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|Holographic flake pigment
|King et al.
|Diffraction efficiency control in holographic elements
|Moss et al.
|Security paper and method of manufacturing the same
|Detrick et al.
|Non-continuous holograms, methods of making them and articles incorporating them
|Waterborne basecoat/high solids clear finish for automotive substrates having an improved appearance
|Electrolessly deposited metal holograms
|Tokas et al.
|Waterbased methylol (meth)acrylamide acrylic polymer and polyurethane containing coating composition
|Den Hartog et al.
|Hologram transfer process
|Yin et al.
|Holographic photopolymer compositions and elements for refractive index imaging
|Trout et al.
|Holographic photopolymer compositions and elements containing a ring-opening monomer
|Smothers et al.
|Dry film process for altering wavelength response of holograms
|Smothers et al.
|Photopolymerizable compositions and elements for refractive index imaging
|Monroe et al.
|Holographic optical elements having a reflection hologram formed in a photopolymer
|Keys et al.
|Automotive wheel covers with spatially stabilized images
|Wreede et al.
|Credit and identification cards having pieces of diffraction grating therein
|Colgate, Jr.
|Opacified latex paint containing plastic polymer particles
|November, 1983
|February, 1989
This is a division of application Ser. No. 08/148,448, filed Nov. 8, 1993 now U.S. Pat. No. 5,415,950.
This invention relates to pigments for decorative coatings. More particularly, this invention relates to holographic flake pigments and compositions containing such pigments.
Reflective and pearlescent flake pigments are used in decorative coatings to provide aesthetically pleasing effect because of both sparkle and "flop". "Flop" is a polychromatic effect whereby, due to the presence of the pigment, a lighter color is evident to the eye when the coated surface is viewed perpendicularly than when viewed at low angle. These variations emphasize the lines and contours of a three dimensional surface.
The weathering resistance of many decorative coatings can be adversely affected by the presence of a reflective pigment or pearlescent pigment. Many synthetic polymers used in coatings are degraded by exposure to the ultraviolet light present in sunlight. Whereas most pigments absorb ultraviolet light, reflective pigments scatter and reflect ultraviolet light throughout the polymer matrix of the coating, increasing its exposure to ultraviolet light. Pearlescent pigments absorb ultraviolet light and catalyze photo-degradation of the polymer matrix of the coating
Reflective flake pigments are typically flakes of metal, such as aluminum, nickel, or steel. Pearlescent pigments are typically mica flakes coated with metal oxides. Certain of these materials are subject to attack by corrosive atmospheres, producing spotting and/or staining of the coating. Metals and metal oxides can enhance photodegradation of the polymer matrix. In addition, these materials may be difficult to disperse in the paint vehicle.
The invention is a holographic flake pigment, the pigment comprising particles that (1) comprise an organic polymer and further comprise one or more volume phase holograms; (2) have a thickness from about 1 micrometer to about 100 micrometers; (3) have an average diameter of about 10 micrometers to about 300 micrometers, wherein said average diameter of the particles is defined to be that which is determined by sieving operations and which is expressed in micrometers; and (4) the thickness to diameter ratio of said flake particles is about 1:2 to about 1:60.
In another embodiment this invention is a process for preparing a holographic flake pigment, said process comprising:
(A) holographically exposing a layer of photosensitive composition to record a volume phase hologram, said photosensitive composition comprising a monomer, a binder, and a photoinitiator system, wherein said binder is present in sufficient amount to form a film when the composition is coated; said photoinitiator system is present in sufficient amount to initiate polymerization of the monomer on exposure to actinic radiation; and said monomer is present in sufficient amount to produce image differentiation on polymerization, and
(B) converting said volume phase hologram to particles that have a thickness of about 1 micrometer to about 100 micrometers, an average diameter of about 10 micrometers to about 300 micrometers, and a thickness to diameter ratio of about 1:2 to about 1:60.
In another embodiment the invention is a fluid coating composition adapted for the preparation of decorative coatings; the composition contains (a) a liquid medium; (b) a film forming polymer; and (c) a pigment dispersed in said medium, the improvement wherein:
the pigment comprises particles that (1) comprise an organic polymer and further comprise one or more volume phase holograms; and (2) have thickness of about I micrometer to about 100 micrometers, an average diameter of about 10 micrometers to about 300 micrometers and a thickness to diameter ratio of about 1:2 to about 1:60.
Another embodiment the invention is an article of a decorative coating on a substrate; the decorative coating contains a film forming polymer and a pigment, wherein the pigment comprises particles that (1) comprise an organic polymer and further comprise a volume phase hologram; and (2) have thickness of about 1 micrometer to about 100 micrometers and an average diameter of about 10 micrometers to about 300 micrometers and a thickness to diameter ratio of about 1:2 to about 1:60.
FIG. 1 shows the reflectance spectrum of a decorative coating containing conventional pearlescent flake pigment applied over a black basecoat.
FIG. 2 shows the reflectance spectrum of a decorative coating containing the holographic flake pigment of this invention applied over a black basecoat.
FIG. 3 shows the reflectance spectrum of a decorative coating containing the holographic flake pigment of this invention applied over a blue basecoat.
The holographic flake pigment comprises particles that comprise an organic polymer and further comprise one or more volume phase holograms. The particles have a thickness of about 1 micrometer to about 100 micrometers, preferably about 5 to 30 micrometers, an average diameter of about 10 micrometers to about 300 micrometers, preferably, 10 to 150 micrometers, and a thickness to diameter ratio of about 1:2 to about 1:60 and preferably, about 1:30. A volume phase hologram is recorded in a photosensitive element, comprising a layer of photosensitive composition on a support. Following holographic exposure, the optical properties of the hologram may be modified by laminating a diffusion donor element to the layer of photosensitive material comprising the hologram. The hologram is then converted to particles of the appropriate size by grinding or an equivalent process.
As is well known to those skilled in the art, reflection holograms reflect only a narrow band of radiation at a given angle. Typically, if exposed object and reference beams are normal to the plane of the layer of photosensitive composition, then the reflected wavelength at normal incidence, is approximately the same as the wavelength used for exposure. As described herein, and in Smothers, U.S. Pat. Nos. 4,959,283 and 5,024,909, and Gambogi, U.S. Pat. No. 5,182,180, the wavelength and bandwidth of reflection may be modified. Thus, by appropriate selection of exposure conditions and by post exposure treatment of the hologram, it is possible to prepare holographic flake pigment that, unlike other flake pigments, reflects the desired range of visible radiation but does not reflect and scatter ultraviolet radiation. Photodegradation of the polymer matrix should be less of a problem with these materials than with other types of flake pigment since they do not increase the exposure of the matrix to ultraviolet radiation.
Unlike metallic flake pigments, holographic flake pigments are not subject to attack by corrosive atmospheres, so they do not cause spotting or staining of the coating in corrosive atmospheres. Further the wavelength of the reflected actinic radiation of the hologram depends on the angle of illumination so holographic flake pigment shows a high degree of "flop". The "flop" is not just a change from a light to dark color as occurs with conventional flake pigments but a change in the dominant wavelength of the color. Since the holographic pigment is an organic polymer, it is also more easily dispersed in the coating composition than is a metallic flake pigment.
Holograms are conveniently recorded by photosensitive materials which produce a spatial pattern of varying refractive index, rather than optical density, when exposed to light. These materials are described in a number of references, such as, for example, L. Solymer and D. J. Cook, Volume Holography and Volume Gratings, Academic Press, New York, 1981, Chapter 10, pp. 254-304. Typically, the photosensitive material is present as a layer on a substrate which provides dimensional stability. In some cases, such as, for example, photopolymerizable compositions, a temporary release film, i.e., a coversheet, is typically also present.
Preferred photosensitive materials are photopolymerizable compositions. Photopolymerizable compositions useful for recording holograms are discussed in "Photopolymers for Holography and Waveguide Applications," by B. M. Monroe and W. K. Smothers, in Polymers for Lightwave and Integrated Optics: Technology and Applications, Part I: Foundations, L. A. Hornak, Ed., Marcel Dekker, New York, 1992, pp. 145-170. Preferred photopolymerizable compositions are disclosed in Keys, U.S. Pat. No. 4,942,102; Monroe, U.S. Pat. No. 4,942,112; and Smothers, U.S. Pat. No. 4,959,284. Particularly preferred compositions are disclosed in Trout, U.S. Pat. No. 4,963,471. In the preferred compositions either the monomer or the binder comprises one or more moieties selected from the group consisting of (1) aromatic moieties selected from the group consisting of (i) substituted or unsubstituted phenyl, (ii) substituted or unsubstituted naphthyl, and (iii) substituted or unsubstituted heterocyclic aromatic moieties having up to three rings; (2) chlorine; (3) bromine, and mixtures thereof; and the other constituent is substantially free of said moiety or moieties. Compositions in which the monomer contains said moiety are more preferred.
For systems in which the monomer contains said moiety and the binder is free of said moiety, preferred liquid monomers are: 2-phenoxyethyl acrylate, 2-phenoxyethyl methacrylate, phenol ethoxylate monoacrylate, 2-(p-chlorophenoxy)ethyl acrylate, p-chlorophenyl acrylate, phenyl acrylate, 2-phenylethyl acrylate, 2-(1-naphthyloxy)ethyl acrylate, o-biphenyl methacrylate, o-biphenyl acrylate, ethyl 1-benzoyl-2-vinyl-1-cyclopropane carboxylate and mixtures thereof. Preferred solid monomers, which may be used to advantage in combination with liquid monomers are: N-vinyl carbazole; 2,4,6-tribromophenyl acrylate or methacrylate; pentachlorophenyl acrylate or methacrylate; 2-naphthyl acrylate or methacrylate; 2-(2-naphthyloxy)ethyl acrylate or methacrylate; and mixtures thereof.
