WO1997016499A1 - Encre effaçable fluidifiante a base aqueuse et stylo a bille roulante la contenant - Google Patents

Encre effaçable fluidifiante a base aqueuse et stylo a bille roulante la contenant Download PDF

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Publication number
WO1997016499A1
WO1997016499A1 PCT/US1996/017553 US9617553W WO9716499A1 WO 1997016499 A1 WO1997016499 A1 WO 1997016499A1 US 9617553 W US9617553 W US 9617553W WO 9716499 A1 WO9716499 A1 WO 9716499A1
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WO
WIPO (PCT)
Prior art keywords
ink
weight
latex emulsion
ball
shear
Prior art date
Application number
PCT/US1996/017553
Other languages
English (en)
Inventor
Herman Abber
Takao Machida
Mark T. Smith
Original Assignee
Avery Dennison Corporation
Ohto Co., Ltd.
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
Priority claimed from US08/551,545 external-priority patent/US5629363A/en
Application filed by Avery Dennison Corporation, Ohto Co., Ltd. filed Critical Avery Dennison Corporation
Priority to JP9517574A priority Critical patent/JP2000509410A/ja
Priority to AU76033/96A priority patent/AU7603396A/en
Priority to EP96938722A priority patent/EP0858487A4/fr
Publication of WO1997016499A1 publication Critical patent/WO1997016499A1/fr

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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
    • C09D11/18—Writing inks specially adapted for ball-point writing instruments
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B43—WRITING OR DRAWING IMPLEMENTS; BUREAU ACCESSORIES
    • B43K—IMPLEMENTS FOR WRITING OR DRAWING
    • B43K1/00—Nibs; Writing-points
    • B43K1/08—Nibs; Writing-points with ball points; Balls or ball beds
    • B43K1/082—Balls
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B43—WRITING OR DRAWING IMPLEMENTS; BUREAU ACCESSORIES
    • B43K—IMPLEMENTS FOR WRITING OR DRAWING
    • B43K1/00—Nibs; Writing-points
    • B43K1/08—Nibs; Writing-points with ball points; Balls or ball beds
    • B43K1/084—Ball beds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B43—WRITING OR DRAWING IMPLEMENTS; BUREAU ACCESSORIES
    • B43K—IMPLEMENTS FOR WRITING OR DRAWING
    • B43K7/00—Ball-point pens
    • B43K7/01—Ball-point pens for low viscosity liquid ink
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
    • C08L9/06—Copolymers with styrene
    • C08L9/08—Latex
    • 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

