CA2079591A1 - Phosphorescent marking material - Google Patents
Phosphorescent marking materialInfo
- Publication number
- CA2079591A1 CA2079591A1 CA002079591A CA2079591A CA2079591A1 CA 2079591 A1 CA2079591 A1 CA 2079591A1 CA 002079591 A CA002079591 A CA 002079591A CA 2079591 A CA2079591 A CA 2079591A CA 2079591 A1 CA2079591 A1 CA 2079591A1
- Authority
- CA
- Canada
- Prior art keywords
- phosphorescent
- particles
- filler
- wax
- mixture
- 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.)
- Abandoned
Links
- 239000000463 material Substances 0.000 title claims abstract description 27
- 239000000203 mixture Substances 0.000 claims abstract description 64
- 239000002245 particle Substances 0.000 claims abstract description 50
- 239000000945 filler Substances 0.000 claims abstract description 33
- 239000000049 pigment Substances 0.000 claims abstract description 19
- 239000003550 marker Substances 0.000 claims abstract description 17
- 231100000252 nontoxic Toxicity 0.000 claims abstract description 11
- 230000003000 nontoxic effect Effects 0.000 claims abstract description 11
- 239000001993 wax Substances 0.000 claims description 37
- 238000000034 method Methods 0.000 claims description 12
- 239000000084 colloidal system Substances 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 3
- 238000003801 milling Methods 0.000 claims description 3
- 230000005855 radiation Effects 0.000 claims description 3
- 238000001125 extrusion Methods 0.000 claims description 2
- 238000000465 moulding Methods 0.000 claims description 2
- 238000002844 melting Methods 0.000 claims 2
- 230000008018 melting Effects 0.000 claims 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000000725 suspension Substances 0.000 claims 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 5
- 238000001816 cooling Methods 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 239000000454 talc Substances 0.000 description 3
- 229910052623 talc Inorganic materials 0.000 description 3
- BXWNKGSJHAJOGX-UHFFFAOYSA-N hexadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCO BXWNKGSJHAJOGX-UHFFFAOYSA-N 0.000 description 2
- 239000004200 microcrystalline wax Substances 0.000 description 2
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- AGVJBLHVMNHENQ-UHFFFAOYSA-N Calcium sulfide Chemical compound [S-2].[Ca+2] AGVJBLHVMNHENQ-UHFFFAOYSA-N 0.000 description 1
- 229920003345 Elvax® Polymers 0.000 description 1
- UOACKFBJUYNSLK-XRKIENNPSA-N Estradiol Cypionate Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H](C4=CC=C(O)C=C4CC3)CC[C@@]21C)C(=O)CCC1CCCC1 UOACKFBJUYNSLK-XRKIENNPSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 101150050192 PIGM gene Proteins 0.000 description 1
- 235000004443 Ricinus communis Nutrition 0.000 description 1
- 240000000528 Ricinus communis Species 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000000211 autoradiogram Methods 0.000 description 1
- 235000013871 bee wax Nutrition 0.000 description 1
- 239000012166 beeswax Substances 0.000 description 1
- 229940092738 beeswax Drugs 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 239000004203 carnauba wax Substances 0.000 description 1
- 235000013869 carnauba wax Nutrition 0.000 description 1
- 229960000541 cetyl alcohol Drugs 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- GOQYKNQRPGWPLP-UHFFFAOYSA-N n-heptadecyl alcohol Natural products CCCCCCCCCCCCCCCCCO GOQYKNQRPGWPLP-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/50—Sympathetic, colour changing or similar inks
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B43—WRITING OR DRAWING IMPLEMENTS; BUREAU ACCESSORIES
- B43K—IMPLEMENTS FOR WRITING OR DRAWING
- B43K19/00—Non-propelling pencils; Styles; Crayons; Chalks
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/02—Use of particular materials as binders, particle coatings or suspension media therefor
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/02—Use of particular materials as binders, particle coatings or suspension media therefor
- C09K11/025—Use of particular materials as binders, particle coatings or suspension media therefor non-luminescent particle coatings or suspension media
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Inorganic Chemistry (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
- Luminescent Compositions (AREA)
- Materials For Medical Uses (AREA)
Abstract
A non-toxic moldable phosphorescent marker (10) has phosphorescent pigment particles (18) that are suspended in a milled mixture (12) of an inert filler (16) and a wax blend base (14). The phosphorescent pigment particles, which impart luminescent properties to the marker, are excited by light. The composition of the marker is such that it leaves a strip of phosphorescent marking material on a surface against which the marker is rubbed. The deposited material contains the suspended phosphorescent particles, which luminesces when excited by light.
