 1310, 80% FunctionalityNH ₂ (CH ₂ ) ₃ SiMe (OEt) ₂ X (CF ₂ ) ₃ O (C ₄ F ₈ O) _p (CF ₂ ) ₃ XX = CONH (CH ₂ ) ₃ SiMe (OR) ₂ , OC ₃ F ₇ R = Me, Et; <P> = approximately 4 9F-PTMOMW 2200, 84% FunctionalNH ₂ (CH ₂ ) ₃ SiMe (OEt) ₂ X (CF ₂ ) ₃ O (C ₄ F ₈ O) _p (CF ₂ ) ₃ XX = CONH (CH ₂ ) ₃ SiMe (OR) ₂ , OC ₃ F ₇ R = Me, Et; <P> = approximately 8 10F-PEOMW 1125, 82% FunctionalityNH ₂ (CH ₂ ) ₃ SiMe (OEt) ₂ XCF ₂ O (C ₂ F ₄ O) _p CF ₂ XX = CONH (CH ₂ ) ₃ SiMe (OR) ₂ , OCF ₃ R = Me, Et; <P> = approximately 8 11F-PEOMW 1800, 78% FunctionalityNH ₂ (CH ₂ ) ₃ SiMe (OEt) ₂ XCF ₂ O (C ₂ F ₄ O) _p CF ₂ XX = CONH (CH ₂ ) ₃ SiMe (OR) ₂ , OCF ₃ R = Me, Et; <P> = approximately 13 12F-PTMOMW 2200, 84% FunctionalNH ₂ (CH ₂ ) ₃ Si (OEt) ₃ X (CF ₂ ) ₃ O (C ₂ F ₄ O) _p (CF ₂ ) ₃ XX = CONH (CH ₂ ) ₃ Si (OR) ₃ , OC ₃ F ₇ R = Me, Et; <P> = approximately 8 Comparative Example AF-PTMOMW 646, 98% FunctionalNH ₂ (CH ₂ ) ₃ SiMe (OEt) ₃ X (CF ₂ ) ₃ O (C ₄ F ₈ O) _p (CF ₂ ) ₃ XX = CONH (CH ₂ ) ₃ Si (OR) ₃ , OC ₃ F ₇ R = Me, Et; <P> = approximately 1 Comparative Example BFOMBLIN Z-DEALradishXCF ₂ O (CF ₂ O) _m (C ₂ F ₄ O) _p CF ₂ X = CO ₂ CH ₃ <m> = 10.2. <P> = 9.6 Comparative Example C--C ₇ F ₁₅ CONHCH ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₃13KRYTOX 157 FS (L) Methyl EsterNH ₂ (CH ₂ ) ₃ Si (OMe) ₃ C ₃ F ₇ O (CF (CF ₃ ) CF ₂ O) _p CF (CF ₃ ) XX = CONH (CH ₂ ) ₃ Si (OME) ₃ <p> = approx. 10 Comparative Example D--KRYTOX 157 FS (L) Carboxylic Acid 14F-MPEGMW 1030NH ₂ (CH ₂ ) ₃ Si (OMe) ₃ CF ₃ O (C ₂ F ₄ O) _p CF ₂ XX = CONH (CH ₂ ) ₃ Si (OMe) ₃ <p> = about 7 Comparative Example E--C ₂ F ₅ OC ₂ F ₄ OCF ₂ XX = CONH (CH ₂ ) ₃ Si (OCH ₃ ) ₃Comparative Example FCF ₃ O (C ₂ F ₄ O) ₂ CF ₂ XX = CO ₂ CH ₃ NH ₂ (CH ₂ ) ₃ SiMe (OEt) ₂ CF ₃ O (C ₂ F ₄ O) ₂ CF ₂ XX = CONH (CH ₂ ) ₃ SiMe (OR) ₂ R = Me, Et Comparative Example G--C ₇ F ₁₅ CH ₂ OCH ₂ CH ₂ CH ₂ Si (OC ₂ H ₅ ) ₃
ExampleResult of the ink test 7Droplet formation after 5 cycles 8Droplet formation after 5 cycles 9Droplet formation after 5 cycles 10Droplet formation in 1 cycle, no drop formation up to 5 cycles, but ink is still removable 11Droplet formation after 5 cycles 12Partial droplet formation, but ink can be removed over 5 cycles Comparative Example ANo droplets formed in one cycle, ink cannot be removed after one cycle Comparative Example BDroplets are formed in one and two cycles, and the ink can be removed over three cycles, but not up to five cycles. Comparative Example CDroplets form in one cycle, and ink cannot be removed up to three cycles. 13Droplet formation after 5 cycles. Comparative Example DDroplets are formed in one cycle, droplets are not formed in five cycles, and ink cannot be removed. 14Droplet formation after 5 cycles. Comparative Example EInk droplets do not form in one cycle, and ink cannot be removed up to four cycles Comparative Example FInk droplets do not form in one cycle, and ink cannot be removed after one cycle Comparative Example GInk droplets do not form in one cycle, and ink cannot be removed after one cycle
The test data of Table 3 is compared with conventional nonalkoxysilane functional materials (Comparative Examples B and D) and alkoxysilane functional fluorine compounds (Comparative Examples C, E, F and G) having a molecular weight of less than about 1000. It clearly shows the performance advantage of more than about 1000 alcoholic silane functional perfluoropolyethers (Examples 7, 11, 13, 14).
Examples 15-28 and Comparative Examples H-J
The compounds listed in Table 4 below were used to prepare 0.1 wt% and 0.25 wt% solutions dissolved in methyl perfluorobutyl ether. Using the coating method described in Examples 1-6 above, each of these solutions was coated onto the substrate as described above. The coated sample was left at 120 ° C. for 2 minutes in a forced air oven, then taken out of the oven and left for 5 days under ambient conditions. The sample was then subjected to 10, 100, or 1000 dry rubs (5, 50, and 500 wear cycles, respectively) as described above, followed by application of SHARPIE black permanent marker ink as described above. Tested. The droplet formation aspect of the ink and the ease of removal by dry wiping were recorded. In addition, reflectance measurements were performed on unweared areas of the sample with uncoated controls. The results of this test are listed in Table 5 below.