Definitions

  • Conventional stationery paper is essentially a mat of randomly oriented cellulose fibers.
  • conventional stationery paper consists of solid structural members, namely cellulose fibers, having numerous minute voids therebetween. From the foregoing, it may readily be seen that the formulator or designer of an erasable ink must prevent the colorant portion of the ink from penetrating, to any substantial degree, into the voids in the surface being written upon because, if there is substantial penetration of the colorant portion of the ink into the voids, the subsequent removal ofthe colorant by mechanical means cannot be accomplished without causing damage to the writing surface.
  • Another approach that has been used in an effort to achieve erasability in a roller-ball or ball-point pen has been to include a mechanically-strippable film- forming or resinous material in the ink that prevents the colorant from penetrating the voids in the paper and from becoming affixed to the solid members ofthe paper substratum.
  • One class of such inks are organic or oil-based inks having a high viscosity, e.g., at least several thousand cps, and are used in ball-point pens.
  • An example of the foregoing type of ink is described in U.S. Patent No. 4,407,985, inventor Muller, which issued October 4, 1983 and which is incorporated herein by reference.
  • the Muller ink composition is said to be characterized by an initial, yet transient, erasability from an absorbent paper-like writing surface by ordinary pencil erasers when applied by a ball-point writing instrument.
  • the Muller ink composition comprises polar elastomers, such as butadiene/acrylonitrile copolymer rubbers and vinyl acetate/ethylene copolymer rubbers, and mixtures thereof, either alone or in admixture with cis-1 ,4-polyisoprene (natural rubber or synthetic rubber), pigment, and a solvent system.
  • the polar elastomer is present in the range of about 14- 25% by weight of the ink and the pigment is present in amount sufficient to impart color and intensity to a trace of the ink when applied to a substrate such as paper.
  • the solvent system essentially comprises a volatile component having a boiling point less than about 180°C and an essentially non-volatile component which includes pigment vehicle having a boiling point greater than about 300°C and low viscosity plasticizer having a boiling point greater than 180°C but less than 300°C, the solvent system being present in amount sufficient to impart a final ink viscosity in the range of about 1.5 million cps.
  • the Mivajima ink comprises a rubber component, a volatile solvent, a pigment and a nonvolatile solvent, which additionally comp ⁇ ses finely divided powders of an inorganic compound inactive to other ink components contained therein, a semisolid substance, a soft solid substance having a melting point not higher than 130°C, a combination of finely divided powders of an inorganic compound inactive to other ink compositions contained therein and a semisolid substance, or a combination of finely divided powders of an inorganic compound inactive to other ink compositions contained therein and a soft solid substance having a melting point not higher than 130°C.
  • aqueous-based inks typically have a comparatively Iower viscosity than do oil- based inks and tend to avoid many of the problems associated with oil-based inks; however, also as a result of their comparatively low viscosity, aqueous-based inks cannot typically be used in conventional ball-point pens. For this reason, aqueous- based inks have traditionally been dispensed from roller-ball pens comprising the combination of an absorbent filler and one or more absorbent feed rods ("nibs"). (See, for example, U.S. Patent No.
  • the filler is typically disposed in the reservoir ofthe pen, and the nibs typically interconnect the reservoir to the environs of the ball and socket of the pen.
  • aqueous- based inks have also been dispensed from roller-ball pens lacking a filler but comprising one or more nibs. Recently, however, for example, in U.S. Patent Nos.
  • aqueous-based, non-erasable inks suitable for use in filler-less, nib-less, roller-ball pens.
  • Such inks include a material which endows the inks with the property of being shear-thinning, i.e., the inks are comparatively highly viscous at rest (although less viscous than the inks traditionally used in ball-point pens), but when subjected to the high shear rates produced during writing, become substantially less viscous, e.g., less than 100 cps.
  • shear-thinning materials disclosed in the aforementioned patents include gums, such as xantham gum.
  • an erasable system including an element having a porous marking surface and an erasable marking composition for applying markings to the porous marking surface.
  • the Lin et al. marking composition comprises an aqueous dispersion of particles of film- forming polymeric materials and a colorant, the Lin et al. marking composition being said to provide an erasable, substantially water-insoluble coalesced residue on a porous marking surface.
  • Especially preferred polymeric materials for the Lin et al. marking composition include copolymers of styrene, such as styrene- butadiene.