Description
W091/15553 PCr/US')1/02197 3~, Title: PHOSP~ORESCENT MARXING MATERIA~
B~C~G~OUNP OF THE IMV~NTIO~
l. Field o~ inven~ion:
The present invention relates to phosphorescent or photoluminescent materials and, more particularly, is directed to a non-toxic phosphorescent marking material and a method of marking same.
B~C~G~OUNP OF THE IMV~NTIO~
l. Field o~ inven~ion:
The present invention relates to phosphorescent or photoluminescent materials and, more particularly, is directed to a non-toxic phosphorescent marking material and a method of marking same.
2. Description o~ the Prior Art:
It has long been rscogniz~d that the appeal of certain toys c~n be enhanced by imparting phosphorescent properties to the various elements thereof. Crayons have bPcome a standard teaching tool ~or children because they allow children to express themselves artistically. Crayons are clean, safe and easy to use. A need ~Xi6t8 for a pho~phorescent marker which is ~a~e for children.
Heretofore it has been po~sible to impart phosphorescent properties to paint and chalk due to their thick ~iscosity. For example, phosphorescent pi~ments can be mixed in paint. U.S. Patent No.
2,396,219 discloses a phosphorescent chalk writing material which i8 toxic and unsa~e ~or uso by children.
In addition, chalk makes dust which is not optimal ~or a p~rmanent clean marking material. The usa Or a phosphore~cent material ~uch as calcium sulphide pho~phor in a crayon i~ not acceptable because calcium ,, , WO91/1~553 PC'r/US~)I/0~!9~
95~
sulphide phosphor i~ toxic and it wlll ~Qttls out. ~he use of non-toxic phosphorQscent pigments in a wax bac~e marking ~aterial ha~ been met with limited success because of the lack of a suitable ~uspension formula and an acceptable ~uspension process. Currently available phosphorescent pigment particles that are encapsulated in glass ~rit are heavy and aannot be ef~ectively made into a phosphore~cent crayon by conventional methods because the particlec; ~ettle out of the formula and/or are not distributed throughout the crayon. Autoradiogram marking pens, ~uch as ~he phosphorescent ink marking pen disclosed in U.S. Patent No. 4,510,392, are sufficient for exposing film, but they have very low luminous properties for visual effects.
While non-toxic phosphore~;cent material is available, the pigm nt is generally unsuitable for use in wax base marking materials because of the pro~lems and dif~iculties in suspending the phosphorescent matexial in the base mixture. U.S. Patent No.
It has long been rscogniz~d that the appeal of certain toys c~n be enhanced by imparting phosphorescent properties to the various elements thereof. Crayons have bPcome a standard teaching tool ~or children because they allow children to express themselves artistically. Crayons are clean, safe and easy to use. A need ~Xi6t8 for a pho~phorescent marker which is ~a~e for children.
Heretofore it has been po~sible to impart phosphorescent properties to paint and chalk due to their thick ~iscosity. For example, phosphorescent pi~ments can be mixed in paint. U.S. Patent No.
2,396,219 discloses a phosphorescent chalk writing material which i8 toxic and unsa~e ~or uso by children.
In addition, chalk makes dust which is not optimal ~or a p~rmanent clean marking material. The usa Or a phosphore~cent material ~uch as calcium sulphide pho~phor in a crayon i~ not acceptable because calcium ,, , WO91/1~553 PC'r/US~)I/0~!9~
95~
sulphide phosphor i~ toxic and it wlll ~Qttls out. ~he use of non-toxic phosphorQscent pigments in a wax bac~e marking ~aterial ha~ been met with limited success because of the lack of a suitable ~uspension formula and an acceptable ~uspension process. Currently available phosphorescent pigment particles that are encapsulated in glass ~rit are heavy and aannot be ef~ectively made into a phosphore~cent crayon by conventional methods because the particlec; ~ettle out of the formula and/or are not distributed throughout the crayon. Autoradiogram marking pens, ~uch as ~he phosphorescent ink marking pen disclosed in U.S. Patent No. 4,510,392, are sufficient for exposing film, but they have very low luminous properties for visual effects.
While non-toxic phosphore~;cent material is available, the pigm nt is generally unsuitable for use in wax base marking materials because of the pro~lems and dif~iculties in suspending the phosphorescent matexial in the base mixture. U.S. Patent No.