ExamplePerfluoropolyether estersAlkoxysilaneproduct 15, 16FOMBLIN Z-DEALNH ₂ (CH ₂ ) ₃ Si (OMe) ₃ XCF ₂ O (CF ₂ O) _m (C ₂ F ₄ O) _p CF ₂ XX = CONH (CH ₂ ) ₃ Si (OMe) ₃ <m> = 10.2, <p> = 9.6 17, 18FOMBLIN Z-DEALNH ₂ (CH ₂ ) ₃ SiMe (OEt) ₂ XCF ₂ (CF ₂ O) _m O (C ₂ F ₄ O) _p CF ₂ XX = CONH (CH ₂ ) ₃ SiMe (OR) ₂ R = Me, Et; <M> = 10.2, <p> = 9.6 19, 20KRYTOX 157 FS (L) Methyl EsterNH ₂ (CH ₂ ) ₃ Si (OMe) ₃ C ₃ F ₇ O (CF (CF ₃ ) CF ₂ O) _p CF (CF ₃ ) XX = CONH (CH ₂ ) ₃ Si (OMe) ₃ <p> = about 10 21, 22KRYTOX 157 FS (L) Methyl EsterNH ₂ (CH ₂ ) ₃ SiMe (OEt) ₂ C ₃ F ₇ O (CF (CF ₃ ) CF ₂ O) _p CF (CF ₃ ) XX = CONH (CH ₂ ) ₃ SiMe (OR) ₂ R = Me, Et; <P> = approximately 10 23, 24F-MPEGMW 1673NH ₂ (CH ₂ ) ₃ Si (OMe) ₃ CF ₃ O (C ₂ F ₄ O) _p CF ₂ XX = CONH (CH ₂ ) ₃ Si (OMe) ₃ <p> = about 13 25, 26F-MPEGMW 1491NH ₂ (CH ₂ ) ₃ Si (OMe) ₃ CF ₃ O (C ₂ F ₄ O) _p CF ₂ XX = CONH (CH ₂ ) ₃ Si (OMe) ₃ <p> = about 11 27, 28F-MPEGMW 1030NH ₂ (CH ₂ ) ₃ Si (OMe) ₃ CF ₃ O (C ₂ F ₄ O) _p CF ₂ XX = CONH (CH ₂ ) ₃ Si (OMe) ₃ <p> = about 7 Comparative Example HFOMBLIN Z-DEALradishXCF ₂ O (CF ₂ O) _m (C ₂ F ₄ O) _p CF ₂ X = CO ₂ CH ₃ <m> = 10.2, <p> = 9.6 Comparative Example I--KRYTOX 157 FS (L) Carboxylic Acid Comparative Example J--C ₇ F ₁₅ CH ₂ OCH ₂ CH ₂ CH ₂ SiCl ₃
ExampleSilane concentration%)reflectivity(%)Dry scrub / ink test results ^a 10 DR100 DR1000 DR 150.10.58--A 160.250.59--A 170.10.54-BC 180.250.69--A 190.10.52-BB 200.250.59--A 210.10.64AAB 220.250.80-AB 230.10.55--A 240.250.53--A 250.10.52ACC 260.250.54--A 270.10.52BDD 280.250.54-BB Comparative Example H0.1-E-- Comparative Example I0.1-E-- Comparative Example J0.1-E-- Comparative Example Kradish0.57E--^a A: Ink forms droplets and is easy to remove by dry wiping (pass) B = Ink forms partial droplets, and easy to remove by dry wiping (pass) C = Ink does not form droplets D = ink does not form droplets, making it difficult to remove by dry wiping (boundary crossing) E = ink does not form droplets, and no removal by dry wiping No (failure)
Example 29
The perfluoropolyether alkoxysilane of Example 1 was used to prepare a 1 wt% solution dissolved in methyl perfluorobutyl ether. The coupon for the CDAR / CFL / CDAR antireflective glass (purchased from Non-Latec Thin Films Inc., Paribold, Minn.) Is an ultrasonic bath filled with a 1: 1 (v / v) ethanol: chloroform mixture. After soaking for several minutes in the air, the final cleaning step was exposed to air plasma for at least 10 minutes in a Harric PDC-3XG plasma washer / sterilizer (Harric Scientific Corporation, Oceanin, NY). Achieved by The coupon is soaked in the coating solution for several seconds to 3.5 minutes. After removal, the samples were washed by sucking for several seconds in fresh methyl perfluorobutyl ether, which contained no perfluoropolyether alkoxysilane. Excess solvent was evaporated, thereby leaving an extremely uniform surface that showed no noticeable change in antireflection when compared to a sample of untreated substrate.
Samples were tested for anti-stain performance by applying black permanent pens from SHARPIE markers. The ink formed small discrete droplets that could be easily wiped off by dry KIMWIPE tissue. This test was repeated a total of 15 cycles without damaging the droplet formation aspect of the ink.
Example 30
Samples of FOBLIN Z-DEAL were vacuum stripped at 90 ° C. under 0.02 mmHg to remove low boiling fractions and increase the number average molecular weight. 10.00 g of sample of distillation residue was treated with 1.41 g of 3-aminopropyltriethoxysilane and the mixture was stirred and left overnight at room temperature. Infrared analysis indicated that the reaction was terminated with less than 0.5% by weight ester carbonyl residues. This gives the perfluoropolyether ester an appropriate analysis of 1567 equivalents or a molecular weight of about 3134. Some of the product was diluted to 0.1% or 0.25% by weight in methyl perfluorobutyl ether. Using the coating method described in Examples 1-6 above, each of these solutions was coated onto the substrate as described above. The coated sample was left at 120 ° C. for 2 minutes in a forced air oven and then taken out of the oven and left for 7 days under ambient conditions. The samples were then subjected to 1000 dry rub cycles as described above, and then the worn areas were tested by applying SHARPIE black permanent marker ink as described above. Both samples gave good ink droplet formation as small discrete droplets that could be easily wiped off with a dry KIMWIPE tissue. Determination of the integral average reflectance at 450-650 nm (as measured by the reflectance measurement method) is 0.1% by weight of the anti-stain composition compared to providing 0.54% for substrates not coated with the anti-stain composition To 0.54% and 0.25% by weight of the anti-stain composition.
