WO2001062867A2 - Durable fluorescent organic pigments and methods of making - Google Patents
Durable fluorescent organic pigments and methods of making Download PDFInfo
- Publication number
- WO2001062867A2 WO2001062867A2 PCT/US2001/005512 US0105512W WO0162867A2 WO 2001062867 A2 WO2001062867 A2 WO 2001062867A2 US 0105512 W US0105512 W US 0105512W WO 0162867 A2 WO0162867 A2 WO 0162867A2
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- WIPO (PCT)
- Prior art keywords
- fluorescent
- pigment
- binder
- retroreflective
- article
- Prior art date
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Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
- C09B67/0097—Dye preparations of special physical nature; Tablets, films, extrusion, microcapsules, sheets, pads, bags with dyes
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
- C09B67/006—Preparation of organic pigments
- C09B67/0061—Preparation of organic pigments by grinding a dyed resin
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
- C09B67/0071—Process features in the making of dyestuff preparations; Dehydrating agents; Dispersing agents; Dustfree compositions
- C09B67/0092—Dyes in solid form
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- E—FIXED CONSTRUCTIONS
- E01—CONSTRUCTION OF ROADS, RAILWAYS, OR BRIDGES
- E01F—ADDITIONAL WORK, SUCH AS EQUIPPING ROADS OR THE CONSTRUCTION OF PLATFORMS, HELICOPTER LANDING STAGES, SIGNS, SNOW FENCES, OR THE LIKE
- E01F9/00—Arrangement of road signs or traffic signals; Arrangements for enforcing caution
- E01F9/50—Road surface markings; Kerbs or road edgings, specially adapted for alerting road users
- E01F9/506—Road surface markings; Kerbs or road edgings, specially adapted for alerting road users characterised by the road surface marking material, e.g. comprising additives for improving friction or reflectivity; Methods of forming, installing or applying markings in, on or to road surfaces
- E01F9/512—Preformed road surface markings, e.g. of sheet material; Methods of applying preformed markings
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- E—FIXED CONSTRUCTIONS
- E01—CONSTRUCTION OF ROADS, RAILWAYS, OR BRIDGES
- E01F—ADDITIONAL WORK, SUCH AS EQUIPPING ROADS OR THE CONSTRUCTION OF PLATFORMS, HELICOPTER LANDING STAGES, SIGNS, SNOW FENCES, OR THE LIKE
- E01F9/00—Arrangement of road signs or traffic signals; Arrangements for enforcing caution
- E01F9/50—Road surface markings; Kerbs or road edgings, specially adapted for alerting road users
- E01F9/576—Traffic lines
- E01F9/578—Traffic lines consisting of preformed elements, e.g. tapes, block-type elements specially designed or arranged to make up a traffic line
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
- Y10T428/24355—Continuous and nonuniform or irregular surface on layer or component [e.g., roofing, etc.]
- Y10T428/24372—Particulate matter
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/25—Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
- Y10T428/254—Polymeric or resinous material
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31507—Of polycarbonate
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31678—Of metal
- Y10T428/31681—Next to polyester, polyamide or polyimide [e.g., alkyd, glue, or nylon, etc.]
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31786—Of polyester [e.g., alkyd, etc.]
Definitions
- the invention relates to fluorescent articles that comprise durable daylight fluorescent pigment particles, for example, retroreflective articles. Such articles are useful for various applications, such as daytime high visibility signaling and marking, pavement markings, personal safety, and signing.
- Fluorescent retroreflective sheeting has been developed to provide increased safety, especially during daytime and periods of reduced visibility.
- Durable fluorescent sheeting has recently been developed that can withstand the demanding outdoor environments, such as extremes in temperature, chemical challenges from atmospheric pollution and road salt, and photo-reaction involving infrared, visible, and ultraviolet radiation from sunlight.
- Only certain combinations of fluorescent dye, stabilizers, and matrix polymers provide durability.
- the matrix polymers found to date may not have the desired features, such as flexibility and economy, sought for many daytime visual signaling and marking applications.
- the relatively expensive fluorescent dyes have been uniformly dispersed throughout past articles, thereby increasing the cost of these prior articles.
- the present invention includes in its first aspect a fluorescent pigment comprising in particle form: a fluorescent dye including thioxanthone, perylene, perylene imide, xanthene compounds and mixtures thereof; and a polymeric matrix including polycarbonate, polyester, and mixtures thereof; wherein the fluorescent dye is incorporated into the polymeric matrix.
- a second aspect of the present invention includes a fluorescent article, comprising: a binder having a first major viewing surface; and fluorescent pigment comprising, in particle form, a fluorescent dye including thioxanthone, perylene, perylene imide, xanthene compounds and mixtures thereof; and a polymeric matrix including polycarbonate, polyester and mixtures thereof; wherein the fluorescent dye is incorporated in the polymeric matrix; and wherein at least some of the fluorescent pigment particles are disposed so as to be visible on the first major viewing surface of the binder.
