CA1268016A - Reflective particles and method of making the same - Google Patents
Reflective particles and method of making the sameInfo
- Publication number
- CA1268016A CA1268016A CA000483245A CA483245A CA1268016A CA 1268016 A CA1268016 A CA 1268016A CA 000483245 A CA000483245 A CA 000483245A CA 483245 A CA483245 A CA 483245A CA 1268016 A CA1268016 A CA 1268016A
- Authority
- CA
- Canada
- Prior art keywords
- spheres
- granule
- granules
- sheet
- glass spheres
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 239000002245 particle Substances 0.000 title claims description 34
- 238000004519 manufacturing process Methods 0.000 title claims description 10
- 239000008187 granular material Substances 0.000 claims abstract description 152
- QXJJQWWVWRCVQT-UHFFFAOYSA-K calcium;sodium;phosphate Chemical compound [Na+].[Ca+2].[O-]P([O-])([O-])=O QXJJQWWVWRCVQT-UHFFFAOYSA-K 0.000 claims abstract description 56
- 239000000463 material Substances 0.000 claims abstract description 47
- 238000007373 indentation Methods 0.000 claims abstract description 42
- 229920001169 thermoplastic Polymers 0.000 claims abstract description 20
- 239000004416 thermosoftening plastic Substances 0.000 claims abstract description 20
- 239000000049 pigment Substances 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims description 8
- 229920003023 plastic Polymers 0.000 claims description 6
- 239000004033 plastic Substances 0.000 claims description 6
- 238000005507 spraying Methods 0.000 claims description 6
- 229920000426 Microplastic Polymers 0.000 claims description 5
- 238000005299 abrasion Methods 0.000 claims description 3
- 239000002985 plastic film Substances 0.000 claims description 3
- 238000007790 scraping Methods 0.000 claims description 2
- 239000012815 thermoplastic material Substances 0.000 claims 9
- 230000015572 biosynthetic process Effects 0.000 claims 1
- 238000004140 cleaning Methods 0.000 claims 1
- 239000003973 paint Substances 0.000 abstract description 32
- 239000003550 marker Substances 0.000 abstract description 21
- 239000000203 mixture Substances 0.000 abstract description 7
- 229920001187 thermosetting polymer Polymers 0.000 abstract description 6
- 238000002310 reflectometry Methods 0.000 description 15
- 229920005989 resin Polymers 0.000 description 15
- 239000011347 resin Substances 0.000 description 15
- 239000007788 liquid Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- -1 polyethylene Polymers 0.000 description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 229920001155 polypropylene Polymers 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 229910052709 silver Inorganic materials 0.000 description 3
- 239000004332 silver Substances 0.000 description 3
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 description 2
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 2
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000002950 deficient Effects 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 150000002118 epoxides Chemical group 0.000 description 2
- 230000014509 gene expression Effects 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920001225 polyester resin Polymers 0.000 description 2
- 239000004645 polyester resin Substances 0.000 description 2
- 239000005060 rubber Substances 0.000 description 2
- 239000005368 silicate glass Substances 0.000 description 2
- HUAUNKAZQWMVFY-UHFFFAOYSA-M sodium;oxocalcium;hydroxide Chemical compound [OH-].[Na+].[Ca]=O HUAUNKAZQWMVFY-UHFFFAOYSA-M 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 229920005992 thermoplastic resin Polymers 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- 239000002023 wood Substances 0.000 description 2
- BKVALJGAKNDDJJ-UHFFFAOYSA-N 3,4-dimethylhexa-1,5-diene Chemical group C=CC(C)C(C)C=C BKVALJGAKNDDJJ-UHFFFAOYSA-N 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- 241000517645 Abra Species 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 240000004543 Vicia ervilia Species 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000001464 adherent effect Effects 0.000 description 1
- 150000001279 adipic acids Chemical class 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 150000001412 amines Chemical group 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 229910000410 antimony oxide Inorganic materials 0.000 description 1
- 150000001536 azelaic acids Chemical class 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 239000001030 cadmium pigment Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical class [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 230000006735 deficit Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 235000021384 green leafy vegetables Nutrition 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 229910000464 lead oxide Inorganic materials 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical class [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 1
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000011236 particulate material Substances 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 239000000088 plastic resin Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 230000032258 transport Effects 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- 150000003673 urethanes Chemical class 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 239000012463 white pigment Substances 0.000 description 1
- NDKWCCLKSWNDBG-UHFFFAOYSA-N zinc;dioxido(dioxo)chromium Chemical class [Zn+2].[O-][Cr]([O-])(=O)=O NDKWCCLKSWNDBG-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- E—FIXED CONSTRUCTIONS
- E01—CONSTRUCTION OF ROADS, RAILWAYS, OR BRIDGES
- E01C—CONSTRUCTION OF, OR SURFACES FOR, ROADS, SPORTS GROUNDS, OR THE LIKE; MACHINES OR AUXILIARY TOOLS FOR CONSTRUCTION OR REPAIR
- E01C7/00—Coherent pavings made in situ
- E01C7/08—Coherent pavings made in situ made of road-metal and binders
- E01C7/35—Toppings or surface dressings; Methods of mixing, impregnating, or spreading them
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C43/00—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor
- B29C43/02—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor of articles of definite length, i.e. discrete articles
- B29C43/04—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor of articles of definite length, i.e. discrete articles using movable moulds
- B29C43/06—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor of articles of definite length, i.e. discrete articles using movable moulds continuously movable in one direction, e.g. mounted on chains, belts
- B29C43/08—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor of articles of definite length, i.e. discrete articles using movable moulds continuously movable in one direction, e.g. mounted on chains, belts with circular movement, e.g. mounted on rolls, turntables
- B29C43/085—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor of articles of definite length, i.e. discrete articles using movable moulds continuously movable in one direction, e.g. mounted on chains, belts with circular movement, e.g. mounted on rolls, turntables and material fed in a continuous form, e.g. as a band
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
- B29D11/00—Producing optical elements, e.g. lenses or prisms
- B29D11/00605—Production of reflex reflectors
- B29D11/00615—Production of reflex reflectors moulded by partially embedding reflective elements, e.g. glass beads, into the surface of a support, e.g. to make prefabricated road markings
-
- 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
- E01F9/524—Reflecting elements specially adapted for incorporation in or application to road surface markings
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/12—Reflex reflectors
- G02B5/126—Reflex reflectors including curved refracting surface
- G02B5/128—Reflex reflectors including curved refracting surface transparent spheres being embedded in matrix
Landscapes
- Engineering & Computer Science (AREA)
- Architecture (AREA)
- Civil Engineering (AREA)
- Structural Engineering (AREA)
- Physics & Mathematics (AREA)
- Mechanical Engineering (AREA)
- Ophthalmology & Optometry (AREA)
- Manufacturing & Machinery (AREA)
- Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Road Signs Or Road Markings (AREA)
- Illuminated Signs And Luminous Advertising (AREA)
- Optical Elements Other Than Lenses (AREA)
- Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)
Abstract
Abstract of the Disclosure A reflective marker for highway striping, signs and other surfaces is produced from a multiplicity of thermoplastic or thermosetting granules in the shape of tetrahedrons. A
plurality of glass spheres having a diameter in the range of from about 6.0 microns to about 0.125 inches are substantially evenly dispersed throughout each granule with some of the spheres protruding through the outer granule surfaces. To form the granules the glass spheres, the granule material and a suitable pigment are mixed together and then applied to a flexible sheet or a roller containing a multiplicity of tetrahedron-shaped indentations. The mixture is urged into each of the indentations and is then cured. The resulting granules are removed from the indentations and are dropped from a random position onto a freshly painted highway line or other surface such that one of the flat faces on each granule is disposed in a downward direction. As the paint dries and hardens, the granules are firmly held in place on the surface to provide a reflective marker.
plurality of glass spheres having a diameter in the range of from about 6.0 microns to about 0.125 inches are substantially evenly dispersed throughout each granule with some of the spheres protruding through the outer granule surfaces. To form the granules the glass spheres, the granule material and a suitable pigment are mixed together and then applied to a flexible sheet or a roller containing a multiplicity of tetrahedron-shaped indentations. The mixture is urged into each of the indentations and is then cured. The resulting granules are removed from the indentations and are dropped from a random position onto a freshly painted highway line or other surface such that one of the flat faces on each granule is disposed in a downward direction. As the paint dries and hardens, the granules are firmly held in place on the surface to provide a reflective marker.
Description
68~6 Back~round of the Invention This invention relates to reflective material and more particularly to reflective particles, a methoa of making them ~nd their use in reflective marking.
~ he present invention, while of general application, is particularly well suited for use on highways to provide reflective markers such as edge and lane striping, signs, etc.
As is well known, it has become common practice to drop small glass spheres onto a painted line on a highway while the paint is still tacky such that the spheres are partially imbedded in the paint when it has dried. The spheres render the line or other marker retroreflective and reflect the light from headlights so that the marker is more visible to the motorist.
In some cases the spheres were imbedded in spherical or irregularly shaped plastic granules prior to being applied to the paint in the manner disclosed in U.S. Patents 3,252,376 and 3,254,563, for example, in an effort to further improve the reflectivity of the marker.