Example 31
KRYTOX 157 FS (M) perfluoropolyether carboxylic acid (purchased from Dupont Company, Wilmington, Delaware, having a molecular weight of about 4600), is 25 g of this acid at 80 ° C. After heating for 1 hour using 5 g, stripping at aspirator pressure, i.e. the residue is extracted with FLUOROINERT FC-72 (purchased from 3M Chemicals, 3M Company, St. Paul, Minn.) It was filtered, and then converted to the chloride of the acid by removal using a rotary evaporator. 14.59 g of the product was charged into a three neck round bottom flask equipped with a magnetic stirrer, an addition funnel, and a nitrogen blanket. Then a solution of 0.64 g of triethylamine dissolved in 10 ml of 1,1,2-trichlorotrifluoroethane was added dropwise while stirring. The mixture became cloudy immediately. Then, a solution of 0.70 g of 3-aminopropyltriepoxysilane dissolved in 10 ml of 1,1,2-trichlorofluoroethane was added dropwise while stirring. After the addition was complete and scavenged under nitrogen, infrared analysis of the sample taken 15 minutes showed that the sample was completely converted to amide. 14.49 g of perfluoropolyether alkoxysilane was obtained by filtration and solvent removal using a rotary evaporator.
The above procedure was repeated and the samples stored in closed containers at room temperature for about 11 years were used to prepare 0.1% and 0.25% solutions, respectively, in methyl perfluorobutyl ether. Using the coating method described in Examples 1-6 above, each of these solutions was coated onto the substrate as described above. The coated sample was left at 120 ° C. for 2 minutes in a forced air oven. When tested for a short time after preparation, the sample did not cause droplet formation of SHARPIE black permanent marker ink, but the ink could be removed by dry wiping. After one week, the samples were retested with 100 dry rubs (using the method described above). In both cases the drop formation of the ink and the ease of removal by dry wipe in the worn area as well as the unweared area were shown, the latter being better in performance. After another week, the samples were retested, demonstrating good drop formation and ease of removal by dry wiping of the inks over both the unweared and worn areas. Determination of the integral average reflectance at 450-650 nm (as measured by the reflectance measurement method) was 0.57% in 0.1% by weight of the antifouling composition compared to providing 0.54% in the substrate which was not coated with the antireflection composition. And 0.57% to 0.25% by weight of the stain resistant composition.
Examples 32-36 and Comparative Example L
The solution of perfluoropolyether trialkoxysilane of Example 2 was prepared at concentrations of 0.025%, 0.05%, 0.1% and 0.2% by weight in methyl perfluorobutyl ether. Each of these solutions was applied on a 20.3 cm width section of the substrate as described above using a gravure roll under the trade name G8 capable of applying a 0.28 mil (7.1 micron) wet state film onto the web. A wet coating with a thickness of 0.28 mil (7.1 microns) has a thickness of 17 mm, 34 mm, 68 mm and 136 mm when the solution of the stain resistant composition is 0.025%, 0.05%, 0.1% and 0.2% by weight, respectively. Switched to dry coating. The concentrations and coating parameters used in Examples 32-36 are listed in Table 6 below. Comparative Example L was the aforementioned antireflective substrate that did not contain an anti-stain coating.
ExampleStain Resistant Composition (wt%)Web speed (meters / minute)Oven Temperature (℃)Pump flow rate (cm ³ / min) 320.0253.0510610 330.0257.6214925 340.057.6214910 350.17.6214910 360.23.0514910
Immediately after coating the samples, these samples were tested for droplet formation of the ink as described above. The results are shown in Table 7 below.
