CN102666750A - Aqueous ink composition for ballpoint pen - Google Patents
Aqueous ink composition for ballpoint pen Download PDFInfo
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- CN102666750A CN102666750A CN2010800535834A CN201080053583A CN102666750A CN 102666750 A CN102666750 A CN 102666750A CN 2010800535834 A CN2010800535834 A CN 2010800535834A CN 201080053583 A CN201080053583 A CN 201080053583A CN 102666750 A CN102666750 A CN 102666750A
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- 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
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Abstract
Provided is a novel aqueous ink composition for ballpoint pens, which has the advantages of both aqueous ballpoint pens and oil-based ballpoint pens. The ink composition for aqueous ballpoint pens contains, in a manner such that the oil emulsifies in the aqueous phase, a colorless oil-based phase, which has a viscosity of 300 to 500,00mPas when the sheer rate is 38/sec, in relation to a colored aqueous phase containing a pigment dispersion, a water-soluble dye, or a mixture thereof.
Description
Technical field
The present invention relates to ballpoint pen use ink composite, the form that relates in particular to oil-in-water emulsion contains through the painted water-based phase and the oiliness ballpoint pen use ink composite mutually of non-coloring.
Background technology
Characteristic as the aqueous ballpoint pen that uses water color ink; Can enumerate LV, ink flow output many, can obtain the distinct line of retouching with the very light impression of wieling the pen; But on the contrary, have as the one of which in the impression of wieling the pen feel obstructed, nib is dry, cause the shortcoming of the phenomenon that can't write easily.And use the oiliness ballpoint pen of oil-based ink because ink viscosity is high, the ink flow output is few, thereby have obstructed sense when not writing, retouch line bleeding advantage seldom, but have the very heavy impression of wieling the pen more.
In recent years, also developed the viscosity that reduces oil-based ink with the wield the pen oiliness ballpoint pen of impression of raising.But, because the ink flow output of low viscous oil-based ink when writing increase, thereby retouch the line drying property and worsen, ink penetration inside paper, thereby cause ink bleed.
Put down in writing the low viscous oiliness ball pen ink of water-in-oil (W/O) type that in organic solvent, contains water in the TOHKEMY 2004-115611 communique.But, the storage stability existing problems of this printing ink, the major part of printing ink composition is an organic solvent in addition, thereby when discharge is write in increase, can permeate.
Disclose in the TOHKEMY 2007-327003 communique through making pigment contain in water composition and become phase-splitting to mix the formed water droplet of the water composition by being dispersed with pigment that obtains with oiliness it in advance and be dispersed to the w/o type emulsion ink compsn in the oiliness composition.Disclose through using this ink composite to improve to wield the pen the ball pen ink of impression etc., but during prolonged preservation, water droplet is unified, localization etc. deficient in stability.In addition, because the amount of the oiliness composition in the ink composite is a lot, thereby increases when writing discharge as aqueous ballpoint pen, the deterioration of permeating, retouching the line drying property is remarkable.
In addition, put down in writing in the japanese kokai publication sho 55-152768 communique will in the polymers soln that solvent constituted, be dispersed with pigment by polymkeric substance, the said polymkeric substance of dissolving use printing ink through painted compsn writing of carrying out in water that emulsification disperses that eraser that form, capable of using eliminates.But when this printing ink was used for ballpoint pen, writing property was poor, and dispersed particle is unified easily in addition, sedimentation, and storage stability also has problem.
Thereby put down in writing in the TOHKEMY 2004-323618 communique when writing with ink composite vibrate with form its write line of unsettled latex short, brokenly the continually varying writing implement to take place use polychrome printing ink, said ink composite is made up of water-based ink that contains water-soluble dye and the oil soluble printing ink that contains oil-soluble colourant.Put down in writing this printing ink and under static condition, can be separated into 2 layers, as common ball pen ink and be not suitable for.
The printing ink proterties that discloses the advantage that possesses aqueous ballpoint pen and oiliness ballpoint pen in the applicant's the Japan special hope 2008-145150 specification sheets is the ballpoint pen use ink composite of oil-in-water emulsion.This printing ink can improve the color depth toning high with carrying out degree of freedom and change; Simultaneously; Owing to must contain painted materials such as dyestuff in mutually in order to obtain water tolerance in oiliness; Thereby have emulsion concentration and retouch the problem that the line drying property worsens when high, also have emulsion concentration in addition and retouch the inadequate problem of line concentration when low.
The prior art document
Patent documentation
Patent documentation 1: TOHKEMY 2004-115611 communique
Patent documentation 2: TOHKEMY 2007-327003 communique
Patent documentation 3: japanese kokai publication sho 55-152768 communique
Patent documentation 4: TOHKEMY 2004-323618 communique
Patent documentation 5: Japan special hope 2008-145150 specification sheets
Summary of the invention
Invent technical problem to be solved
As stated, aqueous ballpoint pen, oiliness ballpoint pen have merits and demerits separately.The object of the present invention is to provide the novel ball-point pen use ink composite of both advantages.
The means that are used for the technical solution problem
The inventor furthers investigate, and the result finds: through making up oiliness phase in the water-based that contains painted materials such as pigment dispersion in mutually with the form of oil-in-water emulsion, can solve above-mentioned problem, thereby accomplish the present invention.
That is, the present invention is:
(1) a kind of ballpoint pen use ink composite; Its form with oil-in-water emulsion contain water-based mutually with oiliness mutually; Said water-based be mutually contain pigment dispersion or water-soluble dye or their mixture through painted water-based phase; Said oiliness is to be that viscosity under 38/ second is 300～500 at 25 ℃, velocity of shear mutually, the oiliness phase of the non-coloring of 000mPas.
(2) above-mentioned (1) described ballpoint pen use ink composite, wherein, said oiliness contains solvent mutually, and boiling point is that the solvent more than 200 ℃ accounts for more than 50% of whole solvents in quality standard.
(3) above-mentioned (1) or (2) described ballpoint pen use ink composite, wherein, oiliness phase composition shared ratio in said ink composite counts 1～30% with quality standard.