Heretofore, difficulties were encountered in the manufacture and use of reflective material of the foregoing type. As an illustration, in many instances the adhesion of the glass spheres to the paint proved deficient, with the result ~hat some of the spheres were loosened by traffic or washed away during rains~orms, 'or example, with a corresponding deterioration in the reflectivity of the surface. In~a~dition, the spheres that remained were subjected to severe ~brasion under heavy traffic conditions and exhibited flattened upper ~26~30~6 surfaces which further impaired the ref}ectivity of the marker. Furthermore, and this has ~een of special moment during periods of heavy rain, the reflectivity of even freshly applied striping or other marking wa~ deficient in a number of respects.
Summary One general object of the invention, therefore, is to provide a new and improved reflective particle for use in highway and other reflective marking.
Another object of the invention is to provide a new and improved method of making such a particle.
More specifically, it is an object of ~his invention to provide a reflective particle that remains in place on a supporting surface for an extended period of time.
A further object of the invention is to provide a reflective marker which exhibits uniform and in some cases improved reflectivity after long periods of use.
Still another object of the invention is to provide a reflective marker which exhibits good reflectivity when in a wet or moistened condition.
A still further object of the invention i5 to provide an improved reflective marker and method of makinq -the same which are economical snd thoroughly reliable in operation. _ -~ 2 ~ ~ 0 ~i In one illustrative embodiment of the invention, the reflective marker comprises a multiplicity of uniquely shaped granules of plastic material. Imbedded in ~t least the exposed ~urfaces of the granules are a plurality of glass spheres which protrude through the surfaces to provide the granules with reflcctive characteristics. For many applications the granules are dropped or otherwise applied to a painted substrate with the paint in a tacky condition, but in other cases the granules may be premixed with paint and then applied to the substrate in a single operation.
$n accordance with one feature of the invention, each of the granules is provided with at least one flat face and is of a shape such that when dropped from a random position onto a horizontal surface the flat face is disposed in a down-ward direction. The flat face is imbedded in the layer of paint to provide optimum adhesion of the granule to the surface.
In accordance with another feature of the invention, in certain particularly important embodiments, each granule is in the shape of a tetrahedron. The tetrahedrons preferably are of a shape such that when sprinkled from a random position onto a painted line of a highway, ~or example, one of the faces of the tetrahedron is disposed downwardly and the remaining faces meet the downward face at an angle of ~bout seventy degrees. With this arrangement the resulti~g marker exhibits high reflectivity with respect to the headlights of a vehicle particularly under wet conditions.
- ~68~
In accordance with a further feature of several advantageous embodiments of the invention, the maximum height of the plastic granules Pbove the surface lies within the range of from about 2 millimeters to about 12 millimeters, and the granules are of at least two distinct sizes. The larger size granules become flattened by traffic to expose a greater quantity of the glass spheres imbedded therein, while the smaller granules retain their tetrahedron shape for an extended period of time. ~he arrangement is such that the reflectivity of the marker remains substantially uniform and in some cases increases during long periods of use.
In accordance with still another feature of the invention, in several good arrangements, the granules are formed by advancing a plastic sheet in a softened conditi~n over a roller containing a multiplicity of tetrahedron-shaped indentations to individually mold each granule. The glass spheres are applied to the sheet prior to the molding operation by spraying the spheres onto the flat surfaces of the sheet and in some cases by mixing additional spheres with the plastic material used to form the sheet. The size and shape of each individual granule is determined by the configuration of the indentations in the roller to provide a very precise control over the reflectivity characteristics of the resulting marker.
The present invention, as well as further~DDjects and features thereof, will be more iully understood_from the following description of certain preferred embodiments, when read with reference to the accompanyiny drawings~
Brief Description of the Drawings Figure 1 is a substantially enlarged perspective view of a molded tetrahedron-shaped granule containing glas~ spheres in accordance with An illustrative embodiment of the invention.
~ igure 2 is a vertical ~ectional view taken along the line 2-2 in Figure 1.
Figure 3 is an enlarged side elevational view of a portion of a roadway having a reflective marker which includes different size granules of the type illustrated in Figure 1.
Figure 4 is a vertical sectional view of the roadway portion of Figure 3.
Figure 5 is a vertical sectional view similar to Figure 4 but showing the reflective marker after it has been subjected to heavy traffic.
Figure 6 is a perspective view with a portion shown in section of a thermoplastic sheet used in the manufacture of the granules.
Figure 7 is a perspective view of the thermoplastic sheet of Figure 6 during the application of glass spheres to its exposed surfaces.
Figure 8 is a partially schematic front elevational view of the thermoplastic sheet as it is advanced between rollers to form the granules.
. Figure 9 is a partially schema~ic side elevational view of the rollers and associated components illus~ra~ed in Figure 8.
6 8 ~ ~
Description of Certain Preferred Embodiments -Referring to Figures 1 and 2 of the drawinqs, there is shown a small reflective particle in the form of a plastic resin granule 20. The granule ~0 has nt least one flat face 22 and ~s of ~ shape such that when dropped from ~ random position onto a horiæontal surface the face 22 is disposed in a downward direction, for purposes that will become more fully ~pparent hereinafter. Advantageously the granule 20 is in the form of a tetrahedron ~nd in addition to the downward face 22 has additional faces 23, 24 ~nd 25. For granules in the shape of an equilateral tetrahedron the angle ~ between the face 2~ and the adjoining faces 23, 24 and 25 is 60.
Particularly good results are achieved with granules h~ving an angle ~ of at least 60 and preferably about 7~.
Evenly dispersed throughout the granule 20 ~re a multiplicity of glass beads or spheres 27. Some of the spheres 27 protrude through the faces 22, 23, 24 and 25 of the granule 20 and similarly arc evenly dispersed throughout the surface area of each face. The spheres 27 are of a type commonly used in reflective marking and have a diameter in the range of from about 6.0 microns to about 0.125 inches depending upon the particular type of reflective marker with which the spheres are to be used. For best results the spheres 27 should have an index of refraction of at least about 1.5, and in situations where particularly good retroreflectivity is desir~ ~he refractive index of the spheres may be up to ~bout 2~0.
In some cases a reflective coating such ~s a silver may be applied to the spheres which provides even higher -12~8t)~6 retroreflectiuity for certain applications. The spheres illustratively may be produced in the manner disclosed in T.~. ~ood U.S. Patent 2,947,115, for example, and for many applications they ~re provided with a suitable coupling agent coating such as the silanes, titanates with vinyl groups, terminal amines or epoxides. For a more detailed discussion of representative coatings for the spheres, reference may be had to James R. Ritter et al ~.S. Patent 3,867,178.
The tetrahedron-shaped granules 20 containing the glass spheres ~7 may ~e employed as illustrated in Figure 3 to provide a reflective marker on a surface 30 which illustratively comprises a roadway or highway sign. A layer 31 of traffic paint or other adherent material is first applied to the surface 30, and while the paint is still tacky the granules 20 are dropped from a random position and become imbedded in the paint.
Because of their configuration the granules 20 come to rest on the painted surface with one of their flat faces 22 disposed in a downward direction irrespective of ~he orientation of the granules at the time of their release. With this arrangement the entire area of the face 22 on each granule is in facing contact with the paint to provide extremely good adhesion between the granules and the roadway surface. Each individual granule is imbedded in the layer of paint, and the paint may exhibit a slight wicking action to further help maintain the granules in position and prevent ~ny substanti~I quanti~y of granules from becoming dislodged even under hcaYy traffic conditions.
~26t3~)16 The size of the plastic granules 20 is carefully controlled such that their height above the roadway surface 30 ranges between about 2 millimeters and about 12 millimeters. For granules having a height much below 2 millimeters the quantity of glass spheres 27 within each granule i5 too small to provide a satisfactory impr~vement in retroreflecti~e properties, particularly during rainy conditions, while for granules above about 12 millimeters in height the surface becomes too rough and there is unnecessary wastage of the granule material due to traffic wear, shearing by snow plows, etc.
In addition, the granules within this range advantageously are divided into two and in some cases three distinct sizes. As illustrated in Figures 3 and 4I for example, the granules applied to the surface 20 comprise comparatively large granules 20a which range in height from about 6 millimeters to about 12 millimeters, medium-size granules 20b which range in height from about 4 millimeters to about 6 millimeters, and small granules 20c which range in height from about 2 millimeters to about 4 millimeters. In cases in which only two size ranges are used for the granules, the large granules have a height of between about 5 millimeters and about 12 millimeters, and the small granules have a height between about 2 millimeters and about S millimeters.
Figure 5 is an illustration of the granule-coated roadway surface 30 after being subjected to abras~on by heavy traffic. The upper portions of the large granules 20a and the medium-size granules 20b have been eroded-to provided flat horizontal surfaces 33, while the upper portions of the small granules 20c have not been subjected to abrasion and retain their ~26~30~6 original tetrahedron shapes. During the erosion of the granules 20a and 20b the glass spheres 27 within the interiors of the granules become exposed and protrude through the upper surfaces 33 to help retain the optical propertieS of these l~rger granules. In ~ddition, the reflective angle Q (~igure 2) remains the same irrespective of the degree vf er~sion and preferably is approximately 70D to provide an optimum reflective angle on a highway for the headlights of a vehicle. The arrange-ment is such that the reflective marker retains good retro-reflective properties even after being exposed to long periods of heavy traffic, and there is very little impairment o~ the retroreflective properties during rainstorms and in other instances where puddles are formed on the roadway. The flat surfaces 33 on the larger granules 20a and 20b in many instances ~re disposed above the puddles, and the glass spheres protruding therefrom retain much of their retro-reflective properties.