3,392,123 discloaes an oxygen activated, wax based, chemlluscent marking material~ The marking material is limited in use because it can be activated only once and the tetrakis (demethylamino) ethylene contained therein ~ 8 rorrosive. A need exlsts ~or a non-toxic wax base marking materlal containing suspended phosphorescent particle~ which can be molded or extruded.
,. , . ,,: . . - , , .. ... . . ... .. .
WO91/15553 PCT/US~ 197 .
~L_ i It i~ an ob~ect o~ the pre~ent inv~ntlon to provide a non-toxic pho~phorescent marXer which does not ~uffer from the disadvantages ~nd limitations o~ existing phosphorescent marker~.
Another objec~ o~ the pre3ent lnvention i~ to provide ~n e~ective phosphore6cant wax base m~rkiny material which can be utllized ~or a varlety o~
applications including u~e as glow in the dark crayons for children.
A further object of the present inventisn is to provide a non-toxic phosphore~cent pigment marker which is composed o~ a wax base and inert filler mixture, the filler being at least partially transparent to actinic radiation. Phosphorescent pi~ent particles are suspended in the wax bafie and l'iller mixture. The weight of phosphorescent part~cles i8 i~ the range of 10% to 50% of the total weight of the marXin~ material.
The composition o~ the marking material is such that a ;~ strip o~ the ~arking materlal L~ rubbed o~ or depo ited on a surface when the marker is rubbed against the surface. The depo3ited material contains the ~u~pended phosphorescent particle~ which lu~inesce when ~xcited by light.
Yet another objoct o~ tha present lnvention is to provide a method ~or ma~ing a non-toxic wax ba~e phosphore6cant ~arker. The process comprises the steps " o~ ~ixlng a plurallty o~ pho~phorescent particle~ with a w~x ba~e having an inert ~ r ~lxed therewith. The wax bAse ~nd ~iller mixture are at lea~t partlally I
' '" ' WO91/1~553 PC'r/US~l/021')7 -r., Q.~.
tran~parent to actinic radiatlon. The wax base and filler ~ixture iB such that it i~ capable o~ keeplng pho~phorescent particle~ suspended therein, the particle 6izes being in the range o~ 5 to 20 microns.
The invention accordingly comprises the ~ethod and apparatus, and together with their steps, parts, elements and interrelationships that are exempli~ied in ~he ~ollowing di~closure, the scope o~ which will be indicated in the appended claims.
B~IEF DESCRIPTION OF THE DRAWINGS
A fuller understanding of the nature and objects of the present invention will become apparent upon consideration o~ the following detailed description taken in connection with the accompanying drawing, wherein the drawing i~ a perspe!ctive YieW of a crayon embodying the invention.
~E~AI~ED DES~RIPTION QE ~H~_PREFERRED E~O~MEN~S
Referring now to the drawing, there is ~hown a marking ~aterial lO in the ~or~ o~ a crayon. Crayon l0 i5 composed of a carrier 12, which includes a ba~e 14 and ~iller particles 16, and a plurality o~
phosphorescent pigment par~lcles ~8 are suspend~d in ~he carri2r.. ~-. . . Ba#e.l4.is composed o~ a ~ateriaI which is .. .-~uitable ~or molding or extrusion.. In:the pre~erred bodlm~nt, ba~e l4 i~ a wax ba~e vehicle, ~or example ~i~ro-c~y~t~lllne wax or bees wax, or a soap base or a ... ..... .... . .. ..... . .. . . . . . .
WO91/15553 PCr/US~ 21~7 . .
blend thareo~. In an alternatlve embodiment, base 1 is composed o~ a plastic that is co~patlble with the other components, ~or example, a pla~tlc ~uch a~ a low density plastic. Non-toxic petrolatu~, such a3 petrol~um ~elly or mlneral oil, is added to base 1~ to form a base mixture that has a somewhat grua~y conrlguration. Staaric acid or cetyl alcohol or stearyl alcohol or hydrogenated castor bean oil ls added to the base mixture to impart a crumbly e~ect.
A wax, for example, Fi~cher Traupe wax or paraflint or carnauba wax, is added to the base mixture for the purpose of imparting hardness to the base mixture. In an alternative embodiment, a low density plastic, for example a polythylene such a that sold under the trade name AC6, iB added to the base ~ixture to impart hardn~s and strength. Also, it ha6 been found that a vinyl resin, such as that ~old under the trade name ELVAX, imparts hardness and 6trength to the base mixture. The base wax mixture is then heated and melt~d to ~orm a ~inal base mixture or base 14, the mixture being heated to a temperature in the range of 160F to 250F, pre~erably 175F to 200 F. It is prePerred that the mixture is remained at a temperature in the range of 170F to 200F during processing.