ExampleInk test1000 dry rubs with 2 Kg force (after 7 days under ambient conditions)1000 dry scrubs with 2 Kg force (stored 29 days under ambient conditions, then exposed to 65 ° C for 48 hours at 95% relative humidity)Average reflectance (%) (450-650 nm) 32Droplet formation of ink is observed after 72 hoursBorder crossingPass0.626 33Droplet formation of ink is observed after 48 hoursfailurePass0.678 34Droplet formation of ink is observed after 48 hoursPassPass0.658 35Droplet formation of ink is observed after 48 hoursPassPass0.729 36Droplet formation of ink is observed after 48 hoursPassPass0.918 Comparative Example LNo droplet formation of ink occurs 0.592
Examples 32-36 did not show droplet formation of the ink compared to Examples 1-6 when tested immediately after coating with the anti-staining composition. This results in a thicker coating of the anti-staining composition being formed in Examples 1-6 (coating manually), while the thinner coating in Examples 32-36 (coating using automated manufacturing equipment). Therefore, it is thought that such a difference appears. However, after a minimum induction period of at least about 48 hours (from the time the coating was applied), Examples 32-36 exhibited excellent droplet formation aspects of the ink. This is believed to be because such induction period is necessary to achieve higher crosslinking density of the anti-staining composition after application on the substrate. It has been found that anti-stain coated substrates can be stored under ambient temperature conditions or at higher temperatures, but not above 70 ° C., to improve the droplet formation aspect of the ink.
Example 33 demonstrated that higher temperatures (ie, 149 ° C. higher than 106 ° C.) contributed to faster curing of the anti-staining composition. This was observed by the development of the droplet forming aspect of the ink of Example 33 after 48 hours compared to 72 hours for Example 32.
In addition, when the stain resistant composition was coated at a faster web speed as shown by Examples 32 and 36 coated at 3 meters / minute compared to Examples 33-35 coated at 7.6 meters / minute, coating uniformity There was no visual difference in gender, but a decrease in durability was observed for Example 33. Durability was obviously increased by exposing the stain resistant coated substrate for longer periods in the oven. Table 7 above shows that after 29 days under ambient storage conditions (ie room temperature, pressure and humidity), by exposure to 65 ° C. for 248 hours under 95% relative humidity (RH), Examples 32-35 exhibit the same high durability. It is shown that the degree of curing (ie crosslinking density) sufficient to be achieved has been achieved.
The antireflective properties of Examples 32 to 36 and Comparative Example L were measured using the reflectance measuring method described above. As shown in Table 7, the data demonstrate that the lower the concentration of the anti-staining composition obtained, the lower the integral mean reflectance (%) (over the range of 450-650 nm). Substrates containing less than 0.1% concentration of the anti-stain composition exhibited a unit increase of average reflectance (%) to 0.086 as shown in Examples 32-34. Substrates containing less than 0.2% staining composition showed an increase in average reflectance (%) by 0.137 units as shown in Example 35. Substrates containing less than 0.2% staining composition showed an increase in average reflectance (%) of 0.326 units as shown in Example 36.
Examples 37-41 and Comparative Example M
The stain protection composition was identical to the perfluoropolyether trialkoxysilane used in Example 1 (perfluoropolyether trialkoxysilane used in Examples 37-41 was the perfluoro used in Examples 32-36). It has a terminal group different from polyether trialkoxysilane). The stain resistant composition was used at a concentration of 0.025 wt% in methyl perfluorobutyl ether and at a concentration of 0.1 wt% in methyl perfluorobutyl ether. Each of these compositions was coated onto an antireflective substrate as described in the anti-stain coating method above. Examples 37-41 were coated using the same gravure rolls as described in Examples 32-36. Table 8 below describes the coating conditions.
ExampleStain Resistant Composition (wt%)Web speed (meters / minute)Oven Temperature (℃)Pump speed (cm ³ / min) 370.0257.6214910 380.13.0514910 390.13.0514915 400.13.0514910 410.13.0514910
Immediately after coating the samples, these samples were tested for ink droplet formation using the ink test method described above. The results are shown in Table 9 below. Comparative Example M was the aforementioned antireflective substrate that did not contain an anti-stain coating.
