WO2014042623A1 - Composition de marquage solide - Google Patents

Composition de marquage solide Download PDF

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Publication number
WO2014042623A1
WO2014042623A1 PCT/US2012/054783 US2012054783W WO2014042623A1 WO 2014042623 A1 WO2014042623 A1 WO 2014042623A1 US 2012054783 W US2012054783 W US 2012054783W WO 2014042623 A1 WO2014042623 A1 WO 2014042623A1
Authority
WO
WIPO (PCT)
Prior art keywords
marking composition
solid marking
wax
solid
resin
Prior art date
Application number
PCT/US2012/054783
Other languages
English (en)
Inventor
Richard J. Kaiser
Francis G. Schiro
Original Assignee
John P. Nissen Jr. Company
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by John P. Nissen Jr. Company filed Critical John P. Nissen Jr. Company
Priority to PCT/US2012/054783 priority Critical patent/WO2014042623A1/fr
Publication of WO2014042623A1 publication Critical patent/WO2014042623A1/fr

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING 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
    • C09D11/00Inks
    • C09D11/16Writing inks

Definitions

  • This invention relates to a solid marking composition which can be used for writing instruments, a marking stick, coating materials, and the like.
  • An improvement to liquid markers in the fabrication process is a solid marker.
  • a solid marker will not stop working if it encounters a dissimilar fluid material. If the solid marker is formulated and constructed properly, it will write through these liquids and make a discernable mark on the materials of construction, thus saving time and money in the fabrication process.
  • the solid marker must have a melting point such that it can be processed into the marker format, and also survive the environment of a typical warm fabrication or repair facility. In addition, it must also survive the rigors of the distribution and shipping system that it will encounter. This is so that the solid marking composition does not fail abruptly at an elevated temperature, but rather slowly across an elevated range of temperatures.
  • the final mark must be waterproof when dry, and also weather resistant. Markers are frequently used in maintenance activities on out-of-the-way locations such as on the top of wind mill generators many hundreds of feet in the air. Here one mechanic may want to leave information for a future mechanic. In certain situations, it may be necessary to remove a mark. To do this, the solid marking composition must be soluble in some solvent.
  • the present invention provides a solid marking composition comprising at least one resin, at least one pigment, at least one dispersant, at least one solvent, and a gelling agent.
  • the solid marking composition provides waterproof and weather resistant marks.
  • the solid marking composition melts at about 50- 75°C.
  • the gelling agent comprises at least one wax and optionally at least one wax modifier.
  • the resin is selected from the group consisting of polyimide, rosin ester and combinations thereof. In certain embodiments, the resin is about 3-15% by weight.
  • the at least one wax is selected from the group consisting of a Montan wax, a synthetic Montan wax, a sorbitol/sebacic acid copolymer behenate, a synthetic wax comprising a C18-C36 acid glycol ester, linoleic acid, stearic acid, oleic acid, and combinations thereof.
  • the waxes are about 10-15% by weight.
  • the optional at least one wax modifier is used and the at least one wax modifier comprises a stearate salt.
  • the wax modifier is about 1 -16% by weight.
  • the at least one solvent is selected from the group consisting of isopropyl alcohol, denatured alcohol, an ester, and combinations thereof.
  • the at least one solvent is about 5-40% by weight.
  • the solid marking composition comprises at least two solvents.
  • the dispersant is a polymer.
  • the dispersant is about 0.5-10% in weight.
  • the present invention provides a method of making a solid marking composition comprising at least one resin, at least one pigment, at least one dispersant, at least one solvent, and at least one gelling agent, wherein the gelling agent comprises at least one wax and optionally at least one wax modifier, comprising the following steps:
  • the present invention was prompted by the need for a marking composition that fulfills the following criteria in addition to the standard features of a marking composition.
  • a marking device that uses a solid marking composition.
  • a solid marker will not stop working if it encounters a fluid material. If the solid marker is formulated and constructed properly, it will write through these liquids and make a discernable mark on construction materials, thus saving time and money in the fabrication process.
  • the markings need to adhere to glass, metal, ceramic, wood, plastic, and the like, or any combination thereof.