The material from which the granules 20 are formed may be selected from a wide variety of ~hermoplastic and thermosetting resins. Suitable thermoplastic resins include the polyolefins, polyethylene, polypropylene, polymethyl methacrylate, acrylonitrile butadiene styrene, etc., while the thermosetting resins that may be used comprise the polyesters, urethanes, methyl methacrylate and ~crylonitrile.
Substantially ~ny thermoplastic or thermosetting ~e~in may be employed ~hat exhibits good wear resist~nce and gives off a minimum of volatile matter during curing.
~ ~ 6 ~
The polyester resins, for example, in general comprise unsaturated alkyd resins which are formed by the reaCtiQn of one or more dicarboxylic acid components and ~ne or more polyhydric alcohols. Illustrative dicarboxylic acid components include ~aturated anhydrides and adipic and azelaic acids, and the unsaturated components fumaric acid and maleic acid. The commonly used dihydric alcohols include glycols o~ ethylene propylene, 1, 3- and 2, 3- butylene, diethylene and dipropylene. The polyester reaction products are mixed with a nonvolatile unsaturated monomeric cross-linking agent for the polyester resin such as a methyl methacrylate. Other unsaturated hydrocarbons that may be employed as a monomeric agent include styrene, vinyl toluene, vinyl acetate, ~rtho and para methyl styrene, divinyl ben~ene, ethyl acrylate and many others. ~he monomeric agent is of the nature such that it is consumed during the curing of the resin without forming volatile materials.
Still other illustrative materials that may be employed to form the granules 20 include the epoxy resins containing both epoxide and hydroxyl groups and the urethane resins resulting from reactions between hydroxyl groups and polyisocyanates. For a more detailed dis~ussion of representative thermoplastic and thermosetting resins which are useful as the granule material, reference may be had, for examole, to De Vries et al U.S. Patents 3,171,827 and 3,254,563.
o~
The resin ma~erial ~or the granules 20 is obtained commercially in liquid, powder or pelletized form. The material is thoroughly mixed with slass spheres having ~
diameter in the range of from about 6.0 microns to about 0.125 inches and nn index of refraction of from about 1.5 to ~bout ~.0 and even higher depending upon the particular application. For highway striping, for example, the glass spheres may be produced from conventional soda lime silicate glass having an index of refraction of about 1.5. For roadways in areas subjected to heavy precipitation, or for signs, motion picture screens and other applications where even better reflectivity is desired, ~he spheres m~y be fabricated from some of the titanium glasses having a higher index of refraction, or they may comprise spheres having varying indices or ~pheres coated with a reflective material such as silver or aluminum. As an illustration, good results may be achieved where the spheres located in the interiorof the granules have an index of refraction of, say, 1.5, and the exposed spheres on the surfaces of the granules have an index of refraction of about 1.9.
A suitable pigment is added to the mixture of resin material and glass spheres to impart reflection to the xesin as well as color and opacity. For edge striping on a highway, for example, a white pigment is employed such as rutile titanium dioxide or anatase titanium dioxid~ or example. Other pigments that may be used to produce white, yellow or other colored mixtures include aluminum oxide, ~L26801~i iron oxide, silicon carbide, antimony oxides, lead oxide, lead chromates, zinc chromates, cadmium pigments, siennas, umbers, inorganic or organic reds, chrome yellows, chrome oranges, chrome greens, etc. The pigments can be oxtended with suitable natural or manufactured granule ma~erials.
~ he thermosetting resins commonly are available in liquid form. Upon being mixed with the glass spheres 27 and the pigment, the liquid is spread onto the upper surface of a flexible rubber sheet or belt which contains a multi-plicity of tetrahedron-shaped indentations. A suitable doctor blade may be employed to urge the material into each indentation. The material is then cured ~t an elevated or room temperature, and the sheet is flexed to discharge the individual tetrahedron granules into appropri~te collecting equipment. Additional spheres may be applied to the surfaces of the tetrahedrons ~s they are formed, nd one preferred embodiment uses spheres having a refractive index of about 1.5 in the interiors of the tetrahedrons to provide rigidity and good wear resist~nce, and surface spheres having a refractive index of about 1.9 for high retrorefl~ctivity.
The thermoplastic resins, on the other hand, for the most part are available commercially in powder or pelleti~ed form. After being mixed with the gl~ss spheres 27 and the pigment, the particulate material is extruded under heat to form a softened flat sheet which is shownib~ the reference character 35 in ~igures 6-9. The sheet 35 includes a multiplicity of the glass spheres 27 substantially evenly dispersed ~herein. At ~his stage in the manufacturing process substantially all of the spheres are imbedded within the resin material, and the gl~ss i5 not exposed to eny great extent on the flat opposed surfaces of the sheet.
As best shown in Figure 7, ~he thermoplastic sheet 35 is then advanced between two spray nozzles 37 and 38. The nozzles 37 and 38 direct additional glass spheres 27 onto the opposed flat surfaces of the sheet 35 to ~artially imbed the additional spheres in the still tacky material.
The sheet 35 containing the glass spheres 2~ dis~ersed therein and on its opposed flat surfaces is advanced through the nip between ~wo rollers 40 and 41 (Figures 8 and 9). The rollers 40 and 41 are rotated at a constant speed by a suitable drive mechanism (not shown). The lowermost of these rollers 40 contains a multiplicity of tetrahedron-shaped indentations ~2 throughout its cylindrical surface, and the indentations correspond in size and configuration to the plas~ic granules 20a, 20b and 20c illustrated in ~igures 3-5. Thus, some of ~he indentations are of a size equal to or only slightly greater than the large granules 20a, other indentations are of a size equal to or only slightly greater than the medium granules 20b, and still other indentations are of a size equal to or only slightly greater than the small granules 20c. The indentations ~erve as molds 126~
for the individual granules, and as the sheet 35 passes between the rollers 40 and 41 the sheet m~terial is urged under pressure into each indentation to thereby form the granules. The glass spheres 27 ~re substantially evenly dispersed throughout each granule with some of the ~pheres protruding through the outer granule surfaces.
As the thus molded granules 20 leave the nip between the rollers 40 and 41, the roller 40 is cleaned by scraping excess resin material from its cylindrical surface through the use of a doctor blade 45. The excess material is discharged into a trough 46 so that it may be recycled to form additional granules, Upon continued rotation of the roller 40, ~he granules 20 within the indentations 42 drop onto a suitable conveyor 50.
The conveyor 50 collects the granules 20 and transports them to a suitable bagging machine or other packaging equipment.
The proportion of the glass spheres ~7 within and on the surfaces of each of the granules 20 should be carefully controlled to provide optimum reflective properties. ~or best results ~he finished granule incorporates about 30 percent to about 60 percent by weight of the spheres. If the weight of the spheres exceeds ~bout 60 percent of the granule material the structural integrity of the granules is too poor to provide a satisfactory product, while with ~ sphere weight below about 30 percent of the granule material th~ _ reflectivity is so low that the granules are unsuit~ble ~L~680~6 for use as a reflective marker. In ~ases in which the weight of the spheres within each granule ~nd on its exposed s~rfaces is about fifty percent the weight of the granule, the gr~nule exhibits particularly good characteristics when employed for l~ne marking and other highway striping.
The thus prepared granules 20 are applied to a roadway or other surface through the use of conventional delineation equipment. ~he granules Are dropped from a random position onto the surface, and each granule comes to rest with one of its flat faces disposed in a downward direction such that it is imbedded in the paint. The different size granules 20a, 20b and 20c are evenly distributed on the surface, ~nd when the paint or other film forming material is fully cured the particles are firmly held in position to provide an extremely effective reflective marker.
In some embodiments of the invention the reflective granules 20 may be pre-mixed with liquid paint prior to being applied to the surface. For highway striping, for example, the mixture of paint and granules is applied directly to the roadway, and a large percentage of the granules become oriented with the faces 22 disposed in a downward direction while the viscosity of the paint is still relatively low. As the paint dries and hardens, the granules are maintained in place, and upon being exposed to traffic the thin layer o pAint adjacen~~the upper portions of the granules is worn ~ff to provide good reflectivity.
~L~68016 In order to more thoroughly disclose the nature of the present invention, the following examples illustrating the invention are given. It should be understood, howe~er, that this is done solely by way of example and is intended neither to delineate the scope of the invention nor limit the ambit of the appended claims.
Example 1 Methyl methacrylate resin in liquid form is mixed with a conventional white highway pigment and with glass spheres manufactured in accordance with the teachings of T~K. Wood V.S. Patent 2,945,326. The spheres are of soda lime silicate glass with an index refraction of 1.5, ~nd they range in diameter from 200 microns to 350 microns.
The spheres are substantially evenly dispersed throughout the resin in a proportion of about 1 part by weight of spheres to about 2 parts by weight of the resin material.
Through the use of a doctor blade, the thus prepared mixture is spread over a flat rubber sheet which contains a multiplicity of tetrahedron-shaped indentations in its upper surface. The mixture i5 urged into each of the ,. _ 1~680~
indentations and is cured through the application of heat to form a multiplicity of tetrahedron-shaped granules containing glass spheres substantially evenly dispersed throughout each granule with some of ~he spheres protruding through the outer faces thereof. The indentations in the sheet are of a size such that approximately one-half of the granules have a height of 6 millimeters and one-half have a height of 4.5 millimeters. The granules are removed from the indentations and placed in bags.