(4) each described ballpoint pen use ink composite of above-mentioned (1) ~ (3), wherein, the median size of the oil droplet of said oil-in-water emulsion is below the 250nm.
(5) each described ballpoint pen use ink composite of above-mentioned (1) ~ (4); It is characterized in that; Said oiliness contains solvent mutually, and the solubleness of this solvent in 20 ℃ water is counted below 5% with quality standard and had the aromatic nucleus more than 1 in the molecular skeleton.
(6) each described ballpoint pen use ink composite of above-mentioned (1) ~ (5) is characterized in that, said oiliness mutually or said water-based phase any one or contain the emulsifying agent that in molecular skeleton, has 1 above aromatic nucleus among both.
(7) a kind of ballpoint pen, it is equipped with each described ballpoint pen use ink composite of above-mentioned (1)～(6).
The invention effect
Ballpoint pen use ink composite of the present invention is characterised in that, contains in water-based to contain painted materials such as pigment in mutually, do not contain the oil-in-water emulsion of coloured material in mutually in oiliness.Thus, except the very light impression of wieling the pen of conduct aqueous ballpoint pen advantage in the past, oil-in-water emulsion is also brought into play following action effect.That is, the oil film through the oiliness phase provides the impression of wieling the pen that do not have obstructed sense, simultaneously water tolerance is provided.The present invention provides the storage stability of the advantage that has aqueous ballpoint pen printing ink and oiliness ball pen ink concurrently good ballpoint pen use ink composite.
Embodiment
Ink composite of the present invention has following formation: water-based contains pigment dispersion or water-soluble dye or their mixture mutually, and contains oiliness phase with the state of oil-in-water emulsion in said water-based in mutually.The composition of ink composite of the present invention below at length is described.
The oiliness of ink composite of the present invention is to be that viscosity under 38/ second is 300～500 at 25 ℃, velocity of shear mutually, the oiliness phase solution of the non-coloring of 000mPas.This oiliness phase solution contains organic solvent.For in the past ballpoint pen with the solvent that uses in the oil-based ink, from require to make its contained dyestuff dissolving and be through the time stable solution viewpoint, according to selecting to have the organic solvent of specific molecular structure with the relation of used dyestuff.But the oiliness of ink composite of the present invention is not mutually owing to contain coloured material, thereby need not to select specific organic solvent, can use any organic solvent that uses in the ball pen ink of prior art.
For example can enumerate following solvent in the spendable solvent in the oiliness phase solution of the present invention.Can enumerate benzylalcohol; The glycol monomethyl phenyl ether; The glycol monomethyl benzylic ether; Ethylene glycol mono hexyl ether; Terepthaloyl moietie 2-ethylhexyl ether; Ucar 35 list phenyl ether; Diethylene Glycol list phenyl ether; Diethylene Glycol single 2-ethyl hexyl ether; The alkylsulphonic acid phenylester; Butyl phthalate; The phthalic acid ethylhexyl; Phthalic acid tridecyl ester; Dimethyl phthalate; Diethyl phthalate; Witcizer 300; DOP; The trimellitic acid ethylhexyl; The Diethylene Glycol dibenzoate; Dipropylene glycol dibenzoate; YLENE; Toluene; Hexanaphthene; Methylcyclohexane; Normal hexane; Octane; N-decane; PC 560; Firpene; N-hexyl alcohol; N-Heptyl alcohol; N-Octanol; Nonyl alcohol; Nonylcarbinol; Hendecanol; N-dodecane alcohol; Exxal 12; Tetradecanol; Heptadecanol; Hexalin; 2 methyl cyclohexanol; α-terpinol; N-hexyl ether; Methyl phenyl ether; Ethylphenyl ether; N-butyl phenyl ether; Methyl n hexyl ketone; Acetic acid-2-ethylhexyl; Cyclohexyl acetate; Acetic acid methyl cyclohexane ester; Benzyl Acetate FFC; Butyl stearate; Amyl stearate; Ethyl abietate; Sad; 2 ethyl hexanoic acid; LAURIC ACID 99 MIN; Tetradecanoic acid; Palmitinic acid; Triple Pressed Stearic Acid; Oleic acid etc.
Press the viewpoint that rises the instabilityization that is caused in the emulsion during from inhibition high temperature, preferred boiling point is the solvent more than 200 ℃.As the example of preferred solvent, can enumerate benzylalcohol, glycol monomethyl phenyl ether, glycol monomethyl benzylic ether, Ucar 35 list phenyl ether, Diethylene Glycol list phenyl ether, alkylsulphonic acid phenylester, butyl phthalate, phthalic acid ethylhexyl, phthalic acid tridecyl ester, trimellitic acid ethylhexyl, Diethylene Glycol dibenzoate, terepthaloyl moietie-2-ethylhexyl ether, Diethylene Glycol list-2-ethylhexyl ether, dipropylene glycol dibenzoate etc.
Solvent can be made up of the a kind of solvent that is selected from the above-mentioned solvent example, perhaps can be made up of multiple solvent.When using multiple solvent, preferred boiling point is that the solvent more than 200 ℃ is the main solvent more than 50% that accounts for whole solvents of oiliness phase in quality standard.Boiling point be solvent more than 200 ℃ less than 50% o'clock, emulsifying stability is poor, and is not preferred.
In addition, consider when storage stability water insoluble in fact, formed emulsion is good, safe to have 1 above aromatic nucleus in the preferred molecular skeleton and the solubleness of solvent in water is counted the solvent below 5% with quality standard under 20 ℃.Solubleness surpasses at 5% o'clock in quality standard, sometimes gained emulsion become unstable and through the time ground be separated.
In addition, in the oiliness phase solution of the present invention, except above-mentioned solvent, also can contain secondary solvent as required.For example can use the solvent that is selected from alcohols, polyalcohols, glycol ethers, hydro carbons, the ester class etc., but owing to can cause the diffusion during the hydrotropisms mutually, the unification of oil droplet with solvent that water ad infinitum dissolves each other, thereby do not answer volume ground to use.In the quality % of the whole solvents in the oiliness phase solution, can be in 10%.