ExampleInk test1000 dry rubs with 2 Kg force (after 7 days under ambient conditions)1000 dry scrubs with 2 Kg force (stored 29 days under ambient conditions, then exposed to 65 ° C for 48 hours at 95% relative humidity)Average reflectance (%) (450-650 nm) 37Droplet formation of ink is observed after 48 hoursBorder crossingBorder crossing0.699 38Droplet formation of ink is observed after 48 hoursPassPass0.708 39Droplet formation of ink is observed after 48 hoursPassPass0.708 40Droplet formation of ink is observed after 48 hoursPassPass0.777 41Droplet formation of ink is observed after 48 hoursPassPass0.849 Comparative Example MNo droplet formation of ink occurs 0.592
Examples 37-41 showed no droplet formation aspect of the ink when tested immediately after coating with the anti-staining composition. However, after a minimum induction period of at least about 48 hours (from the time the coating was applied), Examples 37-41 exhibited excellent droplet formation aspects of the ink. This is believed to be because the induction period is necessary to achieve higher crosslinking density of the stain resistant composition after application on the substrate. The droplet formation aspect of the ink observed in Examples 37 to 41 is the same as that observed in Examples 32 to 36, which is the difference in the alkoxy group of the silane functional group (-OMe in Examples 32 to 36, and Examples 37 to 41). -OEt) did not affect,
The data shown in Table 9 above show that Example 37 and Example 38 exhibit the same high endurance, after 29 days under ambient storage conditions, followed by exposure at 65 ° C. under 95% relative humidity (RH) for 48 hours. Shows that
The antireflection characteristics of Examples 37 to 41 and Comparative Example M were measured using the above-described reflectance measuring method. The data described in Table 9 above show that lower concentrations of the stain resistant composition containing an ethoxysilane group can still yield lower average reflectance (%). Substrates containing less than 0.1% staining composition concentration showed a unit increase of less than 0.1 in average reflectance (%) as shown in Example 37. Substrates containing 0.1% staining composition concentration showed a unit increase of average reflectance (%) to 0.257, as can be seen in Examples 38-41.
Example 42
The thickness effect of the anti-stain coating is described in this Example 42. A solution of 0.025% by weight perfluoropolyether trialkoxysilane of Example 32 was likewise applied on the above-mentioned substrate using the coating method described above, wherein the gravure roll (trade name G4) used to coat Example 42 ) Can apply 0.17 mil (4.3 micron) of the wet coating solution. A wet coating with a thickness of 0.17 mil (4.3 microns) is converted to a dry coating with a thickness of 10.8 mm 3 when the stain resistant composition has a concentration of 0.025 wt%. Process conditions are listed in Table 10 below. It was observed that Example 42 did not even have a droplet formation aspect of the ink, although it was exposed for 48 hours under 95% relative humidity to 65 ° C. even after a 29 day induction period at room temperature. When the theoretical dry thickness of Example 42 of about 11 mm 3 was compared with the theoretical dry thickness of Example 32 of about 17 mm 3, the latter exhibited a better droplet formation aspect of the ink, as described in Table 7.
ExampleStain Resistant Composition (wt%)Web speed (meters / minute)Oven Temperature (℃)Pump flow rate (cm ³ / min) 420.025 (with G4)3.0514910 320.025 (with G8)3.0514925
Examples 43-48 and Comparative Example N
The stain resistant composition of Example 2 was used to prepare a 0.1 wt% solution and 0.2 wt% solution in methyl perfluorobutyl ether. Two different catalysts were added to each formulation. Examples 43 and 45 are dibutyl tin diacetate added at a 4 wt% concentration based on the amount of perfluoropolyether alkoxysilane described in Example 2 as a 1 wt% solution in methyl perfluorobutyl ether (Purchased from Aldrich Chemical Company, Milwaukee, Wisconsin, referred to herein as "DTB"). Examples 44 and 46 are dibutyl bis-acetylacetonate catalysts added at a concentration of 4.0% by weight in methyl perfluorobutyl ether based on the amount of perfluoropolyether alkoxysilane (New York, NY) Purchased from Kaneka America Corporation, which is referred to herein as " NST. &Quot; Examples 47 and 48 did not contain a catalyst. Examples 43-48 were coated as described for the coating method using a gravure roll under the trade name G4. Coating parameters and component concentrations are listed in Table 11 below.