Preferred binders are poly(vinyl butyral) and poly(vinyl acetate). Particularly preferred are fluorine containing binders containing 3 to 23% by weight fluorine. Especially preferred are copolymers of tetrafluoroethylene and/or hexafluoropropylene with vinyl acetate, such the 82:18 (mole %) vinyl acetate/tetrafluoroethylene copolymer, and with vinyl acetate and vinyl alcohol. Other monomers may also be included in the fluorine containing binders.
If crosslinking of the photosensitive composition is desired, up to about five weight percent of at least one multifunctional monomer containing two or more terminal ethylenically unsaturated groups may be incorporated into the composition. The polyfunctional monomer must be compatible with the other components of the composition and is preferably a liquid. Suitable multifunctional monomers include di-(2-acryloxyethyl)ether of bisphenol A, ethoxylated bisphenol A diacrylate, and the like. A preferred crosslinking agent is ethoxylated bisphenol A diacrylate.
The initiator system comprises one or more compounds which directly furnish free-radicals when activated by actinic radiation. (By "actinic radiation" is meant radiation which is active to produce the free-radicals necessary to initiate polymerization of the monomeric material.) It can also comprise a plurality of compounds, one of which yields the free-radicals after having been caused to do so by another compound, or sensitizer, which is activated by the radiation. The photoinitiator system typically contains a photoinitiator and a sensitizer that extends the spectral response of the system to the wavelength of the actinic radiation, typically the visible or near infrared spectral region.
A large number of conventional initiator systems can be used. Photoreducible dyes and reducing agents; ketones; quinones; dye-borate complexes; and trichloromethyl triazines can be used to initiate photopolymerization. Useful discussions systems can be found in "Photopolymers: Radiation Curable Imaging Systems" by B. M. Monroe, in Radiation Curing: Science and Technology, S. P. Pappas, ed., Plenum, New York, 1992, pp. 399-440, and "Free Radical Polymerization" by K. K. Dietliker, in Chemistry and Technology of UV and EB Formulation for Coatings, Inks, and Paints, P. K. T. Oldring, ed.; SITA Technology, London, 1991; Vol. 3, pp. 1-525.
Preferred initiator systems are 2,4,5-triphenylimidazolyl dimers. These compounds are disclosed in: Chambers, U.S. Pat. No. 3,479,185; Cescon, U.S. Pat. No. 3,784,557; Dessauer, U.S. Pat. No. 4,311,783; and Sheets, U.S. Pat. No. 4,622,286. Preferred 2,4,5-triphenylimidazolyl dimers include CDM-HABI, i.e., 2-(o-chlorophenyl)-4,5-bis(m-methoxyphenyl)-imidazole dimer; o-C1-HABI, i.e., 1,1'biimidazole, 2,2'-bis (o-chlorophenyl)4,4'5,5'-tetraphenyl-; and TCTM-HABI, i.e., 1H-imidazole, 2,5-bis(o-chlorophenyl)-4-[3,4-dimethoxyphenyl]-, dimer, each of which is typically used with a hydrogen donor.
Preferred sensitizers include those disclosed in: Baum and Henry, U.S. Pat. No. 3,652,275; Dueber, U.S. Pat. No. 4,162,162; Smothers, U.S. Pat. No. 4,917,977; and Monroe, U.S. Pat. No. 4,987,230. Particularly preferred sensitizers include the following: DEAW, i.e., cyclopentanone, 2,5 bis[4-(diethylamino)phenyl]methylene]-; JAW, i.e., cyclopentanone, 2,5-bis[(2,3,6,7-tetrahydro-1H,5H-benzo[i,j]quinolizin-9-yl)methylene]-; cyclopentanone, 2,5-bis[2-(1,3-dihydro-1,3,3-trimethyl-2H-indol-2-ylidene)ethylidene]; and cyclopentanone, 2,5-bis-[2-ethylnaphtho[1,2d]thiazol-2(1H)-ylidene)ethylidene]. Suitable hydrogen donors include: 2-mercaptobenzoxazole, 2-mercaptobenzothiazole, 4-methyl-4H-1,2,4-triazole-3-thiol, and the like. Other suitable hydrogen donor compounds, which are preferred for compositions which contain N-vinyl carbazole monomer, are 5-chloro-2-mercaptobenzothiazole; 2-mercaptobenzothiazole; 1H-1,2,4-triazole-3-thiol; 6-ethoxy-2-mercaptobenzothiazole; 4-methyl-4H-1,2,4-triazole-3-thiol; 1-dodecanethiol; and mixtures thereof.
Other components conventionally added to photopolymer compositions can be present to modify the physical properties of the recording medium, provided they are compatible with the composition and do not adversely affect the properties of the recording medium or the resulting hologram. Such components include: plasticizers, thermal stabilizers, optical brighteners, ultraviolet radiation absorbing material, adhesion modifiers, coating aids, pigments, dyes, and release agents.
The photopolymerizable compositions are substantially solid, i.e., dry films. The binder must be present in sufficient amount to form a film when the composition is coated. The photoinitiator system must be present in sufficient amount to initiate polymerization of the monomer on exposure to actinic radiation. The monomer must be present in sufficient amount to produce image differentiation, i.e., form a hologram, on polymerization.
Proportions of ingredients in the photopolymerizable composition will generally be within the following percentage ranges, based on the total weight of the composition: binder 25 to 90%, preferably 45 to 75%; monomer(s), 5 to 60%, preferably, 15 to 50%; plasticizer, 0 to 25%, preferably, 0 to 15%; photoinitiator system, 0.1 to 10%, preferably 1 to 7%; and optional ingredients, 0 to 5%, typically 1 to 4%.
The photopolymerizable compositions are typically used as a layer applied to a dimensionally stable support. The composition may be directly coated onto the support by any conventional method, or may be cast as a film and laminated to the support by conventional methods. In either case the support provides dimensional stability for the photopolymerizable composition. If the photopolymerizable composition is to be irradiated through the support, the support must be transparent to actinic radiation. Transparent supports that may be selected to advantage include: glass, polyethylene terephthalate film, poly(methyl methacrylate), polycarbonate, and cellulose triacetate. A preferred support material is polyethylene terephthalate film.
The photosensitive element comprising the photopolymerizable layer and support may also comprise a temporary release film, or coversheet, on the other side of the supported photopolymerizable layer. The coversheet, may be, for example, polyethylene, polypropylene, polyethylene terephthalate, etc. Conventional intermediate layers or coatings may be used to facilitate the adhesive and/or release characteristics needed for the photopolymerizable layer.
The photosensitive composition must be imaged to produce a volume phase hologram. A volume phase hologram comprises a varying pattern of refractive index within the recording material. This varying refractive index pattern modifies the phase and subsequently the direction of light passing through it.
Although the coversheet may be removed prior to exposure, exposure is typically carried out with the coversheet in place. Alternatively, the coversheet may be removed and the photosensitive layer laminated to a temporary substrate, such as a piece of glass or a front surface mirror, prior to exposure. In this situation, the substrate functions as the coversheet. For holographic exposure of the photosensitive layer, coherent light sources, e.g., lasers, are required. Techniques for carrying out holographic exposures are well known to those skilled in the art. A useful discussion of holography is presented in "Holography" by C. C. Guest in Encyclopedia of Physical Science and Technology, Vol. 6, pp. 507-519, R. A. Meyers, Ed., Academic Press, Orlando, Fla., 1987.
Reflection holograms, i.e., holograms which are viewed in reflection, are formed by allowing two beams of coherent radiation, known as the object beam and the reference beam, to simultaneously enter the photosensitive layer from opposite sides so that they are traveling in approximately opposite directions. The interference between these beams is recorded by the photosensitive layer as a spatial pattern of varying refractive index.
Volume phase reflection holograms may be produced by a single-beam on-axis method wherein the reference beam is projected through the photosensitive layer onto an object therebehind. The reflected beam from the object becomes the object beam and interferes with the reference beam. Reflection holograms also may be produced by two-beam on-axis and off-axis methods wherein a reference beam is projected on one side of the photosensitive layer and an object beam is projected on the reverse side of the photosensitive layer. Reflection holograms produced by an off-axis process are disclosed in Hartman, U.S. Pat. No. 3,532,406.
For the production of holographic flake pigment any reflection hologram may be used, but holographic mirrors are preferred. A holographic mirror is the simplest reflection hologram. It can be created by splitting a laser beam and recombining the beams at the photosensitive layer (two-beam method). Alternatively, it can be created by projecting a laser beam through the photosensitive layer onto a mirror (single-beam method). The light reflected by the mirror becomes the object beam, reflecting and then interfering with the reference beam in the plane of the photosensitive layer. In one process, the coversheet is removed and a reflective film, such as aluminized polyethylene terephthalate, is laminated to the photosensitive layer with the aluminized side in contact with the holographic recoding material. Since the holographic recording material may adhere to the aluminized surface, this step is preferably carried out immediately prior to exposure. Holographic exposure is then carried out through the support. The reflective film acts as a mirror during exposure.