As alcohols; Preferred carbon number is the fatty alcohol more than 2; For example can enumerate ethanol, n-propyl alcohol, Virahol, propyl carbinol, isopropylcarbinol, the trimethyl carbinol, 1-amylalcohol, primary isoamyl alcohol, sec.-amyl alcohol, 3-amylalcohol, tertiary amyl alcohol, methyl amyl alcohol, 2-ethyl butanol, 2-enanthol, 3-enanthol, sec-n-octyl alcohol, 2-Ethylhexyl Alcohol, 3; 5,5-trimethyl hexanol or other multiple higher alcoholss etc.
In addition; As polyalcohols, preferred intramolecularly has the polyvalent alcohol of 2 above carbon, 2 above hydroxyls, for example can enumerate terepthaloyl moietie, Diethylene Glycol, 3-methyl isophthalic acid; 3-butyleneglycol, triethylene glycol, dipropylene glycol, 1; Ammediol, 1,3 butylene glycol, 1,5-pentanediol, pinakon, ethohexadiol etc.
As glycol ethers, for example can enumerate methyl isopropyl ether, ethyl ether, ethyl propyl ether, ethyl-butyl ether, isopropyl ether, butyl ether, hexyl ether, 2-ethylhexyl ether, glycol monomethyl-2-ethyl-butyl ether, glycol monomethyl methyl ether, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, TC, Diethylene Glycol single-butyl ether, triethylene glycol single-butyl ether, TEG single-butyl ether, 3-methyl-3-methoxyl group-1-butanols, 3-methoxyl group-1-butanols, propylene glycol monomethyl ether, Ucar 35 list ethyl ether, Ucar 35 list propyl ether, Ucar 35 single-butyl ether, glycol tertiary butyl ether DPGME, dihydroxypropane single-ethyl ether, dipropylene glycol list propyl ether, dipropylene glycol single-butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol single-butyl ether, four Ucar 35 single-butyl ethers etc.
As hydro carbons, can enumerate ring-type hydro carbons such as straight chain hydrocarbon such as isohexane, heptane, nonane or ethylcyclohexane.
As the secondary solvent of ester class, for example can enumerate various esters such as propylene glycol methyl ether acetate, PGDA, 3-methyl-3-methoxyl group butylacetic acid ester, Ucar 35 ethyl ether acetic ester, glycol ethyl ether acetic ester, butyl formate, tetryl formate, isoamyl formate, propyl acetate, N-BUTYL ACETATE, Iso Butyl Acetate, isobutyl acetate, isoamyl acetate, methyl propionate, ethyl propionate, propyl propionate, isobutyl propionate, isopentyl pyruvate, methyl-butyrate, ethyl n-butyrate, propyl butyrate, methyl isobutyrate, ethyl isobutyrate, propyl isobutyrate, methyl valerate, Valeric acid ethylester, propyl valerate, methyl isovalerate, Ethylisovalerate, propyl isovalerate, pivalic methyl esters, pivalic ethyl ester, pivalic propyl ester, methyl caproate, NSC 8882, propyl hexanoate, methyl caprylate, ethyl octylate, propyl caprylate, Laurate methyl, Laurate ethyl, Witconol 2301, OE, tricaprylin, Hydrocerol A tributyl acetic ester, oxygen base octyl stearate, Ucar 35 list ricinoleate, 2-hydroxy-methyl isobutyl acid, 3-methoxyl group butylacetic acid ester.
In addition; The secondary solvent that does not have hydroxyl as intramolecularly; Can use diether or diester; Specifically, for example can enumerate ethylene glycol bisthioglycolate ethyl ether, ethylene glycol bisthioglycolate butyl ether, diethylene glycol diethyl ether, Diethylene Glycol dibutyl ether, diethylene glycol dimethyl ether, dipropylene glycol dimethyl ether, 2,6-naphthalene dicarboxylic acids ethylhexyl etc.
The oiliness of ink composite of the present invention does not contain coloured material mutually.With coloured material oiliness is carried out when painted mutually, can expect the raising of the color depth that printing ink is whole.But, when for example using dyestuff, visible sometimes along with the effluxion dyestuff oozes to writing the situation that infiltration takes place line of retouching on every side as coloured material; When using pigment in addition; Through the time receive the influence of water-based phase, pigment generation aggegation in oil droplet sometimes, thereby not preferred.
For the viscosity of the oiliness phase solution that is used to prepare ink composite of the present invention, be that viscosity under 38/ second is 300～500 at 25 ℃, velocity of shear, 000mPas.Viscosity produces obstructed sense, can't bring into play and process the performance as the oil-based ink one side that oil-in-water-type is brought during less than 300mPas in then writing.And, not preferred to the stability of emulsion yet.In addition, viscosity surpasses 500, during 000mPas, then writes the dry variation of retouching line, not preferred as the ink composite of ballpoint pen.At 25 ℃, velocity of shear is under 38/ second, 1,000～200, and the range of viscosities of 000mPas is preferred especially.
In order to regulate the viscosity of oiliness phase solution, can use normally used resin in the ink composite of ballpoint pen.
Object lesson as the resin that can use in the ink composite of the present invention; Can enumerate ketone resin, sulfonamide resin, maleic acid resin, terpine resin, terpene phenolic resin, ester gum, xylene resin, Synolac, resol, rosin, PVP K120, polyvinyl butyral acetal, Z 150PH, acrylic resin, melamine is natural and synthetic resins such as resin, cellulose-based resin, can use wherein more than a kind or 2 kinds.
Above-mentioned resin roughly is divided into 25 ℃ according to its proterties and is liquid person and solid-like person down.When using liquid resin,, preferably count 10～100%, when using the resin of solid-like, be preferably 5～60% with the quality standard of whole oiliness phase solution as solid component concentration.Solid component concentration is difficult to give sufficient viscosity during less than this scope.And when surpassing this scope, then resin through the time separate out, become and can't write, thereby not preferred as the ink composite of ballpoint pen.
