MXPA97004446A - Composition of borrable ink and marker instrument that contains the mi - Google Patents

Abstract

An erasable ink composition containing a water-insoluble polymer dye is obtained from the polymerization of at least two co-reactive polyfunctional monomers, with at least one of the monomers possessing a dye residue covalently attached thereto. The ink is intended to be used on any of a variety of marker instruments, particularly in a redon dot pen

Description

COMPOSITION OF BORRADLE INK AND MARKER INSTRUMENT CONTAINING THE SAME BACKGROUND OF THE INVENTION This invention relates to an erasable ink composition and to a marker instrument, for example a ballpoint pen, containing the composition. More particularly, this invention relates to an erasable ink composition containing a water-soluble polymer dye component, that is, a polymer having a part of the dye that is covalently attached to it. Numerous erasable ink compositions are known, for example the compositions described in U.S. Patent Nos. 3,834,823, 3,875,105, 3,949,132, 4,097,290, 4,232,676, 4,227,930, 4,256,494, 4,297,260, 4,329,262, 4,329,264, 4,349,639, 4,357,431, 4,367,966, 4,368,076, 4,379,867, 4,389,499, 4.3C? 3,646, 4,391,927, 4,407,985, 4,410,643, 4,419,464, 4,441,928, 4,509,982, 4,525,216, 4,557,618, 4,578,117, 4,596,846, 4,606,769, 4,629,748, 4,687,791, 4,721,739, 4,738,725, 4,760,104, 4,786,198, 4,830,670, 4,954,174, 4,960,464, 5,004,763, 5,004,763, 5,024,898, 5,037,702, 5,082,495, 5,114,479, 5,120,359 and 5,217,255. These inks are formulated by mixing a dye (here in the broad sense to include "pigment", "dye", "crophane" and other terms having a similar meaning) with various combinations of polymer and carrier / sol liquid to form a fluid matrix of dye / polymer. The polymer component is chosen for its film-forming properties and its ability to be easily removed from the substrate on which it is applied, for example, cellulose paper, through the abrasive action of a rubber. However, a common problem with these erasable ink compositions refers to the residual dye remaining after erasure. An incomplete erasure can be attributed to an inadequate removal of the dye / polymer matrix from the paper substrate and / or migration of the dye into the pores of its time. SUMMARY OF THE INVENTION In accordance with the present invention, there is provided an erasable ink composition comprising (a> a water-insoluble polymer colorant obtained by accepting the polymerization of a polymer formation reaction medium containing the minus two co-reactive polymeric monomers with at least one of the monomers possessing a portion of dye covalently bonded therein and <b) a liquid vehicle susceptible to evaporation where the polymer dye is dissolved, dispersed or swollen, the composition of Erasable ink when applied to the substrate and when dried on said substrate is (1) sufficiently adherent on the substrate to resist peeling and (2) substantially erasable. Since the dye is covalently bonded to the polymer in the erasable ink composition of this invention, there is little opportunity for it to separate from the polymer and free on a porous substrate. Accordingly, the barray ink composition of this invention leaves residual ink significantly less after erasure than the known erasable ink compositions wherein the ink is simply physically combined with the polymer component (s). DESCRIPTION OF THE PREFERRED MODALITIES The polymer dye component of the erasable ink composition of this invention is prepared by the polymerization of at least two co-reactive polyfunction monomers with at least one of the monomers possessing a covalently covalent dye portion. united there. At least one of the monomers must be sufficiently hydrophobic so that the resulting polymer dye is insoluble in water. Part or all of the polifunctional monomers may be oligomeric or polymeric in nature. The e: < "monomeric pol i fune ional" pressure characterizes compounds that possess at least two reactive functional groups (not counting unsaturation sites that can be found) such as, but not limited to, hydroxyl, sulfhydryl, carboxylic acid, amine groups, nitrile, acyl halide and isocyanate. The expression also includes qu >compounds; 3, under the polymerization reaction conditions, they have polynuclearity, such as, for example, lactones and lactams which, when their rings are opened, are chemically equivalent to alpha, omega-1-hydroxycarboxylic acids and alpha-acids. omega-a i nsc rbo í 1 ico, respectively. Polymeric dyes of the type that are useful in the erasable ink composition of this invention are known (but for applications other than in erasable ink compositions) or can be prepared by appropriate modification of known processes of polymer formation. By way of illustration, such known polymeric dyes are presented in U.S. Patent Nos. 4,778,742, 5,104,93.3, and 5,194,463, the contents of which are incorporated herein by reference. A preferred polymer colorant for its. used herein is a dye prepared by means of a water borne process, ie, a polymerization process wherein the resulting polymer is provided in the form of an aqueous emulsion or a dispersion of polymer dye particles. The polymer dye emulsion with or without the addition of other components can, if desired, be used directly as the erasable ink composition of this invention thus eliminating additional manufacturing operations < unlike in the case of bulk polymer dyes that would require a spray to the desired particle size, followed by the addition of a suitable liquid vehicle to evaporate). In accordance with US Pat. No. 4,778,742, a polymeric dye of the general formula (-OA-DYE-A-0-B-) n wherein A can be prepared by means of a solution or interfacial polymerization process. is selected from the group consisting of alkylene and arylene, B is selected from the group 0 0 0 oo -C II-, -C 11 -R-C II- and -C «O-R-OCII- where P is an alkylene group, an arylene segment or a polyether segment, DYE is a dye portion and n is from approximately 2 to approximately 100 and preferably from approximately 5 to approximately 35. In the solution polymerization, stoichiometric amounts of Polymeric monomers, specifically a bisphenoxy functional dye and a dialkyl halogen, react in a suitable solvent medium, for example an aliphatic halogenated hydrocarbon such as methylene chloride, in the presence of an excess of a tertiary amine such as a trie and laminate base.