Filler particles 16 are added to th~ melted base mixture 14. The ~iller particles 16 which are composed o~ an inert ~iller material such a~ ma~ne~ium silicate or powdered talc, having particle ~izes in the range o~
8-lO microns, are tran~parent or partiaily transparent to actinlc radiatlon. In addltion, ~iller particles 16 h~v~ a low d~nsity 80 that th~y remaln ~uspended in the ,. ", , ,, , ", ,, - ,, , , WO91/15553 PCr/U59l/021t)~
2 ~ 6-ba~e mixture 14. The quantlty o~ ~iller particles 16 by percent o~ total weight i~ in the range o~ 10% to 30% and preferably, 13% to 20%. The ~iller particles 16 are dispersed uniformly in the base material by mixing or milling or whipping. Preferably, the base/~iller mixture is milled using, rOr example, a Tr~-~omo colloid mill which is operating at 3700 rpm.
The basetfi.ller mixture exhibits anti-settl.ing properties ~or the phosphorescent pi~ment E~artic1es 18 so that the phosphorescent particles remain suspended in the base/filler mixture and do not settle to the bottom of the base/filler mixture.
Next, phosphorescent pigment particles 18, for example, a non-toxic pigment having particle:sizes in the range of 5-20 microns, are added and stirred or whipped into the base/filler mi.xture until the particles are evenly disbursed therein. In one ~embodiment, the base/~iller/pic~ent particle mixture was whipped at appxoximately 1000 rpm ~or 2-~ minutes using a standard Lightning mixq~r that was equlpped with a shear blade. The quantity ol' phosphorescent pigment particles by percent o~ total weight iB in the range o~
20~ to 50% and, pre~erably, ~n the range o~ 25~ to 35~.
The resulting mixture is suited to be molded or extruded without settling over a temperature ran~e of 170to 275 F.
; In a speci~ic embodiment Or the invention, approximately twelve phosphorescent crayons were made i by ~irst combining or mixing 20 grams-o~ pararrin wax, 15 grama Or Mobil 2305 micro wax, 7.5 gram~ Or p~trol~um ~elly, 5 gram~ o~ stearic ~cid and 2.5 grams ' ' ' ' '' - , . . . ...
~' ' , : , WO 91/lS553 PCr/U$'31/r)2197 _7_ 26~ 3"~;;n,~, of Fisher Traupe wax. Then, th~ mlxture l~ heated to a temperature in the ~ange of 195~F to 200F to ~orm a melted base mixture. Once heated, the mixture is ~aintain~d at a temperature ln the approxima~e range of 170F to 200F until it i6 ~inally cooled. Next, 15 grams o~ No. 1250 micro talc i~ added to the ba3e mixture and milled usiny a colloid mill to ~orm a base/filler mixture. Next, 25 grams of phosphorous pigment, such as Hanovia Brand Pl000, i~ added to the base/filler mixture and whipped at approximately l000 rpm for 2-3 minutes to ~orm a final marki~g mixture.
The final marking mixture is poured into a mold and cooled. It is pre~erred that the poured mixture and/or mold is actively cooled. After cooling, the crayon is removed from the mold. The cr.ayon marked well on a variety of surfaces. The phosphorescent pigment particles impart luminescent properties to the crayon and luminesce when excited by light. In one test, the marking material was rubbed onto a ~ur~ace. The strip left on the sur~ace luminesced brightly ~or ~our to ten seconds and continued to lumines~e ~or approximately six hours. It is to be understood that, in another embodiment, the crayons are extruded rather than molded.
In another embodiment o~ the invention, a base ~ixture composed o~ a mixture o~ 20 grams o~ para~in wax, 15 gram~ o~ Mobil 2305 micro wax, 9.5 grams of petroleum ~elly, 5 gram~ o~ stear~c acid and 2.5 grams o~ Fisher ~raupe w~x ls heated to a temperature in the range o~ 195 F to 200 F until the mixture ls melted.
once heated, tha l~lxture 1~ ~aintained at a tamperature WO91/15553 Pcr/ust)l/
in the approximate range o~ 170F to 200F untll ~inal cooling. Next, 15 grams o~ No. 1250 mlcro talc i~
added to the melted mixture and milled using a colloid mill to ~orm a base/filler ~ixture. Next, 35 grams of phosphorescent pigment particles tP1000~ is added to the base/filler mixture and the r~ulting mixture is whipped 3t at approximately 1000 rpm ~or 2-3 minutes to form a ~inal marking mixture. Next, the final marking mixture is poured into a mold haviny a desired shape, for example the shape of a crayon. The poured mixture and/or mold is passively or actively coolecl. Finally, after cooling, the ~inished crayon 10 is remov~d ~rom the mold. Alternately, the res;ulting whipped mixture is ~ed to an extruder and extruded into a desired shape.