ExampleCatalyst (% by weight)Stain Resistant Composition (wt%)Web speed (meters / minute)Oven Temperature (℃)Pump flow rate (cm ³ / min) 434.0 (DBT)0.17.621497 444.0 (NST)0.17.621497 454.0 (DBT)0.27.621497 464.0 (NST)0.27.621497 4700.27.621497 4800.17.621497
Examples 43-48 were evaluated using the ink test and reflectance measuring method mentioned above. The results are shown in Table 12 below. Comparative Example N was the aforementioned antireflective substrate that did not contain an antifouling composition.
ExampleSHARPIE ink droplet formation aspect (after 24 hours storage under ambient conditions)Easy removal of SHARPIE inks (after 96 hours storage under ambient conditions)Average reflectance (%) (450-650 nm) 43Good droplet formation of the ink was observedThe ink is removed with a little effort0.783 44Good droplet formation of the ink was observedInk is removed with minimal effort0.733 45Drop formation of ink is observedInk is removed with minimal effort0.775 46Excellent liquid crystal formation in inkExcellent ink removal0.885 47Good droplet formation of the ink was observedTraces of Ink Remain0.766 48Good droplet formation of the ink was observedTraces of Ink Remain0.664 Comparative Example NNo droplet formation of ink occurs 0.592
As can be seen from the observations described in Table 12 above, the addition of tin catalyst could reduce the time it takes for the coated substrate to improve stain protection properties. Examples 44-46 showed better ink removal than Examples 47-48 without containing a catalyst. The reflectance of Examples 43-46 showed a higher increase than the addition of tin catalyst. However, in order to increase the reflectance to a minimum, one choice can be made to omit the addition of the catalyst and to provide a longer period of room temperature storage to obtain improved stain prevention characteristics.
Comparative Example O and Comparative Example P
Perfluoropolyether carboxylate salts of long-chain alkyl amines are prepared in a glass bottle with 2 g of KRYTOX 157 FS (L) perfluoropolyether carboxylic acid and octadecylamine (Aldrich Chemical Company, Milwaukee, WI). Prepared by mixing 0.27 g. The mixture was warmed with a hot gun to melt the amine and the reagents were stirred and mixed. After cooling, the product became an opaque fat. Infrared analysis showed that the acid carbonyl group disappeared and was converted to the ammonium carboxylate salt. Foreign material was used in Comparative Example O.
Ammonia gas was bubbled through 2 g of FOMBLIN Z-DEAL perfluoropolyether diester at 760 mmHg and room temperature for several minutes in a small glass bottle. Infrared analysis of the liquid product showed that the ester carbonyl group disappeared completely and converted to primary amine. This material was used in Comparative Example P.
The products were used to prepare coating solutions by diluting some to 0.1% or 0.25% by weight in methyl perfluorobutyl ether. In Comparative Example O the coating composition was both opaque, whereas in Comparative Example P the coating composition was transparent. Using # 6 wire wound rods, each of these solutions was coated onto the substrate as described in Examples 1-6 as described above. The coated sample was left at 120 ° C. for 2 minutes in a forced air oven. After cooling out of the oven, the samples were left in air for 2 days at room temperature. The sample was then tested by applying SHARPIE black permanent marker ink as described above. All samples showed no droplet formation of the applied ink, and the ink could not be completely removed from all samples by dry wipe. The same results were obtained after the sample had been subjected to 10 dry rubs as described above and the worn area was tested.
The entire disclosures of all patents, patent documents, and publications cited herein are hereby incorporated by reference. The foregoing detailed description and examples have been given merely to clarify the understanding of the present invention. The invention is intended to be included within the scope of the invention as defined by the claims, and is not to be limited by the detailed description which illustrates and exemplifies obvious variations for those skilled in the art.