  • Lin et al. marking composition may include ingredients for controlling or adjusting the rheological properties of the marking composition. Such ingredients are said to include thixotropic or gelling agents such as clays, silicas or water-insoluble, water-soluble or water-miscible polymeric binder materials or polymeric shear thinning providing materials, such as xanthan gum, among others.
  • Xanthan gum is said to be the preferred material for controlling rheological properties, and preferred amounts of xanthan gum are amounts between about 0.05 to about 2 percent by weight of the composition.
  • PLIOLITE ® 2108 which is said to have a styrene-butadiene ratio of 29:71 and which is said to be commercially available from Goodyear Tire and Rubber Company, is said to be a particularly preferred resin for use in the Santini et al. composition.
  • the Santini et al. composition may further include additives, such as coalescing agents, water-soluble or associative thickeners, release agents, surfactants which are preferably non-carboxylated, and the like.
  • the Santini et al. composition is said to be suitable for use in porous- tipped writing instruments, such as felt tipped markers; however, the Santini et al. composition is said not to be limited to such markers and may be used in ballpoint and fountain pens, as paints for application with brushes, rollers, air brushes and the like.
  • the composition is adapted for use in fillerless, nibless, roller-ball pens and comprises a non-carboxylated styrene-butadiene latex emulsion, a water-insoluble pigment and tragacanth gum.
  • the composition may further include additives such as a fluorochemical surfactant and a 2:1 mixture of Sorbitol and glycerine.
  • the aforementioned patent also discloses using a ceramic ball, instead of a metal ball, in a roller-ball or ball-point pen.
  • a "porous marking substrate” is defined to mean a marking substrate which is sufficiently porous to permit the penetration thereinto of colorants of the type typically found in conventional non-erasable inks and which, when contacted with the present composition, causes the emulsion therein to break.
  • conventional porous marking substrates include, but are not limited to, conventional stationery papers and similar papers which have been treated in such a way that, when contacted with water, ions (e.g., protons and/or cations) are dissolved therefrom.
  • non-porous marking substrate is defined to mean a substrate which is insufficiently porous to permit the penetration thereinto of colorants of the type typically found in conventional non-erasable inks and which, when contacted with the present composition, causes the emulsion therein to break.
  • non-porous marking substrates include, but are not limited to, smooth-surfaced writing panels made of glass, plastic, metal, sealed-wood, coated paper and the like.
  • substantially non-abrasive mechanical means is intended to include, but is not limited to, dry cloths, tissues, ordinary pencil erasers and the like.
  • an ink that is erasable from both porous and non-porous marking substrates by substantially non-abrasive mechanical means, said ink comprising: (a) a latex emulsion blend comprising a first non-carboxylated styrene-butadiene latex emulsion and a second non-carboxylated styrene-butadiene latex emulsion, said latex emulsion blend being characterized by its ability to be transformed, upon being contacted with the surface of a porous marking substrate, from a first state in which said latex emulsion blend is stable to a second state in which said latex emulsion blend is unstable and the styrene-butadiene phase
  • the shear-thinning, viscosity-adjustment agent comprises an inorganic clay material, such as a hydrous sodium lithium magnesium silicate synthetic smectite type clay, which is added to the ink in sufficient quantity to give the ink a viscosity of about 30 to 300 cps when measured at 20°C using a rotary viscometer in which a tapered cone is rotating at a fixed velocity to give a shear rate of 0.2 reciprocal seconds.
  • an inorganic clay material such as a hydrous sodium lithium magnesium silicate synthetic smectite type clay
  • the aforementioned latex emulsion blend comprises a first non-carboxylated styrene-butadiene latex emulsion which contains about 40% total solids by weight and which has a Brookfield viscosity at 25°C of about 30 cps, a pH of about 10.5-11.7, a Mooney value of about 150-160, a surface tension of about 55-65 dynes/cm, a particle size of about 650 Angstroms and a bound styrene content of about 21-29% (preferably about 21-25%), and a second non-carboxylated styrene-butadiene latex emulsion which contains about 70% total solids by weight and which has a Brookfield viscosity at 25°C of about 1200 cps, a pH of about 10.0-10.5, a Mooney value of about 70-75, a surface tension of about 32-36 dynes/cm, and a bound sty
  • said first non-carboxylated styrene-butadiene latex emulsion constitutes about 45-50%, by weight, of the total composition
  • said second non-carboxylated styrene-butadiene latex emulsion constitutes about 20-25%, by weight, of the total composition
  • said first and said second non- carboxylated styrene-butadiene latex emulsions together constituting approximately 70%, by weight, of the total composition.