Since certain changes may be made in the foregoing disclosure without departing ~rom the scope of the invention herein involved, it is intended that - all matter contained ln the above descrlption and depicted in the accompanying dx-awings b~ construsd in an illustrative and not in a li.miting sense.
', .
,
,. , . ,,: . . - , , .. ... . . ... .. .
WO91/15553 PCT/US~ 197 .
~L_ i It i~ an ob~ect o~ the pre~ent inv~ntlon to provide a non-toxic pho~phorescent marXer which does not ~uffer from the disadvantages ~nd limitations o~ existing phosphorescent marker~.
Another objec~ o~ the pre3ent lnvention i~ to provide ~n e~ective phosphore6cant wax base m~rkiny material which can be utllized ~or a varlety o~
applications including u~e as glow in the dark crayons for children.
A further object of the present inventisn is to provide a non-toxic phosphore~cent pigment marker which is composed o~ a wax base and inert filler mixture, the filler being at least partially transparent to actinic radiation. Phosphorescent pi~ent particles are suspended in the wax bafie and l'iller mixture. The weight of phosphorescent part~cles i8 i~ the range of 10% to 50% of the total weight of the marXin~ material.
The composition o~ the marking material is such that a ;~ strip o~ the ~arking materlal L~ rubbed o~ or depo ited on a surface when the marker is rubbed against the surface. The depo3ited material contains the ~u~pended phosphorescent particle~ which lu~inesce when ~xcited by light.
Yet another objoct o~ tha present lnvention is to provide a method ~or ma~ing a non-toxic wax ba~e phosphore6cant ~arker. The process comprises the steps " o~ ~ixlng a plurallty o~ pho~phorescent particle~ with a w~x ba~e having an inert ~ r ~lxed therewith. The wax bAse ~nd ~iller mixture are at lea~t partlally I
' '" ' WO91/1~553 PC'r/US~l/021')7 -r., Q.~.
tran~parent to actinic radiatlon. The wax base and filler ~ixture iB such that it i~ capable o~ keeplng pho~phorescent particle~ suspended therein, the particle 6izes being in the range o~ 5 to 20 microns.
The invention accordingly comprises the ~ethod and apparatus, and together with their steps, parts, elements and interrelationships that are exempli~ied in ~he ~ollowing di~closure, the scope o~ which will be indicated in the appended claims.
B~IEF DESCRIPTION OF THE DRAWINGS
A fuller understanding of the nature and objects of the present invention will become apparent upon consideration o~ the following detailed description taken in connection with the accompanying drawing, wherein the drawing i~ a perspe!ctive YieW of a crayon embodying the invention.
~E~AI~ED DES~RIPTION QE ~H~_PREFERRED E~O~MEN~S
Referring now to the drawing, there is ~hown a marking ~aterial lO in the ~or~ o~ a crayon. Crayon l0 i5 composed of a carrier 12, which includes a ba~e 14 and ~iller particles 16, and a plurality o~
phosphorescent pigment par~lcles ~8 are suspend~d in ~he carri2r.. ~-. . . Ba#e.l4.is composed o~ a ~ateriaI which is .. .-~uitable ~or molding or extrusion.. In:the pre~erred bodlm~nt, ba~e l4 i~ a wax ba~e vehicle, ~or example ~i~ro-c~y~t~lllne wax or bees wax, or a soap base or a ... ..... .... . .. ..... . .. . . . . . .
WO91/15553 PCr/US~ 21~7 . .
blend thareo~. In an alternatlve embodiment, base 1 is composed o~ a plastic that is co~patlble with the other components, ~or example, a pla~tlc ~uch a~ a low density plastic. Non-toxic petrolatu~, such a3 petrol~um ~elly or mlneral oil, is added to base 1~ to form a base mixture that has a somewhat grua~y conrlguration. Staaric acid or cetyl alcohol or stearyl alcohol or hydrogenated castor bean oil ls added to the base mixture to impart a crumbly e~ect.