权利要求:
Claims (25)
[1" claim-type="Currently amended] An antireflective article comprising an antireflective surface and a substrate having an antireflective coating that is at least partially cured on the surface,
Wherein the anti-stain coating comprises an fluorinated siloxane prepared by applying a coating composition represented by formula (I) and comprising at least one fluorinated silane having a number average molecular weight of at least about 1000:
Formula I
R _f- [R ¹ -SiY _3-x R ² _x ] _y
In the above formula,
R _f is a monovalent or divalent polyfluoropolyether group,
R ¹ is a divalent alkylene group, arylene group or a mixture thereof,
R ² is a lower alkyl group,
Y is a halide, lower alkoxy group or lower acyloxy group,
x is 0 or 1,
y is 1 or 2.
[2" claim-type="Currently amended] The antireflective article of claim 1, wherein the antireflective surface comprises a metal oxide film having one or more metal oxides.
[3" claim-type="Currently amended] The antireflective article of claim 2, wherein the antireflective surface comprises a vacuum deposited metal oxide film.
[4" claim-type="Currently amended] The antireflective article of claim 1, wherein the anti-stain coating has a thickness of at least about 15 mm 3 and less than about 150 mm 3.
[5" claim-type="Currently amended] 5. The antireflective article of claim 1, wherein the first surface antireflection differs by less than about 0.5% from that of the same article that does not contain a stain resistant coating. .
[6" claim-type="Currently amended] 6. The antireflective article of claim 1, wherein the coating is made by applying a coating composition comprising at least one fluorinated silane wherein R _f is a perfluoropolyether group.
[7" claim-type="Currently amended] 7. The antireflective article of claim 1, wherein the anti-stain coating composition further comprises an alkyl perfluoroalkyl ether.
[8" claim-type="Currently amended] An antistain coating composition comprising one or more fluorinated silanes represented by formula (I) and having a number average molecular weight of at least about 1000 and an alkyl perfluoroalkyl ether:
Formula I
R _f- [R ¹ -SiY _3-x R ² _x ] _y
In the above formula,
R _f is a monovalent or divalent polyfluoropolyether group,
R ¹ is a divalent alkylene group, arylene group or a mixture thereof,
R ² is a lower alkyl group,
Y is a halide, lower alkoxy group or lower acyloxy group,
x is 0 or 1,
y is 1 or 2.
[9" claim-type="Currently amended] The compound of claim 8, wherein R _f is —CF ₂ 0 (CF ₂ O) _m (C ₂ F ₄ O) _p CF ₂ —, —CF (CF ₃ ) O (CF (CF ₃ ) CF ₂ O) _p CF (CF ₃ )-, -CF ₂ O (C ₂ F ₄ O) _p CF ₂ -and-(CF ₂ ) ₃ O (C ₄ F ₈ O) _p (CF ₂ ) _3- Having an approximate average structure, wherein m has an average value of 0 to about 50, and p has an average value of 0 to about 50, provided that both m and p are non-zero in the same group.
[10" claim-type="Currently amended] Applying an anti-stain coating to a substrate having an anti-reflective surface comprising treating the anti-reflective surface with a coating composition represented by formula (I) below and comprising one or more fluorinated silanes having a number average molecular weight of about 1000 or more How to:
Formula I
R _f- [R ¹ -SiY _3-x R ² _x ] _y
In the above formula,
R _f is a monovalent or divalent polyfluoropolyether group,
R ¹ is a divalent alkylene group, arylene group or a mixture thereof,
R ² is a lower alkyl group,
Y is a halide, lower alkoxy group or lower acyloxy group,
x is 0 or 1,
y is 1 or 2.
[11" claim-type="Currently amended] The method of claim 10, wherein the coating composition further comprises an unsalted solvent selected from the group consisting of fluorinated alkanes, alkyl perfluoroalkyl ethers, and mixtures thereof.
[12" claim-type="Currently amended] The method of claim 10 or 11, wherein the coating is XCF ₂ O (CF ₂ O) _m (C ₂ F ₄ O) _p CF ₂ X, C ₃ F ₇ O (CF (CF ₃ ) CF ₂ O) _p CF (CF ₃ ) X, XCF (CF ₃ ) O (CF (CF ₃ ) CF ₂ O) _p CF (CF ₃ ) X, XCF ₂ O (C ₂ F ₄ O) _p CF ₂ X, CF ₃ O ( Coating comprising fluorinated silane selected from the group consisting of C ₂ F ₄ O) _p CF ₂ X, X (CF ₂ ) ₃ O (C ₄ F ₈ O) _p (CF ₂ ) ₃ X and mixtures thereof Prepared by applying the composition, wherein -X is -R ¹ -SiY _3-x R ² _x as defined in formula (I) or (C _n F _{2n + 1} )-, (C _n F _{2n + 1} O )-, (X'C _n F _2n O)-and (X'C _n F _{2n + 1} O)-, wherein X 'is H, Cl or Br, and is a single molecule At least one X must be silane,
the mean value of m is in the range of about 1 to about 50,
and the mean value of p is in the range of about 4 to about 40.
[13" claim-type="Currently amended] The method of claim 10, wherein the treating step comprises coating the composition at room temperature and then heating the coated composition at a temperature of about 100 ° C. or higher.
[14" claim-type="Currently amended] The method of claim 10, wherein the coating composition comprising fluorinated silane comprises less than about 2.0 weight percent of fluorinated silane.
[15" claim-type="Currently amended] The method of claim 10, wherein the treating step comprises a continuous roll coating of the composition onto the substrate.
[16" claim-type="Currently amended] The method of claim 15, wherein the continuous roll coating comprises: feeding the coating composition to the doctor blade, moving the coating composition from the doctor blade to the gravure roll, and transferring the coating composition from the gravure roll to the antireflective surface of the substrate. Applying step.
[17" claim-type="Currently amended] The method of claim 16, wherein coating the anti-stain coating composition further comprises applying a soft roll to the opposite surface of the anti-reflective surface of the transparent substrate.
[18" claim-type="Currently amended] 18. The method of any one of claims 10-17, wherein the antistain coating composition further comprises an unsalted solvent.
[19" claim-type="Currently amended] The method of claim 18, wherein the solvent is an alkyl perfluoroalkyl ether.
[20" claim-type="Currently amended] A transparent substrate having a first surface and a second surface,
An antireflective coating located on at least a portion of the first surface, and
Anti-stain coating comprising siloxane groups and polyfluoropolyether segments covalently bonded to silicon via organic crosslinking groups and having an average molecular weight of at least about 1000
Anti-reflective article comprising a.
[21" claim-type="Currently amended] The antireflective article of claim 20, wherein the organic crosslinking group comprises a nitrogen atom.
[22" claim-type="Currently amended] 22. The antireflective article of claim 21, wherein the antistain coating has an atomic ratio of fluorine to nitrogen of about 25 to about 150.
[23" claim-type="Currently amended] The antireflective article of claim 20, wherein the transparent substrate comprises a flexible organic polymeric material.
[24" claim-type="Currently amended] The antireflective article of claim 23, further comprising an adhesion enhancing coating disposed between the flexible organic polymer substrate and the antireflective coating.
[25" claim-type="Currently amended] 25. The antireflective article of any one of claims 20 to 24, further comprising a pressure sensitive adhesive layer disposed on the second surface of the substrate.