  • said latex emulsion blend comprises the above-described first and second non-carboxylated styrene-butadiene latex emulsions and further comprises a third non-carboxylated styrene-butadiene latex emulsion, said third non-carboxylated styrene-butadiene latex emulsion containing about 47% total solids by weight and having a Brookfield viscosity at 25°C of about 200 cps, a pH of about 9.5-10.0, a Mooney value of about 70-75, a surface tension of about 60-65 dynes/cm, a particle size of about 640-720 Angstroms and a bound styrene content of about 22-26%.
  • said first non-carboxylated styrene- butadiene latex emulsion constitutes about 30-50% (more preferably about 40%), by weight, of the total composition
  • said second non-carboxylated styrene- butadiene latex emulsion constitutes about 5-20% (more preferably about 10%), by weight, of the total composition
  • said third non-carboxylated styrene-butadiene latex emulsion constitutes about 10-30% (more preferably about 20%), by weight, of the total composition
  • said latex emulsion blend comprises the above-described first and third non-carboxylated styrene-butadiene latex emulsions.
  • said first non-carboxylated styrene-butadiene latex emulsion constitutes about 30-50%, by weight, of the total composition
  • said third non- carboxylated styrene-butadiene latex emulsion constitutes about 10-30%, by weight, of the total composition
  • said first and said third non-carboxylated styrene- butadiene latex emulsions together constituting approximately 70%, by weight, of the total composition.
  • the erasable ink of the present invention preferably further includes an antioxidant, such as a tocopherol (vitamin E), which is used to extend the period of time over which the composition remains erasable after being applied to a marking substrate.
  • an antioxidant such as a tocopherol (vitamin E)
  • the time-extending effect of the tocopherol may be further enhanced by combining the tocopherol with vitamin C.
  • the above-described erasable ink preferably further comprises an anti- corrosion agent, such as EDTA and/or benzotriazol, which is used to prevent corrosion caused by the ink to the tip of a pen containing the ink.
  • an anti- corrosion agent such as EDTA and/or benzotriazol
  • the above-described erasable ink preferably further comprises a shear- stabilizing agent which is included in the composition to prevent coagulation of the discontinuous rubber phase under conditions of high shear, such as during formulation (i.e., mixing) of the composition or during application of the composition to a marking substrate.
  • a particularly preferred shear-stabilizing agent is potassium oleate.
  • the above-described erasable ink preferably further comprises a pH- adjusting agent, which is used to shift the pH of the composition to a pH of about 9-10.
  • a particularly preferred pH-adjusting agent is triethanolamine (TEA).
  • the above-described erasable ink preferably further comprises an anti-drying agent.
  • the anti-drying agent comprises a 1 :1 , 2:1 or 3:1 mixture of sorbitol and glycerine, respectively.
  • a 3:1 mixture of sorbitol to glycerine is particularly preferred.
  • the above-described erasable ink may further include an alkyl acrylate copolymer emulsion for use in improving the smoothness of writing of the ink.
  • the present invention is also directed to the combination of the above- described erasable ink and a writing instrument.
  • the writing instrument is a filler-less, nib-less, roller-ball pen.
  • the filler-less, nib-less, roller-ball pen preferably comprises (a) a barrel adapted for storing a quantity of ink, said barrel having an open top end; (b) a hollow tip, said hollow tip being made of metal or polyoxymethylene and having a top end and a bottom end, said top end being shaped to define a ball socket; (c) a ball rotatably received in said ball socket, said ball being made of a non-metallic material; and (d) an elongated hollow connector, said elongated hollow connector having an open top end adapted to receive the bottom end of said tip and an open bottom end adapted to be received in the open top end of said barrel.
  • Fig. 2 is an enlarged fragmentary section view of the filler-less, nib-less, roller-ball pen shown in Fig. 1 , illustrating details of the writing end of the pen.
  • FIG. 1 there is illustrated one embodiment of a filler-less, nib- less, roller-ball pen constructed according to the teachings of the present invention, said filler-less, nib-less, roller-ball pen being represented generally by reference numeral 11.
  • Pen 11 comprises a barrel member 13, which has an open top end 15 and an open bottom end 17. A quantity of an ink 101 to be hereinafter described is loaded into barrel member 13, as is a highly-viscous, jelly-like follower 20.
  • barrel member 13 is made of polypropylene.
  • Pen 11 also comprises an elongated hollow connector 21. Connector 21 has an open top end 23 and an open bottom end 25, open bottom end 25 being securely mounted within open top end 15 of barrel 13.
  • Connector 21 is preferably made of a polyoxymethylene.
  • Pen 11 additionally comprises a hollow tip 29, tip 29 having a top end 31 and a bottom end 33.
  • Top end 31 is shaped to include a ball socket 35.
  • Bottom end 33 is securely mounted within top end 23 of connector 21.