The bags of reflective particles produced in this example are transported to a roadway, ~nd the particles are dropped from a random position onto a line of moist white traffic paint having a thickness of ~pproximately 0.75 millimeters. Each of the particles drops onto the paint with one of the faces of the particle disposed in a downward direction such that it is imbedded in the paint. As the paint dries, the particles are firmly held in position on the roadway to prcvide an extremely effective reflective marker. After repeated exposure of the soadway to heavy traffic, the upper portions of some of the larger reflective particles are flattened by abrasion, but substantially all 12680~i of the particles remain imbedded in the paint, and there is only a very slight decrease in reflectivity even after extended periods of use.
Example 2 Acrylonitrile butadiene styrene resin in powder form is mixed with glass spheres produced in accordance with the teachings of T.K. Wood et al U.S. Patent 3,279,905. A titanium glass is used for the spheres to provide an index of refraction of 1.9, and the diameter of the spheres ranges between about 350 microns and about 630 microns. The resin-sphere mixture is extruded at an elevated temperature to form a thin tacky sheet, and additional glass spheres are sprayed onto both of the flat surfaces of the sheet to partially imbed the additional spheres therein.
The sheet in a softened condition is then advanced through the nip between a pair of continuously rotating rollers of the type illustrated in Figures 8 and 9 of the drawings. One of the rollers is provided with a multiplicity of indentations in its cylindrical surface which are each in the shape of an equilateral tetrahedron. As the sheet moves between the rollers the sheet material is urged into these indentations to form a multiplicity of tetrahedron-shaped thermoplastic granules containing glass spheres substantially evenly dispersed throughout each granule with ~ome of the spheres protruding through the outer ~rfaces thereof. The indentations in the roller are of ~wo_diferent sizes such that approximately 50 percent of ~he tetrnhedron-shaped granules have a height of 4 millimeters and the 1~:6801~;
remaining 50 percent have a height of 6 millimeters. The weight of spheres within each granule is equal to that of the granule material.
~ he granules are removed from the indentations in the roller and ~re transported to ~ highway, where they are dropped from random positions onto a yellow line of still tacky traffic paint along the center of the highway.
Each granule comes to rest with one of its flat faces disposed in a downward direction and imbedded in the paint. After the paint has dried the granules remain in position during periods of heavy rain and after long use.
Example 3 Polypropylene recin in pelletized form is extruded at a temperature of 180C to form a thin flat sheet. Glass spheres having a size of between 50 and 100 mesh U.S. Standard are sprayed onto the opposite faces of the sheet while the sheet is maintained in a softened condition at about 120C to about 140C. The spheres are of barium titinate glass with an index of refraction of 1.9 and are partially imbedded in the faces of the sheet. The sheet is then advanced in a softened condition over a roller which cont~ins a multiplicity of tetrahedron-shaped indentations in its ~ylindrical surface to urge material from the sheet into the indentations and thereby form a multiplicity of te~r~hedron-shaped granules containing glass spheres. The indentations are of equal size to simil~rly produce equal-~ize granules having a height of 4.5 millimeters. The proportion of spheres 126~
to the polypropylene resin is about 3 parts by weight of spheres to about 5 parts of resin.
The tetrahedron-shaped granules are transported to a highway and dropped onto a line of tacky traffic paint in the manner descr~bed above. Upon the hardening of the paint the granules remain in position and exhibit good reflectivity characteristics.
Exampla 4 In each of the foregoing examples a pigment of the same color as that used for the highway line is admixed with the resin material prior to the time the material is extruded.
The resulting granules have a corresponding color and provide a further improvement in the reflectivity of the line.
Exam~le 5 A thin coating of silver is applied to the glass spheres in the manner more fully described in British patent
~ he present invention, while of general application, is particularly well suited for use on highways to provide reflective markers such as edge and lane striping, signs, etc.
As is well known, it has become common practice to drop small glass spheres onto a painted line on a highway while the paint is still tacky such that the spheres are partially imbedded in the paint when it has dried. The spheres render the line or other marker retroreflective and reflect the light from headlights so that the marker is more visible to the motorist.
In some cases the spheres were imbedded in spherical or irregularly shaped plastic granules prior to being applied to the paint in the manner disclosed in U.S. Patents 3,252,376 and 3,254,563, for example, in an effort to further improve the reflectivity of the marker.
Heretofore, difficulties were encountered in the manufacture and use of reflective material of the foregoing type. As an illustration, in many instances the adhesion of the glass spheres to the paint proved deficient, with the result ~hat some of the spheres were loosened by traffic or washed away during rains~orms, 'or example, with a corresponding deterioration in the reflectivity of the surface. In~a~dition, the spheres that remained were subjected to severe ~brasion under heavy traffic conditions and exhibited flattened upper ~26~30~6 surfaces which further impaired the ref}ectivity of the marker. Furthermore, and this has ~een of special moment during periods of heavy rain, the reflectivity of even freshly applied striping or other marking wa~ deficient in a number of respects.
Summary One general object of the invention, therefore, is to provide a new and improved reflective particle for use in highway and other reflective marking.
Another object of the invention is to provide a new and improved method of making such a particle.
More specifically, it is an object of ~his invention to provide a reflective particle that remains in place on a supporting surface for an extended period of time.
A further object of the invention is to provide a reflective marker which exhibits uniform and in some cases improved reflectivity after long periods of use.
Still another object of the invention is to provide a reflective marker which exhibits good reflectivity when in a wet or moistened condition.
A still further object of the invention i5 to provide an improved reflective marker and method of makinq -the same which are economical snd thoroughly reliable in operation. _ -~ 2 ~ ~ 0 ~i In one illustrative embodiment of the invention, the reflective marker comprises a multiplicity of uniquely shaped granules of plastic material. Imbedded in ~t least the exposed ~urfaces of the granules are a plurality of glass spheres which protrude through the surfaces to provide the granules with reflcctive characteristics. For many applications the granules are dropped or otherwise applied to a painted substrate with the paint in a tacky condition, but in other cases the granules may be premixed with paint and then applied to the substrate in a single operation.
$n accordance with one feature of the invention, each of the granules is provided with at least one flat face and is of a shape such that when dropped from a random position onto a horizontal surface the flat face is disposed in a down-ward direction. The flat face is imbedded in the layer of paint to provide optimum adhesion of the granule to the surface.
In accordance with another feature of the invention, in certain particularly important embodiments, each granule is in the shape of a tetrahedron. The tetrahedrons preferably are of a shape such that when sprinkled from a random position onto a painted line of a highway, ~or example, one of the faces of the tetrahedron is disposed downwardly and the remaining faces meet the downward face at an angle of ~bout seventy degrees. With this arrangement the resulti~g marker exhibits high reflectivity with respect to the headlights of a vehicle particularly under wet conditions.
- ~68~
In accordance with a further feature of several advantageous embodiments of the invention, the maximum height of the plastic granules Pbove the surface lies within the range of from about 2 millimeters to about 12 millimeters, and the granules are of at least two distinct sizes. The larger size granules become flattened by traffic to expose a greater quantity of the glass spheres imbedded therein, while the smaller granules retain their tetrahedron shape for an extended period of time. ~he arrangement is such that the reflectivity of the marker remains substantially uniform and in some cases increases during long periods of use.
In accordance with still another feature of the invention, in several good arrangements, the granules are formed by advancing a plastic sheet in a softened conditi~n over a roller containing a multiplicity of tetrahedron-shaped indentations to individually mold each granule. The glass spheres are applied to the sheet prior to the molding operation by spraying the spheres onto the flat surfaces of the sheet and in some cases by mixing additional spheres with the plastic material used to form the sheet. The size and shape of each individual granule is determined by the configuration of the indentations in the roller to provide a very precise control over the reflectivity characteristics of the resulting marker.
The present invention, as well as further~DDjects and features thereof, will be more iully understood_from the following description of certain preferred embodiments, when read with reference to the accompanyiny drawings~
Brief Description of the Drawings Figure 1 is a substantially enlarged perspective view of a molded tetrahedron-shaped granule containing glas~ spheres in accordance with An illustrative embodiment of the invention.
~ igure 2 is a vertical ~ectional view taken along the line 2-2 in Figure 1.
Figure 3 is an enlarged side elevational view of a portion of a roadway having a reflective marker which includes different size granules of the type illustrated in Figure 1.
Figure 4 is a vertical sectional view of the roadway portion of Figure 3.
Figure 5 is a vertical sectional view similar to Figure 4 but showing the reflective marker after it has been subjected to heavy traffic.
Figure 6 is a perspective view with a portion shown in section of a thermoplastic sheet used in the manufacture of the granules.
Figure 7 is a perspective view of the thermoplastic sheet of Figure 6 during the application of glass spheres to its exposed surfaces.
Figure 8 is a partially schematic front elevational view of the thermoplastic sheet as it is advanced between rollers to form the granules.
. Figure 9 is a partially schema~ic side elevational view of the rollers and associated components illus~ra~ed in Figure 8.
6 8 ~ ~
Description of Certain Preferred Embodiments -Referring to Figures 1 and 2 of the drawinqs, there is shown a small reflective particle in the form of a plastic resin granule 20. The granule ~0 has nt least one flat face 22 and ~s of ~ shape such that when dropped from ~ random position onto a horiæontal surface the face 22 is disposed in a downward direction, for purposes that will become more fully ~pparent hereinafter. Advantageously the granule 20 is in the form of a tetrahedron ~nd in addition to the downward face 22 has additional faces 23, 24 ~nd 25. For granules in the shape of an equilateral tetrahedron the angle ~ between the face 2~ and the adjoining faces 23, 24 and 25 is 60.