Preferred holographic flake pigments have a band center wavelength of about 380-1100 nm and have an effective bandwidth of about 10-200 nm. Also, preferably the holographic flake pigment specularly reflects light incident only from a limited solid angular region that is determined by the optical and spectral configurations used in recording the hologram in the organic polymer of the pigment. Other preferred pigments contain multiple single-beam or two-beam holograms or both. Other useful pigments have single-beam, mirror-like holograms in which the angle of maximum reflected light is other than the usual, mirror-like, specular reflectance angle and contains a mixture of single-beam, mirror-like reflecting holograms and two-beam holograms to provide a range of angular widths of the specular lobe. By specular lobe is meant the angular distribution of light about normal, mirror-like, specular reflectance direction.
As disclosed in Keys, U.S. Pat. No. 4,942,102, following holographic exposure, the photosensitive element may be exposed overall to actinic radiation. Coherent radiation is not required for the overall exposure. Exposure may be carried out with any convenient source of actinic radiation, such as a graphics arc light source, laser, sunlight, etc.
If the wavelength of reflection is to be modified as described below, overall exposure following holographic exposure may be carried out to only partly polymerize any remaining monomer or may be omitted entirely. Holograms with wider bandwidths are typically produced if overall exposure is omitted before the wavelength shifting step. However, if the modification step is to be omitted, overall exposure is preferred before the hologram is converted to pigment particles.
If the binder is poly(vinyl butyral), poly(vinyl acetate), or a copolymer of vinyl acetate with tetrafluoroethylene and/or hexafluoropropylene containing 3 to 23% by weight fluorine, the refractive index modulation of the hologram can be enhanced by heating to 100°-150° C. for about 1-90 minutes following overall exposure.
Following overall exposure and thermal processing the wavelength and bandwidth of the reflection hologram may be modified as described in Smothers, U.S. Pat. Nos. 4,959,283 and 5,024,909, and Gambogi, U.S. Pat. No. 5,182,180. A diffusion donor element is laminated to the surface of the reflection hologram. The diffusion donor element typically comprises a substantially solid diffusion layer that comprises a diffusion agent, a binder, and, optionally, a photoinitiator system. The diffusion layer is coated on a support. The diffusion agent is a material that can diffuse from the diffusion layer into the hologram, typically a liquid plasticizer or a liquid monomer.
Diffusion may be allowed to proceed at ambient temperature or may be carried out at an elevated temperature. The degree of swelling of the hologram caused by diffusion may vary across the thickness of the hologram. Thus, a diffusion gradient may be produced causing nonuniform fringe spacing and an increased bandwidth of light reflected by the hologram. The amount of diffusion can be controlled by variation of the amount of diffusion agent in the diffusion donor element, the diffusibility of the diffusion agent (typically a function of its molecular weight), the diffusion time, and the temperature at which the diffusion is carried out. If the diffusion agent is a monomer, the hologram may be fixed by overall exposure following diffusion. If desired, especially broad band reflection may be obtained by (1) laminating a diffusion donor element whose diffusion layer, preferably between 3 and 25 micrometers thick, comprises a binder, an initiator system, a plasticizer, and a polymerizable monomer that contains two or more acrylate and/or methacrylate groups, preferably a methacrylate or pentaerythritol triacrylate, and (2) rapidly heating the resulting laminate to 100°-150° C., preferably 120° -150° C., for at least 1 minute. By this process, holographic mirrors with reflection bandwidths (transmission optical density greater than or equal to 0.8) greater than about 50 nm may be prepared.
The support for the photosensitive layer is removed before the hologram is converted to pigment particles. If a diffusion element is present, the support for the diffusion element is also removed, but the diffusion layer may be left in place, if desired.
The hologram can be converted to pigment particles of the desired size by any conventional means, such as sand grinding, ball milling, attritor grinding, two roll milling, etc. One method that can be used to advantage is to cool the hologram below its glass transition, for example, in liquid nitrogen, before grinding with a pestle in a mortar that had been precooled with liquid nitrogen. Another method is to grind the hologram in cold water, such as in ice water. Alternatively, the grinding apparatus can be refrigerated to cool the hologram to below its glass transition temperature.
Following conversion to pigment particles, particles of the desired size may be separated by any conventional means, such as sieving, wet sieving or air classification. Particles that are too large may be separated and converted to the desired size.
The pigment particles have a thickness of about 1 micrometer to about 100 micrometers, an average diameter of about 10 micrometers to about 300 micrometers and a thickness to diameter ratio of about 1:2 to about 1:60. The thickness of the particle is determined by the thickness of the photosensitive layer in the photosensitive element plus the thickness of the shifting film (diffusion donor element), if present. A preferred range for pigment particles is an average thickness of about 5 micrometers to about 30 micrometers, an average diameter of about 10 micrometers to about 150 micrometers, and a thickness to diameter ratio of about 1:2 to about 1:30.
The fluid coating composition of this invention contains: (a) a liquid medium; (b) a film forming binder; and (c) a holographic flake pigment dispersed in the liquid medium. The holographic flake pigment will typically comprises 0.5-2.0% by weight of the composition, although higher levels could be used, if desired. Preferably, the holographic flake pigment has an index of refraction equal to or within plus/minus 0.05 refraction units of the index of refraction of the film forming binder of the composition. Other ingredients that are conventional components of coating compositions may also be present provided the ingredient is compatible with the other ingredients of the composition and its presence does not adversely affect the properties of the composition.
The fluid coating composition containing the holographic flake pigment may be advantageously applied as mid-coat. The composition may be applied over a conventional pigmented base coat and covered with a conventional clear coat, i.e., a coating without pigments (as the top-coat). Alternatively, the holographic flake pigment, with or without additional conventional pigment or pigments, may be included in the basecoat. Alternatively, the coating comprising holographic flake pigment, with or without additional conventional pigment or pigments, can be used without a clear coat.
Whether or not the holographic flake pigment is used with other pigments and whether or not the coating comprising the holographic flake pigment is used with a basecoat and/or a clear coat will depend on the application. Conventional high quality automotive finishes, for example, typically comprise a clear coat over a colored basecoat.
When used in a mid-coat without added conventional pigment, the holographic flake pigment will typically comprises 0.5-5.0% by weight of the composition, although higher or lower levels could be used, if desired. Higher levels will be required when the holographic flake pigment is used in a coating composition that contains added conventional pigments and lower levels when used without other pigments.
Waterborne coating compositions are preferred for coating compositions containing holographic flake pigment. Some organic solvents may adversely affect the properties, especially the optical properties, of the holographic flake pigment. Waterborne coating compositions suitable for use as basecoats, as described below, will typically be suitable for use as decorative coatings comprising holographic flake pigment.
Conventional basecoats typically contain: (a) a liquid medium; (b) a film forming binder; and (c) a pigment dispersed in the liquid medium, including the holographic flake pigments.
The film-forming binder can comprise any of the film forming resins conventionally used as binders in coating compositions. Particularly useful binders include: fluorinated polymers, acrylic polymers, polyesters, alkyds, and polyurethanes.
Thermoplastic fluorinated polymers can be used such as polyvinyl fluoride, polyvinylidine fluoride, or copolymers and terpolymers thereof. One useful composition contains about 50-80% by weight polyvinylidine fluoride and 20-50% by weight of polyalkyl methacrylate. Useful waterborne basecoats are disclosed, for example, in Chang, U.S. Pat. No. 5,100,735, and Den Hartog, U.S. Pat. No. 5,006,413.
The acrylic polymers are copolymers of one or more alkyl esters of acrylic and/or methacrylic acid. One or more other ethylenically unsaturated monomers may also be present. These polymers may be of either the thermoplastic or thermosetting type.
Suitable alkyl esters of acrylic or methacrylic acid include esters in which the alkyl group contains 1-12 carbon atoms, preferably 1-8 carbon atoms, such as: methyl methacrylate, ethyl methacrylate, 1-propyl methacrylate, n-butyl methacrylate, n-pentyl methacrylate, methyl acrylate, ethyl acrylate, n-butyl acrylate, and 2-ethylhexyl acrylate, etc. Suitable ethylenically unsaturated monomers that may also be present include: vinyl aromatics, such as styrene and vinyl toluene; nitriles, such as acrylonitrile and methacrylonitrile; vinyl and vinylidene halides, such as vinyl chloride and vinylidene fluoride; and vinyl esters, such as vinyl acetate. If the polymer is of the thermosetting crosslinking type, suitable functional monomers are included. Typical functional monomers are hydroxy alkyl acrylates having 1-4 carbon atoms in the alkyl group, such as hydroxyethyl acrylate and methacrylate, hydroxypropyl acrylate and methacrylate; unsaturated carboxylic acids, such as acrylic acid and methacrylic acid; and polyisocyanates and blocked polyisocyanates.
Crosslinking agents such as monomeric and/or polymeric partially and/or fully alkylated melamine formaldehyde crosslinking agents, such as "Cymel" resins, usually are included. Particularly useful resins are the partially and fully alkylated melamine formaldehyde resins having 1-6 carbon atoms in the alkyl group. Organic polyisocyanate crosslinking agents also can be used.