  • Tip 29 is preferably made of a stainless steel (e.g., felite SUS 430 wherein C ⁇ 0.05%, Si ⁇ 1.00%, Mn ⁇ 2.00%, P ⁇ 0.050%, SO.150%, Pb ⁇ 0.30%, Te ⁇ 0.08%, Cr ⁇ 19.00-21.00% and Mo ⁇ 1.5-2.5%), a "nickel-silver" alloy (e.g., Cu ⁇ 57.0-61.0%, Ni ⁇ 14.0-16.0%, Mn ⁇ 0-0.5%, Fe ⁇ 0.25%, Pb -2.5-3.5% and Zn-residual) or a polyoxymethylene.
  • a stainless steel e.g., felite SUS 430 wherein C ⁇ 0.05%, Si ⁇ 1.00%, Mn ⁇ 2.00%, P ⁇ 0.050%
  • Pen 11 further comprises a ball 41 rotatably received in ball socket 35.
  • Ball 41 is made of a non-metallic material, preferably a sintered ceramic, such as a silicon-carbide, zirconium oxide or aluminum oxide. Tungsten-carbide may also be used as a ball material but is not as preferred as sintered ceramics.
  • suitable combinations of tips 29 and balls 41 include, but are not limited to, the following: (1) polyoxymethylene tip/SiC ball; (2) stainless steel tip/SiC ball; (3) nickel-silver tip/tungsten carbide ball; (4) nickel-silver tip/SiC ball; and (5) stainless steel tip/tungsten carbide ball.
  • ball 41 and socket 35 Additional details of ball 41 and socket 35 are shown in Fig. 2.
  • ball 41 has a diameter d of approximately 0.7 mm or greater.
  • Socket 35 has a maximum internal width w that exceeds the diameter of ball by approximately 0.015-0.025 mm.
  • socket 35 is shaped to enable ball 41 to move axially therewithin a distance c of approximately 0.03-0.07 mm.
  • ink 101 is an erasable ink that is erasable from both porous and non-porous marking substrates by substantially non-abrasive mechanical means.
  • ink 101 comprises (a) a latex emulsion blend comprising two or more non-carboxylated styrene-butadiene latex emulsions, said latex emulsion blend being characterized by its ability to be transformed, upon being contacted with the surface of a porous marking substrate, from a first state in which said latex emulsion blend is stable to a second state in which said latex emulsion blend is unstable and the styrene- butadiene phase rapidly agglomerates to form a cohesive film deposited directly on the surface of the porous marking substrate with low adhesion thereto; (b) a colorant dispersed in the latex emulsion blend, the colorant being characterized by its association with the cohesive rubber
  • the shear-thinning, viscosity-adjustment agent comprises an inorganic clay material, such as a hydrous sodium lithium magnesium silicate synthetic smectite type clay.
  • an inorganic clay material include Laponite ® XLG rheological additive, Laponite ® S rheological additive and Laponite ® RD rheological additive, all of which are commercially available from Southern Clay Products, Inc., Gonzales, TX.
  • the clay material is added to the ink in the form of a solution of Laponite ® XLG or Laponite ® RD in glycerine and water (3% Laponite ® /40% glycerine/57% water), the 3% Laponite ® solution constituting about 3-10%, preferably about 7%, by weight, of ink 101.
  • the addition of the aformentioned amount of the shear-thinning viscosity-adjustment agent gives ink 101 a viscosity of about 30 to 300 cps when measured at 20°C using a rotary viscometer in which a tapered cone is rotating at a fixed velocity to give a shear rate of 0.2 reciprocal seconds.
  • the colorant of ink 101 is preferably a water-insoluble or water-dispersible pigment that is also oliophilic.
  • Such pigments may be selected from among standard industry pigments which are known to be well-suited for being dispersed in aqueous systems and which are capable of associating with the rubber phase of a non-carboxylated styrene-butadiene latex emulsion, as opposed to being associated with the water phase thereof. Examples of such pigments are carbon black and ultra-fine fluorescent pigments, as well as mixtures thereof. Other pigments, dyes and toners which behave in the same manner may also be used in ink 101. Generally, the colorant is present in an amount constituting about 2-5%, by weight, of ink 101.
  • the aforementioned latex emulsion blend comprises a first non-carboxylated styrene-butadiene latex emulsion which contains about 40% total solids by weight and which has a Brookfield viscosity at 25°C of about 30 cps, a pH of about 10.5-11.7, a Mooney value of about 150-160, a surface tension of about 55-65 dynes/cm, a particle size of about 650 Angstroms and a bound styrene content of about 21-29% (preferably about 21-25%), and a second non-carboxylated styrene-butadiene latex emulsion which contains about 70% total solids by weight and which has a Brookfield viscosity at 25°C of about 1200 cps, a pH of about 10.0-10.5, a Mooney value of about 70-75, a surface tension of about 32-36 dynes/cm, and a bound sty
  • said latex emulsion blend comprises the above-described first and said second non-carboxylated styrene-butadiene latex emulsions and further comprises a third non-carboxylated styrene-butadiene latex emulsion, said third non-carboxylated styrene-butadiene latex emulsion containing about 47% total solids by weight and having a Brookfield viscosity at 25°C of about 200 cps, a pH of about 9.5-10.0, a Mooney value of about 70-75, a surface tension of about 60-65 dynes/cm, a particle size of about 640-720 Angstroms and a bound styrene content of about 22-26%.
  • said first non-carboxylated styrene- butadiene latex emulsion constitutes about 30-50% (more preferably about 40%), by weight, of the total composition