- a third aspect of the present invention includes a method of making a fluorescent article, comprising the steps of: providing at least one fluorescent dye including thioxanthone, perylene, perylene imide, xanthene compounds, and mixtures thereof; providing a polymer matrix including polycarbonate, polyester, and mixtures thereof; extruding a mixture of said fluorescent dye and the polymer matrix; fracturing the extrudate to form a fluorescent pigment in a particle form; and disposing the fluorescent pigment with a binder to form a fluorescent article.
- the third aspect of the present invention may include the additional steps of: fracturing the binder to yield a binder particulate; providing micro structured surfaces on the fluorescent pigment to form retroreflective fluorescent pigment; mixing the fluorescent retroreflective pigment with the binder particulate to form a powder blend; and flame spraying the powder blend onto a suitable substrate.
- the third aspect of the present invention may include the additional steps of: providing the binder as a liquid dispersion; providing microstructured surfaces on the fluorescent pigment to form retroreflective fluorescent pigment; mixing the retroreflective fluorescent pigment with the liquid binder to form a liquid blend; coating the liquid blend onto a suitable substrate; and curing the liquid blend onto the substrate to form a retroreflective fluorescent article.
- the above fluorescent articles containing fluorescent pigment are especially useful in pavement markings.
- FIGS. 1 a-c are cross-sectional views of various retroreflective embodiments of durable fluorescent pigment. These figures, which are idealized, are not to scale and are intended to be merely illustrative and non-limiting.
- the phrases “weatherable” or “outdoor durability” refer to the capability of the article to withstand the environment when used for its intended purpose.
- weathering shall mean exposing an article to either natural or artificial environments that include heat, light, moisture, and ultraviolet radiation, and combinations thereof.
- fluorescent pigment refers to a particle which includes one or more fluorescent dyes in a polymeric matrix including 1 a polycarbonate, a polyester or a mixture thereof.
- the particle may be of any size and shape depending on the desired use.
- fracturing refers to breaking up a sheet of a polymeric matrix and a fluorescent dye incorporated therein into particles by grinding or milling, by way of example.
- equivalent diameter shall mean the size that passes a rectangular opening in a screen of that dimension.
- the luminance factor (CIE tristimulus value Y) is a standard measure of the amount of light (electromagnetic radiant power that is visually detectable by the normal human observer) radiating from a surface weighted by the eye!s efficiency to convert the light to luminous sensation. It is defined as the ratio of tiie total luminance of a specimen to that of a perfect diffuser illuminated and viewed under the same conditions.
- the luminance factor is the sum of two quantities, the reflected luminance factor (Y R ) and the fluorescence luminance factor (YF).
- the fluorescence luminance factor (Y F ) is the ratio of the!
- fluorescence luminance luminance due to emitted light
- Y Y R +Y F .
- fluorescence luminance Y F 0
- the fluorescence luminance factor (Y F ) measured under specified illumination and viewing conditions is a measure of a material's efficiency to convert absorbed electromagnetic radiant power into luminous sensation.
- the present invention provides fluorescent articles comprising durable fluorescent pigment that meet one or more of the prior unmet needs.
- the fluorescent pigment is surprisingly sufficiently durable for pavement markings, with some embodiments having the ability to be flame processed without loss of fluorescence.
- the fluorescent pigment may also be made from waste or rejected production scrap resulting from the manufacture of fluorescent prismatic retroreflective sheeting.
- the combination of the durable fluorescent pigment with a suitable binder results in durable fluorescent articles having conformability and/or other selected desirable features heretofore unavailable.
- the ability to mix the fluorescent pigment with other particles, such as retroreflective elements and anti-skid particles also results in durable fluorescent articles heretofore unavailable.
- fluorescent pigment onto only a portion of the viewing surface of a binder or of a sheet results in more efficient use of the expensive dye.
- Some of the inventive fluorescent articles have a spotty fluorescent appearance when viewed with the naked eye at short distances of about one meter or less, but appear surprisingly uniformly fluorescent when viewed by a motorist in a vehicle at longer distances of about 30 meters or more.
- the fluorescent pigments have a fluorescence luminance, Y F , greater than 2, preferably greater than 5.
- Polymeric Matrix The polymeric matrix serves as the host for the dye and whatever adjuvants are desired.
- the polymeric materials selected for the polymeric matrix are preferably relatively inflexible, hard, and rigid materials relative to other polymers. Thus, these polymers may be fractured at room temperature or lower temperatures.
- the polymeric matrix is preferably substantially optically clear. Notably, such polymers retain their transparency and their shape under adverse conditions.