A wax, for example, Fi~cher Traupe wax or paraflint or carnauba wax, is added to the base mixture for the purpose of imparting hardness to the base mixture. In an alternative embodiment, a low density plastic, for example a polythylene such a that sold under the trade name AC6, iB added to the base ~ixture to impart hardn~s and strength. Also, it ha6 been found that a vinyl resin, such as that ~old under the trade name ELVAX, imparts hardness and 6trength to the base mixture. The base wax mixture is then heated and melt~d to ~orm a ~inal base mixture or base 14, the mixture being heated to a temperature in the range of 160F to 250F, pre~erably 175F to 200 F. It is prePerred that the mixture is remained at a temperature in the range of 170F to 200F during processing.
Filler particles 16 are added to th~ melted base mixture 14. The ~iller particles 16 which are composed o~ an inert ~iller material such a~ ma~ne~ium silicate or powdered talc, having particle ~izes in the range o~
8-lO microns, are tran~parent or partiaily transparent to actinlc radiatlon. In addltion, ~iller particles 16 h~v~ a low d~nsity 80 that th~y remaln ~uspended in the ,. ", , ,, , ", ,, - ,, , , WO91/15553 PCr/U59l/021t)~
2 ~ 6-ba~e mixture 14. The quantlty o~ ~iller particles 16 by percent o~ total weight i~ in the range o~ 10% to 30% and preferably, 13% to 20%. The ~iller particles 16 are dispersed uniformly in the base material by mixing or milling or whipping. Preferably, the base/~iller mixture is milled using, rOr example, a Tr~-~omo colloid mill which is operating at 3700 rpm.
The basetfi.ller mixture exhibits anti-settl.ing properties ~or the phosphorescent pi~ment E~artic1es 18 so that the phosphorescent particles remain suspended in the base/filler mixture and do not settle to the bottom of the base/filler mixture.
Next, phosphorescent pigment particles 18, for example, a non-toxic pigment having particle:sizes in the range of 5-20 microns, are added and stirred or whipped into the base/filler mi.xture until the particles are evenly disbursed therein. In one ~embodiment, the base/~iller/pic~ent particle mixture was whipped at appxoximately 1000 rpm ~or 2-~ minutes using a standard Lightning mixq~r that was equlpped with a shear blade. The quantity ol' phosphorescent pigment particles by percent o~ total weight iB in the range o~
20~ to 50% and, pre~erably, ~n the range o~ 25~ to 35~.
The resulting mixture is suited to be molded or extruded without settling over a temperature ran~e of 170to 275 F.
; In a speci~ic embodiment Or the invention, approximately twelve phosphorescent crayons were made i by ~irst combining or mixing 20 grams-o~ pararrin wax, 15 grama Or Mobil 2305 micro wax, 7.5 gram~ Or p~trol~um ~elly, 5 gram~ o~ stearic ~cid and 2.5 grams ' ' ' ' '' - , . . . ...
~' ' , : , WO 91/lS553 PCr/U$'31/r)2197 _7_ 26~ 3"~;;n,~, of Fisher Traupe wax. Then, th~ mlxture l~ heated to a temperature in the ~ange of 195~F to 200F to ~orm a melted base mixture. Once heated, the mixture is ~aintain~d at a temperature ln the approxima~e range of 170F to 200F until it i6 ~inally cooled. Next, 15 grams o~ No. 1250 micro talc i~ added to the ba3e mixture and milled usiny a colloid mill to ~orm a base/filler mixture. Next, 25 grams of phosphorous pigment, such as Hanovia Brand Pl000, i~ added to the base/filler mixture and whipped at approximately l000 rpm for 2-3 minutes to ~orm a final marki~g mixture.
The final marking mixture is poured into a mold and cooled. It is pre~erred that the poured mixture and/or mold is actively cooled. After cooling, the crayon is removed from the mold. The cr.ayon marked well on a variety of surfaces. The phosphorescent pigment particles impart luminescent properties to the crayon and luminesce when excited by light. In one test, the marking material was rubbed onto a ~ur~ace. The strip left on the sur~ace luminesced brightly ~or ~our to ten seconds and continued to lumines~e ~or approximately six hours. It is to be understood that, in another embodiment, the crayons are extruded rather than molded.