  • said second non-carboxylated styrene- butadiene latex emulsion constitutes about 5-20% (more preferably about 10%), by weight, of the total composition
  • said third non-carboxylated styrene-butadiene latex emulsion constitutes about 10-30% (more preferably about 20%), by weight, of the total composition
  • said latex emulsion blend comprises the above-described first and third non-carboxylated styrene-butadiene latex emulsions.
  • said first non-carboxylated styrene-butadiene latex emulsion constitutes about 30-50%, by weight, of the total composition
  • said third non- carboxylated styrene-butadiene latex emulsion constitutes about 10-30%, by weight, of the total composition
  • said first and said third non-carboxylated styrene- butadiene latex emulsions together constituting approximately 70%, by weight, of the total composition.
  • PLIOLITE ® LPF-2108 Goodyear Tire and Rubber Company, Akron, Ohio
  • PLIOLITE ® LPF-3757 which, apparently, is different in composition from the PLIOLITE ® LPF-3757 emulsion referred to in Lin et al.
  • An example of said second non-carboxylated styrene-butadiene latex emulsion is BUTONAL ® NS 104 (BASF Corporation, Charlotte, NC)
  • an example of said third non-carboxylated styrene-butadiene latex emulsion is BUTOFAN ® NS 103 (BASF Corporation, Charlotte, NC).
  • inks containing a blend of two or more of the above-described latex emulsions are superior to corresponding inks containing only a single such latex emulsion in that the inks containing a blend permit greater control over the suface tension of the final ink composition than do inks containing a single latex emulsion. This is significant because surface tension has an effect on the extent of penetration of the ink into the marking substrate.
  • the erasability of ink 101 may be extended by including therein an antioxidant, such as a tocopherol (vitamin E).
  • the time-extending effect of the tocopherol may be further enhanced by the concurrent addition of vitamin C to ink 101.
  • Oxynex ® K liquid a commercially available antioxidant preparation from E. Merck (Germany) which includes both a tocopherol (constituting about 30% by weight of the preparation) and vitamin C (constituting about 6% by weight of the preparation).
  • Oxynex ® K is added to the present composition in an amount constituting about 0.1-0.7%, preferably 0.15%, by weight of ink 101.
  • Ink 101 preferably further comprises a shear-stabilizing agent which is included in the composition to prevent coagulation of the discontinuous rubber phase under conditions of high shear, such as during formulation (i.e., mixing) of the composition or during application of the composition to a marking substrate.
  • the shear-stabilizing agent is preferably a fatty acid salt.
  • Potassium oleate is a particularly preferred shear-stabilizing agent and is preferably present in ink 101 in an amount constituting about 0.2-1.5%, dry weight, of the dry weight of the non- carboxylated styrene-butadiene copolymer of the latex emulsion blend. More preferably, potassium oleate constitutes about 0.6%, by weight, of ink 101.
  • a shear-stabilizing agent is Modicol ® S, a sulfated fatty acid commercially available from Henkel Corporation, Ambler, PA.
  • Ink 101 preferably further comprises a pH-adjusting agent, which is used to shift the pH of the composition to a pH of about 9-10.
  • the pH-adjusting agent is triethanolamine (TEA), which is present in an amount constituting about 0.5-1.5% (preferably about 1.0%), by weight, of ink 101.
  • Ink 101 preferably further comprises an anti-drying agent.
  • said anti-drying agent includes one or more water-soluble organic ketones, esters and alcohols that do not have a significant deleterious effect on the composition or its properties and whose boiling point is relatively high, e.g., from about 140°C to about 300°C.
  • Suitable anti-drying agents include sorbitol (preferably of a non-crystallizing variety), glycerine, urea or a mixture thereof.
  • the anti-drying agent comprises a 1:1 , 2:1 or 3:1 mixture of sorbitol to glycerine, respectively.
  • a mixture comprising a 3:1 ratio of sorbitol to glycerine is more preferred, and such a 3:1 mixture constitutes about 3-15%, preferably about 7%, by weight, of ink 101.
  • Ink 101 preferably further includes an anti-corrosion agent.
  • said anti-corrosion agent is benzotriazol and/or EDTA present in a total amount constituting about 0.2-0.5% (preferably about 0.2%), by weight, of ink 101.
  • Ink 101 may also include an alkyl acrylate copolymer emulsion for use in improving the smoothness of writing of the ink. Best results are obtained when such an alkyl acrylate copolymer emulsion, if used, is added to non-carboxylated styrene-butadiene latex emulsion blends of the type not containing BUTONAL ® NS 104.
  • Deionized water 12.35 pH of composition 9.58 viscosity of composition (measured at 20°C using a rotary viscometer in which a tapered cone is rotating at a fixed velocity to give a shear rate of 0.2 reciprocal seconds) 74.7 cps
  • pH of composition 9.65 viscosity of composition (measured at 20°C using a rotary viscometer in which a tapered cone is rotating at a fixed velocity to give a shear rate of 0.2 reciprocal seconds) 52.7 cps