Typical polyesters are formed from the condensation of: a polyol, such as pentaerythritol; a glycol; a monocarboxylic acid; an aromatic dicarboxylic acid; and an aliphatic carboxylic acid. Branched chain glycols, preferably those with 8 or fewer carbon atoms, such as neopentyl glycol and pinacol, may be used. The monocarboxylic acid is primarily used to control the molecular weight of the polymer. Any aromatic or saturated aliphatic carboxylic acid having 18 of fewer carbon atoms may be used. Typical acids are: benzoic, triethyl benzoic, toluic, acetic, propionic, stearic, lauric, pelargonic, etc. Preferred dicarboxylic acids are those with 4-12 carbon atoms, such as succinic, phthalic, isophthalic, terephthalic, etc.
Polyurethanes of the reaction product of a polyol and a polyisocyanate can be used. Polyurethanes of hydroxy containing acrylic polymers, hydroxyl containing polyesters or polyethers reacted with an organic polyisocyanate also can be used.
The use of conventional ingredients is well known to those skilled in the art. Each ingredient, if present, is used to modify the composition in conventional form and in the amount required to achieve the desired effect without adversely affecting the properties of the composition. Such ingredients include, for example: ultraviolet stabilizers, thickeners and rheology control agents, wetting agents, defoamers, surfactants, pigment dispersants, biocides, etc.
To improve the weatherability of the finish, about 0.1-5% by weight, based on the weight of the binder, of a photostabilizer or combination of stabilizers may be added. Stabilizers are disclosed in Barsotti, U.S. Pat. No. 5,093,391, column 5, line 16, to column 6, line 28. Typical photostabilizers include: o-hydroxybenzophenones, such as 2,4-dihydroxybenzophenone and 2,4-dihydroxy-3',5'-di-t-butylbenzophenone; triazines, such as 3,5-dialky-4-hydroxyphenyl triazine derivatives; triazoles, such as 2-(2'-hydroxyphenyl) benzotriazole; benzoates, such as octylphenyl benzoate; hindered amines, such as derivatives of 4-hydroxy-2,2,6,6,-tetramethylpiperidine; nickel compounds, such as bis(phenyldithiocarbamato)nickel(II); etc. Other conventional photostabilizers are well known to those skilled in the art.
Thickeners and rheology control agents can be added in amounts of about 0.5-5% by weight of the coating composition to provide the desired spray viscosity. Typical agents are: acrylic polymers such as polyacrylic acid, clays, cellulosics, urethanes, etc.
The pigmented basecoat contains conventional pigments in a pigment to binder ratio of 1:100-50:100. Any of the conventional pigments used in coating compositions may be used in the basecoat. These include, for example: metallic oxides, such as titanium dioxide, zinc oxide, and iron oxide; chromates, such as lead chromate; carbon black; silica; talc; china clay; organometallics, such as copper phthalocyanine; organic pigments, such as quinacridones and azo pigments; etc. Numerous other conventional pigments are well known to those skilled in the art.
The pigments are formulated into a mill base by mixing the pigments with a dispersing resin which may be the same as the binder of the composition or may be another compatible dispersing resin or agent. The pigment dispersion is formed by conventional means such as sand grinding, ball milling, attritor grinding, two roll milling, etc. The mill base is then blended with the binder to form the coating composition.
The substrates over which the basecoat is applied are those conventionally used for automobile and truck bodies such as: cold roll steel, phosphatized steel, polyester reinforced fiber glass, reaction injection molded urethane, crystalline amorphous polyamide, and the like. Typically these substrates are coated with a pigmented layer of alkyd resin primer, polyester primer, epoxy resin primer, and the like. Conductive primers, useful when it is desired to prepare a conductive surface for electrostatic spraying, are described in Mirabeau, U.S. Pat. No. 5,114,756. The primer typically is about 12 to about 75 micrometers thick.
The coating composition may be applied to the substrate by conventional techniques, such as: spraying, electrostatic spraying, dipping, brushing, flowcoating, and the like. After coating, the composition is dried at ambient temperature or baked at elevated temperature to allow solvent to evaporate before the clear coat is applied. Typical clear coat/basecoat finishes have a clear coat about 25-50 micrometers thick and a basecoat of about 5-50 micrometers thick.
The clear coating used contains a liquid medium and a film forming binder. Any of the aforementioned film forming binders used for the base coat such as acrylic polymers, polyesters, alkyds and polyurethanes and the melamine or polyisocyanate crosslinking agents can be used. The clear coating composition maybe solvent or waterborne. Typically, the composition can contain any of the aforementioned photo stabilizers or combinations of stabilizers, thickeners and rheology control agents. Small amounts of transparent pigments can be used to improve durability and weatherability of the clear coat. It may be possible to incorporate some holographic flake pigment in to the clearcoat.
One useful clear coating composition is shown in Harper U.S. Pat. No. 5,215,783 issued Jun. 1, 1993.
Holographic flake pigments are useful for the preparation of decorative coatings that can be used to emphasize the lines and contours of a three dimensional surface. These pigments are particularly useful for the preparation of exterior finishes for automobiles. The pigments also can be used in molded plastics to provide a decorative appearance, in tiles and the like.
The advantageous properties of this invention can be observed by reference to the following examples which illustrate, but do not limit, the invention. All parts and percentages are on a weight basis unless otherwise indicated.
Brij ® 30
Polyoxyethylene(4) lauryl ether;
o-Cl-HABI Biimidazole, 2,2'-bis[o-chlorophenyl]-4,4',5,5'-
tetraphenyl-; CAS 7189-82-4
Cyasorb ® W-24
2,2' Dihydroxy-4-methoxybenzophenone;
Elvacite ® 2051
Poly(methyl methacrylate); MW 350,000;
E. I. du Pont de Nemours and Company,
Wilmington, DE
FC-430 Fluorad ® FC-430; fluoroaliphatic polymeric
esters; CAS 11114-17-3; 3M Company,
St. Paul, MN
JAW Cyclopentanone, 2,5-bis[(2,3,6,7-tetra-
MMT 4-Methyl-4H-1,2,4-triazole-3-thiol;
Photomer ® 4039
Phenol ethoxylate monoacrylate;
Henkel, Ambler, PA
Sartomer 349
Ethoxylated bisphenol A diacrylate;
Sartomer, West Chester, PA
TAOBN 1,4,4-Trimethyl-2,3-diazobicyclo-
Tinopal ® SFG
Ciba-Geigy, Hawthorne, NY
Tinopal ® PCR
sulfonic acid phenyl ester; CAS 6994-51-0;
Ciba-Geigy, Ardsley, NY
TMPTMA Trimethylolpropane trimethacrylate
TEOTA Triacrylate ester of ethoxylated
Vinac ® B-15
Poly(vinyl acetate); MW 90,000; CAS 9003-
20-7; Air Products and Chemicals, Allentown,
The binder was a vinyl acetate/tetrafluoroethylene copolymer containing about 78% by weight vinyl acetate and about 22% by weight tetafluoroethylene, prepared by a process similar to that described in Trout, U.S. Pat. No. 4,963,471. Inherent viscosity about 1.45 (0.2% in tetrahydrofuran).
Holographic Recording Material
A coating solution containing the following was made up in 75:25 2butanone/toluene (All percentages are % by weight of total solids): 66.0% binder; 17.0% Photomer® 4039; 3.0% Sartomer 349; 7.9% N-vinyl carbazole; 3.7% o-CL HABI; 2.1% MMT; 0.2% FC-430; and 0.1% JAW. It should by understood that "total solids" refers to the total amount of non-volatile components in the composition even though some of the components may be non-volatile liquids rather than solids at room temperature. JAW was dissolved in dichloromethane (about 32.5 g of dichloromethane/g of JAW) prior to addition. All subsequent operations on coating solutions or resulting films were performed under red lights.
The solution was filtered. A web coater equipped with an extrusion dye, 3.7 m drier set at 50°-70° C., and a laminator station was used to coat the solution onto an about 50 micrometers thick support of clear polyethylene terephthalate. A coversheet of about 23 micrometers thick polyethylene terephthalate was laminated to the coating as it emerged from the drier to produce a photosensitive element consisting of coversheet, holographic recording material, and support. The holographic recording material was about 20 micrometers thick.
Immediately prior to holographic exposure, the coversheet was removed from the holographic recording material. A 50 micrometers thick piece of aluminized polyethylene terephthalate was laminated to the holographic recording material in its place with the aluminized side in contact with the holographic recording material. The holographic recording material was exposed through the support using the apparatus described in Armstrong, U.S. Pat. No. 4,995,685. Imaging was carried out at 514 nm using an exposure of about 40 mJ/cm2 at normal incidence. The holographic recording material was then overall exposed to about 150 mJ/cm2 of ultraviolet and visible light.
The aluminized polyethylene terephthalate was removed from the exposed holographic recording material. An about 8 micron thick diffusion element was laminated to it. The diffusion element had the following composition (% by weight): Elvacite® 2051, 32.4%; Vinac® B-15, 12.64%; TMPTMA, 35.55%; TEOTA, 7.90%; o-C1 HABI 1.58%; 2-mercaptobenzoxazole, 0.71%; Tinopol® PCR, 0.20%; Tinopol® SFG, 0.99%; Cyasorb® W-24, 0.08%; Brij® 30, 7.9%; hydroquinone, 0.05%; and TAOBN, 0.03%. The laminate of diffusion element and holographic recording material was heated in an oven at about 120° C. for about 0.5 hr. Heating was carried out in an oven with good air circulation so that the laminate was heated rapidly to 120° C.