- Suitable polymers include thermoplastic or thermosetting material, as desired. In sum, a suitable polymeric matrix is often selected for one or more of the following reasons: thermal stability, dimensional stability, environmental stability, clarity, excellent release from tooling or a mold, and capability of receiving a reflective coating.
- Polycarbonate is the preferred polymeric matrix of the present invention.
- polymeric matrix examples include polymers selected from the class of polycarbonate and polyester blends.
- the fluorescent pigment composition preferably comprises at least 50 %, more preferably at least 90 %, and most preferably at least 95 % by weight of a polymeric matrix.
- the fluorescent dyes and colorants of the invention are preferably visible- activated fluorescent colorants as opposed to UV activated fluorescent colorants.
- visible activated refers to sunlight or other light having a spectrum containing substantially all of the visible wavelengths of sunlight.
- the preferred dyes and/or colorants of this invention are brilliantly fluorescent and also bright in color in daylight. Dyes having such properties have been disclosed in U. S. Pat. Nos. 5,387,458 (Pavelka); 5,605,761 (Burns) and 5,674,622 (Burns).
- the dyes for the invention are preferably from the perylene, perylene imide, thioxanthone, and xanthene classes of compounds.
- fluorescent dye concentrations are between about 0.01 and about 2 weight percent of the pigment particle, preferably between about 0.05 and about 0.7 weight percent, and most preferably between about 0.1 and about 0.5 weight percent.
- Other concentration ranges of dyes may be used depending on the thickness of the article. The above ranges are based on fluorescent pigment particles containing the dyes that have equivalent diameters between about 500 ⁇ m and about 2000 ⁇ m (microns, i.e. micrometers).
- Articles having high concentrations of dyes tend to exhibit brighter fluorescence than articles having low concentrations of dyes.
- articles having a high dye concentration may exhibit a self-quenching phenomenon which occurs when molecules of the fluorescent dye absorb the energy emitted by neighboring fluorescent dye molecules. This self-quenching phenomenon causes an undesirable decrease in fluorescent brightness. 1
- a single fluorescent dye or colorant may be used or a combination of j ⁇ ne or more fluorescent dyes and one or more conventional colorants may be usedjto create fluorescent articles of the invention.
- Adjuvants The function of some of the desirable adjuvants is to improve the durability of the dye in the polymeric matrix. Adjuvants may also be present in the fluorescent pigment for other desired improvements, such as to improve processing in extrusion equipment.
- HALS hindered amine light stabilizers
- HALS hindered amine light stabilizers
- TINUVIN-144, -292, -622, -770 trade designations "TINUVIN-144, -292, -622, -770”
- CHJMASSORB-944 trade designations "CHJMASSORB-944.”
- HALS are preferably added at about 0.1 to 2 weight percent of the flu'orescent pigment, although larger amounts may also be added if desired.
- Illustrative examples of UV absorbers include derivatives of benzotriazole, such as those commercially available from Ciba-Geigy Corp. under the trade designations "TINUVLN-327, -328, -900, -1130," and "TINUVIN-P" ⁇ chemical derivatives of benzophenone, such as those commercially available from BASF Corp.
- UV absorbers are preferably added at about 0.5 to 2 weight percent of the fluorescent pigment, although again different amounts may also be used if desired.
- Free radical scavengers or antioxidants may be used.
- suitable antioxidants include hindered phenolic resins, such as those commercially available from the Ciba-Geigy Corp.
- processing aids may be added to improve the matrix polymer's processability, such as in extrusion equipment.
- Useful processing aids include: (1) fatty acid esters, or fatty acid amides; (2) metallic stearates; or (3) waxes, oils, and release agents for aid in extrusion processes.
- Anti-sticking powders such as talc, fumed silica, clay, and calcium carbonate, may also be used to aid in extrusion processes.
- adjuvants are added in amounts th ⁇ .t do not significantly reduce transparency of the matrix polymer and yet provide the desired i function. Such adjuvants are typically no more than about one percent; by weight of the fluorescent pigment, but may be more or less as noted to serve functionally.
- the durable fluorescent pigment may be either (1) non-retroreilective, or (2) structured so as to be retroreflective.
- Fluorescent pigment includes particles of a variety of shapes, i cluding spherical, platelets such as may result from fracturing thin films and sheets, flakes, fibrous, and odd shapes. Since shape may vary so widely, a useful measure of pigment size is to measure in terms of equivalent diameter, or the size that passes a rectangular opening in a screen of that dimension. Since the shape may vary so widely, the equivalent diameter of the fluorescent pigment may also vary over a wide range depending on the desired effect. A preferred range of equivalent diameter is from about 10 to about 5000 ⁇ m.
- the fluorescent pigment may include retroreflective elements such as microspheres and microstructured elements. These result from fracturing retroreflective sheets.
- retroreflective elements include those described in the foregoing retroreflective sheeting patents.