  • the solid marking composition must have a melting point such that it can be processed into the marker format and also survive the environment of a typical warm fabrication or repair facility. In addition, it must also survive the rigors of the distribution and shipping system that it will encounter. This is so that the solid marking composition does not fail abruptly at an elevated temperature, but rather slowly across an elevated range of temperatures.
  • the melting range of the solid composition may be about, for example, 50-75 °C.
  • the final dry mark must be waterproof and weather resistant.
  • marking devices are frequently used, for instance, in maintenance activities on out-of-the-way locations such as on the top of wind mill generators many hundreds of feet above ground. The marks are exposed to the elements in these situations. Often times, one mechanic may want to leave information for a future mechanic.
  • the final marks need to be removable when necessary. In certain situations, it may be necessary to remove the markings on the work surfaces.
  • the present invention has provided solutions to the requirements above.
  • the inventors provide a solid marking composition comprising a resin, a pigment, a dispersant, a gelling agent, and at least one solvent, wherein the gelling agent comprises at least one wax and an optional wax modifier.
  • the solid marking composition of the invention also comprises other additives.
  • the inventors also provide a method of making the solid marking composition of the invention.
  • the method comprises admixing the above- mentioned components uniformly.
  • the resin component for the solid marking composition is not particularly restricted. It is important that the resin is soluble in the carrier solvent of choice for ease of manufacture, and soluble in a widely used solvent so that the markings may be removed when desired.
  • Convenient solvents which may be used in the invention include, for example, low molecular weight alcohols (such as ethyl alcohol, propanol, and isopropyl alcohol) and esters (such as ethyl acetate, and ethyl lactate) solvents.
  • the resin needs to be water resistant and therefore insoluble in water.
  • the resin needs to be soluble in the solvents such as ethyl alcohol, isopropyl alcohol and ester, but insoluble in water.
  • suitable resins include rosin, polyamide resin, polyimide resin, fumaric resin, maleic resin, acrylate resin, ketone resin, xylene resin.
  • resins are rosin resin, polyamide resin, and polyimide resin.
  • the rosin resin can be exemplified by the trade name "Resinall 807A.”
  • the resin content depends on the type of resin used but is typically used in the amount of about 3 - 15%, and preferably about 9 - 12%.
  • solvent examples include alcohols (such as methanol, ethanol, propanol, isopropanol), esters, naturally derived plant esters, blends of bio-based plant esters, blends of bio-based plant esters and petrochemical based solvents, trimethylol propane, glycol ethers (such as ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, dipropylene glycol monomethyl ether and dipropylene glycol monopropyl ether), and combinations thereof. Alcohols are readily available, safe to use, and low cost.
  • a particular example of a solvent is IPAR 100 which is a blend of three bio-based plant esters that have a solubility similar to isopropyl alcohol, but have a higher flash point.
  • the content of the first solvent is about 5-20% by weight with respect to the total amount of a solid marking composition.
  • the optimum content of a solvent in particular, somewhat varies depending on kinds of solvents, it is about 10-15 % by weight.
  • a second solvent may be used to impart improved writing characteristics.
  • An example of a second solvent is Soyclear 1500, which is a methyl ester derivative of soybean oil, imparts smoother writing characteristics to the solid marker.
  • the second solvent can be present in concentrations of, for example, about 1 -20%, and preferably from about 5- 15%.
  • pigments are used to serve a range of functions known in the art. It is important that pigments should not react with other pigments. Further, it is preferable that a pigment be dispersible. Suitable pigments for use in the present invention are those generally well-known in the art.
  • pigments include, for example, traditional pigments, inorganic pigments such as carbon black and titanium oxide, organic pigments such as copper phthalocyanine pigments, threne pigments, azo pigments, quinacridon pigments, anthraquinone pigments, dioxane pigments, indigo pigments, thioindigo pigments, perinone pigments, perylene pigments, indolenone pigments and azomethine pigments and the like, and fluorescent pigments, and the like.
  • organic pigments such as copper phthalocyanine pigments, threne pigments, azo pigments, quinacridon pigments, anthraquinone pigments, dioxane pigments, indigo pigments, thioindigo pigments, perinone pigments, perylene pigments, indolenone pigments and azomethine pigments and the like, and fluorescent pigments, and the like.