In another embodiment o~ the invention, a base ~ixture composed o~ a mixture o~ 20 grams o~ para~in wax, 15 gram~ o~ Mobil 2305 micro wax, 9.5 grams of petroleum ~elly, 5 gram~ o~ stear~c acid and 2.5 grams o~ Fisher ~raupe w~x ls heated to a temperature in the range o~ 195 F to 200 F until the mixture ls melted.
once heated, tha l~lxture 1~ ~aintained at a tamperature WO91/15553 Pcr/ust)l/
in the approximate range o~ 170F to 200F untll ~inal cooling. Next, 15 grams o~ No. 1250 mlcro talc i~
added to the melted mixture and milled using a colloid mill to ~orm a base/filler ~ixture. Next, 35 grams of phosphorescent pigment particles tP1000~ is added to the base/filler mixture and the r~ulting mixture is whipped 3t at approximately 1000 rpm ~or 2-3 minutes to form a ~inal marking mixture. Next, the final marking mixture is poured into a mold haviny a desired shape, for example the shape of a crayon. The poured mixture and/or mold is passively or actively coolecl. Finally, after cooling, the ~inished crayon 10 is remov~d ~rom the mold. Alternately, the res;ulting whipped mixture is ~ed to an extruder and extruded into a desired shape.
Since certain changes may be made in the foregoing disclosure without departing ~rom the scope of the invention herein involved, it is intended that - all matter contained ln the above descrlption and depicted in the accompanying dx-awings b~ construsd in an illustrative and not in a li.miting sense.
', .
,
Claims (18)
1. A phosphorescent marking material composed of a wax base vehicle filler particles and phosphorescent particles, said phosphorescent particles suspended in a mixture of said wax based vehicle and said filler particles, said filler particles being at least partially transparent to actinic radiation.
2. The marking material as claimed in claim 1 wherein said phosphorescent particles are in the size range of 5-20 microns.
3. The marking material as claimed in claim 1 wherein said phosphorescent particles by percent of total weight is in the range of 20% to 50%.
4. A method of suspending pigment particles in a wax medium to allow molding and extrusion, said method comprising the steps of:
(a) preparing a blend of waxes;
(b) melting said wax blend;
(c) mixing an inert filler material with said wax blend to form a wax/filler mixture;
(d) milling said wax/filler mixture to form a uniform non-settling suspension;
(e) mixing pigment particles into said milled wax/filler mixture to form a final blend;
and (f) whipping said final blend.
(a) preparing a blend of waxes;
(b) melting said wax blend;
(c) mixing an inert filler material with said wax blend to form a wax/filler mixture;
(d) milling said wax/filler mixture to form a uniform non-settling suspension;
(e) mixing pigment particles into said milled wax/filler mixture to form a final blend;
and (f) whipping said final blend.
5. The method as claimed in claim 4 wherein said wax/filler mixture is milled in a colloid mill.
6. The method as claimed in claim 4 wherein the percent by total weight of said inert filler material is in the range of 10% to 30%.
7. The phosphorescent marker as claimed in claim 12 wherein the quantity of said inert filler by total weight is in the range of 13% to 20%.
8. The method as claimed in claim 6 wherein said inert filler material is inert filler particles having a particle size in the range of 8 to 10 microns.
9. The method as claimed in claim 4 wherein said inert material is at least partially transparent to actinic radiation.
10. The method as claimed in claim 4 wherein the percent by total weight of said phosphorescent particles is in the range of 20% to 50%.
11. The method as claimed in claim 10 wherein said phosphorescent particles have particle sizes in the range of 5-20 microns.
12. The phosphorescent marker as claimed in claim 11 wherein the quantity of said phosphorescent particles by total weight is in the range of 25% to 35%.
13. A method of making a phosphorescent marker having a wax blend base comprising the steps of:
(a) melting a wax blend;
(b) adding a filler material to the melted wax blend;
(c) milling the filler and melted wax blend;
(d) adding phosphorescent pigment particles to the milled filler and melted wax blend;
(e) whipping the phosphorescent pigment particles and milled filler and melted wax blend; and (f) forming the whipped phosphorescent pigment particles and milled filler and melted wax blend into a desired shape.
(a) melting a wax blend;
(b) adding a filler material to the melted wax blend;
(c) milling the filler and melted wax blend;
(d) adding phosphorescent pigment particles to the milled filler and melted wax blend;
(e) whipping the phosphorescent pigment particles and milled filler and melted wax blend; and (f) forming the whipped phosphorescent pigment particles and milled filler and melted wax blend into a desired shape.
14. A non-toxic phosphorescent marker composed of a whipped mixture of a milled filler and wax base blend, and phosphorescent particles, said phosphorescent particles being suspended in said whipped mixture.
15. The phosphorescent marker as claimed in claim 14 wherein the percent by total weight of said phosphorescent particles is in the range of 20% to 50%.
16. The phosphorescent marker as claimed in claim 15 wherein said filler and wax blend includes an inert filler having particles in the size range of 8 to 10 microns.