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

Abstract

L'invention concerne une encre effaçable fluidifiante à base aqueuse ainsi qu'un stylo à bille roulante la contenant. Dans un mode préféré de réalisation, cette encre comprend un mélange de trois émulsions aqueuses différentes non carboxylées de styrène-butadiène, un pigment insoluble dans l'eau ou dispersible dans l'eau et un agent fluidifiant de réglage de la viscosité sous la forme d'une argile au silicate. L'encre renferme également une préparation anti-oxydante comprenant du tochophérol et de la vitamine C en vue d'accroître la durée pendant laquelle l'encre demeure effaçable après avoir été appliquée sur un substrat, un agent stabilisant le cisaillement sous la forme d'un oléate de potassium en vue d'empêcher une coagulation non désirée du copolymère de styrène-butadiène par suite du cisaillement, un agent de réglage du pH sous la forme d'un triéthanolamine pour faire passer le pH de l'encre à un pH d'environ 9-10, et un antisiccatif sous la forme d'un mélange de sorbitol et de glycérine à raison de 3 pour 1. Le stylo comporte un corps (13) permettant le stockage d'une certaine quantité d'encre, ce corps étant réalisé en polypropylène et présentant une extrémité supérieure ouverte (15); une pointe creuse (29) constituée d'un acier inoxydable, d'un alliage nickel-argent ou d'un polyoxyméthylène et munie d'une extrémité supérieure (31) et d'une extrémité inférieure (33), l'extrémité supérieure étant configurée pour définir une alvéole de bille (35); une bille (41) logée rotative dans cette alvéole (35) et constituée d'un matériau céramique fritté; et un élément de raccordement (21) creux allongé constitué d'un polyoxyméthylène et comportant une extrémité supérieure ouverte (23) adaptée pour recevoir l'extrémité inférieure de la pointe creuse, et une extrémité inférieure ouverte (25) adaptée pour se loger dans l'extrémité supérieure ouverte (15) du corps. La bille (41) présente un diamètre minimal d'environ 0,7 mm. L'alvéole (35) présente une largeur interne maximale excédant le diamètre de la bille (41) d'approximativement 0,015-0,025 mm et est configurée pour permettre à la bille de s'y déplacer axialement sur une distance d'approximativement 0,03-0,07 mm.
PCT/US1996/017553 1995-11-01 1996-10-30 Encre effaçable fluidifiante a base aqueuse et stylo a bille roulante la contenant WO1997016499A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
JP9517574A JP2000509410A (ja) 1995-11-01 1996-10-30 水性ベースの剪断希釈式の消去可能インキ及びそれを含むローラーボールペン
AU76033/96A AU7603396A (en) 1995-11-01 1996-10-30 Aqueous-based, shear-thinning, erasable ink and roller-ball pen containing same
EP96938722A EP0858487A4 (fr) 1995-11-01 1996-10-30 Encre effa able fluidifiante a base aqueuse et stylo a bille roulante la contenant

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US08/551,545 US5629363A (en) 1994-02-10 1995-11-01 Aqueous-based, shear-thinning, erasable ink and roller-ball pen containing same
US58519996A 1996-01-11 1996-01-11
US08/551,545 1996-01-11
US80/585,199 1996-01-11

Publications (1)

Publication Number Publication Date
WO1997016499A1 true WO1997016499A1 (fr) 1997-05-09

Family

ID=27069799

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1996/017553 WO1997016499A1 (fr) 1995-11-01 1996-10-30 Encre effaçable fluidifiante a base aqueuse et stylo a bille roulante la contenant

Country Status (5)