The resulting holographic mirror had a reflection bandwidth (optical density greater than or equal to 0.8) of about 80 nm. The band was centered at about 592 nm.
Pigment Preparation
The diffusion element support was carefully removed from the exposed and processed holographic recording material. The hologram was carefully peeled from the support. The resulting polymer layer, consisting of the exposed and processed holographic recording material and diffusion layer was cooled in liquid nitrogen. The cooled polymer layer was placed in a mortar that had been precooled with liquid nitrogen and ground with a pestle. The holographic recording material was initially broken into large flakes. More liquid nitrogen was added and additional grinding carried out.
The ground holographic recording material was wet sieved. It was placed on a wire mesh screen stack and washed with a large volume of water. Particles less than about 38 micrometers (0.0015 in; 400 mesh screen sieve) were discarded. Particles greater than about 38 micrometers and less than about 76 micrometers (0.003 in; 200 mesh screen size) were collected. Particles greater than about 76 micrometers were dried and ground again.
Preparation of Coating
Tri-coated panels were prepared. To form the basecoats, conventional waterborne basecoats containing pigment, acrylic latex, and dispersant resin were sprayed onto primed aluminum panels. A midcoat containing about 1.5% of holographic flake pigment was prepared in a conventional waterborne system similar to that used in the basecoat. The midcoat was applied in two coats and flashed for 10-30 min. A conventional polyurethane clear coat was sprayed over the midcoat and baked and then sanded and recoated with the clear to provide a film build that was 35-50 micrometers thick.
One coating containing conventional pearl flake and two coatings containing holographic flake were prepared. A mid-coat containing the pearl flake was sprayed over a base coat containing black. A mid-coat containing holographic flake was sprayed over two base coats, one containing black and one containing blue. In each case, a clear top-coat was then applied.
Evaluation of Coatings
Reflectance spectra were measured using the spectrophotometer similar to that described in Lee, U.S. Pat. No. 4,412,744. Reflectance spectra were measured at near specular or NSP (i.e., 45° illumination and -30° viewing) flat (i.e., 45° illumination and 0°, surface normal, viewing) and high (i.e., 45° illumination and 65° viewing) positions. The measured values are referenced to a white diffuse reflecting standard.
FIG. 1 shows the reflectance spectra of a mid-coat containing conventional pearl flake over a black base coat. This pearl flake was used as a comparison panel because it nearly matches the color of the holographic flake (i.e., the pearl flake over black has a hue angle of about 90° and the holographic flake over black has a hue angle of about 100°. Hue angles are in CIE L* a* b* color space derived using a CIE D65 source and a CIE 10 degree standard observer. The pearl flake is made with materials (e.g., TiO2) which have high indices of refraction relative to that of the vehicle (e.g., 2.2 versus 1.5). The interfaces between the flake and the vehicle mostly scatter the incident light at angles that are not equal to the specular reflectance angle. The effects of this non-specular scattered light is most noticeable on the NSP curve (10) at 410 to 450 nm where the reflectance value averages about 20%. The flat (12) and high (14) curves in the 600 to 700 nm region have reflectances of 30 and 12% respectively. If the light reflected to these two positions comes from a scattered (i.e., diffuse) reflected component the light observed at the flat (i.e., 65° viewing) position would be about 0.42 (i.e., cosine 65°) of the value reflected to the flat, surface normal, viewing position. Indeed, the 12% reflectance of (14) is 0.4 of the 30% value reflected in the direction of the surface normal (12).
FIG. 2 shows the spectra of the holographic flake mid-coat over a black base coat. The holographic polymer has almost the same index of refraction as the vehicle. Therefore, very little scattering occurs at the vehicle-flake interface. This lack of scattering is illustrated by comparing the ratio of the maximum NSP (10) and high (14) reflectances of the conventional pearl flake to that of the maximum ratio for the holographic flake panel (i.e. curves 20 and 24). The pearl panel has a 15 to 1 ratio while the holographic panel has a ratio of 43 to 1. At the flat (24) viewing position, the holographic flake is essentially transparent and most of the light is being reflected by the black base coat (e.g., a blacker base coat would result in a ratio higher than the 43 noted above).
FIG. 3 illustrates the above point by showing the spectra for the holographic flake over a blue base coat. At NSP (30), the hue angle is little changed from that of the holographic flake over black, 105° for curve 30 versus 100° for curve 20. At the flat (32) and high (34) viewing positions, the flake has become substantially transparent and the blue base coat is the principal reflecting element. At these viewing positions the hue angle of the spectra has shifted by about 180° to 286° for the flat (32) viewing the position and 283° for the high (34) viewing the position. None of the currently manufactured non-holographic flake pigment can be fabricated into panels that show such a dramatic hue shift.
The above experimental measurements thus demonstrate that the holographic flake does not substantially scatter light into angular regions outside the desired specular reflectance angular region, while the pearl flake does substantially scatter light into angular regions outside the designed specular reflectance angular region.
Having described the invention, we now claim the following and their equivalents.


text:
From NBC's Shawna Thomas and Carrie Dann
House Majority Leader Eric Cantor just announced that the House will consider another short-term government funding measure next week.
It is expected that this funding measure will be for three weeks. This continuing resolution would keep the government open beyond the March 18th deadline if the Senate passes it.
This three-week spending bill is expected to show cuts of $2 billion per week, totalling another $6 billion in cuts.
President Barack Obama said Friday that he is open to "one more" stopgap measure to avert a shutdown, but he called on congressional leaders to "compromise on prudent cuts" and agree on a long-term budget to fund the government through the end of the fiscal year.
"We can't keep running the government based on two-week extensions," Obama said during a news conference. "That's irresponsible."

subset: commoncrawl


text:
Changing Asia's Labor Conditions
Some of Europe's biggest retailers signed an agreement to improve safety conditions at Bangladesh's garment factories. Asia Monitor Resource Center's Sanjiv Pandita tells the WSJ's Deborah Kan why he doubts some of these guidelines will be regulated.
This transcript has been automatically generated and may not be 100% accurate.
... the the ... slices retailers have signed a legally binding agreement committing to improving the safety of workers following ... the factory collapsed in Bangladesh cycled over a thousand people ... and ever con joining me now is Sunday and eat at front Asia Monitor Resource Center agency said Sunday ... okay so how the reinforced something like this if companies are saying ok yes we're going to take a legal responsibility ... is really up to them to make sure ... not to our workers are are are saying ... in ... a bid to move things in the morning news it's very important and ... um he's BCP be ... that these ... and that the nations of the unseen Beatles ... then for spenders and informational get a ... lump in companies should be loading enforcement ... in autumn Goldman is because I mean you don't use the ... the one that isn't the coolest ... company is adding gold in enforcement of many places to visit for looking mechanism ... men's clothes and should be as being ... Steve Madden and a ... nice to have the strength in the ... bottle in the space to enforce a stand with the most ... of course in that building collapse at there were a lot of different companies ... manufacturing and got critique and their ... building as there are in and many garment factories in Bangladesh said ... do you feel not done this tragedy is actually going to camp to ion and the ... labor rights in that country and and we are are are some of the shortcomings ... ha we don't understand this the the this is a system in the system and structural problem ... and in the accident cannot fool it because the problem that thing we know is ... that a lot of attention and but one song that sings lead on ... people move again ... but this is an opportunity to change some things today ... but he handles to understand that things won't change a light ... but the change things that need to be some institutions and don't ... you see the problem is that is the lack of democratic institutions and don't be in yours ... end of an infection in a tree ... and a new nations and of the page ... so those institutions need to be string them ... along with the logos of AWB's it ... that includes the new Wealth associations ... Tribune and rates and other middlemen ... the same as we see a lot of manufacturing living out of China and to honor I in Southeast Asia and ... nations ... um oh what countries do you believe have the worst lines and bass laws to protect our ... labor rights ... some good review ... what is most other countries have some was diverted logos ... the problem is implementation ... you see you may have been sold and it has been as as long as they loaded the bus ... China has sold with most of the bill of goods ... Indonesia Hezbollah's India's middle of the ... problem has been notified ... but on the days I can say is to countries of the beach don't have an open mostly they can stay ... on to me is that they don't have those institutions if they are still in the process of ... formation of laws ... but what I was am ... given a group of the report is good ... the problem has ... been at ups in the end of lesson though ... you don't implement those little ... he has seen most of the countries in Asia ... the SEC chains victory ... is the link in ... the ... Bhagavad and it's even begun ... so they did the program is seeing is that it ... was uh don't have that feeling budget cuts ... all the inspection so face for the US ... yes I think the problems of enforcement ESI Scion Bangladesh thanks Fran much Sandy's idea joining us from Hong Kong ... for more on that star a pink added Avista dot com under for time ...


text:
Meeting Notices
S.O.S. Al-Anon — Family Group will meet on Fridays at 7 p.m. at St. John's Lutheran Church, Hopkins Street, Sayre.
Recovery House Meetings — AA Group of Towanda meets Mon.-Fri., noon; Mon., Thurs., Fri., Sat., 8 p.m., Sun., 8 a.m. and 8 p.m. NA meetings are held Tuesdays at 7 p.m. Speaker meeting every first Sunday, 8 p.m. All meetings at 205 Main St., Towanda (please use rear, lower entrance).
Compassionate Friends — of the Endless Mountains will hold their meetings on the second Tuesday of every month at 7 p.m. in the Endless Health Community Center, Montrose. TCF is open to all families who have lost a child from any cause at any age. There are no membership dues or fees of any kind. For more information, call 965-0901 (evenings) or 278-1658 or e-mail firstname.lastname@example.com.