Particularly good results are achieved with granules h~ving an angle ~ of at least 60 and preferably about 7~.
Evenly dispersed throughout the granule 20 ~re a multiplicity of glass beads or spheres 27. Some of the spheres 27 protrude through the faces 22, 23, 24 and 25 of the granule 20 and similarly arc evenly dispersed throughout the surface area of each face. The spheres 27 are of a type commonly used in reflective marking and have a diameter in the range of from about 6.0 microns to about 0.125 inches depending upon the particular type of reflective marker with which the spheres are to be used. For best results the spheres 27 should have an index of refraction of at least about 1.5, and in situations where particularly good retroreflectivity is desir~ ~he refractive index of the spheres may be up to ~bout 2~0.
In some cases a reflective coating such ~s a silver may be applied to the spheres which provides even higher -12~8t)~6 retroreflectiuity for certain applications. The spheres illustratively may be produced in the manner disclosed in T.~. ~ood U.S. Patent 2,947,115, for example, and for many applications they ~re provided with a suitable coupling agent coating such as the silanes, titanates with vinyl groups, terminal amines or epoxides. For a more detailed discussion of representative coatings for the spheres, reference may be had to James R. Ritter et al ~.S. Patent 3,867,178.
The tetrahedron-shaped granules 20 containing the glass spheres ~7 may ~e employed as illustrated in Figure 3 to provide a reflective marker on a surface 30 which illustratively comprises a roadway or highway sign. A layer 31 of traffic paint or other adherent material is first applied to the surface 30, and while the paint is still tacky the granules 20 are dropped from a random position and become imbedded in the paint.
Because of their configuration the granules 20 come to rest on the painted surface with one of their flat faces 22 disposed in a downward direction irrespective of ~he orientation of the granules at the time of their release. With this arrangement the entire area of the face 22 on each granule is in facing contact with the paint to provide extremely good adhesion between the granules and the roadway surface. Each individual granule is imbedded in the layer of paint, and the paint may exhibit a slight wicking action to further help maintain the granules in position and prevent ~ny substanti~I quanti~y of granules from becoming dislodged even under hcaYy traffic conditions.
~26t3~)16 The size of the plastic granules 20 is carefully controlled such that their height above the roadway surface 30 ranges between about 2 millimeters and about 12 millimeters. For granules having a height much below 2 millimeters the quantity of glass spheres 27 within each granule i5 too small to provide a satisfactory impr~vement in retroreflecti~e properties, particularly during rainy conditions, while for granules above about 12 millimeters in height the surface becomes too rough and there is unnecessary wastage of the granule material due to traffic wear, shearing by snow plows, etc.
In addition, the granules within this range advantageously are divided into two and in some cases three distinct sizes. As illustrated in Figures 3 and 4I for example, the granules applied to the surface 20 comprise comparatively large granules 20a which range in height from about 6 millimeters to about 12 millimeters, medium-size granules 20b which range in height from about 4 millimeters to about 6 millimeters, and small granules 20c which range in height from about 2 millimeters to about 4 millimeters. In cases in which only two size ranges are used for the granules, the large granules have a height of between about 5 millimeters and about 12 millimeters, and the small granules have a height between about 2 millimeters and about S millimeters.
Figure 5 is an illustration of the granule-coated roadway surface 30 after being subjected to abras~on by heavy traffic. The upper portions of the large granules 20a and the medium-size granules 20b have been eroded-to provided flat horizontal surfaces 33, while the upper portions of the small granules 20c have not been subjected to abrasion and retain their ~26~30~6 original tetrahedron shapes. During the erosion of the granules 20a and 20b the glass spheres 27 within the interiors of the granules become exposed and protrude through the upper surfaces 33 to help retain the optical propertieS of these l~rger granules. In ~ddition, the reflective angle Q (~igure 2) remains the same irrespective of the degree vf er~sion and preferably is approximately 70D to provide an optimum reflective angle on a highway for the headlights of a vehicle. The arrange-ment is such that the reflective marker retains good retro-reflective properties even after being exposed to long periods of heavy traffic, and there is very little impairment o~ the retroreflective properties during rainstorms and in other instances where puddles are formed on the roadway. The flat surfaces 33 on the larger granules 20a and 20b in many instances ~re disposed above the puddles, and the glass spheres protruding therefrom retain much of their retro-reflective properties.
The material from which the granules 20 are formed may be selected from a wide variety of ~hermoplastic and thermosetting resins. Suitable thermoplastic resins include the polyolefins, polyethylene, polypropylene, polymethyl methacrylate, acrylonitrile butadiene styrene, etc., while the thermosetting resins that may be used comprise the polyesters, urethanes, methyl methacrylate and ~crylonitrile.
Substantially ~ny thermoplastic or thermosetting ~e~in may be employed ~hat exhibits good wear resist~nce and gives off a minimum of volatile matter during curing.
~ ~ 6 ~
The polyester resins, for example, in general comprise unsaturated alkyd resins which are formed by the reaCtiQn of one or more dicarboxylic acid components and ~ne or more polyhydric alcohols. Illustrative dicarboxylic acid components include ~aturated anhydrides and adipic and azelaic acids, and the unsaturated components fumaric acid and maleic acid. The commonly used dihydric alcohols include glycols o~ ethylene propylene, 1, 3- and 2, 3- butylene, diethylene and dipropylene. The polyester reaction products are mixed with a nonvolatile unsaturated monomeric cross-linking agent for the polyester resin such as a methyl methacrylate. Other unsaturated hydrocarbons that may be employed as a monomeric agent include styrene, vinyl toluene, vinyl acetate, ~rtho and para methyl styrene, divinyl ben~ene, ethyl acrylate and many others. ~he monomeric agent is of the nature such that it is consumed during the curing of the resin without forming volatile materials.
Still other illustrative materials that may be employed to form the granules 20 include the epoxy resins containing both epoxide and hydroxyl groups and the urethane resins resulting from reactions between hydroxyl groups and polyisocyanates. For a more detailed dis~ussion of representative thermoplastic and thermosetting resins which are useful as the granule material, reference may be had, for examole, to De Vries et al U.S. Patents 3,171,827 and 3,254,563.
o~
The resin ma~erial ~or the granules 20 is obtained commercially in liquid, powder or pelletized form. The material is thoroughly mixed with slass spheres having ~
diameter in the range of from about 6.0 microns to about 0.125 inches and nn index of refraction of from about 1.5 to ~bout ~.0 and even higher depending upon the particular application. For highway striping, for example, the glass spheres may be produced from conventional soda lime silicate glass having an index of refraction of about 1.5. For roadways in areas subjected to heavy precipitation, or for signs, motion picture screens and other applications where even better reflectivity is desired, ~he spheres m~y be fabricated from some of the titanium glasses having a higher index of refraction, or they may comprise spheres having varying indices or ~pheres coated with a reflective material such as silver or aluminum. As an illustration, good results may be achieved where the spheres located in the interiorof the granules have an index of refraction of, say, 1.5, and the exposed spheres on the surfaces of the granules have an index of refraction of about 1.9.
A suitable pigment is added to the mixture of resin material and glass spheres to impart reflection to the xesin as well as color and opacity. For edge striping on a highway, for example, a white pigment is employed such as rutile titanium dioxide or anatase titanium dioxid~ or example. Other pigments that may be used to produce white, yellow or other colored mixtures include aluminum oxide, ~L26801~i iron oxide, silicon carbide, antimony oxides, lead oxide, lead chromates, zinc chromates, cadmium pigments, siennas, umbers, inorganic or organic reds, chrome yellows, chrome oranges, chrome greens, etc. The pigments can be oxtended with suitable natural or manufactured granule ma~erials.
~ he thermosetting resins commonly are available in liquid form. Upon being mixed with the glass spheres 27 and the pigment, the liquid is spread onto the upper surface of a flexible rubber sheet or belt which contains a multi-plicity of tetrahedron-shaped indentations. A suitable doctor blade may be employed to urge the material into each indentation. The material is then cured ~t an elevated or room temperature, and the sheet is flexed to discharge the individual tetrahedron granules into appropri~te collecting equipment. Additional spheres may be applied to the surfaces of the tetrahedrons ~s they are formed, nd one preferred embodiment uses spheres having a refractive index of about 1.5 in the interiors of the tetrahedrons to provide rigidity and good wear resist~nce, and surface spheres having a refractive index of about 1.9 for high retrorefl~ctivity.
The thermoplastic resins, on the other hand, for the most part are available commercially in powder or pelleti~ed form. After being mixed with the gl~ss spheres 27 and the pigment, the particulate material is extruded under heat to form a softened flat sheet which is shownib~ the reference character 35 in ~igures 6-9. The sheet 35 includes a multiplicity of the glass spheres 27 substantially evenly dispersed ~herein. At ~his stage in the manufacturing process substantially all of the spheres are imbedded within the resin material, and the gl~ss i5 not exposed to eny great extent on the flat opposed surfaces of the sheet.
As best shown in Figure 7, ~he thermoplastic sheet 35 is then advanced between two spray nozzles 37 and 38. The nozzles 37 and 38 direct additional glass spheres 27 onto the opposed flat surfaces of the sheet 35 to ~artially imbed the additional spheres in the still tacky material.