- Retroreflective sheeting The types of retroreflective sheeting are described in "Standard Specification for Retroreflective Sheeting for Traffic Control", ASTM D 4956-94. Brightness or retroreflectivity of the sheeting may be expressed as the Coefficient of Retroreflection, R A . This is measured in units of candelas/lux/square meter and is determined using standardized test ASTM E 810-94.
- encapsulated lens retroreflective sheeting Illustrative examples of encapsulated lens retroreflective sheeting are disclosed in U. S. Pat. Nos. 3,190,178 (McKenzie); 4,025,159 (McGrath); 4,663,213 (Bailey); 5,069,964 (Tolliver); 5,714,223 (Araki); 5,812,316 (Ochi); and 5,784,198 (Nagaoka).
- Illustrative examples of encapsulated prismatic-type retroreflective sheeting are disclosed in U. S. Pat. Nos.
- prismatic-type retroreflective fluorescent articles comprising the durable fluorescent pigment are illustrated in Figures la-c.
- An embodiment of the present invention includes the retroreflective members of the Figures which are now described in more detail.
- Fig. la illustrates a structured reflector-coated prismatic-type retroreflective fluorescent pigment 10a resulting from fracturing a reflector-coated prismatic retroreflective sheet containing a retroreflective member 12 having a first major
- the microstructured surface preferably contains retroreflective elements, such as prisms or cubes, with a reflective coating 16 thereon.
- the retroreflective member may have a face member, overlay, cover film, top film, front face, top layers, or top coat thereon.
- the retroreflective member may comprise a multilayer film.
- Suitable retroreflective members provide a substantially transparent retroreflective surface that protects the retroreflective elements on the microstructured surface from a variety of possible destructive effects, such as dirt, water, and exposure to weather and outdoor conditions.
- Polymers selected for the retroreflective member i are preferably dimensionally stable, durable, weatherable, and readily formable into a desired configuration.
- Polymers are selected for the retroreflective member in view of the properties desired of the resultant article, the methods used for forming the retroreflective surface, the desired bondability to a sealing member (if present), and the nature of any other members of the retroreflective pigment.
- Polymers selected for the retroreflective member preferably should form cube corner elements that are dimensionally stable so that precise geometry 1 desired for retroreflection is maintained, regardless of various geometric designs.
- the retroreflective elements may also be called cube corners, prisms, micr prisms, or i triple mirrors.
- the basic cube corner retroreflective element is generally a tetrahedral structure having, for example, a base triangle and three mutually substantially perpendicular optical faces that cooperate to retroreflect incident light.
- the optical faces preferably intersect at an apex, with the base triangle lying opposite the apex.
- Each cube corner element also has an optical axis, which is the axis that extends through the cube corner apex and trisects the internal space of the cube corner element.
- Light incident on the first major retroreflective surface enters the base triangle and is transmitted into the internal space of the cube, is reflected from each of the three optical faces, and is redirected back in the same general direction as the incoming incident light.
- it is optional whether the faces of the cubes are exposed to an air interface as provided by a sealing member or coated with a reflective coating, such as aluminum.
- the microstructured surface may be molded to yield a cube layer using any of a variety of techniques known to those skilled in the art.
- the retroreflective member is preferably sufficiently thick to provide the above desirable properties.
- the thickness of the retroreflective member preferably is between about 0.01 mm to 0.3 mm thick, and more preferably between 0.02 mm to 0.2 mm.
- All of the polymers and various members of the retroreflective article may i contain adjuvants for various purposes.
- Colorants, UV absorbers, fluorescent dyes in addition to those in the polymer matrix of the pigment of the present invention, light stabilizers, free radical scavengers or antioxidants, processing aids such as antiblocking agents, releasing agents, lubricants, additives to improve weathering and heat stability, and other additives may be added to the various polymers or materials as desired.
- Fig. lb illustrates a fluorescent pigment 10b having a sealing member 16 attached to the microstructured surface 14, thus obviating the need for a reflective coating on the microstructured surface.
- Fluorescent pigment 10b also includes a retroreflective member 12 having a first major retroreflective surface 1 ! 3 thereon, as previously shown in Fig. la.
- a retroreflective member 12 having a first major retroreflective surface 1 ! 3 thereon, as previously shown in Fig. la.
- materials for the sealing member include thermoplastic, heat-activated, ultraviolet cured, and electron beam cured polymer systems.
- the bonding portions between the retroreflective member and sealing member form seal legs. These legs have a height sufficient to provide an air interface for the microstructured surface.
- the seal legs may be formed, for example, by application of heat and pressure to the retroreflective member and the face member as disclosed in U.S. Pat. No.