S.O.S. Al-Anon — Family Group will meet on Fridays at 7 p.m. at St. John's Lutheran Church, Hopkins Street, Sayre.
Caregivers' Support Group sponsored by the Law Office of Leslie Wizelman and the B/S/S/T Area Agency on Aging meets at noon the second and fourth Tuesday of each month at the Library at Memorial Hospital Personal Care Home in Towanda. Caregivers and family members of long term care facility residents are welcome. For information, call Bob Bachisin at the Law Office of Leslie Wizelman at (570) 746-3844.
Twelve Steps on the Way, a Christian recovery group, will meet at the Wyalusing Presbyterian Church on Mondays at 7 p.m. Use door in the rear of the church.
Al-Anon meetings are held every Monday at 7:30 p.m. at the Holy Name of Mary Parish Center, S. Main St., Montrose.
Lupus Foundation of Pennsylvania — Monthly support group meeting; first Tuesday of every month at 7 p.m. at the Tunkhannock Public Library, W. Tioga Street. For more information, visit www.lupuspa.org or call 1-888-99LUPUS.
Diabetes Support Group - meeting the first Thursday of every month at the Guthrie Clinic office in Towanda beginning at 5:30 p.m. There is no charge and all diabetics and family members are welcome. For more information, call Dawn at Guthrie Clinic at 570- 265-6165 during regular business hours.
TOPS PA #1134 — Laceyville, meets each Tuesday evening at the Braintrim Baptist Church in Laceyville. Weigh-ins from 5:15 to 6 p.m., meeting from 6-7 p.m. For more information, call 965-2493 or 869-1834. Tollfree 1-800-932-8677.
AA Meeting — Wednesdays at 8 p.m. in the basement of the Wyalusing Presbyterian Church. Open meeting, nonsmoking.
MOPS — Mothers of Preschoolers meet every first and third Wed. of the month from 9 to 11 a.m., September through May. Meetings are held at the First Presbyterian Church, 5 Court St., Towanda. All mothers of preschoolers are welcome. Child care is provided for children, ages infant through five years old. For more information, contact the church at 570-265-5575.
Towanda-Wysox Kiwanis Club meets every second and fourth Wednesday of each month at the Weigh Station Café at 7:30 a.m. in Towanda. They find ways to help the children in the community. Contact Eileen Sheets at 570-265- 2350 for more information.
Addictions to Victory. Faithbased support for addictions. Program will be held the first and third Thursday of each month at 7 p.m. at New Generation Church, Milan, 570-888- 1967.
Bradford County Cancer Support Group meets the 4th Wednesday of every month at Memorial Hospital in Conference Room A, beginning at 6:30 p.m. For more information, call 1-888-227-5445, Option 3.
The New Albany Widowed Persons Group will meet on Wednesday, May 2 at 11:30 a.m. at the New Albany Fire Hall Rummage Sale for lunch. Please note change in time and meeting place. Call 570-363-2454 for more information.
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Saluting a true enforcer: Dave Semenko
Jim Matheson did a good article about Matt Clackson's dad, Kim. Matt Clackson is the guy that Sheldon Souray recently broke his hand on fighting. Kim Clackson was a pugilistic warrior, himself, having gone against the likes of Dave Semenko in an epic battle that just didn't seem to ever end (they fought 3 times in the same altercation). Here's an excerpt from Dave Semenko's autobiography, Looking Out For Number One, on the events that transpired: Continue reading 'Saluting a true enforcer: Dave Semenko'»


text:
Stripped To The Metal, We Root For The Abstract
11/10/2012 – Michigan 38, Northwestern 31 (OT) – 7-3, 5-1 Big Ten
College sports are a rich-get-richer kind of operation. American pro sports reward their best teams with crappy draft picks and salary caps that make it hard to keep successful operations together. Yes, successful operations can keep their heads above water for periods, and the Lions can be awful for 50 years. A relentless gravity still pulls everyone towards .500.
In college, success adds to success. You can tell recruits they'll go to the Sugar Bowl and the Rose Bowl instead of, like, Nashville or wherever. Your pile of money is larger than someone else's pile of money and you can put up buildings where every brick is an XBox. You can point to some guy making millions in the NFL and promise recruit X will as well. You can tell recruits that you're not going to be fired and replaced by some guy from the Sun Belt, unlike every other school recruiting Derrick Green. The more you win, the higher your draft picks are.
Gravity has no place in college sports, just entropy. Entropy: the tendency of things to move from ordered states to disordered ones. Entropy: the gradual decline and fall of the Carr era. Entropy: Greg Robinson. Entropy: Northwestern football. With 18 seconds left there's a fifty-yard pass on the way, and things are about to get disordered.
I mean, what can you say when your glorious victory is so clearly a gift from the cosmic random number generator? I have seen many things in my time as a sports fan. None of them have been an opposing safety taking a pass that is about to sail into the turf 10, 20 yards further downfield and flailing at it in such a way as to send it into the arms of the Michigan receiver he'd battered to the ground, gently. Feather-like. After all of that… easy.
Meanwhile, that event had been immediately preceded by a Northwestern fourth-and-one conversion on which the ref had to make sure every chain was ramrod straight and get his nose down to the field level before awarding the Wildcats a first down they probably didn't get but could not be overturned from above. Fitzgerald Toussaint's only decent run of the day ended with a bizarre pop-up fumble. Trevor Siemian came in and tore Michigan's secondary to shreds.
I like it better when the randomness is under a nice ol' narrative. When it's in your face so spectacularly, it's like the gods of math are taunting you for daring to care about anything they have their fickle fingers in. Go home, get a pen, and root for Fibonacci psuedo-randomness, they are saying. What you are doing is the equivalent of rooting for 3, they say. The number. The literal number. Woo 3. Go 3. You are so much more prime than 4. That's so 3! Oh god those people who like 4 are just animals. They poop in coolers, you know, and drive trucks. They're so… divisible.
Stripped of the narrative bit the mind goes back to a game of partial information, high stress, and plain evidence that worshipping the gods of math gets you nowhere. Big stacks matter in tournament poker, too. With many chips you can lean on people, play with the numbers on your side, and force people to decisions for all their chips. You get to be the gorilla. You get the good recruits.
Back in the day when laws were unclear and jerks hadn't yet banned online poker by attaching a rider to a bill about port security, I played a lot. I was pretty good. I played online satellites until I'd gotten a buy-in to the World Series of Poker, and went. I made the second day in rough shape, and started repairing my busted stack by chopping off preflop raisers. While I'd risk more, I'd be in fewer hands, give off a tight image and get 5-6 blinds instead of 1.5. I would have no illusions about whether I should GTFO if someone played back at me. It was working, and I caught a couple hands. I was on my way to day three.
I'd done this to the guy to my right two or three times already, and his frustration was evident the last go-round. He raised preflop again, and I looked at kings. Long story short, we ended up all-in, he turned over aces instead of anything else, and I did not suck out. Short-stacked after, it was a matter of time.
Brady Hoke hasn't had kings, but he has sucked out, and sucked out, and sucked out.
With 11-2 and a BCS win in the rear view, Michigan picked up the kind of momentum that saw them lock down a top-five class by March. Getting there took a series of desperate heaves to Junior Hemingway. This year the heaves have been a little less desperate but twice Michigan has had 18 seconds and needed big chunks of yards to set up do-or-die field goals and got them. They're not getting every break—see refs in all Nebraska games—but with a combination of skill and fortune Hoke is building quite a stack for himself.
The latest chip is a 2013 starting quarterback out of nowhere, a guy who had looked basically awful in any extended playing time before Denard's elbow injury forced Devin Gardner into the Minnesota game. And even if Saturday was too transparently chaotic to go down as an all-timer, it's another step through this rough patch as Michigan waits for the large, mean cavalry to arrive.
In the meantime let's all just stay here on the floor breathing heavily and slathering narrative over the terrifying randomness of the universe.
Football looks hurty sometimes, and by sometimes I mean all the time.
Also, here's Gardner chucking that TD to Funchess:
Brad at Maize and Blue Nation had a day with his shots. He's the guy who grabbed the shots that lead the post and then this is pretty great too:
Also, nightmare fuel!
Full gallery here.
The News got a great shot of Gardner:
David Guralnick/Detnews
That's Bryant in the extremely large track jacket BTW.
More videos posted by Thorin on the board. UMGoBlog shots. Favorites from Mike DeSimone's page.
Brady Hoke Epic Double Point Of The Week. Roy Roundtree, come on down. Not only did you spawn a strange and likely short-lived meme when the Larrys, about whom more later, made a bizarre joke about how he would be better at catching the ball if his name was "Squaretree"—because square things are good at catching I guess—but you also put up 139 yards receiving, including the game-saving deep miracle. Also on 'Tree's docket: a beautiful corner route catch, getting run over on third and seventeen, and a critical hitch-and-run in OT.
Honorable Mention. Devin Gardner (at this rate will be Vince Young by next year, too bad about plateaus and such), Jeremy Gallon (hitch/bomb/punt return/let's ignore those other punt return opportunities), Kenny Demens (a close, close #2 with back to back OT TFLs).
Epic Double Point Standings.