The sheet 35 containing the glass spheres 2~ dis~ersed therein and on its opposed flat surfaces is advanced through the nip between ~wo rollers 40 and 41 (Figures 8 and 9). The rollers 40 and 41 are rotated at a constant speed by a suitable drive mechanism (not shown). The lowermost of these rollers 40 contains a multiplicity of tetrahedron-shaped indentations ~2 throughout its cylindrical surface, and the indentations correspond in size and configuration to the plas~ic granules 20a, 20b and 20c illustrated in ~igures 3-5. Thus, some of ~he indentations are of a size equal to or only slightly greater than the large granules 20a, other indentations are of a size equal to or only slightly greater than the medium granules 20b, and still other indentations are of a size equal to or only slightly greater than the small granules 20c. The indentations ~erve as molds 126~
for the individual granules, and as the sheet 35 passes between the rollers 40 and 41 the sheet m~terial is urged under pressure into each indentation to thereby form the granules. The glass spheres 27 ~re substantially evenly dispersed throughout each granule with some of the ~pheres protruding through the outer granule surfaces.
As the thus molded granules 20 leave the nip between the rollers 40 and 41, the roller 40 is cleaned by scraping excess resin material from its cylindrical surface through the use of a doctor blade 45. The excess material is discharged into a trough 46 so that it may be recycled to form additional granules, Upon continued rotation of the roller 40, ~he granules 20 within the indentations 42 drop onto a suitable conveyor 50.
The conveyor 50 collects the granules 20 and transports them to a suitable bagging machine or other packaging equipment.
The proportion of the glass spheres ~7 within and on the surfaces of each of the granules 20 should be carefully controlled to provide optimum reflective properties. ~or best results ~he finished granule incorporates about 30 percent to about 60 percent by weight of the spheres. If the weight of the spheres exceeds ~bout 60 percent of the granule material the structural integrity of the granules is too poor to provide a satisfactory product, while with ~ sphere weight below about 30 percent of the granule material th~ _ reflectivity is so low that the granules are unsuit~ble ~L~680~6 for use as a reflective marker. In ~ases in which the weight of the spheres within each granule ~nd on its exposed s~rfaces is about fifty percent the weight of the granule, the gr~nule exhibits particularly good characteristics when employed for l~ne marking and other highway striping.
The thus prepared granules 20 are applied to a roadway or other surface through the use of conventional delineation equipment. ~he granules Are dropped from a random position onto the surface, and each granule comes to rest with one of its flat faces disposed in a downward direction such that it is imbedded in the paint. The different size granules 20a, 20b and 20c are evenly distributed on the surface, ~nd when the paint or other film forming material is fully cured the particles are firmly held in position to provide an extremely effective reflective marker.
In some embodiments of the invention the reflective granules 20 may be pre-mixed with liquid paint prior to being applied to the surface. For highway striping, for example, the mixture of paint and granules is applied directly to the roadway, and a large percentage of the granules become oriented with the faces 22 disposed in a downward direction while the viscosity of the paint is still relatively low. As the paint dries and hardens, the granules are maintained in place, and upon being exposed to traffic the thin layer o pAint adjacen~~the upper portions of the granules is worn ~ff to provide good reflectivity.
~L~68016 In order to more thoroughly disclose the nature of the present invention, the following examples illustrating the invention are given. It should be understood, howe~er, that this is done solely by way of example and is intended neither to delineate the scope of the invention nor limit the ambit of the appended claims.
Example 1 Methyl methacrylate resin in liquid form is mixed with a conventional white highway pigment and with glass spheres manufactured in accordance with the teachings of T~K. Wood V.S. Patent 2,945,326. The spheres are of soda lime silicate glass with an index refraction of 1.5, ~nd they range in diameter from 200 microns to 350 microns.
The spheres are substantially evenly dispersed throughout the resin in a proportion of about 1 part by weight of spheres to about 2 parts by weight of the resin material.
Through the use of a doctor blade, the thus prepared mixture is spread over a flat rubber sheet which contains a multiplicity of tetrahedron-shaped indentations in its upper surface. The mixture i5 urged into each of the ,. _ 1~680~
indentations and is cured through the application of heat to form a multiplicity of tetrahedron-shaped granules containing glass spheres substantially evenly dispersed throughout each granule with some of ~he spheres protruding through the outer faces thereof. The indentations in the sheet are of a size such that approximately one-half of the granules have a height of 6 millimeters and one-half have a height of 4.5 millimeters. The granules are removed from the indentations and placed in bags.
The bags of reflective particles produced in this example are transported to a roadway, ~nd the particles are dropped from a random position onto a line of moist white traffic paint having a thickness of ~pproximately 0.75 millimeters. Each of the particles drops onto the paint with one of the faces of the particle disposed in a downward direction such that it is imbedded in the paint. As the paint dries, the particles are firmly held in position on the roadway to prcvide an extremely effective reflective marker. After repeated exposure of the soadway to heavy traffic, the upper portions of some of the larger reflective particles are flattened by abrasion, but substantially all 12680~i of the particles remain imbedded in the paint, and there is only a very slight decrease in reflectivity even after extended periods of use.
Example 2 Acrylonitrile butadiene styrene resin in powder form is mixed with glass spheres produced in accordance with the teachings of T.K. Wood et al U.S. Patent 3,279,905. A titanium glass is used for the spheres to provide an index of refraction of 1.9, and the diameter of the spheres ranges between about 350 microns and about 630 microns. The resin-sphere mixture is extruded at an elevated temperature to form a thin tacky sheet, and additional glass spheres are sprayed onto both of the flat surfaces of the sheet to partially imbed the additional spheres therein.
The sheet in a softened condition is then advanced through the nip between a pair of continuously rotating rollers of the type illustrated in Figures 8 and 9 of the drawings. One of the rollers is provided with a multiplicity of indentations in its cylindrical surface which are each in the shape of an equilateral tetrahedron. As the sheet moves between the rollers the sheet material is urged into these indentations to form a multiplicity of tetrahedron-shaped thermoplastic granules containing glass spheres substantially evenly dispersed throughout each granule with ~ome of the spheres protruding through the outer ~rfaces thereof. The indentations in the roller are of ~wo_diferent sizes such that approximately 50 percent of ~he tetrnhedron-shaped granules have a height of 4 millimeters and the 1~:6801~;
remaining 50 percent have a height of 6 millimeters. The weight of spheres within each granule is equal to that of the granule material.
~ he granules are removed from the indentations in the roller and ~re transported to ~ highway, where they are dropped from random positions onto a yellow line of still tacky traffic paint along the center of the highway.
Each granule comes to rest with one of its flat faces disposed in a downward direction and imbedded in the paint. After the paint has dried the granules remain in position during periods of heavy rain and after long use.
Example 3 Polypropylene recin in pelletized form is extruded at a temperature of 180C to form a thin flat sheet. Glass spheres having a size of between 50 and 100 mesh U.S. Standard are sprayed onto the opposite faces of the sheet while the sheet is maintained in a softened condition at about 120C to about 140C. The spheres are of barium titinate glass with an index of refraction of 1.9 and are partially imbedded in the faces of the sheet. The sheet is then advanced in a softened condition over a roller which cont~ins a multiplicity of tetrahedron-shaped indentations in its ~ylindrical surface to urge material from the sheet into the indentations and thereby form a multiplicity of te~r~hedron-shaped granules containing glass spheres. The indentations are of equal size to simil~rly produce equal-~ize granules having a height of 4.5 millimeters. The proportion of spheres 126~
to the polypropylene resin is about 3 parts by weight of spheres to about 5 parts of resin.
The tetrahedron-shaped granules are transported to a highway and dropped onto a line of tacky traffic paint in the manner descr~bed above. Upon the hardening of the paint the granules remain in position and exhibit good reflectivity characteristics.
Exampla 4 In each of the foregoing examples a pigment of the same color as that used for the highway line is admixed with the resin material prior to the time the material is extruded.
The resulting granules have a corresponding color and provide a further improvement in the reflectivity of the line.
Exam~le 5 A thin coating of silver is applied to the glass spheres in the manner more fully described in British patent
2,115,396. The thus coated spheres are used to produce plastic granules in the manner set forth in Examples 1-4, and the granules are dropped from a random position onto the horizontally disposed painted surface of a highway sign while the paint is in a tacky condition. The granules remain in place on the sign for an extended period of time and provide an even further improvement in the overall reflectivity.
8~ L6 The terms and expressions which have been employed ~re used as terms of description and not of limitation, and there is no intention in the use of such terms and expressions of excluding any equivalents of the features shown and described ~r portions thereof, but it is recognized that various modifications are possible within the scope of the invention claimed.
8~ L6 The terms and expressions which have been employed ~re used as terms of description and not of limitation, and there is no intention in the use of such terms and expressions of excluding any equivalents of the features shown and described ~r portions thereof, but it is recognized that various modifications are possible within the scope of the invention claimed.
Claims (16)
1. A small reflective particle comprising a tetrahedron-shaped granule of plastic material, and a plurality of glass spheres substantially evenly dispersed throughout the granule with some of the spheres protruding through the outer surface thereof, the proportion of said spheres to the granule material being about 30 to 60 percent by weight.
2. A plurality of small reflective particles of the character set forth in claim 1, in which the particles are of two different sizes.
3. A small reflective particle comprising a tetrahedron-shaped granule of plastic material, and a plurality of glass spheres substantially evenly dispersed throughout the granule with some of the spheres protruding through the outer surface thereof, the glass spheres having a diameter in the range of from about 6.0 microns to about 0.125 inches, and the proportion of said spheres to the granule material being about 30 to 60 percent by weight.