- the seal legs may form a sealing pattern that comprises individual air cells each having a small area on the first major retroreflective surface 13 of the fluorescent pigment. Seal legs may also be called sealing walls, bonds, bond lines, septa, or seal leg members. The sealing member may be colored to complement or contrast with the fluorescent pigment as desired.
- Fig. lc illustrates a fluorescent pigment 10c that is made by laminating together the sealing layers 16 of two fluorescent pigments of Fig. lb.
- Fluorescent pigment 10c also comprises two retroreflective members 12 having a first major retroreflective surface 13 and a second opposing major retroreflective surface 15, respectively.
- the advantage of the fluorescent pigment of Fig. lc is that these pigment particles are more retroreflective regardless of their orientation in the fluorescent article.
- the equivalent diameters of the retroreflective fluorescent pigment preferably comprise at least one retroreflective element and more preferably comprise at least several elements.
- Retroreflective fluorescent pigment, such as shown in Fig. la may have equivalent diameters of at least about 10 ⁇ m, more preferably of at least about 70 ⁇ m, and most preferably of at least about 200 ⁇ m.
- Retroreflective fluorescent pigment such as shown in Fig. lb, may have equivalent diameters of at least about 200 ⁇ m, more preferably of at least about 5000 ⁇ m, and most preferably of at least about 10,000 ⁇ m.
- Retroreflective fluorescent pigment such as shown in Fig. lc, may have equivalent diameters of at least about 500 ⁇ m, more preferably of at least about 10,000 ⁇ m, and most preferably of at least about 20,000 ⁇ m.
- equivalent diameters are given as general ranges, equivalent diameters depend on the type of retroreflective article, such as the thickness of retroreflective member, the thickness of the sealing layer, and the sealing pattern or relative size of the individual cells.
- the equivalent diameter of the retroreflective fluorescent pigment lc is larger than that of pigment la in order to retain reflectivity when used in a binder or sheeting.
- each retroreflective fluorescent pigment comprises at least one retroreflective element, the equivalent diameter of the pigment may be of the order of 60 ⁇ m or more.
- anti-skid particles such as disclosed in U. S. Pat. Nos. 5,125,178 (Haenggi); ceramic beads such as disclosed in U.S. Pat. No. 4,772,551 (Wood); glass beads such as disclosed in U. S. Pat. No. 5,716,706 (Morris); retroreflective: elements such as disclosed in U. S. Pat. No. 5,774,265 (Mathers); and colored particles such as disclosed in U. S. Pat. No. 5,269,840 (Morris).
- Fluorescent articles comprising the durable fluorescent pigment, either non-retroreflective or retroreflective, have numerous embodiments. Some of these embodiments include the following:
- Non-fluorescent sheeting comprising either fluorescent pigment or retroreflective fluorescent pigment or combinations thereof;
- Fluorescent sheeting comprising the fluorescent pigment or retroreflective fluorescent pigment or combinations thereof;
- Retroreflective sheeting comprising the fluorescent pigment or retroreflective fluorescent pigment or combinations thereof;
- Binder systems comprising either fluorescent or retroreflective fluorescent pigment or combinations thereof;
- Fluorescent binder systems comprising either fluorescent or retroreflective fluorescent pigment or combinations thereof.
- Retroreflective binder systems comprising either fluorescent or retroreflective fluorescent pigment or combinations thereof. Numerous other combinations and variations are apparent to those skilled in the art based on the teachings herein.
- Suitable carriers for the fluorescent pigment are preferably a polymeric binder or a polymeric sheet.
- Sheeting and other useful articles may be made by compounding the fluorescent pigment described above with a suitable binder, preferably a polymeric binder of a different composition than that of the polymeric matrix.
- Binders may be thermoplastic or thermosetting, may be adhesives, and may be a liquid that is later cured, such as for paints.
- Binders are preferable polymeric for many applications relate ⁇ 10 transportation safety.
- a particularly preferred polymeric binder is polyurethane.
- polyurethane typically includes polymers having urethane and/or urea linkages, and such is the intended meaning herein.
- Suitable urethane polymers or copolymers for use in this layer include polyether polyurethanes, polyester polyurethanes, polycarbonate polyurethanes and blends thereof.
- Suitable urethanes include aliphatic' or aromatic urethanes or blends thereof.
- thermoplastic polyurethanes typically include three main components: an aliphatic and/or aromatic diisocyanate; a chain extender (such as an ethylene-, propylene- or butane- diol); and a soft segment polyol (such as polyether or polyester, e.g., polyethyleneoxide, polyadipate, or polycaprolactone).
- Suitable urethane polymers include thermoplastic polyurethane polymers commercially available from Morton International, Chicago, IL, under the trade designation "MORTHANE,” and others including aliphatic and aromatic polyurethanes, such as disclosed in U.S. Pat. No. 5,117,304 (Huang). 1
- binders and sheets comprising substantially solventless plasticized polyvinyl chloride (PVC) are known in the retroreflective art, such as published in WO 99/20688 (White). Fluorescent articles comprising PVC binders or sheets and fluorescent pigment have many desirable features, such as economy and flexibility.