For down being the amount of solid resin at 25 ℃ in the said oiliness phase solution,, preferably count 5～60% with the quality standard of whole oiliness phase solution as solid component concentration.Solid component concentration became and can't give sufficient viscosity less than 5% o'clock.Surpass at 60% o'clock, then resin through the time separate out, become and can't write, thereby not preferred as the ink composite of ballpoint pen.The solid component concentration of resin is preferably 15%～50% scope especially.
The water-based of ballpoint pen use ink composite of the present invention contains pigment dispersion or water-soluble dye or their mixture mutually.As pigment, can use mineral dyes such as carbon black, titanium oxide; Various pigment dyestuffs such as phthualocyanine pigment, azo pigment, diketopyrrolo-pyrrole series pigments, anthraquione pigmentss 、 perylene pigments, isoindoline ketone series pigments, quinacridone pigment.
For example can enumerate C.I. Pigment black 1,7; C.I. Pigment Yellow 73 1,2, and 3,12,13,14,16,17,20,24,34,35,42,53,55; 65,73,74,75,81,83,86,93,94,95,97,98,99,100; 101,104,108,109,110,114,117,120,125,128,129,137,138,139; 147,148,150,151,153,154,155,166,167,168,173C, 174,180,185 etc.; C.I. Pigment red 1,2,3,5,7,8,9,10,12,16,17,19,22,38,41,43,48,48:2,48:3; 49,50:1,52,53,53:1,57,57:1,58:2,60,63:1,63:2,64:1,86,88,90,9,112,122,123; 127,146,149,166,168,170,175,176,177,179,180,181,184,185,189,190,192,194,198; 202,206,207,209,215,216,217,220,223,224,226,227,228,238,240,245,254,225 etc.; C.I. pigment blue 1,2,3,15:1,15:2,15:3,15:4,15:6,16,17,22,25,60,64,66 etc.; C.I. pigment orange 5,10,13,16,36,40,43,48,49,51,55,59,61,71 etc.; C.I. pigment violet 1,3,5:1,16,19,23,29,30,31,33,36,37,38,40,42,50 etc.; C.I. pigment Green 7,10,36 etc.; C.I. pigment brown 23,25, and 26 etc.
The coloured material that uses in mutually when water-based can use all dyestuffs that can be dissolved or dispersed in the aqueous medium, its object lesson of following illustration during as dyestuff.
As matching stain, can use famille rose (C.I.16255), Tartrazol yellow (C.I.19140), acid blue-black 10b (C.I.20470), Geordie green (C.I.42085), brilliant blue FCF (C.I.42090), acid violet 6B N (C.I.43525), solvent blue (C.I.42755), naphthalene green (C.I.44025), eosin (C.I.45380), Fu Luokexin dyestuff (C.I.45410), tetraiodofluorescein (C.I.45430), nigrosine (C.I.50420), acid flavine (C.I.56205) etc.
As basic dyestuff, can use 2 basic orange 2 (C.I.11270), pyoktanin blue FN (C.I.42535), Viola crystallina (C.I.42555), Victoria Green WPB (C.I.42000), victoria blue FB (C.I.44045), rhodamine B (C.I.45170), SP 15 Lemon Yellow NS (C.I.46005), methylene blue B (C.I.52015) etc.
As substantive dyestuff, can use Congo red (C.I.22120), direct acid blue 5B (C.I.24400), purple BB (C.I.27905), direct deep black EX (C.I.30235), direct fast black G (C.I.35225), direct fast black G (C.I.35255), phthalocyanine blue (C.I.74180) etc.
Above-mentioned dyestuff can use a kind of or two or more suitable mixing back is used, and can use with the scope of 1～25 quality % in the ink composite, preferred 2～15 quality %.
As long as the coloured material of water-based in mutually can be kept the stability of emulsion, then can use above-mentioned pigment and above-mentioned dyestuff with combination arbitrarily.When pigment and dyestuff were used in combination, the amount of dyestuff was preferably counted below 10% with the quality standard of water-based phase solution.Its amount surpasses at 10% o'clock, and problem can take place the stability of emulsion.
The amount of employed pigment is 1～20%, is preferably 3～15% with respect to the ink composite total mass.The amount of pigment is less than 1% o'clock, and as the principal constituent of coloured material, photostabilization variation and the concentration sense of retouching line also are short of.The amount of pigment surpasses at 20% o'clock, is not preferred from dispersing of pigments stability aspect.
Pigment dispersion that water-based is used in mutually has been to use the pigment dispersion of ion exchanged water, Purified Water.
The dispersion agent that is used to obtain pigment dispersion can use various commercially available article; Do not have special qualification; From with the suitability, the aspect of storage stability of the oil-in-water emulsion of coexistence; Preferred high molecular resin system dispersion agent is preferably with the material material different that forms used emulsifying agent as emulsion.For example can use styrene acrylic resin or T 46155 is dispersion agent.Special preferred dispersing agent is the styrene-propene acid resin as high molecular polymer.
From taking into account the viewpoint of dispersing of pigments stability and emulsion stability, the amount of preferred employed dispersion agent reaches 20～100% scope with respect to the total mass of the pigment of pigment dispersion.
Pigment for example can use at the dispersing method of water-based in mutually and utilize mixing and blending machine with the mixed uniformly method of each composition; Also can use dispersion machines such as ball mill, ball mill, roller mill, intimate mixing machine, decollator, ultrasonic dispersing machine, high pressure homogenizer.
In addition; Water-based can contain printing ink when preventing low temperature mutually and freeze or prevent that the ink setting of nib from being the additive of purpose; Can enumerate terepthaloyl moietie, Diethylene Glycol, triethylene glycol, Ucar 35, polyoxyethylene glycol, 1 particularly; Glycolss such as 3-butyleneglycol, thio-diethylene glycol, glycerine, ethers such as glycol monomethyl methyl ether, diethylene glycol monomethyl ether etc. can use or mix use separately.The usage quantity of additive is counted 0～50%, is preferably 0～30% with the quality standard of water-based phase.Add 50% when above, problem can take place in the stability of gained emulsion.