  • pigments as well as synthetic pigments such as micaeous, glitter, glass flake, polymeric chromophores, and metallic pigments can be incorporated into the composition.
  • synthetic pigments such as micaeous, glitter, glass flake, polymeric chromophores, and metallic pigments
  • the present invention can use one species of a pigment or can use two or more species of pigments in combination.
  • they can be mixed with opacifying pigments including, for example, a variety of inorganic or organic white pigments such as titanium oxide, barium sulfate, alkylene bismelamine derivatives, polymeric pigments (synthetic resin particle pigments such as acrylates that include a hollow polymer shell and a void space for air) with opacifying power of various shapes including spherical shapes, oblate shapes either alone or in combination with two or more of them. Proper visibility and color adjustment can be accomplished by the use of an opaque pigment.
  • opacifying pigments including, for example, a variety of inorganic or organic white pigments such as titanium oxide, barium sulfate, alkylene bismelamine derivatives, polymeric pigments (synthetic resin particle pigments such as acrylates that include a hollow polymer shell and a void space for air) with opacifying power of various shapes including
  • pigments are used to improve the writing properties of the composition.
  • the unique shape of Wollastonite or Talc pigments enhances the flow of the molten solid composition when it melts from frictional forces during the marking process.
  • Wollastonite is a calcium metasilicate mineral that may contain small amounts of iron, magnesium and manganese. Its plate like morphology imparts a smoother flow to the solid marker.
  • the content of a pigment is about 0.5 - 30% by weight with respect to the total amount of the solid marking composition. More preferably, the content of a pigment is about 2 - 25%.
  • Wollastonite or Talc pigment when present, it can be in the range of about 2 - 15%, preferably about 4 - 12%.
  • An opacifying pigment can be incorporated at about 1 -30%, preferably at about 5-25%.
  • Pigments may be stabilized by dispersants, such as polymeric dispersants or surfactants, to produce a stable dispersion of the pigment when the pigments and resin are subjected to a gelling agent.
  • dispersants such as polymeric dispersants or surfactants
  • Pigments that are stabilized by added dispersing agents may be prepared by methods known in the art. It is generally desirable to make the stabilized pigment in a concentrated form.
  • the stabilized pigment may be first prepared by premixing the selected pigment(s) and polymeric dispersant(s) in a carrier medium, and then dispersing or deflocculating the pigment.
  • the dispersing step may be accomplished, for example, in a 3-roll mill, media mill, a horizontal mini mill, a ball mill, an attritor, or by passing the mixture through a plurality of nozzles within a liquid jet interaction chamber at a liquid pressure of at least 5,000 psi to produce a uniform dispersion of the pigment particles in the carrier medium (microfluidizer).
  • the concentrates may be prepared by dry milling the polymeric dispersant and the pigment under pressure. After the milling process is complete the pigment concentrate may be "let down" into a solvent system. "Let down” refers to the dilution of the concentrate with mixing or dispersing, the intensity of the mixing/dispersing normally being determined by trial and error using routine methodology, and often being dependent on the combination of the polymeric dispersant, solvent and pigment.
  • the stabilized pigment can be prepared with a dispersant using a traditional high speed Cowles mixer/dissolver.
  • the dispersant used to stabilize the pigment is preferably a polymeric dispersant similar to that used in the coatings field.
  • Some examples are polyacrylate, polyurethane and polyurethane acrylate.
  • the following commercial products may be used: EFKATM 4008 (modified polyurethane), EFKATM 4009 (modified polyurethane) or EFKATM 4300 (acrylic block copolymer) from BASF.
  • EFKATM 4008 modified polyurethane
  • EFKATM 4009 modified polyurethane
  • EFKATM 4300 acrylic block copolymer
  • hydrophobic monomers used in polymers are methyl methacryiate, n-butyl methacrylate, 2-ethylhexyl methacrylate, benzyl methacrylate, 2-phenylethyl methacrylate and the corresponding acrylates.
  • hydrophilic monomers are methacrylic acid, acrylic acid, dimethylaminoethyl(meth)acrylate and salts thereof. Also quaternary salts of dimethylaminoethyl(meth)acrylate may be employed.
  • the dispersant may be present in about 0.5 - 10%, preferably about 2 - 8%.
  • the liquid dispersion containing the resin and pigment needs to be gelled in order to be useful for marking functions.
