CA2140652C - Permanent aqueous marker inks - Google Patents
Permanent aqueous marker inksInfo
- Publication number
- CA2140652C CA2140652C CA002140652A CA2140652A CA2140652C CA 2140652 C CA2140652 C CA 2140652C CA 002140652 A CA002140652 A CA 002140652A CA 2140652 A CA2140652 A CA 2140652A CA 2140652 C CA2140652 C CA 2140652C
- Authority
- CA
- Canada
- Prior art keywords
- ink
- marker
- surfactant
- pigment
- film
- 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 - Fee Related
Links
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
- C09D11/16—Writing inks
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S260/00—Chemistry of carbon compounds
- Y10S260/38—Ink
Abstract
Permanent aqueous marker inks are provided which include surfactant, a pigment, a film-forming polymer, and water. The surfactant may be a combination of a hydrocarbon, preferably an alkylphenol etho xylate and a fluorocarbon, or it may be a silicone.
Description
W094/02~2 2 1 4 0 6 5 2 PCT/US93/06571 PERNANENT Auu~uS ~ INRS
Bac~lou~d of the Invention This invention relates to marking compositions.
Traditionally, permanent inks for use in markers have been provided in liquid form, as sol~ent-based or aqueous solutions. Sol~ent-based in~s generally provide good adhesion and wetting on a wide ~ariety of smooth, diffieult to wet substrates, e.g., glass, plastie and metal. However, there is an increasing desire in the field to reduee or el;m;nate solvent use, due to en~ironmental and safety eoncerns, and, o~eo~ ily, to a~oid tho unpleasant odor of sol~ent-based inks. Aqueous inks, formulated to replaee solvent based inks, generally do not wet all substrat-s, particularly plastics, glass and metal, and are often not water-fast.
The invention features permanent aqueous marker inks that ean be used to mark, e.g., paper, plasties, glass, and motal.
One aspeet of the in~ention features an aqueous marker ink whieh ineludes a hydroearbon surfaetant, a fluoroearbon surfaetant, a pigment, a film-forming aerylie polymer, and water. In preferrod eompositions, the aerylic polymer i~ provided in the form of 214065~
W094/02~2 PCT/US93/06571 an emulsion, and the acrylic is a thermoplastic acrylic, more preferably polymethyl methacrylate. Preferably, the hydrocarbon and fluorocarbon surfactants are pro~ided in a weight ratio of about 1:1.
In another aspect, the in~ention featuree an aqueous marker ink which includes an alkylphenol ethoxylate surfactant, a fluorocarbon surfactant, a pigment, a film-forming polymer, and water. In preferredcompositions, the alkylphenol ethoxylate surfactant is an octylphenol ethoxylate.
In a third aspect, the invention features an aqueous marker ink which includes a silicone surfactant, a film-forming polymer, a pigment, and water. In preferred compositions, the silicone surfactant is a siloxane or silane surfactant and the silicone surfactant is fluorinatsd. The compositions may further includ- a fluorocarbon and/or a hyd~oc~on surfactant.
Preferred inks include, by weight, about 0.1 to 1, more preferably 0.2 to 0.6 percent of the surfacta~t(s), about 10 to 40, more preferably 20 to 30 percent of the film-forming polymer, about 2 to 8 percent pigment, and sufficient water to provide a ~iscosity of le88 than about 20 cps. The ink may also include a small quantity (preferably 1-10%) of a low (less than 5) carbon alcohol.
The invention also features a method of marking a substrate, e.g., glass, plastic or metal. The method includes the steps of providing a marker ha~ing a reservoir, the reservoir cont~; n; ng one of the featured inks, and making a mark with the marker on the substrate.
Preferred marker inks advantageou~ly do not incl~de any solvent. The term "~olvent", as used herein, refer~ to liquids which are defined as Volatile Organic Compounds (VO~
Further, they are permanent, i.e., water-fast and fade resistant, and write well on a wide variety of substrates, including difficult to wet substrates such as glass, metal, and plastics, e.g., polypropylenq, polyethylene and PVC film (SARAN film). Preferred inks have a surface tension of from about 18 to 34 dynes/cm.
Other features and advantage~ of the invention will be apparent from the Description of the Preferred Embodiments thereof, and from the claims.
Preferred marker inks include a surfactant, or combination of surfactants, to reduce the surface tension of the ink composltion to less than about 35 dynes/cm, an acrylic film formlng polymer, a water-dispersible pigment, a humectant, and water.