3: Jake Ryan (ND, Purdue, Illinois) deytikerjerbs
2: Denard Robinson (Air Force, UMass)
1.3: Jeremy Gallon(Alabama, 1/3 Minnesota), Drew Dileo (Michigan State, 1/3 Minnesota), Roy Roundtree (1/3 Minnesota, Northwestern)
1: Craig Roh(Nebraska).
Brady Hoke Epic Double Fist-Pump Of The Week. NEW NEW NEW NEW NEW
This must be awarded to the play that spawned it, which is Demens decleating Northwestern to end the game. In the future awarded to the BOOM YES play of the week.
Honorable mention: Kenny Demens stones Northwestern on third and one too, Treezy to the rescue, Devin Gardner kind of balletically flings a ball way high except it's to Devin Funchess so it's on the money, Jibreel Black forces a Colter fumble, Jordan Kovacs implodes Colter's back.
Epic Double Fist-Pumps Past.
11/10/2012: Mattison baits Fitz, Kenny Demens decleats Northwestern, game over.
Our hipster quarterback. WHICH ONE OF THESE DUDES IS DEVIN GARDNER
you've probably never heard of me
Probably the one on the left. PROBABLY
Open contempt. Northwestern fans were pretty hype on Nick Van Hoose as the cornerback who might rescue their secondary from its overwhelming Northwesternness; Van Hoose did not play. The Northwestern secondary was overwhelming in its Northwesternness.
This manifested on second down after second down when Michigan generally followed up a one yard run by going with a 2TE I-Form set and throwing a hitch in front of a helpless cornerback, or a corner at a helpless cornerback, or a hitch and go well past a helpless cornerback. I get pretty irritated when Michigan, which cannot run from under center even a tiny little bit, goes OOPS POW SURPRISE PLAY ACTION on obvious passing downs, but in this game it worked because every hitch route came with either a first down or some YAC baked in.
I have no idea why Northwestern didn't just bracket Michigan's single WR hard and dare Michigan to make them pay by getting to the second level—something it seemed they were four or five blocks from on every play. But they didn't. So, yeah.
RUUUUUUUUUUUU—oh you are nevermind. IIRC, Michigan did not have any called runs for Gardner except the goal line rollout (and that did have a pass option). He got sacked once. That means his seven other rushing attempts were all scrambles. That's more than Denard has acquired in eight games. They were also effective—an average pickup of almost seven yards without any of those coming on fruitless third and longs.
Yeah, that is Vince Young-like. The combination of effective deep balls and a willingness to take off is potentially deadly. Covering four verts and containing Gardner seems hard, and add in dumpoffs to space players like Norfleet and Hayes, and that's a nice recipe. Hopefully Michigan explores that once they don't have to minimize QB impact at all costs.
[UPDATE: After checking out the Gardner errysnap video, Michigan did have another called QB run in a goal-to-go situation that went for five or six yards, so six scrambles.]
not always pretty, but so far so good / Upchurch
Air check. We should erase the desperation bomb to Roundtree, which was a throw Gardner had to attempt, missed, and got a miracle deflection to complete it. That excised, Gardner was 15 of 28 for 8.3 YPA, two touchdowns, and a turrible interception. Add in the scrambles and that's good in a vacuum. Your context: Gardner was playing a poor defense minus its best cornerback and on an offense that can't run the ball even a little.
Those probably balance out, leaving Michigan with a good performance from a guy who'd been playing WR two weeks ago and has eligibility next year. That is huge.
Unlike last week, I can't remember anything particularly outlandish that happened to alter Gardner's stats since we've already set aside the desperation heave at the end of the game. Gardner actually lost a long completion to Jerald Robinson, and there was nothing on the order of Roundtree, Dileo, and Gallon going all circus for their QB in the Minnesota game. When Gardner missed, it wasn't by much. Minnesota was some good throws interspersed with a lot of shaky ones on which the receivers were great; Northwestern required a lot less heroism from the WRs.
You'd expect rapid improvement from a guy getting almost his first extended playing time and transitioning back to reps at QB from reps at WR; Gardner leapt even that high bar.
Y'all be jumpin'. Michigan has now pulled opponents offsides five times in two weeks with Gardner under center, with Northwestern threatening to go three or four more times.
That's a credit to Gardner's hard count and evidence of how much more comfortable Borges is with an offense that operates from under center. To run those freeze plays you have to be under center quickly enough to try it and then try something else if it doesn't work, something that has not often been the case for most of the year when Michigan was struggling just to get plays in. Against Northwestern, how often did you think "GET OUT OF THE HUDDLE" to yourself? For me, it was zero times. That's down a half-dozen from most games this year.
SIDE NOTE: I've seen a lot of credit going to Gardner for having the awareness to fling those fades when guys go offsides. That's a misunderstanding of what's going on. The way it works is this:
- Gardner huts his hut real hard, and then waits.
- Guy jumps or does not jump.
- If guy jumps, Mealer snaps it, free play.
- If guy does not jump, Michigan checks into something else.
So if Gardner gets the ball he knows someone is offsides and he has a free play and just throws the fade. He only gets the ball if he has a free play. The credit should go to Borges and Mealer.
SIDE SIDE NOTE: Yeah, Michigan did try to do similar things under RR from the gun. Bizarrely, what seemed to happen is that Michigan would get a guy to jump but he would get back before Michigan could snap the ball, leaving Michigan to burn a down on a low-percentage play.
Hello, Fitz. Not that Fitz. Hey, three broken tackles en route to a touchdown on a nothing dumpoff: that is a play. I enjoy Fitzgerald Toussaint making plays. he also picked up a bunch of bonus yards on his 50-yard inverted veer give, and then fumbled. That's his first fumble, right? I guess he gets a pass for it. Even Mike Hart finally broke.
A tip, I say, a palpable tip. Did anyone else notice Michigan removing AJ Williams for Devin Funchess on the third and goal in OT, and think to themselves "rollout to Funchess's side"? Lo, it transpired, and Northwestern covered Funchess but had no one else on the edge once a playside LB tried to shoot inside Omameh and got walled off.
I require more Dileo. Michigan finally had enough of seeing punts hit the ground and put Dennis Norfleet back there in place of Gallon; Norfleet let the next punt hit the ground. Dileo fair-caught the next one. Meanwhile, balls are being tossed at the thus-far ineffective Jeremy Jackson and Jerald Robinson as Dileo watches from the sideline. I humbly request more targets for Dileo, who gets separation and catches passes, instead of larger receivers who do neither of these things
Maize and Blue Nation
Kenny Damn Demens. Remember when he was getting lined up two inches behind a nose tackle on a three man line and obliterated by guards releasing clean? Yeah. Demens isn't going to be a guy who makes every #25 in the future wear his name on the chest, but any time he walks into a bar for the rest of his life sporting that mustache of his someone is going to be like "CONSECUTIVE TFLS TO WIN 2012 NORTHWESTERN" and buy him a beer, and I love it when that happens. See also: Jerome Jackson, 2005 Iowa.
Demens did get beat by Northwestern's #1 WR on their last touchdown, but that's an RPS thing and a function of Michigan's LB slide plus Northwestern consistently gashing Michigan on the corners. Projected % of Michigan fans instantly reminded of Chris Graham against Anthony Gonzalez: 37%.
So sexy. Michigan came out with a a weird three man line featuring Jibreel Black as the NT that all but begged Northwestern to run up the middle on their fourth down, with the results noted above: Ryan gets cut off by the backside G, Black shoots playside of the tackle and forces a cutback on the handoff NW was baited into, BOOM.
That was exactly the plan:
"The last tackle there — number one, I like the call that (defensive coordinator Greg Mattison) made because it was one where it may have talked (Northwestern) into running the football because of some of the space inside," said Michigan coach Brady Hoke. "And then Kenny just did a nice job of just working inside out to the ball, where maybe a little bit earlier he was maybe getting too far ahead of it."
Michigan's defense finally got gashed, but man did they dial it up at the end.
Will it happen again? Ohio State is going to be checking out the Northwestern film quite a lot, but I'm not sure they have a Mark-like back to hit that edge. They've got a couple thumpers who will challenge tackling skills more than speed.
Linebacker switching. I didn't notice this live but a lot of people have said Desmond Morgan had a rough game, which seems logical since after a couple weeks of limited linebacker swapping we saw a lot of James Ross, including on the final two Northwestern drives. Ross was the guy who came an inch away from stuffing the Northwestern fourth and one. I'll get to the bottom of what went down in the UFR.
Pipkins comes on. Also receiving a lot more PT: Ondre Pipkins, who had a rough few plays against Minnesota before getting the hook. Again not sure why but probably based on Northwestern being one of those hurry-up outfits that puts a heavy demand on opposing defense's depth. Insert usual desire to be a team that puts that kind of pressure on the opponent.
Getting edged. Michigan's really got to do something about their option scheme, probably. I'll have to check it out to see if it was much different than what happened against Air Force.
Oblig. Kovacs number switch bitching.
Me = Dude (obvs)
Car = Kovacs
Flame = #11
Nihilists = Brandon (obvs)
He's still JKovacs32 on twitter, at least.
"I've worn No. 32 for quite some time, I think I'll always be No. 32," Kovacs said
Yes. Dammit that needs to be the walk-on-who-plays number. Does no one understand how to make things? /wireseason2
Oblig. game theory bit. Big points to Pat Fitzgerald for going for it on fourth and short with around three minutes left. That is a spot in which it's easy to go NFL and derp your way to shrugging postgame coverage, but the obvious play is going. One yard and you've got the other team trying to complete a 50-yard miracle to tie. Punt and even Michigan's languorous two-minute drill still has time to ease down the field.