Water-based for said oiliness mutually solution mix and form stable emulsion, can freely select to use commercially available emulsifying agent.Its concrete example of following illustration.Can enumerate tetradecanoic acid glyceryl ester; Glyceryl monostearate; Single Tegin ISO; XU 61518.10; NOFABLE GO-902P; Distearin; Stearinsaeure two glyceryl ester; Single oleic acid two glyceryl ester; Two oleic acid, two glyceryl ester; Single Unimac 5680 two glyceryl ester; Three Unimac 5680s, two glyceryl ester; Stearinsaeure four glyceryl ester; Single oleic acid four glyceryl ester; Three Triple Pressed Stearic Acid, four glyceryl ester; Five stiffness resin acid four glyceryl ester; Five oleic acid, four glyceryl ester; Mono laurate six glyceryl ester; Single tetradecanoic acid six glyceryl ester; Stearinsaeure six glyceryl ester; Single oleic acid six glyceryl ester; Three Triple Pressed Stearic Acid, six glyceryl ester; Four mountain Yu acid, six glyceryl ester; Five stiffness resin acid six glyceryl ester; Five oleic acid, six glyceryl ester; Dimerized linoleic acid six glyceryl ester; Mono laurate ten glyceryl ester; Single tetradecanoic acid ten glyceryl ester; Stearinsaeure ten glyceryl ester; Single Unimac 5680 ten glyceryl ester; Single oleic acid ten glyceryl ester; Single linolic acid ten glyceryl ester; Distearyl acid ten glyceryl ester; Two Unimac 5680s, ten glyceryl ester; Three Triple Pressed Stearic Acid, ten glyceryl ester; Three oleic acid, ten glyceryl ester; Five stiffness resin acid ten glyceryl ester; Penta hydroxy group Triple Pressed Stearic Acid ten glyceryl ester; Five Unimac 5680s, ten glyceryl ester; Five oleic acid, ten glyceryl ester; Seven Triple Pressed Stearic Acid, ten glyceryl ester; Seven oleic acid, ten glyceryl ester; Ten Triple Pressed Stearic Acid, ten glyceryl ester; Ten Unimac 5680s, ten glyceryl ester; Ten oleic acid, ten glyceryl ester; Gather ricinoleic acid ten glyceryl ester; The T 46155 glyceryl monostearate; The T 46155 XU 61518.10; Span-20; Sorbitan monopalmitate; Sorbitan monostearate; The sorbitan sesquistearate; Sorbitan tristearate; Sorbitan list isostearate; Sorbitan sesquialter isostearate; Sorbitan monooleate; Span-83; Sorbitan trioleate; TWEEN40; Polyox-yethylene sorbitan monostearate; Polyox-yethylene sorbitan tristearate; Polyoxyethylene sorbitol acid anhydride list isostearate; Polyoxyethylene sorbitan monooleate; Polyoxyethylene sorbitan trioleate; The polyoxyethylene sorbitol mono-laurate; Polyoxyethylene sorbitol six stearates; The polyoxyethylene sorbitol tetrastearate; Polyoxyethylene sorbitol four oleic acid esters; Witconol 5909; Polyoxyethylene hydrogenates the Oleum Ricini; The T 46155 plant sterol; The T 46155 phytostanols; The T 46155 Dihydrocholesterol; Polyoxyethylene laurel ether; Polyoxyethylene cetyl ether; Polyoxyethylene stearyl ether; The polyoxyethylene polyoxypropylene cetyl ether; Polyoxyethylene polyoxypropylene decyl myristyl ether; Polyethylene glycol mono-; YMS 2; Polyethylene glycol monooleate; Unister E 275; The Diethylene Glycol SUNSOFT Q-182S; Polyglycol distearate; The polyoxyethylene glycol diisopstearate; T 46155 styrenated phenyl ether; The T 46155 naphthyl ether; Nonionic surfactants such as T 46155 phenyl ether.The T 46155 chain end that in addition, can also use mentioned emulsifier is anionic surfactant of sulfuric ester or SULPHOSUCCINIC ACID ESTER etc.
From with oiliness of the present invention mutually the main solvent of solution mix mutually to form the viewpoint of emulsion steady in a long-term, have the emulsifying agent of 1 above aromatic nucleus in the preferred molecular skeleton.For example can enumerate nonionic surfactants such as T 46155 styrenated phenyl ether, T 46155 naphthyl ether, T 46155 phenyl ether, polyoxyethylene alkyl phenyl ether.The T 46155 chain end that in addition, also can use them is anionic surfactant of sulfuric ester or SULPHOSUCCINIC ACID ESTER etc.
The emulsifying agent that has 1 above aromatic nucleus in this molecular skeleton is because high to the affinity of oiliness phase as the aromatic nucleus of oleophilic group, thereby can form emulsion steady in a long-term.This emulsifying agent also can contain in oiliness phase solution.
Emulsifying agent can change its character according to the difference of oxyethane (EO) addition mole number usually.About the main solvent that uses in the oiliness phase solution, optimization ethylene oxide addition mole number is the above person of 20mol, more preferably oxyethane addition mole number is the above person of 40mol.This is owing to the unification that can suppress particle through the ethylene oxide chain of long-chain.
Can be the above emulsifying agent of 20mol with above-mentioned oxyethane addition mole number uses with the emulsifier combination that at the very strong oxyethane addition mole number of orientation of oiliness in mutually is 3～15mol.This be since through will oiliness mutually in the very strong emulsifying agent of orientation be orientated very strong emulsifier combination in water-based in mutually, the micellar concentration at interface increases, the increase of the stability of emulsion.
For HLB value (hydrophile-lipophile balance value), it is the emulsifying agent more than 15 that nonionic surfactant preferably uses the value of HLB at least more than a kind.When the many and HLB value of oxyethane addition mole number was also very low, emulsifying agent can exceedingly be sucked oiliness phase side even if this is.
As emulsifying agent with the above oxyethane of 20mol, can enumerate with above ethylene oxide chains of nonionic surfactant addition 20mol such as T 46155 list styrenated phenyl ether, T 46155 toluylene phenyl ether, T 46155 triphenylethylene phenyl ether, T 46155 naphthyl ether, polyoxyethylene alkyl phenyl ether, T 46155 cumyl phenyl ethers and the material that obtains with and anionic surfactant such as sulfuric ester.Oxyethane addition mole number is preferably more than the 20mol and below the 100mol.When surpassing 100mol, unsuitable situation can take place in rising significantly, using in viscosity.