The surfactant(s) can be either:
(a) a combination of fluorocarbon and hydrocarbon surfactants, (b) a silicone surfactant, or (c) a combination of a silicone surfactant and a fluorocarbon surfactant and/or a hydrocarbon surfactant. The total amount of the surfactant in the composition iB preferably from about 0.1 to 1, more preferably 0.2 to 0.6 percent by weight. It is preferred that the amount of the surfactant(s) included, and the ratio of ~ur~actants, if a combination is used, be selected 80 aa to provide a composition having a surface tension between about 18 and 34 dynes/cm. Too little surfactant(s) may prevent the composition from properly wetting dlfficult ~ub~trates, while too much may cau~e the ink to A * Trade-mark "soak through" when used on paper.
- In the embodiments in which a combination of fluorocarbon and hydrocarbon surfactants i8 used, the ratio of fluorocarbon surfactant to hydrocar~on ~urfactant is preferably about 1:1.
Suitable fluorocarbon surfactants include at least one aliphatic fluorocarbon group. Preferred fluorocarbon surfactants include ZONYL ~SA and FSN fluorosurfactants, available from Dupont, which contain, respectively, lithium 3, [(lH, lH, 2H, 2H-fluoroalkyl) thio]proprionate and telomer B
monoether with polyethylene glycol (CAS No.
65545-80-4). Other suitable surfactants are fluorinated alkyl alkoxylates, available ~rom 3M
under the tradename FLUORAD , e.g., FLUORAD
FC-171 surfactant.
~ydrocarbon surfactant~ include at least one aliphatic group. Suitable hydrocarbon 6urfactants include alkylphenol ethoxylates in which the alkyl group ha~ between 6 and 12 carbons. The preferred alkylphenyl ethoxylate is octylphenol ethoxylate, e.g., TRITON~ X-100 2S non-ionic surfactant, available from Union Carblde, Danbury, CT.
Sultable silicone surfactants include, silane~ and ~iloxanes. Example~ are polyoxyethylene modlfied polydimethyl~iloxane~
(referred to in the art as "silicone glycol copolymersn), e.g., DOW CORNING~ Q2-5211 and Q2-5212 ~uper-wetting agent~, available from Dow Corning Corp., Midland, MI. Also preferred are fluorinated silicone surfactants, e.g., fluorinated polysilanes, available from Ecology Chemical Co., Watertown Massachusetts, under the tradename LEVELENE 100.
* Trade-mark A
J; ~ 7 The choice of surfactant will depend upon the properties desired from the ink, and cost and atability factors. Typically, the hydrocarbon/fluo~ocarbon combination provides wetting properties that are stable over a long storage period, while the silicone surfactant provides good wetting and allows the use of a single surfactant.
Enough pigment should be included in the ink to provide an adequate color intensity, but not eo much that viscosity becomes excessively high. The preferred inks include between approximately 2% and 8% pigment by weight, more preferably between approximately 5%
and 7%. Pigments that may be used in the invention include water dispersible pigments, and preferably the pigment is provided in the form of an aqueous dispersion, for accurate measurement and uniform mixing. Suitable dispersions include those available from Hoechst Celanese under the tradename PLEXONYL or *
HOSTAFINE, those available from ~V~ U.S.A. Inc.
under the tradename PREDISOL, those available from Heucotech Ltd. under the tradename HEUCOSPERSE, those available from Nippon Reiko ~agaku, Ltd. under the tradename LUMI~OL, and those availa~le from Mikuni Color Works, Inc.
under the tradename TITICACA. The total amount of the pigment dispersion to be added will depend upon the solids level of the dispersion, and will be selected to give an effective amount of the pigment, as described above. It iB
preferred that the pigment have a relatively small particle size, preferably less than 0.5 micron, to prevent settling. The s~all particle size also i~ more suitable for use in capillary feed marker~.
* Trade-mark A
W094/02542 ~~ ! ' PCT/US93/06571 The acrylic polymer is preferably provided in the form of an emulsion. Ho~evel, if desirod, a water soluble acrylic may be used.