4. A small reflective particle of the character set forth in claim 3, in which said particle is in the shape of an equilateral tetrahedron.
5. A plurality of small reflective particles of the character set forth in claim 3 for use on a roadway, in which the particles are of two different sizes such that the smaller size particles are subjected to less traffic abrasion on the roadway than the larger particles.
6. A small reflective particle for use on a roadway, the particle comprising a tetrahedron-shaped plastic granule having all flat faces, the height of the granule above said roadway being between about 2 millimeters and about 12 millimeters, and a plurality of glass spheres substantially evenly dispersed throughout the granule with some of the spheres protruding through the outer surface thereof, the glass spheres having a diameter in the range of from about 6.0 microns to about 0.125 inches, and the proportion of said spheres to the granule material being about 30 to 60 percent by weight.
7. A small reflective particle of the character set forth in claim 6, in which one of the flat faces of said granule meets said roadway at an angle of about 70 degrees.
8. A small reflective particle of the character set forth in claim 6, in which the granule is in the shape of an equilateral tetrahedron.
9. A plurality of small reflective particles of the character set forth in claim 6, in which a first group of said granules has an average height above said roadway of about 6.0 millimeters, and a second group of said granules has an average height above said roadway of about 4.5 millimeters.
10. A method of making small reflective particles, the method comprising:
forming a flat plastic sheet;
applying glass spheres to the flat surfaces of the sheet by spraying said spheres onto said surfaces to partially imbed the spheres therein, the glass spheres having a diameter in the range of from about 6.0 microns to about 0.125 inches;
advancing the sheet containing said spheres over a roller having a multiplicity of tetrahedron-shaped indentations in the cylindrical surface thereof, to urge material from said sheet into said indentations and thereby form a multiplicity of tetrahedron-shaped granules containing glass spheres sub-stantially evenly dispersed throughout each granule with some of the spheres protruding through the outer surface thereof, the proportion of said spheres to the granule material being about 30 to about 60 percent by weight; and removing the thus formed granules from said indentations and collecting the same.
forming a flat plastic sheet;
applying glass spheres to the flat surfaces of the sheet by spraying said spheres onto said surfaces to partially imbed the spheres therein, the glass spheres having a diameter in the range of from about 6.0 microns to about 0.125 inches;
advancing the sheet containing said spheres over a roller having a multiplicity of tetrahedron-shaped indentations in the cylindrical surface thereof, to urge material from said sheet into said indentations and thereby form a multiplicity of tetrahedron-shaped granules containing glass spheres sub-stantially evenly dispersed throughout each granule with some of the spheres protruding through the outer surface thereof, the proportion of said spheres to the granule material being about 30 to about 60 percent by weight; and removing the thus formed granules from said indentations and collecting the same.
11. A method of making small reflective particles, the method comprising:
mixing glass spheres and a plastic material, the glass spheres having a diameter in the range of from about 6.0 microns to about 0.125 inches;
forming a flat plastic sheet from said material, the sheet containing said glass spheres substantially evenly dispersed therein;
applying additional glass spheres to the flat surfaces of the sheet by spraying said additional spheres onto said surface to partially imbed the additional spheres therein;
advancing the sheet over a roller containing a multi-plicity of tetrahedron-shaped indentations in the cylindrical surface thereof, to urge material from said sheet into said indentations and thereby form a multiplicity of tetrahedron-shaped granules containing glass spheres substantially evenly dispersed throughout each granule with some of the spheres protruding through the outer surface thereof, the proportion of said spheres to the granule material being about 30 to 60 percent by weight; and removing the thus formed granules from said indentations and collecting the same.
mixing glass spheres and a plastic material, the glass spheres having a diameter in the range of from about 6.0 microns to about 0.125 inches;
forming a flat plastic sheet from said material, the sheet containing said glass spheres substantially evenly dispersed therein;
applying additional glass spheres to the flat surfaces of the sheet by spraying said additional spheres onto said surface to partially imbed the additional spheres therein;
advancing the sheet over a roller containing a multi-plicity of tetrahedron-shaped indentations in the cylindrical surface thereof, to urge material from said sheet into said indentations and thereby form a multiplicity of tetrahedron-shaped granules containing glass spheres substantially evenly dispersed throughout each granule with some of the spheres protruding through the outer surface thereof, the proportion of said spheres to the granule material being about 30 to 60 percent by weight; and removing the thus formed granules from said indentations and collecting the same.
12. A method of the character set forth in claim 11, which further comprises:
adding pigment to the plastic material prior to the formation of said sheet.
adding pigment to the plastic material prior to the formation of said sheet.
13. A method of making small reflective particles, the method comprising:
mixing glass spheres and a particulate thermoplastic material, the glass spheres having a diameter in the range of from about 6.0 microns to about 0.125 inches;
extruding the thermoplastic material to form a flat thermoplastic sheet containing glass spheres substantially evenly dispersed therein;
applying additional glass spheres to the flat surfaces of the thermoplastic sheet by spraying said additional spheres onto said surfaces to partially imbed the additional spheres therein;
advancing the thermoplastic sheet over a roller con-taining a multiplicity of tetrahedron-shaped indentations in the cylindrical surface thereof, to urge material from said sheet into said indentations and thereby form a multiplicity of tetrahedron-shaped thermoplastic granules containing glass spheres substantially evenly dispersed throughout each granule with some of the spheres protruding through the outer surface thereof, the proportion of said spheres to the granule material being about 30 to about 60 percent by weight; and removing the thus formed granules from said indentations and collecting the same.
mixing glass spheres and a particulate thermoplastic material, the glass spheres having a diameter in the range of from about 6.0 microns to about 0.125 inches;
extruding the thermoplastic material to form a flat thermoplastic sheet containing glass spheres substantially evenly dispersed therein;
applying additional glass spheres to the flat surfaces of the thermoplastic sheet by spraying said additional spheres onto said surfaces to partially imbed the additional spheres therein;
advancing the thermoplastic sheet over a roller con-taining a multiplicity of tetrahedron-shaped indentations in the cylindrical surface thereof, to urge material from said sheet into said indentations and thereby form a multiplicity of tetrahedron-shaped thermoplastic granules containing glass spheres substantially evenly dispersed throughout each granule with some of the spheres protruding through the outer surface thereof, the proportion of said spheres to the granule material being about 30 to about 60 percent by weight; and removing the thus formed granules from said indentations and collecting the same.
14. A method of making small reflective particles, the method comprising:
mixing glass spheres and a particulate thermoplastic material, the glass spheres having a diameter in the range of from about 6.0 microns to about 0.125 inches;
adding pigment to the thermoplastic material;
extruding the thermoplastic material to form a flat thermoplastic sheet containing glass spheres substantially evenly dispersed therein;
applying additional glass spheres to the flat surfaces of the thermoplastic sheet by spraying said additional spheres onto said surfaces to partially imbed the additional spheres therein;
advancing the thermoplastic sheet over a roller con-taining a multiplicity of tetrahedron-shaped indentations in the cylindrical surface thereof, to urge material from said sheet into said indentations and thereby form a multiplicity of tetrahedron-shaped thermoplastic granules containing glass spheres substantially evenly dispersed throughout each granule with some of the spheres protruding through the outer surface thereof, the proportion of said spheres to the granule material being about 30 to about 60 percent by weight; and removing the thus formed granules from said indentations and collecting the same.
mixing glass spheres and a particulate thermoplastic material, the glass spheres having a diameter in the range of from about 6.0 microns to about 0.125 inches;
adding pigment to the thermoplastic material;
extruding the thermoplastic material to form a flat thermoplastic sheet containing glass spheres substantially evenly dispersed therein;
applying additional glass spheres to the flat surfaces of the thermoplastic sheet by spraying said additional spheres onto said surfaces to partially imbed the additional spheres therein;
advancing the thermoplastic sheet over a roller con-taining a multiplicity of tetrahedron-shaped indentations in the cylindrical surface thereof, to urge material from said sheet into said indentations and thereby form a multiplicity of tetrahedron-shaped thermoplastic granules containing glass spheres substantially evenly dispersed throughout each granule with some of the spheres protruding through the outer surface thereof, the proportion of said spheres to the granule material being about 30 to about 60 percent by weight; and removing the thus formed granules from said indentations and collecting the same.
15. A method of the character set forth in claim 14, in which the indentations in the cylindrical surface of said roller are of two different sizes, to thereby form different size granules.
16. A method of making small reflective particles, the method comprising:
mixing glass spheres and a particulate thermoplastic material, the glass spheres having a diameter in the range of from About 6.0 microns to about 0.125 inches;
adding pigment to the thermoplastic material;
extruding the thermoplastic material under heat to form a softened flat thermoplastic sheet containing glass spheres substantially evenly dispersed therein;
applying additional glass spheres to the flat surfaces of the thermoplastic sheet by spraying said additional spheres onto said surfaces to partially imbed the additional spheres therein;
advancing the thermoplastic sheet is a softened condition over a roller containing a multiplicity of tetrahedron-shaped indentations in the cylindrical surface thereof, to urge material from said sheet into said indentations and thereby form a multiplicity of tetrahedron-shaped thermoplastic granules containing glass spheres substantially evenly dispersed throughout each granule with some of the spheres protruding through the outer surface thereof, the proportion of said spheres to the granule material being about 30 to about 60 percent by weight;
removing the thus formed granules from said indentations and collecting the same; and cleaning the cylindrical surface of said roller by scraping excess thermoplastic material therefrom.
mixing glass spheres and a particulate thermoplastic material, the glass spheres having a diameter in the range of from About 6.0 microns to about 0.125 inches;
adding pigment to the thermoplastic material;
extruding the thermoplastic material under heat to form a softened flat thermoplastic sheet containing glass spheres substantially evenly dispersed therein;
applying additional glass spheres to the flat surfaces of the thermoplastic sheet by spraying said additional spheres onto said surfaces to partially imbed the additional spheres therein;
advancing the thermoplastic sheet is a softened condition over a roller containing a multiplicity of tetrahedron-shaped indentations in the cylindrical surface thereof, to urge material from said sheet into said indentations and thereby form a multiplicity of tetrahedron-shaped thermoplastic granules containing glass spheres substantially evenly dispersed throughout each granule with some of the spheres protruding through the outer surface thereof, the proportion of said spheres to the granule material being about 30 to about 60 percent by weight;
removing the thus formed granules from said indentations and collecting the same; and cleaning the cylindrical surface of said roller by scraping excess thermoplastic material therefrom.