  • the key to the optimal performance properties is a final material that does not have a sharp melting point, but rather a melting range higher than the ambient use temperature.
  • the melting point of the composition spans a broad range (for example, about 50-75°C), not a specific single point. This is important because a sharp melting point near the usage temperature could render the marking device liquid and inoperable.
  • One of the methods is blending at least two dissimilar (with respect to chemical composition or melting point) waxes together.
  • Another exemplary method is blending a wax and a softening wax, or wax modifier.
  • a Montan wax, synthetic Montan wax, Prisorine 3800 currently known as SyncrowaxTM ORM, a sorbitol/sebacic acid copolymer behenate
  • SynchrowaxTM ERLC a synthetic wax composed of a CI 8- C36 acid glycol ester.
  • Waxes can be present in about 10-35%, and preferably in about 20-30% of the total weight of the composition.
  • a wax modifier can be used to further harden the gel, hence improve the writing properties of the stick comprising a solid marking composition.
  • a wax modifier can be used in about 1 -16%, and preferably in about 10-16%. Generally, amounts above about 16% may degrade the writing properties.
  • Waxes can be mixed with other materials to lower or raise the melting point and the flow point when the mixture is subjected to shear.
  • the wax modifier can be a higher melting point steramide, for example INCROMIDETM SMEA-PW-(AP).
  • Another example is solvents that are miscible with the wax such as isoparaffinic solvents.
  • the proper selection of the solvent flashpoint is an important consideration for plant safety, the length of time the solvent remains in the original mark made with the mixture, and the effect on the ability of the mixture to make an effective mark.
  • Solvents that are non-volatile can act as permanent plasticizers for the film imparting long term flexibility.
  • methyl esters of soybean oil high molecular weight ester compounds
  • oxygenated solvents such as high molecular weight glycol ethers similar to dipropylene glycol methyl ether.
  • Low molecular weight alcohols, esters, and ethers can also modify waxes when blended together.
  • the low molecular weight alcohols, such as isopropanol, low molecular weight esters, such as ethyl lactate, and low molecular weight ethers, such as tetrahydrofuran can depress the melting point of blends with waxes. This will make the wax mixture softer and easier to mark with.
  • the low molecular weight alcohols, ethers, and esters will soon evaporate from wax films and leave the waxes unchanged in the dry film.
  • a gel network can be established in the writing composition to improve glide and rigidity. This may be done with plant oils that include linoleic acid, stearic acid and oleic acid. Synthetic saturated linear carboxylic acid prepared from ethylene can also be used, for example Performacid 350 (New Phase Technologies). These plant or synthetic acids can be hardened with aluminum stearate to form gels. The acid or salt is present in about 5-25%, and preferably about 10-20%, in the writing matrix to form rigid gels.
  • a small amount of low melting point polyethylene such as Marcus 200 Polyethylene may be used at a concentration of about 0.5-10%, and preferably about 1 -5%.
  • additives may include pigment wetting agent, filler agent, leveling agent, viscosity modifier, drying agent, etc. in suitable amounts.
  • natural plant oils such as linseed oil, safflower oil and castor oil
  • metal organic acid compounds such as Troymax 12%, Troymax Zirconuim 12% from Troy Chemical or WD Cobalt 12%, WD Zirconium 12% from Westdry Industries
  • These materials increase the oxidation and cross linking rate of the organic acid components of the oils. Additionally oxidation may be facilitated by the addition of an organic catalyst such as Opti-dry, a 2,2-bipyridyl solution from Westdry Industries.
  • a cobalt drier is a fast surface drier and zirconium and manganese driers are through film driers.
  • Some commercial examples of the additives are ZeeospheresTM W610, TroymaxTM Cobaltl2%, TroymaxTM Zirconium 12%, and Opti-dryTM.
  • the marking composition in Table 1 is prepared according to the method below: 1 ) Charge to a sealable container:
  • Table 2 details a formulation that provides adequate marking and adhesive properties.
  • V Wax OP and INCROMIDE® SMEA waxes are melted continue mixing for 10 minutes then cast into a suitable mold.
  • V Wax OP and or INCROMIDE® SMEA can be melted and moved into the first step.
  • Table 3 is an example of how rigid gels may be formed in the marking composition to provide structure and glide when writing.
  • the aluminum stearate when heated with the linseed oil forms a gel that is a soap. Additionally the Performacid 350 crosslinks with the aluminum stearate to form a rigid but smooth gliding gel.
  • Titanium dioxide (Tioxide TR-93)