In addition; As oxyethane addition mole number is 3～15, can enumerate with nonionic surfactant addition 3～15mol ethylene oxide chains such as T 46155 list styrenated phenyl ether, T 46155 toluylene phenyl ether, T 46155 triphenylethylene phenyl ether, T 46155 naphthyl ether, polyoxyethylene alkyl phenyl ether, T 46155 cumyl phenyl ethers and alkylphenol type nonionic surfactants such as anionic surfactant, polyoxyethylene alkyl phenyl ether such as the material that obtains and sulfuric ester thereof etc.
Except pigment dispersion, water-soluble dye, the emulsifying agent; Water-based also can contain normally used various additives in the used with water ball-point pens aqueous ink compsn mutually, for example tackifier such as rust-preventive agent, sanitas, PH regulator, lubricant, wetting Agent for Printing Inks, resin, natural polysaecharides etc.
The shared ratio of oiliness phase composition is counted 1～30%, is preferably 3～20%, more preferably 5～15% with quality standard in the ballpoint pen use ink composite of the present invention.The ratio of oiliness phase composition was less than 1% o'clock, and writing property can't obtain satisfactory performance, compare no any variation with common aqueous ballpoint pen.In addition, when the ratio of oiliness phase composition greater than 30% the time since with the interaction of pigment dispersion, emulsion becomes unstable sometimes, because oil content increases, thereby can cause detrimentally affect to retouching the line drying property in addition.
The median size of emulsion is preferably below the 250nm, more preferably below the 200nm.Making median size is to be for the sedimentation that suppresses particle, the unification that collision caused between the particle below the 250nm.The adjusting of particle diameter can through after the emulsification method stated control, use the mechanical shear stress of mulsers such as high pressure homogenizer also can carry out miniaturization even if utilize in addition.
The emulsification method of oil-in-water emulsion of the present invention can use various emulsification method well known in the prior art, for example reverses emulsion process, D phase emulsion process, PIT emulsion process, machinery emulsification method mutually.For example, reversing mutually in the emulsion process, oil-in-water emulsion of the present invention is through following operation manufacturing:
A) in organic solvent, the oily solution composition that contains at least as the resin of viscosity imparting agent is stirred so that solids component dissolved operation;
B) in the aqueous solution composition, add emulsifying agent and stir and make its dissolved operation;
C) on one side the oily solution of operation a gained is stirred, slowly adds the aqueous solution of operation b gained on one side and obtain the operation of water-in-oil emulsion;
D) while stirring the aqueous solution that adds operation b gained, obtaining the operation of oil-in-water emulsion through changing mutually.
The operation that preparation contains the aqueous solution of pigment dispersion can be employed in the known method of using in the preparation of water-based paint printing ink in the past.For example:
E) operation of using stirrer pigment, dispersion agent, solvent and pH regulator agent to be stirred 3 hours;
F) operation of using sand mill to disperse 5 hours;
G) operation of utilizing separating centrifuge that the oversize particle of above-mentioned dispersible pigment dispersion is removed;
H) above-mentioned dispersible pigment dispersion is diluted and adds the operation of other compositions.
With oil-in-water emulsion and the water-based that contains pigment dispersion of as above preparation mutually solution contain the water-based phase solution of dyestuff or contain pigment dispersion and the water-based of dyestuff mutually solution mix.This mixes for example can adopt and utilizes mixing and blending machine with the mixed uniformly method of each composition; Use dispersion machines such as ball mill, ball mill, roller mill, intimate mixing machine, decollator, ultrasonic dispersing machine, high pressure homogenizer each composition to be carried out the method for dispersing and mixing.At this moment, can with oil-in-water emulsion and above-mentioned water-based mutually solution side by side mix or dispersing and mixing, can also mix successively or dispersing and mixing.
Need to prove that the pigment dispersion of water-based phase composition also can cause detrimentally affect to pigment dispersion system through reversing mutually when emulsification etc. changes mutually, thereby preferred oil-in-water emulsion manufacturing process and colo(u)rant dispersion operation are carried out separately.
For the viscosity of the ballpoint pen use ink composite of the present invention of final acquisition, be that viscosity under 380/ second is 1～100mPas, more preferably 7～70mPas preferably at 25 ℃, velocity of shear.Be 100mPas when above, the viscosity of printing ink increases, worsening of the printing ink in the pen core as a result with the property sent, thereby not preferred.
Embodiment
Below through the most representative embodiment optimal way of the present invention and excellent effect thereof are described particularly.Need to prove that part hereinafter is meant that all mass parts, % all are meant quality %.
For embodiment 1～10, carry out the preparation of ink composite as follows.
At first, on one side the oily solution composition put down in writing of stirring table 1, be heated to 50 ℃～60 ℃ temperature on one side, these compositions are fully dissolved.Oily solution viscosity in the table is the value of this solution.On the other hand, make its dissolving while in Purified Water, stir, thereby made emulsifier aqueous solution with its emulsifying agent of table 2 being put down in writing differently.Need to prove, when cooperating the very strong emulsifying agent of orientation to the oiliness phase, also can be added in this oily solution and stir at normal temperatures.
Then, slowly be added in the oily solution while stir said emulsifier aqueous solution, thereby be converted to O/W mutually, obtain the emulsion of oil-in-water-type from W/O.Afterwards, use commercially available high pressure homogenizer to carry out emulsifying until the median size that reaches regulation.
The mensuration of median size uses particle size determination device N4Plus (COULTER corporate system) to measure.During mensuration, the sample water is diluted to the recommended density that arrives N4Plus, under 25 ℃ temperature condition, measures.Need to prove that the term of the median size of using in the present specification is meant meso-position radius.
Contain the operation of the aqueous solution of pigment dispersion according to above-mentioned preparation, made pigment concentration in addition and be 20% pigment dispersion.