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同族专利:

---

公开号 | 公开日

---

CA2317613A1|1999-07-29|

---

DE69832819D1|2006-01-19|

---

EP1051448A1|2000-11-15|

---

AU739635B2|2001-10-18|

---

AU7959398A|1999-08-09|

---

EP1051448B1|2005-12-14|

---

CN1284105A|2001-02-14|

---

WO1999037720A1|1999-07-29|

---

US6277485B1|2001-08-21|

---

KR100557257B1|2006-03-07|

---

CN1308402C|2007-04-04|

---

JP2002506887A|2002-03-05|

---

AU739635C|2002-08-29|

---

DE69832819T2|2006-09-14|

引用文献:

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公开号 | 申请日 | 公开日 | 申请人 | 专利标题

---

法律状态:
1998-01-27|Priority to US09/014,341

---

1998-01-27|Priority to US09/014,341

---

1998-06-11|Application filed by 스프레이그 로버트 월터, 미네소타 마이닝 앤드 매뉴팩춰링 캄파니

---

2001-04-25|Publication of KR20010034441A

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2006-03-07|Application granted

---

2006-03-07|Publication of KR100557257B1

优先权:

---

申请号 | 申请日 | 专利标题

---

US09/014,341|1998-01-27|

---

US09/014,341|US6277485B1|1998-01-27|1998-01-27|Antisoiling coatings for antireflective surfaces and methods of preparation|