- PVC polyvinyl chloride
- Suitable polymers for binders or sheets include: • copolymers of ethylene with vinyl acetate (EVA), e.g. those commercially available from DuPont, Wilmington, DE, under the trade designation “EL VAX”; from Equistar Chemicals, Houston, TX under the tirade designation “ULTRATHENE”; and from AT Plastics, Brampton, ON, Canada, under the trade designation "ATEVA”;
- EVA vinyl acetate
- EVAs e.g. those commercially available from DuPont under the trade designation "ELVAX”; from Equistar Chemicals under the trade designation “ULTRATHENE”; and from DuPont under the designation “BYNEL” series 1100, 3000, 3800 and 3900 resins; • other modified EVAs, such as acid or anhydride-/acrylate-modif ⁇ ed EVAs commercially available from DuPont under the trade designation "BYNEL", series 3100 resins;
- ESA ethylene ethyl acrylate copolymers
- EMA ethylene methyl acrylate copolymers
- EAA acid- or anhydride-modified ethylene acrylate materials
- ethylene vinyl acetate, carbon monoxide terpolymers e.g., commercially available from DuPont under the trade designation "ELVALOY”;
- Binders holding the fluorescent pigment in a suitable position are selected to form a satisfactory fluorescent article.
- the binder may have the fluorescent pigment dispersed throughout, either randomly or oriented to provide maximum visibility performance, or the fluorescent pigment may be only on the viewing surface of the binder, or various combinations thereof.
- the amount of fluorescent pigment is sufficient to attain the desired fluorescent appearance for the article.
- the amount of fluorescent pigment is preferably a minimum to achieve both economy and fluorescence for the article.
- the amount of fluorescent pigment is dependent on the equivalent diameter of the pigment. For example, for pigment having an equivalent diameter of approximately 3000 ⁇ m, an application rate of approximately 50 grams per square i meter on a binder or on a sheet is sufficient to make a fluorescent article. The application rate of fluorescent pigment may also be adjusted to achieve total coverage of the surface of the binder or sheet, as desired.
- a non-fluorescent binder or sheet having fluorescent pigment disposed in selected positions to form fluorescent articles results in articles that dq not have the dye uniformly dispersed throughout the article.
- Such articles have not heretofor been available.
- the inventive articles have considerable economy by being i fluorescent without substantial use of fluorescent dye. Contrary to prior articles, the inventive articles are particularly useful for various applications, such as for pavement markings.
- the fluorescent pigment in combination with a binder preferably a thermoplastic, may be adhered to a pavement marking surface or suitable substrate to form fluorescent pavement marking articles.
- Suitable substrates for 1 pavement markers are known to be typically either concrete or asphalt. Flame sprayed thermoplastic pavement marking systems have relatively low cost, and are especially quick and easy to apply, even on roughened or cracked surfaces or under extremely low temperatures.
- the delivery rate of the fluorescent pavement marking powder can be reliably controlled.
- Flame sprayable materials typically have melt indices above about 80, more preferably above about 200, and most preferably above about 500.
- the melt index of a material may be determined according to Condition 190/2.16 and the procedure given in ASTM D1238-95.
- Fluorescent pigment may be added to liquid binders, sprayed onto a road surface, and cured to form liquid pavement marking articles.
- Preferred liquid binders are either water-borne or solvent-free, such as those disclosed in U. S. Pat. Nos. 5,714,527 (Jilek); 5,747,626 (Krepski); 5,756,633 (Larson); andiU. S. Serial No. 09/096,923 (Purgett).
- the fluorescent pigment in combination with a binder or sheetj may be placed on a helmet or other articles to provide increased visibility and durability in
- Fluorescent pigment may be made by grinding sheets of binder materials containing dye to form particles. Such binder materials are described !in U. S. Pat. Nos. 5,605,761 (Burns); and 5,674,622 (Burns).
- the fluorescent pigmjent may also be made by grinding fluorescent pellets used for making fluorescent articles, or fluorescent film or fluorescent cube layers, for example as described in U. S. Pat. Nos. 5,605,761 (Burns); and 5,674,622 (Burns). Alternately the fluorescent pellets may be used as is for fluorescent pigment.
- Retroreflective sheeting of various types, for example as described in the above Burns patents, may also be ground to equivalent diameters suitable for making fluorescent articles. Suitable grinding methods, also more generally known as comminution, are disclosed in "Mining and Treatment of Raw Materials", by Norton, Elements of Ceramics, Chapt. 6, 57- 62, (1974). This reference also discloses Tyler Series Screens and size classification of particles using such screens. Equivalent diameter of the fluorescent pigment corresponds to the size of the opening in the screen at which 100 weight percent of the particles pass through the opening.