Preferred acrylic polymers include thermoplastic acrylics, e.g., polymethacrylates, such as polymethyl methacrylate and other methyl acrylates. A preferred aerylic emulsion i8 RHOPLEX~ AC-261 emulsion, available from Rohm and Haas Co., Philadelphia, PA. Rhoplex AC 261 is an all-acrylic co-polymer combination, a butyl acrylate/methyl methacrylate blend ha~ing a low acid content, a molecular weight of around 1,000,000 and a glass transition temperature of between 15 and 20. The resin is thermoplastic and in use forms a film on the substrate by coalescQnee after the correction fluid is applied. Preferred compositions contain from about 20 to 30 weight percQnt of the acrylic polymer. Too much of the acrylic may result in undesirably high viscosity at an effective level of pigment, while too little may result in an ink having poor water resistance when dry.
Preferred humectants are glycols, such as diethyle,ne, or di~ lene glycol or glycerol.
A ~ re preferred hume,ctant is ~ o~rlene glycol.
The humeetant ~ ~ts dry-out of the marker when the eap is le,ft off. Aeeordingly, too mueh may cau~e the in~ to dry too slowly, while too little may not ~.~v_~t drying out of the marker.
Prefe,rred compositions include from 1 to 25 weight percent of the humectant, preferably from about 5 to 15 weight porcent.
Other conventional ingredients may be included in the eomposition, e.g., bioeides.
Suffieient water should be ineluded in the ink 80 that its Brookfield viscosity at 25~C. is less than about 20 eps, ~ re preferably ., .~ .
., ~ j '~ 2~40652 ~
between about 2 Cp8 and lO CpR. If the ~iscosity is too low, the composition may not contain effective amounts of the active ingredients. If the ~iseosity is too high, the ink may be too thick for practical use, particularly in capillary feed systems.
A preferred procedure for preparing the compositions of the invention is to provide the pigment in the form of a dispersion, add to this dispersion the super-wetting surfactant (if a blend of surfaetants is used, these are preferably mixed prior to addition to the pigment dispersion), then add the humecta~t, the water, a~d, finally, the acrylie emulsion, mixing between eaeh ~ddition. The ingredients can be mixed using any conventional mixer, under conditio~s of relatively low shoar.
The following examples illustrate the invention.
A series of ink compositions were prepared using the preferred procedure deseribed above. The formulations for these eompositions are gi~en in Table l. Each ink was tested by forming a line on a series of sub~tratos ~PVC
film (SARAN wrap), polyethylone, pol~ lene, metal, glass and eellophane tape) and observing wh-ther the line driod without shrin~ag- and/or ~ g. Each ink formod a uniform line, without b~ g or shrinkage, on oaeh of the tost substrates.
Inqredient Sample #
HOSTAFINE TS Pigment dlspers'n 15 HOSTAFINE*B-2G n n 15 FLEXONYL*ACB ~ n 10 10 FLEXONYL AB26 n 1l 10 Propylene Glycol 10 10 10 10 10 x TRITO~ X-100 hydrocarbon surf. 0.25 0.5ZONYL*FSA fluorocarbon surf. 0.25 0.25 SUPERWETTER* Q2-5212 sillcone 0.5 LEVELENE*100 hydrocarbon aurf. 1 0.5 0.5 bacteriocide 0.1 0.1 0.1 0.1 0.1 RHOPLEX*AC261 acryllc polymer 50 50 50 50 50 water 24 24 29 29 29 * Trade-mark .~;
~3~
Other Embodiment~
- Other embodimenta are within the claim. For exa~ple, a ~mall amount (lee~ than 10%) of 2-propanol may be added to the ink to decrea~e the drying time. An example of such an ink i~:
Inqredient~: Weiqht Percentaqe Ho~tifine*Black 2 to 8% pigment weight Propylene glycol 2 to 10%
Rhoplex*AC261 50%
Triton*X-100 0.1 to 0.5%
Zonyl*FSA 0.1 to 0.5%
Bac~lou~d of the Invention This invention relates to marking compositions.
Traditionally, permanent inks for use in markers have been provided in liquid form, as sol~ent-based or aqueous solutions. Sol~ent-based in~s generally provide good adhesion and wetting on a wide ~ariety of smooth, diffieult to wet substrates, e.g., glass, plastie and metal. However, there is an increasing desire in the field to reduee or el;m;nate solvent use, due to en~ironmental and safety eoncerns, and, o~eo~ ily, to a~oid tho unpleasant odor of sol~ent-based inks. Aqueous inks, formulated to replaee solvent based inks, generally do not wet all substrat-s, particularly plastics, glass and metal, and are often not water-fast.