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)

Abstract

L'invention concerne une composition de marquage solide comprenant au moins une résine, au moins un pigment, au moins un agent dispersant, au moins un solvant et un agent gélifiant. L'invention concerne aussi un procédé de fabrication de cette composition de marquage solide.
PCT/US2012/054783 2012-09-12 2012-09-12 Composition de marquage solide WO2014042623A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PCT/US2012/054783 WO2014042623A1 (fr) 2012-09-12 2012-09-12 Composition de marquage solide

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/US2012/054783 WO2014042623A1 (fr) 2012-09-12 2012-09-12 Composition de marquage solide

Publications (1)

Publication Number Publication Date
WO2014042623A1 true WO2014042623A1 (fr) 2014-03-20

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019067757A1 (fr) 2017-09-29 2019-04-04 Sanford, L.P. Formulations d'encre et instruments d'écriture associés

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08120209A (ja) * 1994-10-21 1996-05-14 Mitsubishi Pencil Co Ltd 固形状筆記具
US20030029354A1 (en) * 2001-06-11 2003-02-13 Koji Seki Solid glitter marker
JP2004107546A (ja) * 2002-09-20 2004-04-08 Pilot Precision Co Ltd 固形筆記体およびその製造法
EP2065450A1 (fr) * 2006-09-04 2009-06-03 Sakura Color Products Corporation Crayon et son procédé de production
US20090247668A1 (en) * 2006-07-12 2009-10-01 Kotaro Sumitomo Process for production of black crayon

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08120209A (ja) * 1994-10-21 1996-05-14 Mitsubishi Pencil Co Ltd 固形状筆記具
US20030029354A1 (en) * 2001-06-11 2003-02-13 Koji Seki Solid glitter marker
JP2004107546A (ja) * 2002-09-20 2004-04-08 Pilot Precision Co Ltd 固形筆記体およびその製造法
US20090247668A1 (en) * 2006-07-12 2009-10-01 Kotaro Sumitomo Process for production of black crayon
EP2065450A1 (fr) * 2006-09-04 2009-06-03 Sakura Color Products Corporation Crayon et son procédé de production

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019067757A1 (fr) 2017-09-29 2019-04-04 Sanford, L.P. Formulations d'encre et instruments d'écriture associés
EP3676339A4 (fr) * 2017-09-29 2021-07-28 Sanford, L.P. Formulations d'encre et instruments d'écriture associés

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