- a matrix polymer, dye, and HALS mixture was prepared as follows:
- the matrix polymer was polycarbonate pellets designated as Makrolo'n FCR-2407 from Bayer Corporation, Pittsburgh, Pa., USA.
- the dye was SY98, designated CI Solvent Yellow 98 thioxanthene, commercially available from Clariant.
- the HALS was "TINUVIN 622", commercially available from Ciba Geigy.
- the composition of the mixture was 99.3 wt % polycarbonate, 0.2 wt % SY98, and 0.5 jwt % HALS. The mixture was dried overnight to remove moisture.
- the polycarbonate, dye, and HALS mixture was then extruded into approximate 0.1 mm thick film using a single screw extruder having three heating zones set at 260°C, 260°C, and 304°C.
- the temperature profile was such that the lowest temperature started at the feed hopper and progressed to 304°C at the die end of the extruder.
- the extruder was a 2 centimeter single screw for the Haake Rheocord from Haake, Düsseldorf, Germany.
- the film was ground, milled, or diced into fluorescent yellow ⁇ green
- the pigment contains particles ranged in equivalent diameter, as determined by sieves, from dust to approximately 5000 ⁇ m platelets. However most of the fluorescent pigment was in the range of 10 ⁇ m to
- a flame sprayable pavement marking powder commercially available from
- 3M Minnesota Mining and Manufacturing Company
- STAMARK Thermal Spray System Series 3100 was dry blended with the fluorescent pigment powder in a ratio of about 40 weight % fluorescent pigment powder with about 60 weight % pavement marking powder. This mixture was flame sprayed to a thickness of about 2 mm onto aluminum paneljs using a striping machine commercially available from 3M under the trade designation
- the daytime color of a sample of the fluorescent marking construction was measured in the laboratory using a Labsphere BFC-450 Bispectral Colorimeter
- Fluorescent yellow-green pigment was prepared as per Example 1.
- a liquid binder was prepared per U. S. Ser. No. 09/096,923 (Purgett).
- the liquid binder consisted of 23 grams of an aspartic ester diamine ("DESMOPHEN XP-7059", commercially available from Bayer Corp, Pittsburgh, PA),j28 grams of an aspartic ester diamine (“DESMOPHEN XP-7053” commercially available from Bayer Corp.), and 40.95 grams of polyisocyanate ("DESMODUR N-3;300” commercially available from Bayer Corp.).
- the two aspartic ester diamines were mixed for about 1 minute and then the mixed diamines were mixed with the polyisocyanate for an additional minute to form a clear polyurea liquid binder.
- the fluorescent pigment of Example 1 was added to the clear polyurea liquid binder to form a castable blend. This castable blend was doctor 'b laded onto aluminum panels to form fluorescent coatings that were approximately 0.4 mm thick.
- the fluorescent coatings gave a daylight fluorescent yellow-green appearance when viewed under pavement marking conditions at a distance of 30 meters and at an observation angle of about 88 degrees.
- the daytime color of a sample of the fluorescent marking construction was measured in the laboratory using a Labsphere BFC-450 Bispectral Colorimeter.
- Example 3 Fluorescent Pavement Marking Incorporating Fluorescent Pigment Particles
- a yellow fluorescent marking construction was prepared in place as follows. The marking was applied directly to the curbstone forming a stripe nominally 0.3 m wide and 124 m in length. First a base coat of alkyd paint commercially available from Atomikusu Company (Japan) under the trade designation "Hard-Line" was applied with a sponge roller at a coverage rate of 115 g/m. The paint was allowed to dry 10-20 minutes. Next a fluorescent clear coat was applied over the paint.
- the fluorescent clear coat was composed of 50 parts by weight of an acrylic polymer (commercially available from Rohm and Haas under the trade designation "ACRYLOID B66”), and 0.15 part a perylene imide dye (commercially available from BASF, under the trade designation "LUMOGEN F240”), dissolved in 100 parts propylene glycol methylether acetate (commercially available from Dow Chemical under the trade designation "DOWANOL PMA”).
- the fluorescent clear coat was applied over the paint with a sponge roller at a rate of 77 g/m. A mixture of glass beads and the fluorescent pigment particles were then spray applied onto the fluorescent clear coat while it was still wet.
- the glass beads were 1.5 index beads with a nominal particle size of 500-710 microns j commercially available from Gakunann Koki Company (Japan).
- the jfluorescent pigment particles were produced by first melt blending 150 parts by weight polycarbonate resin, commercially available from Mitsubishi Engineering Plastics Corp., Japan under the trade designation "IUPILON S-2000U”, 0.03 part dye, commercially available from BASF under the trade designation "LUMOGEN F240", and 0.5 parts ultraviolet light absorber (UVA), commercially available from Ciba-Geigy under the trade designation "TINUVIN 324".