The invention features permanent aqueous marker inks that ean be used to mark, e.g., paper, plasties, glass, and motal.
One aspeet of the in~ention features an aqueous marker ink whieh ineludes a hydroearbon surfaetant, a fluoroearbon surfaetant, a pigment, a film-forming aerylie polymer, and water. In preferrod eompositions, the aerylic polymer i~ provided in the form of 214065~
W094/02~2 PCT/US93/06571 an emulsion, and the acrylic is a thermoplastic acrylic, more preferably polymethyl methacrylate. Preferably, the hydrocarbon and fluorocarbon surfactants are pro~ided in a weight ratio of about 1:1.
In another aspect, the in~ention featuree an aqueous marker ink which includes an alkylphenol ethoxylate surfactant, a fluorocarbon surfactant, a pigment, a film-forming polymer, and water. In preferredcompositions, the alkylphenol ethoxylate surfactant is an octylphenol ethoxylate.
In a third aspect, the invention features an aqueous marker ink which includes a silicone surfactant, a film-forming polymer, a pigment, and water. In preferred compositions, the silicone surfactant is a siloxane or silane surfactant and the silicone surfactant is fluorinatsd. The compositions may further includ- a fluorocarbon and/or a hyd~oc~on surfactant.
Preferred inks include, by weight, about 0.1 to 1, more preferably 0.2 to 0.6 percent of the surfacta~t(s), about 10 to 40, more preferably 20 to 30 percent of the film-forming polymer, about 2 to 8 percent pigment, and sufficient water to provide a ~iscosity of le88 than about 20 cps. The ink may also include a small quantity (preferably 1-10%) of a low (less than 5) carbon alcohol.
The invention also features a method of marking a substrate, e.g., glass, plastic or metal. The method includes the steps of providing a marker ha~ing a reservoir, the reservoir cont~; n; ng one of the featured inks, and making a mark with the marker on the substrate.
Preferred marker inks advantageou~ly do not incl~de any solvent. The term "~olvent", as used herein, refer~ to liquids which are defined as Volatile Organic Compounds (VO~
Further, they are permanent, i.e., water-fast and fade resistant, and write well on a wide variety of substrates, including difficult to wet substrates such as glass, metal, and plastics, e.g., polypropylenq, polyethylene and PVC film (SARAN film). Preferred inks have a surface tension of from about 18 to 34 dynes/cm.
Other features and advantage~ of the invention will be apparent from the Description of the Preferred Embodiments thereof, and from the claims.
Preferred marker inks include a surfactant, or combination of surfactants, to reduce the surface tension of the ink composltion to less than about 35 dynes/cm, an acrylic film formlng polymer, a water-dispersible pigment, a humectant, and water.
The surfactant(s) can be either:
(a) a combination of fluorocarbon and hydrocarbon surfactants, (b) a silicone surfactant, or (c) a combination of a silicone surfactant and a fluorocarbon surfactant and/or a hydrocarbon surfactant. The total amount of the surfactant in the composition iB preferably from about 0.1 to 1, more preferably 0.2 to 0.6 percent by weight. It is preferred that the amount of the surfactant(s) included, and the ratio of ~ur~actants, if a combination is used, be selected 80 aa to provide a composition having a surface tension between about 18 and 34 dynes/cm. Too little surfactant(s) may prevent the composition from properly wetting dlfficult ~ub~trates, while too much may cau~e the ink to A * Trade-mark "soak through" when used on paper.
- In the embodiments in which a combination of fluorocarbon and hydrocarbon surfactants i8 used, the ratio of fluorocarbon surfactant to hydrocar~on ~urfactant is preferably about 1:1.
Suitable fluorocarbon surfactants include at least one aliphatic fluorocarbon group. Preferred fluorocarbon surfactants include ZONYL ~SA and FSN fluorosurfactants, available from Dupont, which contain, respectively, lithium 3, [(lH, lH, 2H, 2H-fluoroalkyl) thio]proprionate and telomer B
monoether with polyethylene glycol (CAS No.
65545-80-4). Other suitable surfactants are fluorinated alkyl alkoxylates, available ~rom 3M
under the tradename FLUORAD , e.g., FLUORAD
FC-171 surfactant.
~ydrocarbon surfactant~ include at least one aliphatic group. Suitable hydrocarbon 6urfactants include alkylphenol ethoxylates in which the alkyl group ha~ between 6 and 12 carbons. The preferred alkylphenyl ethoxylate is octylphenol ethoxylate, e.g., TRITON~ X-100 2S non-ionic surfactant, available from Union Carblde, Danbury, CT.