17. The phosphorescent marker as claimed in claim 16 wherein said inert filler is at least partially transparent to actinic acid.
18. The phosphorescent marker as claimed in claim 14 wherein said phosphorescent particles are phosphorescent pigment particles which impart luminescent properties to the phosphorescent marker, said phosphorescent pigment particles luminescing when excited by light.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US50488490A | 1990-04-05 | 1990-04-05 | |
| US504,884 | 1990-04-05 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2079591A1 true CA2079591A1 (en) | 1991-10-06 |
Family
ID=24008123
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002079591A Abandoned CA2079591A1 (en) | 1990-04-05 | 1991-03-29 | Phosphorescent marking material |
Country Status (5)
| Country | Link |
|---|---|
| EP (1) | EP0523177A4 (en) |
| JP (1) | JPH06500131A (en) |
| AU (1) | AU642837B2 (en) |
| CA (1) | CA2079591A1 (en) |
| WO (1) | WO1991015553A1 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5529615A (en) * | 1994-06-15 | 1996-06-25 | Playstation Inc. | Marking material and method for suspending pigment particles |
| NZ522758A (en) * | 2000-04-26 | 2004-09-24 | Dennis James O Connell | Luminescent marking of piece to be cut or welded |
| RU2493192C1 (en) * | 2012-09-07 | 2013-09-20 | Федеральное Государственное Унитарное Предприятие "Гознак" (Фгуп "Гознак") | Marking composition based on inorganic luminophors, method of metal products marking and metal product |
Family Cites Families (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE7830645U1 (en) * | 1979-12-20 | Schwan-Stabilo Schwanhaeusser Gmbh & Co, 8500 Nuernberg | Pen with a wax-based lead | |
| US966251A (en) * | 1909-09-04 | 1910-08-02 | Francis Cook Simson | Illuminating composition. |
| FR411058A (en) * | 1909-12-29 | 1910-06-07 | Frank Cook Simson | Bright composition in the dark |
| US2380126A (en) * | 1941-09-11 | 1945-07-10 | Fred A Sturm | Marking crayon |
| USRE22530E (en) * | 1941-10-08 | 1944-08-15 | Pencil for laundry marking | |
| US2317159A (en) * | 1941-10-13 | 1943-04-20 | Rhode Island Lab Inc | Writing device |
| US3057806A (en) * | 1959-07-23 | 1962-10-09 | Switzer Brothers Inc | Fluorescent crayons |
| US3392123A (en) * | 1962-10-17 | 1968-07-09 | Du Pont | Chemiluminescent formulations |
| US3565815A (en) * | 1967-12-28 | 1971-02-23 | Ind Mfg Co Inc | Phosphor containing plastic polystyrene |
| JPS5470132A (en) * | 1977-11-16 | 1979-06-05 | Osawa Kenji | Method of making fluorescent color pencil lead capable of writing on paper* metal* glass* cellophane* vinyl* film* ceramic* etc* |
| DE3050023C2 (en) * | 1980-05-20 | 1986-02-06 | Peter 7630 Lahr Kollmer | Method for marking vehicle tires or footballs |
| DE3421408A1 (en) * | 1984-06-08 | 1986-01-02 | Johann Froescheis LYRA-Bleistift-Fabrik GmbH & Co, 8500 Nürnberg | Refill for writing, labelling or marking purposes in the form of a solid refill |
| JPS61123686A (en) * | 1984-11-19 | 1986-06-11 | Sakura Color Prod Corp | Production of solid marking material |
| JPH0453979Y2 (en) * | 1986-06-30 | 1992-12-18 | ||
| GB8724570D0 (en) * | 1987-10-20 | 1987-11-25 | De La Rue Thomas & Co Ltd | Fluorescent compounds |
-
1991
- 1991-03-29 CA CA002079591A patent/CA2079591A1/en not_active Abandoned
- 1991-03-29 WO PCT/US1991/002197 patent/WO1991015553A1/en not_active Application Discontinuation
- 1991-03-29 AU AU76748/91A patent/AU642837B2/en not_active Ceased
- 1991-03-29 EP EP19910908128 patent/EP0523177A4/en not_active Withdrawn
- 1991-03-29 JP JP3507630A patent/JPH06500131A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| EP0523177A1 (en) | 1993-01-20 |
| AU642837B2 (en) | 1993-10-28 |
| JPH06500131A (en) | 1994-01-06 |
| EP0523177A4 (en) | 1993-08-11 |
| WO1991015553A1 (en) | 1991-10-17 |
| AU7674891A (en) | 1991-10-30 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| FZDE | Discontinued |