- the polycarbonated/dye/UVA blend was ground into particles with a partiple size less than 1000 ⁇ m using a Victory-mill VP-1 from Hosokawa Mikuron Co. apan).
- the application rate for the glass beads was nominally 56 g/m and 22 g/m for the fluorescent pigment particles.
- the marking construction was allowed to air dry for 20-30 minutes after applying the glass beads and fluorescent pigment particles.
- the fluorescent marking gave a daylight fluorescent yellow appearance when viewed under pavement marking conditions at a distance of 30 meters and at an observation angle of about 88 degrees.
- the daytime color of a sample of the fluorescent marking construction was measured in the laboratory using a Labsphere BFC-450 Bispectral Colorimeter.
- the measurements were carried out as described in Burns, D M. and N.L. Johnson, "Metrology of Fluorescent Retroreflective Materials anjd its Relationship to their Daytime Visibility," Analytica Chimica Acta, Veil. 380, 1999, pp. 211-226.
- Example 4 Extruded Film Incorporating Fluorescent Pigment Particles Fluorescent yellow-green pigment as per Example 1 in equivalent diameter from 10 microns to 100 microns was blended into ethylene acrylic acid resin pellets (commercially available from Dow Chemical Co., Midland MI under the trade designation "PRIMACOR 3440") at 40 wt%. The dry-blended mixture was then extruded into film of about 0.01 cm thick using a single screw extruder with three heating zones set at 350°C, 380°C, 400°C and a film die set at 400°C. The extruder was a 3/4-inch single screw extruder for the Haake Rheocord commercially available from Haake of Düsseldorf, Germany.
- the daytime color of a sample of the fluorescent extruded film was measured in the laboratory using a Labsphere BFC-450 Bispectral Colorimeter.
Abstract
Description
Claims
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
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CA 2399716 CA2399716A1 (en) | 2000-02-22 | 2001-02-22 | Durable fluorescent organic pigments and methods of making |
EP20010912874 EP1259568A2 (en) | 2000-02-22 | 2001-02-22 | Durable fluorescent organic pigments and methods of making |
AU2001241613A AU2001241613A1 (en) | 2000-02-22 | 2001-02-22 | Durable fluorescent organic pigments and methods of making |
JP2001562642A JP2003528171A (en) | 2000-02-22 | 2001-02-22 | Durable fluorescent organic pigment and method of manufacture |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
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US18407300P | 2000-02-22 | 2000-02-22 | |
US60/184,073 | 2000-02-22 | ||
US09/781,671 | 2001-02-12 | ||
US09/781,671 US6533961B2 (en) | 2000-02-22 | 2001-02-12 | Durable fluorescent organic pigments and methods of making |
Publications (2)
Publication Number | Publication Date |
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WO2001062867A2 true WO2001062867A2 (en) | 2001-08-30 |
WO2001062867A3 WO2001062867A3 (en) | 2002-03-07 |
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PCT/US2001/005512 WO2001062867A2 (en) | 2000-02-22 | 2001-02-22 | Durable fluorescent organic pigments and methods of making |
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US (2) | US6533961B2 (en) |
EP (1) | EP1259568A2 (en) |
JP (1) | JP2003528171A (en) |
AU (1) | AU2001241613A1 (en) |
CA (1) | CA2399716A1 (en) |
WO (1) | WO2001062867A2 (en) |
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WO2008052669A2 (en) * | 2006-10-31 | 2008-05-08 | Bayer Materialscience Ag | Substrate materials for transparent injection mouldings |
WO2008052669A3 (en) * | 2006-10-31 | 2008-07-17 | Bayer Materialscience Ag | Substrate materials for transparent injection mouldings |
RU2468043C2 (en) * | 2006-10-31 | 2012-11-27 | Байер Матириальсайенс Аг | Substrate materials for transparent articles made by pressure casting |
GB2505017A (en) * | 2013-01-18 | 2014-02-19 | Pro Teq Surfacing Uk Ltd | Forming self illuminating ground surface by coating sprayed base layer containing particles with photoluminescent liquid sealant |
GB2505017B (en) * | 2013-01-18 | 2015-02-25 | Pro Teq Surfacing Uk Ltd | Self-illuminating ground surface |
Also Published As
Publication number | Publication date |
---|---|
AU2001241613A1 (en) | 2001-09-03 |
US20030102460A1 (en) | 2003-06-05 |
US20020002929A1 (en) | 2002-01-10 |
WO2001062867A3 (en) | 2002-03-07 |
EP1259568A2 (en) | 2002-11-27 |
CA2399716A1 (en) | 2001-08-30 |
JP2003528171A (en) | 2003-09-24 |
US6533961B2 (en) | 2003-03-18 |
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