Sultable silicone surfactants include, silane~ and ~iloxanes. Example~ are polyoxyethylene modlfied polydimethyl~iloxane~
(referred to in the art as "silicone glycol copolymersn), e.g., DOW CORNING~ Q2-5211 and Q2-5212 ~uper-wetting agent~, available from Dow Corning Corp., Midland, MI. Also preferred are fluorinated silicone surfactants, e.g., fluorinated polysilanes, available from Ecology Chemical Co., Watertown Massachusetts, under the tradename LEVELENE 100.
* Trade-mark A
J; ~ 7 The choice of surfactant will depend upon the properties desired from the ink, and cost and atability factors. Typically, the hydrocarbon/fluo~ocarbon combination provides wetting properties that are stable over a long storage period, while the silicone surfactant provides good wetting and allows the use of a single surfactant.
Enough pigment should be included in the ink to provide an adequate color intensity, but not eo much that viscosity becomes excessively high. The preferred inks include between approximately 2% and 8% pigment by weight, more preferably between approximately 5%
and 7%. Pigments that may be used in the invention include water dispersible pigments, and preferably the pigment is provided in the form of an aqueous dispersion, for accurate measurement and uniform mixing. Suitable dispersions include those available from Hoechst Celanese under the tradename PLEXONYL or *
HOSTAFINE, those available from ~V~ U.S.A. Inc.
under the tradename PREDISOL, those available from Heucotech Ltd. under the tradename HEUCOSPERSE, those available from Nippon Reiko ~agaku, Ltd. under the tradename LUMI~OL, and those availa~le from Mikuni Color Works, Inc.
under the tradename TITICACA. The total amount of the pigment dispersion to be added will depend upon the solids level of the dispersion, and will be selected to give an effective amount of the pigment, as described above. It iB
preferred that the pigment have a relatively small particle size, preferably less than 0.5 micron, to prevent settling. The s~all particle size also i~ more suitable for use in capillary feed marker~.
* Trade-mark A
W094/02542 ~~ ! ' PCT/US93/06571 The acrylic polymer is preferably provided in the form of an emulsion. Ho~evel, if desirod, a water soluble acrylic may be used.
Preferred acrylic polymers include thermoplastic acrylics, e.g., polymethacrylates, such as polymethyl methacrylate and other methyl acrylates. A preferred aerylic emulsion i8 RHOPLEX~ AC-261 emulsion, available from Rohm and Haas Co., Philadelphia, PA. Rhoplex AC 261 is an all-acrylic co-polymer combination, a butyl acrylate/methyl methacrylate blend ha~ing a low acid content, a molecular weight of around 1,000,000 and a glass transition temperature of between 15 and 20. The resin is thermoplastic and in use forms a film on the substrate by coalescQnee after the correction fluid is applied. Preferred compositions contain from about 20 to 30 weight percQnt of the acrylic polymer. Too much of the acrylic may result in undesirably high viscosity at an effective level of pigment, while too little may result in an ink having poor water resistance when dry.
Preferred humectants are glycols, such as diethyle,ne, or di~ lene glycol or glycerol.
A ~ re preferred hume,ctant is ~ o~rlene glycol.
The humeetant ~ ~ts dry-out of the marker when the eap is le,ft off. Aeeordingly, too mueh may cau~e the in~ to dry too slowly, while too little may not ~.~v_~t drying out of the marker.
Prefe,rred compositions include from 1 to 25 weight percent of the humectant, preferably from about 5 to 15 weight porcent.
Other conventional ingredients may be included in the eomposition, e.g., bioeides.
Suffieient water should be ineluded in the ink 80 that its Brookfield viscosity at 25~C. is less than about 20 eps, ~ re preferably ., .~ .
., ~ j '~ 2~40652 ~
between about 2 Cp8 and lO CpR. If the ~iscosity is too low, the composition may not contain effective amounts of the active ingredients. If the ~iseosity is too high, the ink may be too thick for practical use, particularly in capillary feed systems.
A preferred procedure for preparing the compositions of the invention is to provide the pigment in the form of a dispersion, add to this dispersion the super-wetting surfactant (if a blend of surfaetants is used, these are preferably mixed prior to addition to the pigment dispersion), then add the humecta~t, the water, a~d, finally, the acrylie emulsion, mixing between eaeh ~ddition. The ingredients can be mixed using any conventional mixer, under conditio~s of relatively low shoar.