To the pigment dispersion of made, reach that kind shown in the table 2 according to ultimate constituent amount and carry out above-mentioned h) dilution of operation and the interpolation of other compositions.Need to prove, reduce the amount of each composition that uses in the said emulsifier aqueous solution this moment and adjust.
As shown in table 3, as comparative example, prepared the different comparative example 1 of oiliness phase viscosity and 2 and in addition as the comparative example 3 of no oiliness water color ink mutually.
Table 3
※ 1:Huels corporate system, ※ 3:ISP JAPAN corporate system, ※ 4:Fudow corporate system, ※ 5: ponding chemical company system, ※ 6: the system MA-100 of Mitsubishi Chemical Ind, ※ 10:BASF corporate system Joncryl 61J
Utilize decollator with above-mentioned oil-in-water emulsion and pigment dispersion mixing stirring,, stir the tackifier composition at last so that its dissolving, thereby obtain aqueous ink compsn of the present invention embodiment 1～3,5～10 and comparative example 1～3.
HAAKE corporate system mobilometer RheoStress600 is used in viscosimetric analysis in this specification sheets.It is the cone of 1 degree as 35mm, pitch angle that cone uses diameter.Condition determination in the mensuration of oily solution be under 25 ℃, velocity of shear are 38/ second condition, measure 30 seconds, with stable numerical value as viscosity; In the mensuration of printing ink be under 25 ℃, velocity of shear are 380/ second condition, measure 30 seconds, with stable numerical value as viscosity.
After packing into the aqueous ink compsn that produces in each aqueous ink compsn that produces among the embodiment 1～10 and the comparative example 1～3 in the system UMR-05 of the Mitsubishi Pencil K. K pen core, carry out following evaluation.
＜estimate＞
(a) anti-settleability test
Rotation radius be 20cm, rotating speed be under the condition of 2000rpm (about 900G) with nib portion towards the pen core of centrifugal direction carry out 5 hours centrifugal, on writing, write the circle that diameter is about 2cm afterwards with paper, compare with the line concentration of retouching before the centrifugal treating.
◎: with do not have concentration difference before the centrifugal treating.
Zero: though retouch line dense a bit write no problem.
△: though it is dense to retouch line, can clearly discern, can write.
◆: it is dense and to write the style of calligraphy characterized by hollow strokes obvious to retouch line, is not durable.
*: can't write.
(b) pen sense weight test
On writing,, judge the weight of pen sense as follows around drawing 5 circles with paper.
◎: very light.
Zero: very light.
△: general.
◆: very heavy.
*: be not durable.
(c) obstructed sense test
The obstructed sense of writing when the following pen sense weight of judging that (b) put down in writing is tested.
◎: do not mind fully.
Zero: feel slightly, but be out of question.
△: have slightly and mind.
◆: quite mind.
*: mind.
(d) water tolerance test
Water will be write at the line of writing with on the paper of retouching and get wet, observe the state after 1 minute.
◎: retouch line and do not change fully.
Zero: observe slightly and retouch the line infiltration, but be out of question.
△: can see and retouch the line infiltration obviously.
*: distinguish difficulty.
(e) retouch the test of line drying property
The line of writing writing with on the paper of retouching was nuzzled up with plastic sheet after 10 seconds, confirm the extent and the spot of retouching line.
◎: not extending, retouch line does not fully have spot yet.
Zero: not extending, retouch line does not basically have spot yet.
△: retouching line has extension slightly.
*: retouching line has spot.
(f) printing ink ink bleed property
3 calligraphies are write with Japan paper is overlapping, counted the 1st with writing used paper, the printing ink of following judgement to the 3rd Japan paper sees through situation.
◎: printing ink does not see through the dorsal part to the 1st Japan paper.
Zero: printing ink sees through the dorsal part to the 1st Japan paper.Printing ink does not see through to the 2nd Japan paper.
△: table side but printing ink that printing ink moves to the 2nd Japan paper see through to dorsal part.
◆: printing ink sees through the dorsal part to the 2nd Japan paper.But printing ink does not see through to the 3rd Japan paper.
*: printing ink sees through to the 3rd Japan paper.
(g) storage stability test
Under 50 ℃ condition, handwriting was placed 3 months, confirm writing property.
◎: compare no change with preliminary phase.
Zero: with preliminary phase than changing slightly but write no problem.
△: observe the deterioration of retouching line, but can write.
◆: the deterioration of retouching line is obvious.
*: can't write.
The result of above-mentioned test is shown in table 4, table 5.Can know that by these results ink composite of the present invention and comparative example printing ink (the application's scope is outer, water color ink) are compared, and have shown more excellent result.
Table 5
Claims (7)
1. ballpoint pen use ink composite; Its form with oil-in-water emulsion contain water-based mutually with oiliness mutually; Said water-based be mutually contain pigment dispersion or water-soluble dye or their mixture through painted water-based phase; Said oiliness is to be that viscosity under 38/ second is 300～500 at 25 ℃, velocity of shear mutually, the oiliness phase of the non-coloring of 000mPas.
2. ballpoint pen use ink composite according to claim 1, wherein, said oiliness contains solvent mutually, and boiling point is that the solvent more than 200 ℃ accounts for more than 50% of whole solvents in quality standard.
3. ballpoint pen use ink composite according to claim 1 and 2 is characterized in that, oiliness phase composition shared ratio in said ink composite counts 1～30% with quality standard.
4. according to each described ballpoint pen use ink composite of claim 1 ~ 3, it is characterized in that the median size of the oil droplet of said oil-in-water emulsion is below the 250nm.
5. according to each described ballpoint pen use ink composite of claim 1 ~ 4; It is characterized in that; Said oiliness contains solvent mutually, and the solubleness of this solvent in 20 ℃ water is counted below 5% with quality standard and had the aromatic nucleus more than 1 in the molecular skeleton.
6. according to each described ballpoint pen use ink composite of claim 1 ~ 5, it is characterized in that, said oiliness mutually or said water-based phase any one or contain the emulsifying agent that has 1 above aromatic nucleus in the molecular skeleton among both.