Applications Claiming Priority (2)
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US65394384A | 1984-09-21 | 1984-09-21 | |
US653,943 | 1984-09-21 |
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CA1268016C CA1268016C (en) | 1990-04-24 |
CA1268016A true CA1268016A (en) | 1990-04-24 |
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CA000483245A Expired CA1268016A (en) | 1984-09-21 | 1985-06-05 | Reflective particles and method of making the same |
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JP (1) | JPS6177803A (en) |
AU (1) | AU573898B2 (en) |
BR (1) | BR8503932A (en) |
CA (1) | CA1268016A (en) |
DE (1) | DE3524661A1 (en) |
FR (1) | FR2570726B1 (en) |
GB (1) | GB2164762B (en) |
MX (1) | MX170384B (en) |
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CA1307971C (en) * | 1988-06-09 | 1992-09-29 | Thomas Peter Hedblom | Patterned pavement marking |
NL8802472A (en) * | 1988-10-10 | 1990-05-01 | Homer Hollandse Meet En Regels | DOCUMENT INCLUDING RANDOM INFORMATION, CARRIER OF THIS RANDOM INFORMATION AND METHOD AND DEVICE FOR READING THIS RANDOM INFORMATION. |
DE4238168A1 (en) * | 1992-10-15 | 1994-04-21 | Gerhard Cammann | Light reflecting surfaces for road marking |
DE9205350U1 (en) * | 1992-04-17 | 1992-06-17 | Swarco Vestglas Vestische Strahl- und Reflexglas GmbH, 4350 Recklinghausen | Reflective bodies, especially for road markings |
DE19521847A1 (en) * | 1995-06-16 | 1996-12-19 | Gerhard Cammann | Light reflective agglomerates for road markings, reflective structural blocks etc. |
US5835271A (en) * | 1995-06-29 | 1998-11-10 | Minnesota Mining And Manufacturing Company | Encased retroreflective elements and method for making |
AUPO430296A0 (en) * | 1996-12-20 | 1997-01-23 | Rogers, Barry Heith | Marking composition |
SE9700064L (en) * | 1997-01-10 | 1998-07-11 | Qualisys Ab | Method and apparatus for the manufacture of a coated body |
JP2001500993A (en) * | 1997-07-16 | 2001-01-23 | ミネソタ マイニング アンド マニュファクチャリング カンパニー | Pavement marking with raised protrusions and method of manufacture |
DE19962953B4 (en) * | 1999-12-24 | 2006-01-26 | Bundesdruckerei Gmbh | Method for coding thermoplastic products |
GB0213727D0 (en) * | 2002-06-14 | 2002-07-24 | Prismo Ltd | Retroreflective device and method of manufacture thereof |
GB2402694B (en) | 2003-06-11 | 2006-03-15 | Prismo Ltd | Method and apparatus for manufacturing a retroflective device |
KR100586406B1 (en) * | 2004-06-11 | 2006-06-08 | 김현대 | Cube corner type retroreflective device manufacturing method and retroreflective device |
FR2885363B1 (en) * | 2005-05-04 | 2007-09-28 | Appia | REFLECTING MATERIAL FOR COVERING CIRCULATION PATHWAY |
ATE553164T1 (en) | 2007-02-23 | 2012-04-15 | Triflex Beschichtungssysteme Gmbh & Co Kommanditgesellschaft | PRIMER AND MARKING COMPOSITIONS |
US9207373B2 (en) | 2007-04-10 | 2015-12-08 | Stoncor Group, Inc. | Methods for fabrication and highway marking usage of agglomerated retroreflective beads |
US10308816B2 (en) | 2014-05-05 | 2019-06-04 | Potters Industries, Llc | Coatings for pelletized thermoplastic pavement marking compositions |
WO2016012101A1 (en) * | 2014-07-25 | 2016-01-28 | Heidelbergcement Ag | Structuring elements for road surfaces, use thereof and method for producing road surfaces |
CN108025958B (en) | 2015-09-11 | 2021-04-09 | 3M创新有限公司 | Durable retroreflective elements with bead blends |
AU2018225296A1 (en) * | 2017-02-23 | 2019-09-19 | Lam Nguyen | Improved coatings for pelletized thermoplastic pavement marking compositions |
Family Cites Families (19)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB688310A (en) * | 1950-09-02 | 1953-03-04 | R S Clare & Company Ltd | Improvements in or relating to road marking means and compositions |
FR1211669A (en) * | 1957-09-18 | 1960-03-17 | Minnesota Mining & Mfg | Granular material that reflects light, especially for road marking |
US3036928A (en) * | 1959-12-18 | 1962-05-29 | Cataphote Corp | Retroreflective composition and method of applying same |
US3171827A (en) * | 1960-10-31 | 1965-03-02 | Prismo Safety Corp | Reflective granules |
US3247158A (en) * | 1962-02-07 | 1966-04-19 | Standard Oil Co | Filled plastisol compositions |
US3252376A (en) * | 1962-02-16 | 1966-05-24 | Prismo Safety Corp | Reflex reflective granule and marking material made thereof |
US3254563A (en) * | 1963-11-12 | 1966-06-07 | Prismo Safety Corp | Retro-reflective particles and reflective markers and compositions containing such particles |
US3518221A (en) * | 1967-10-30 | 1970-06-30 | Monsanto Co | Reinforcing fillers in a matrix of two thermosetting resins |
FR1604009A (en) * | 1968-08-05 | 1971-06-28 | Reflective element, eg a road marker - stud | |
FR2082537A5 (en) * | 1970-03-19 | 1971-12-10 | Tech Tuiles Briques Centre | Tetrahedral ceramic granules - for use in road surfacing concrete etc |
FR2101024A1 (en) * | 1970-08-07 | 1972-03-31 | France Etat | PAVEMENT COATING, ITS MANUFACTURING AND IMPLEMENTATION PROCESS |
IT1001490B (en) * | 1972-05-24 | 1976-04-20 | Eigenmann Ludwig | IMPROVEMENT TO HORIZONTAL ROAD SIGN MATERIALS AND RELATED HIGH VISIBILITY IMPROVED MATERIALS ADHESION AND RESISTANCE TO WEAR |
US3859407A (en) * | 1972-05-15 | 1975-01-07 | Corning Glass Works | Method of manufacturing particles of uniform size and shape |
FR2194192A5 (en) * | 1972-07-27 | 1974-02-22 | Loing Verreries | |
US3867178A (en) * | 1972-09-05 | 1975-02-18 | Potters Industries Inc | Method for coating discrete particles |
JPS5131735A (en) * | 1974-09-13 | 1976-03-18 | Ookee Kasei Kk | |
GB1531480A (en) * | 1974-12-20 | 1978-11-08 | Bagshaw R | Retroreflective elements |
DE2632107C2 (en) * | 1975-07-16 | 1986-01-09 | Ludwig Dr. Vacallo Tessin Eigenmann | Reflective unit for marking material for horizontal road marking |
US4388359A (en) * | 1982-04-23 | 1983-06-14 | Minnesota Mining And Manufacturing Company | Embossed pavement-marking sheet material |
-
1985
- 1985-06-05 CA CA000483245A patent/CA1268016A/en not_active Expired
- 1985-06-19 GB GB08515548A patent/GB2164762B/en not_active Expired
- 1985-06-26 JP JP60138045A patent/JPS6177803A/en active Pending
- 1985-07-04 MX MX205892A patent/MX170384B/en unknown
- 1985-07-10 DE DE19853524661 patent/DE3524661A1/en active Granted
- 1985-08-19 BR BR8503932A patent/BR8503932A/en not_active IP Right Cessation
- 1985-09-18 AU AU47565/85A patent/AU573898B2/en not_active Expired
- 1985-09-19 FR FR8514159A patent/FR2570726B1/en not_active Expired
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FR2570726B1 (en) | 1987-08-21 |
CA1268016C (en) | 1990-04-24 |
MX170384B (en) | 1993-08-18 |
AU4756585A (en) | 1986-03-27 |
JPS6177803A (en) | 1986-04-21 |
AU573898B2 (en) | 1988-06-23 |
FR2570726A1 (en) | 1986-03-28 |
BR8503932A (en) | 1986-05-27 |
DE3524661A1 (en) | 1986-04-03 |
GB2164762A (en) | 1986-03-26 |
GB2164762B (en) | 1988-05-18 |
GB8515548D0 (en) | 1985-07-24 |
DE3524661C2 (en) | 1989-07-20 |
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