The following examples illustrate the invention.
A series of ink compositions were prepared using the preferred procedure deseribed above. The formulations for these eompositions are gi~en in Table l. Each ink was tested by forming a line on a series of sub~tratos ~PVC
film (SARAN wrap), polyethylone, pol~ lene, metal, glass and eellophane tape) and observing wh-ther the line driod without shrin~ag- and/or ~ g. Each ink formod a uniform line, without b~ g or shrinkage, on oaeh of the tost substrates.
Inqredient Sample #
HOSTAFINE TS Pigment dlspers'n 15 HOSTAFINE*B-2G n n 15 FLEXONYL*ACB ~ n 10 10 FLEXONYL AB26 n 1l 10 Propylene Glycol 10 10 10 10 10 x TRITO~ X-100 hydrocarbon surf. 0.25 0.5ZONYL*FSA fluorocarbon surf. 0.25 0.25 SUPERWETTER* Q2-5212 sillcone 0.5 LEVELENE*100 hydrocarbon aurf. 1 0.5 0.5 bacteriocide 0.1 0.1 0.1 0.1 0.1 RHOPLEX*AC261 acryllc polymer 50 50 50 50 50 water 24 24 29 29 29 * Trade-mark .~;
~3~
Other Embodiment~
- Other embodimenta are within the claim. For exa~ple, a ~mall amount (lee~ than 10%) of 2-propanol may be added to the ink to decrea~e the drying time. An example of such an ink i~:
Inqredient~: Weiqht Percentaqe Ho~tifine*Black 2 to 8% pigment weight Propylene glycol 2 to 10%
Rhoplex*AC261 50%
Triton*X-100 0.1 to 0.5%
Zonyl*FSA 0.1 to 0.5%
2-Propanol 2 to 10%
Suttocide~'A 0.1%
Water i~ added to make up the difference to 100%.
* Trade-mark
Suttocide~'A 0.1%
Water i~ added to make up the difference to 100%.
* Trade-mark
Claims (19)
OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. An aqueous permanent marker ink comprising a hydrocarbon surfactant including at least 1 aliphatic group and a fluorocarbon surfactant, a pigment, a film-forming acrylic polymer, and water.
2. A marker ink of claim 1, wherein said acrylic polymer is a thermoplastic acrylic.
3. A marker ink of claim 2, wherein said acrylic polymer is polymethacrylate.
4. A marker ink of claim 1, wherein the ink comprises, by weight, about 0.1 to 1 percent total of said hydrocarbon surfactant and said fluorocarbon surfactant, about 20 to 30 percent of said acrylic polymer, about 2 to 8 percent of said pigment, and sufficient water to provide a viscosity of less than about 20 cps.
5. A marker ink of claim 1, wherein said hydrocarbon surfactant and said fluorocarbon surfactant have a weight ratio of about 1:1.
6. The marker ink of claim 1, further comprising a small quantity of a low carbon alcohol.
7. The marker ink of claim 1, wherein said ink includes no volatile organic solvents.
8. An aqueous permanent marker ink comprising an alkylphenol ethoxylate surfactant and a fluorocarbon surfactant, a pigment, and a film-forming polymer.
9. A marker ink of claim 8, wherein said alkylphenol ethoxylate surfactant is an octylphenol ethoxylate.
10. A marker ink of claim 8, wherein the ink comprises, by weight, about 0.1 to 1 percent total of said alkylphenol ethoxylate and said fluorocarbon surfactant, about 20 to 30 percent of said film-forming polymer, about 2 to 8 percent of said pigment, and sufficient water to provide a viscosity of less than about 20 cps.
11. A marker ink of claim 8, wherein said film-forming polymer is an acrylic emulsion.
12. The marker ink of claim 8, further comprising a small quantity of a low carbon alcohol.
13. The marker ink of claim 8, wherein said ink includes no volatile organic solvent.
14. A marker ink of claim 1 or 8, wherein said ink further comprises a humectant.
15. A marker ink of claim 1 or 8, wherein said ink has a surface tension of less than about 35 dynes/cm.
16. A method of marking a substrate including the steps of providing a marker having a reservoir, the reservoir containing an ink comprising a hydrocarbon surfactant including at least 1 aliphatic group and a fluorocarbon surfactant, a pigment, a film-forming acrylic polymer, and water, and making a mark with said marker on said substrate.