7. ballpoint pen, it is equipped with each described ballpoint pen use ink composite of claim 1 ~ 6.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2009279762A JP5676875B2 (en) | 2009-12-09 | 2009-12-09 | Water-based ink composition for ballpoint pens |
| JP2009-279762 | 2009-12-09 | ||
| PCT/JP2010/072510 WO2011071181A1 (en) | 2009-12-09 | 2010-12-08 | Aqueous ink composition for ballpoint pen |
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| Publication Number | Publication Date |
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| CN102666750A true CN102666750A (en) | 2012-09-12 |
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| CN2010800535834A Pending CN102666750A (en) | 2009-12-09 | 2010-12-08 | Aqueous ink composition for ballpoint pen |
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|---|---|
| JP (1) | JP5676875B2 (en) |
| KR (1) | KR101492700B1 (en) |
| CN (1) | CN102666750A (en) |
| WO (1) | WO2011071181A1 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2013221051A (en) * | 2012-04-13 | 2013-10-28 | Mitsubishi Pencil Co Ltd | Ink composition for water base ball-point pen |
| CN104220538A (en) * | 2012-03-27 | 2014-12-17 | 三菱铅笔株式会社 | Water-based ink composition for ballpoint pen |
| CN106345366A (en) * | 2016-08-29 | 2017-01-25 | 江苏四新界面剂科技有限公司 | Preparation method of polydimethylsiloxane emulsifier |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5773826B2 (en) * | 2011-09-29 | 2015-09-02 | 三菱鉛筆株式会社 | Water-based ballpoint pen ink composition |
| CN104356757B (en) * | 2014-10-08 | 2017-11-10 | 王宝林 | The preparation method of oil ink in a kind of oil-in-water type emulsion |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS55152768A (en) * | 1979-05-18 | 1980-11-28 | Pilot Pen Co Ltd:The | Writing ink |
| CN1133057A (en) * | 1993-10-15 | 1996-10-09 | 吉莱特公司 | Aqueous inks |
| JP2001200185A (en) * | 2000-01-20 | 2001-07-24 | Asahi Kasei Corp | Aqueous emulsion type ink composition |
| JP2003213191A (en) * | 2002-01-28 | 2003-07-30 | Sakura Color Prod Corp | Aqueous erasable marking pen ink composition |
| US20040147632A1 (en) * | 2003-01-14 | 2004-07-29 | Keiko Nakamura | Water base erasable ink composition for use in marking pens |
| CN1550530A (en) * | 2003-04-02 | 2004-12-01 | ��˹��ŵ�� | Water based ink for ball-point pen |
| WO2008101146A1 (en) * | 2007-02-15 | 2008-08-21 | Sanford, L.P. | Ink compositions containing an emulsion |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3305809B2 (en) * | 1993-06-04 | 2002-07-24 | 御国色素株式会社 | Aqueous ballpoint pen ink composition |
| JPH1112521A (en) * | 1997-06-20 | 1999-01-19 | Riso Kagaku Corp | Stencil printing emulsion ink |
| JP2004323618A (en) * | 2003-04-23 | 2004-11-18 | Bunchou:Kk | Multicolor ink for writing utensil, and marking pen |
| JP4806173B2 (en) * | 2004-08-17 | 2011-11-02 | 東北リコー株式会社 | Emulsion ink for ink jet, ink cartridge, ink recorded matter, ink jet recording apparatus and ink jet recording method |
| JP2007008990A (en) * | 2005-06-28 | 2007-01-18 | Sumika Color Kk | Method for producing azo pigment composition for lithographic ink |
| JP5446254B2 (en) * | 2007-12-27 | 2014-03-19 | ぺんてる株式会社 | O / W emulsion ink composition for ballpoint pens |
-
2009
- 2009-12-09 JP JP2009279762A patent/JP5676875B2/en not_active Expired - Fee Related
-
2010
- 2010-12-08 CN CN2010800535834A patent/CN102666750A/en active Pending
- 2010-12-08 KR KR1020127014732A patent/KR101492700B1/en active IP Right Grant
- 2010-12-08 WO PCT/JP2010/072510 patent/WO2011071181A1/en active Application Filing
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS55152768A (en) * | 1979-05-18 | 1980-11-28 | Pilot Pen Co Ltd:The | Writing ink |
| CN1133057A (en) * | 1993-10-15 | 1996-10-09 | 吉莱特公司 | Aqueous inks |
| JP2001200185A (en) * | 2000-01-20 | 2001-07-24 | Asahi Kasei Corp | Aqueous emulsion type ink composition |
| JP2003213191A (en) * | 2002-01-28 | 2003-07-30 | Sakura Color Prod Corp | Aqueous erasable marking pen ink composition |
| US20040147632A1 (en) * | 2003-01-14 | 2004-07-29 | Keiko Nakamura | Water base erasable ink composition for use in marking pens |
| CN1550530A (en) * | 2003-04-02 | 2004-12-01 | ��˹��ŵ�� | Water based ink for ball-point pen |
| WO2008101146A1 (en) * | 2007-02-15 | 2008-08-21 | Sanford, L.P. | Ink compositions containing an emulsion |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104220538A (en) * | 2012-03-27 | 2014-12-17 | 三菱铅笔株式会社 | Water-based ink composition for ballpoint pen |
| JP2013221051A (en) * | 2012-04-13 | 2013-10-28 | Mitsubishi Pencil Co Ltd | Ink composition for water base ball-point pen |
| CN106345366A (en) * | 2016-08-29 | 2017-01-25 | 江苏四新界面剂科技有限公司 | Preparation method of polydimethylsiloxane emulsifier |
| CN106345366B (en) * | 2016-08-29 | 2018-07-17 | 江苏四新界面剂科技有限公司 | A kind of polydimethylsiloxane emulsified dose of preparation method |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20120091324A (en) | 2012-08-17 |
| JP2011122031A (en) | 2011-06-23 |
| WO2011071181A1 (en) | 2011-06-16 |
| JP5676875B2 (en) | 2015-02-25 |
| KR101492700B1 (en) | 2015-02-11 |
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Application publication date: 20120912 |