Country Link
EP (1) EP0858487A4 (fr)
JP (1) JP2000509410A (fr)
AU (1) AU7603396A (fr)
CA (1) CA2236379A1 (fr)
WO (1) WO1997016499A1 (fr)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2761637A1 (fr) * 1997-04-03 1998-10-09 Mitsubishi Pencil Co Ensemble de pointe d'un stylo a bille
EP1093936A1 (fr) * 1998-05-27 2001-04-25 Mitsubishi Pencil Kabushiki Kaisha Instrument d'ecriture
EP1340624A1 (fr) * 2000-11-09 2003-09-03 Mitsubishi Pencil Kabushiki Kaisha Article pour ecrire dont la pointe ne desseche pas, meme sans capuchon
EP1413457A1 (fr) * 2002-10-22 2004-04-28 The Pilot Ink Co., Ltd. Stylo à bille
WO2014106241A1 (fr) * 2012-12-31 2014-07-03 Sanford, L.P. Compositions pour générer des surfaces d'écriture à effacement à sec à la demande, applicateurs de fluide les contenant et procédés

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US5338793A (en) * 1992-06-02 1994-08-16 The Gillette Company Erasable ink
US5362167A (en) * 1991-12-18 1994-11-08 The Gillette Company Fiber marker including an erasable ink
US5389717A (en) * 1992-03-23 1995-02-14 Binney & Smith Inc. Erasable marking composition

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US4145148A (en) * 1976-10-01 1979-03-20 Sakura Color Products Corporation Ball-point pen for a low-viscosity ink
FR2404537A1 (fr) * 1977-09-29 1979-04-27 Pilot Ink Co Ltd Stylo a bille
JPS5980476A (ja) * 1982-10-29 1984-05-09 Pilot Pen Co Ltd:The 消去可能なボ−ルペン用インキ
US4686246A (en) * 1985-12-23 1987-08-11 The Gillette Company Shock resistant ink compositions and writing instruments including the compositions
US5217255A (en) * 1986-09-15 1993-06-08 Lin Nan J Erasable system including marking surface and erasable ink composition
TW294703B (fr) * 1992-10-23 1997-01-01 Avery Dennison Corp

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Publication number Priority date Publication date Assignee Title
US5362167A (en) * 1991-12-18 1994-11-08 The Gillette Company Fiber marker including an erasable ink
US5389717A (en) * 1992-03-23 1995-02-14 Binney & Smith Inc. Erasable marking composition
US5338793A (en) * 1992-06-02 1994-08-16 The Gillette Company Erasable ink

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP0858487A4 *

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2761637A1 (fr) * 1997-04-03 1998-10-09 Mitsubishi Pencil Co Ensemble de pointe d'un stylo a bille
US6161977A (en) * 1997-04-03 2000-12-19 Mitsubishi Pencil Kabushiki Kaisha Point assembly of a ball-point pen
EP1093936A1 (fr) * 1998-05-27 2001-04-25 Mitsubishi Pencil Kabushiki Kaisha Instrument d'ecriture
EP1093936A4 (fr) * 1998-05-27 2004-03-31 Mitsubishi Pencil Co Instrument d'ecriture
EP1340624A1 (fr) * 2000-11-09 2003-09-03 Mitsubishi Pencil Kabushiki Kaisha Article pour ecrire dont la pointe ne desseche pas, meme sans capuchon
EP1340624A4 (fr) * 2000-11-09 2004-12-01 Mitsubishi Pencil Co Article pour ecrire dont la pointe ne desseche pas, meme sans capuchon
US7001094B2 (en) 2000-11-09 2006-02-21 Mitsubishi Pencil Kabushiki Kaisha Writing utensil having excellent cap-off performance
EP1413457A1 (fr) * 2002-10-22 2004-04-28 The Pilot Ink Co., Ltd. Stylo à bille
US6805511B2 (en) 2002-10-22 2004-10-19 The Pilot Ink Co., Ltd. Ball point pen
EP1621363A1 (fr) * 2002-10-22 2006-02-01 The Pilot Ink Co., Ltd. Stylo à bille
CN100411883C (zh) * 2002-10-22 2008-08-20 百乐墨水株式会社 圆珠笔
WO2014106241A1 (fr) * 2012-12-31 2014-07-03 Sanford, L.P. Compositions pour générer des surfaces d'écriture à effacement à sec à la demande, applicateurs de fluide les contenant et procédés

Also Published As

Publication number Publication date
AU7603396A (en) 1997-05-22
CA2236379A1 (fr) 1997-05-09
EP0858487A4 (fr) 1999-05-12
EP0858487A1 (fr) 1998-08-19
JP2000509410A (ja) 2000-07-25

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