17. A method of marking a substrate including the steps of providing a marker having a reservoir, the reservoir containing an ink comprising an alkylphenol ethoxylate surfactant and a fluorocarbon surfactant, a pigment, a film-forming polymer, and water, and making a mark with said marker on said substrate.
18. A marker comprising an outer body wall defining an ink reservoir, the reservoir containing an ink comprising a hydrocarbon surfactant including at least 1 aliphatic group and a fluorocarbon surfactant, a pigment, a film-forming acrylic polymer, and water; and a tip in fluid communication with said reservoir for delivering said ink to a substrate by capillary action.
19. A marker comprising an outer body wall defining an ink reservoir, the reservoir containing an ink comprising an alkylphenol ethoxylate surfactant, and a fluorocarbon surfactant, a pigment, a film-forming polymer, and water; and a tip in fluid communication with said reservoir for delivering said ink to a substrate by capillary action.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA002237071A CA2237071A1 (en) | 1992-07-21 | 1993-07-13 | Permanent aqueous marker inks including silicone |
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US91745592A | 1992-07-21 | 1992-07-21 | |
| US917,455 | 1992-07-21 | ||
| US968,001 | 1992-10-28 | ||
| US07/968,001 US5512623A (en) | 1992-07-21 | 1992-10-28 | Permanent aqueous marker inks |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002237071A Division CA2237071A1 (en) | 1992-07-21 | 1993-07-13 | Permanent aqueous marker inks including silicone |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2140652A1 CA2140652A1 (en) | 1994-02-03 |
| CA2140652C true CA2140652C (en) | 1999-03-16 |
Family
ID=27129724
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002140652A Expired - Fee Related CA2140652C (en) | 1992-07-21 | 1993-07-13 | Permanent aqueous marker inks |
Country Status (8)
| Country | Link |
|---|---|
| US (4) | US5512623A (en) |
| EP (1) | EP0652907A4 (en) |
| JP (1) | JPH07509271A (en) |
| AU (1) | AU678374B2 (en) |
| CA (1) | CA2140652C (en) |
| MX (1) | MX9304371A (en) |
| MY (1) | MY110667A (en) |
| WO (1) | WO1994002542A1 (en) |
Families Citing this family (29)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5512623A (en) * | 1992-07-21 | 1996-04-30 | The Gillette Company | Permanent aqueous marker inks |
| US5869564A (en) * | 1994-12-21 | 1999-02-09 | International Business Machines Corporation | Ink composition |
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-
1992
- 1992-10-28 US US07/968,001 patent/US5512623A/en not_active Expired - Lifetime
-
1993
- 1993-07-13 JP JP6504526A patent/JPH07509271A/en active Pending
- 1993-07-13 WO PCT/US1993/006571 patent/WO1994002542A1/en not_active Application Discontinuation
- 1993-07-13 AU AU46754/93A patent/AU678374B2/en not_active Ceased
- 1993-07-13 CA CA002140652A patent/CA2140652C/en not_active Expired - Fee Related
- 1993-07-13 EP EP93917143A patent/EP0652907A4/en not_active Ceased
- 1993-07-20 MX MX9304371A patent/MX9304371A/en not_active IP Right Cessation
- 1993-07-20 MY MYPI93001417A patent/MY110667A/en unknown
-
1994
- 1994-02-02 US US08/190,287 patent/US5470904A/en not_active Expired - Lifetime
-
1995
- 1995-06-05 US US08/461,043 patent/US5686519A/en not_active Expired - Lifetime
- 1995-06-05 US US08/460,920 patent/US5804633A/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH07509271A (en) | 1995-10-12 |
| AU678374B2 (en) | 1997-05-29 |
| WO1994002542A1 (en) | 1994-02-03 |
| MY110667A (en) | 1999-01-30 |
| US5686519A (en) | 1997-11-11 |
| CA2140652A1 (en) | 1994-02-03 |
| EP0652907A1 (en) | 1995-05-17 |
| US5470904A (en) | 1995-11-28 |
| MX9304371A (en) | 1994-05-31 |
| US5804633A (en) | 1998-09-08 |
| EP0652907A4 (en) | 1996-04-17 |
| US5512623A (en) | 1996-04-30 |
| AU4675493A (en) | 1994-02-14 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EEER | Examination request | ||
| MKLA | Lapsed |