Northwestern got it by a few molecules thanks to what seemed like a favorable spot, albeit not one that is ever going to get overturned by the Big Ten's milquetoasty replay officials. (After the Penn State TD debacle they are now the Rod Gilmore Memorial Big Ten Replay Officials.)
Fitzgerald gives back about half of those points on the punt. You hate variance if you are Northwestern punting the ball back with 25 seconds left. NW…
- took a delay of game penalty instead of using a timeout
- ran out their rugby guy to bash a line drive into Gallon's chest
- got a net of 11 yards as a result
Rugby punts are generally effective but tend to be more unpredictable than regular stuff: shanks are easier, and if the returners are positioned correctly they get an opportunity like Gallon got. The play there was to take a timeout and hang one in the air to force a fair catch. The upside of that is about equal to the rugby punt and the downside is nil.
Michigan didn't really face any major decisions. They could have taken a shot at the endzone after the Roundtree completion but chose to kick. The difference between that decision and the end of last year's ND game was one second on the clock and a timeout, which they had against ND but not here. The Roundtree completion took six seconds, and it's easy to see that last one slip off the clock for any number of reasons.
FWIW, Michigan played their TOs right by taking all of them immediately once they were facing do-or-die time on defense.
Git R Done, for values of R that equal racism. If you don't follow me on twitter you missed the saga of the Larry The Cable Guy clan in my immediate vicinity, a group of redneck yahoos that said a lot of things like "LEZ GO CUMONG" and "GIT EM CUMONG," which was annoying when they did that really loudly after a four yard run—now my hopes are all up and it's second and six—but mostly harmless.
That ceased on a Norfleet kickoff return on which one of them screamed "run like you stole it" and I was processing the I am somewhat uncomfortable with the racial overtones that statement displays thing when one of them almost certainly dropped the n-word. I looked at the MGoWife, and she looked at me to confirm, and then I just really hoped that it wouldn't come up again because if that happens a second time, well… words will be exchanged and I'm trying to panic myself to death at a football game thanks, please let's not get in a screaming match.
It did not come up again. Hurrah. There's no real lesson here except it's not very fun to be surrounded by Larry the Cable Guy.
BONUS BONUS BONUS: a Larry next to me left after the Gardner INT, which lol. I moved over because there was a tall guy in front of me… directly into the path of a woman with four pom-poms whose thought process in relation to those was:
I bet if I shake these really hard they're invisible.
If only, lady. If only.
* NW ended up with 431 total offense yards. That's the same amount that Alabama,
the greatest team ever assembled, a pretty good offense, had against us. I never would have guessed that Alabama and NW would be equivalent at anything. After the Alabama game, I wrote, "If we can hold everyone else under 431, I'll be happy." NW didn't get more than 431, so I'm not unhappy, I'm just confused.
* Thomas Gordon led us in tackles with 11, not a good sign. Demens and Morgan were next with 9 apiece. Considering Mattison substituted freely with the LBs, that's a lot of tackles.
I bumped Best And Worst but in case you didn't click through:
…this week's game definitely felt like the first one to showcase Al Borges's "preferred offense." It was a number of shorter passes, a dedication to running the ball with the RB, and play-calling that couldn't fall back on a Dilithium-fueled QB if the first and second reads were not open. Minnesota showed this a bit in the first quarter, but that game felt over at halftime and so I'm not sure what you could glean from it except that the offensive line still couldn't get a push inside.
mGrowOld's kid meets Kovacs. MGoUsers of little faith.
Opponent stuff. The Northwestern blog POV includes an analysis of Northwestern's success on speed option pitches, misery, more misery, and misery. Lake The Posts:
Does it need to be said much more than that? Inches decide ball games, particularly close ball games. Against Nebraska inches separated Northwestern from a clinching interception and a devastating blown lead and loss. Against Michigan, those inches mattered even more.
You can slake your schadenfreude needs if you're weird and hold some sort of grudge against Northwestern at the SoP postgame thread.
Blog stuff. The Ann Arbor Chronicle has a photoessay documenting everyone recording the football game. Meta.
not actually photos of the Roundtree catch
KENNY DEMENS – He didn't play a perfect game but he did make the tackle of his life – TWICE! It's a play and situation you dream of as a kid growing up playing Pop Warner Football. Demens not only made the big stop to win the game on 4th Down, but he also made the stop the play before on 3rd Down! OUTSTANDING!
Michigan struggled on defense in this game for a number of different reasons. Jake Ryan and Frank Clark both lost contain frequently which gave Northwestern big gains on the ground. In addition, and I think Mattison figured this out before the fourth quarter, but Michigan was defending the speed option in an unsound manner. The playside linebacker was always playing the quarterback, forcing a pitch to the running back who had nothing but blockers in front of him. I think Mattison assumed his corners and safeties could get off of their blocks on the outside the help contain the rushing attack, but Michigan's corners aren't very good at doing this. By the fourth quarter, Michigan started forcing the runs back inside.
I cannot agree with Maize and Blue Nation about this:
The running game. It showed signs of life this week. I think the more pro-style offense that Gardner runs suits Michigan better on offense. We're still trained to run the spread-option, but I don't think it's working for Fitz. He's a downhill runner. I really like that Rawls can come in and compliment Fitz...although, it might be the other way around, actually. I thought the line blocked better this week. Hoke stayed with the same lineup he's had all year across the line, so it was encouraging to see the interior especially, play better.
Michigan got a 50-yard gain on an inverted veer give—blocking not relevant unless you're a WR—and 41 yards on six Gardner scrambles. They also lost six yards on a Hayes jet sweep that's now scouted by opponents. Their other 23 carries went for 49 yards. Death. If Michigan finds itself trailing against OSU there's going to be a point at which it'll be time to run the quarterback from the shotgun even if it's Gardner and the backup option is Jack Kennedy. Michigan just can't move the ball on the ground without the numerical advantage provided by using the QB.
U-M Student Section Sucks
And I thought the key play nonsense was bad.
The empty seats are past the point of ridiculous now. Michigan has been reduced to having its football players make videos begging fans (read: students) to show up on time for the games. WTF?! This isn't Ball State. Bo's probably rolling over in his grave.
I'm not sure what more can be done since the athletic department already instituted the points system. But seeing all those empty seats up there after the game starts is a slap in the face to Hoke and the Michigan players.
That should be "30% of the student section sucks." 70% of them are there. The solution is to give out t-shirts.
FWIW, the key play thing has not been done in probably ten years.
It wasn't a perfect day. The Toussaint fumble was maddening, but a great play by the Wildcat defense. Special K remembered where "In The Big House" was on his hard drive. There weren't enough holes in the offensive line to run through, things of this ilk.
But it was sunny, warmish for a November day. Al Wistert got a tremendous ovation from the Michigan Stadium crowd, the MMB put on a funny show, Devin Gardner continued to look good, Roy Roundtree remembered that he's a heck of a receiver, Gibbons is still money, and in the end, Michigan was victorious, Really, that's more than we should be able to ask for from the football gods. After all, you need to stay humble.
Warmish? High standards over at the Hoover Street Rag.
Recaps from Maize and Go Blue, TTB, MVictors, Holdin' The Rope,
Mainstream stuff. Meinke on the division race. Wojo:
For Michigan, it's never over until the last pass is thrown, and tipped, and cradled, and caught. For Devin Gardner, same thing — it's not over even when others think it is.
Nothing is over for the Wolverines, and it's just getting started for Gardner. How many times can a game, or a season, or a young career twist? Gardner was a receiver a couple of weeks ago, hoping to be a quarterback again. Now he's directing a team contending for the Big Ten title.
The Daily on Brady Hoke's magic:
The last time Brady Hoke and Northwestern coach Pat Fitzgerald were at Michigan Stadium together was Oct. 7, 1995.
Hoke was a first-year defensive line coach on the home sideline. Fitzgerald was Northwestern's burly junior middle linebacker, wearing a white No. 51 jersey and terrorizing Michigan quarterback Brian Griese.
With the Wildcats leading 19-13 and just 1:40 remaining on the clock, Griese and the Michigan offense were 41 yards from the end zone facing a third-and-15. Fitzgerald had ended the previous drive by tipping a pass out of harm's way.
Nesbitt FTW; great great angle there. Hadn't even thought about it. Also Estes on not saying sorry.
Gardner saying the right things:
Gardner on Denard Robinson : "This is Denard's team, and this is always going to be Denard's team. He's done way too much for two games to change that."
Meinke has like another column—indefatigable! And another! Baumgardner numbers. Game story.


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Special Purpose Exam (SPEX®)
The SPEX, administered by computer, is an objective and standardized, cognitive examination of current knowledge requisite for the general, undifferentiated practice of medicine.
The examination is intended for physicians who currently hold, or who have previously held, a valid, unrestricted license to practice medicine in a US or Canadian jurisdiction.
Appropriate candidates for SPEX include physicians seeking licensure reinstatement or reactivation after some period of professional inactivity, or physicians involved in disciplinary proceedings in which the board determines the need for evaluation. SPEX is also appropriate for physicians applying for licensure by endorsement who are several years beyond initial licensure.
For more information on the SPEX please check the FSMB website.
National Board of Medical Examiners
3750 Market Street
Philadelphia, PA 19104