The polymerization is then carried out at a temperature of about 5 ° C to approximately 30 ° C and is completed in approximately 0.5 to 3 hours.In the interfacial polymerization, a dye with bisphenoxy functionality is initially dissolved in an aqueous alkaline solution in the presence of an emulsifying agent, then the resulting solution is stirred and treated with a solution of a suitable bifupeanal monomer such as, for example, a di acyl chloride or a bisha loform or in a solvent which can not be mixed with water such as tz. The ethylene polymer is used to obtain, respectively, the polyester dye or the polycarbonate dye, or the polymer dyes from the solution polymerization process are subsequently reacted by washing the reaction mixture with water. followed by the precipitation of the methylene chloride solution from the dyes from a non-solvent such as hexane or methanol Likewise, with the interfacial process, the polymeric dyes are separated by simple filtration followed by the complete washing with water. Examples of dye monomers with bisphenoxy funtion that can be used to prepare the polymer dyes of U.S. Patent No. 4,778,742, include 3, 5-bis (p-hydrexy-phenyl-11-anuqu). inona, l, 8-bis (p-hydroxy-phenylthio) anthraquinone, 1,5-bis (p-hydroxy-phenylthio) -4,4-bi.s (phenyl-11-phenyl), 1,3-b. is (2- ipil idrox i feni 1) et i lamino) an raqui nona, 1, 5-b is (2- (ph i drox if ni 1) et i lami o) an raqui non, 1, 4-bi ( 2- (ph idrox i feni lmi no) antraqu i none, 1, 4-b is (2- (ph idrox i feni 1) ethylamino) an raqu i none, 1, 4-b is (2- (p -hydrox i feni 11 io) anthraquinone and 6-phenyl 11 io-1,4-b is (2- (ph idraxy pheny1) ethylamino) anthraquinone Examples of diacyl halide monomers which can react with the dye monomers with Functionalization of bisphenoxy to provide the polymeric dye of North American Patent No. 4,778,742 include succinyl chloride, glutaryl chloride, adipoyl chloride, dihydrogen chloride, sebacoyl chloride, phthaloyl chloride , isophthaloyl chloride, terephthaloyl chloride and the like Examples of useful bisalphase include b ischloroform to diet and lengl icol, bise loroforma to de t iet i lengl. icol, b ischloroform or of tetraeti lengl icol, bischlorofor ato of bifenoxi, b isc loroforma to de propi lengl. icol, dipropi lengl bischloroformate. icol, b iscloraforma de ta but i lengl icol, bisbromoforma to de e i lengl icol, b isbromofor ato de prop i lengl icol, and the like. The polymeric dye of US Pat. No. 5,104,913 is obtained by polymerizing a functional polimer monomer having a portion of dye covalently bonded therein, a terephonic acid and / or 2,6-naphthaldicarboxylic acid. , and a branched-chain diol of the general formula where R 1 is hydrogen or an alkyl residue, cycloalkyl or substituted or unsubstituted aryl and R 2 is an unsubstituted or substituted alkyl, cycloalkyl or aryl radical. The dye-containing monomer can be selected from anthraquinone, ethin, bis-ethine, anthrapidine, acid 2-diaryl ester or ester., eau.ma ri na, quinsf ta canvas, perylene and other thermally stable dye compounds having functional groups that react with the carboxylic groups and / or hydrix.la of the other monomers, ie, hydroxyl, carboxy, ester , amine, alkylate, etc., groups such that the dye will be incorporated into the resulting polyester. Examples of dye-containing monomers include anthraquinone dyes and methine dyes having two reactive functional groups selected from the above-mentioned types. U.S. Patent No. 5,194,463 discloses a polymer dye in the form of a polyurethane of the general formula wherein R is a radially selected lens selected from C2-C10 alkylene, C3-C8 cycloalkylene, arylene, alkylene. Cl-C4-ar i lenalqui log CI-C4, C1-C4-C4 alkylene cycloalkyl C3-C8-C1-C4 alkylene or C1-C4 alkylene, 2, 3, 4, 5,, 7- octah idronaf ta lena-2,6- ii l-Cl-C4-alkyl optionally substituted; R1 is an organic divalent lens radical comprising approximately 1 to 100 mol percent of the residue of a dye attached to two hydroxyl groups through the alkylene portions and any residue of R1 comprises the residue of organic diols of the formula H0 -R2-0H where P.2 is a radical of the selected lens within the group that? consists of: C2-C18 alkylene, C3-C8 cycloalkylene, C1-C4-1 alkylene, 2, 3,4, 5, 6, 7,8-oc tah idronaf ta leno-2,6-di i 1-alkylated C1-C4, alkyl-Cl-C4-cycloalkyl, C3-C8-alkylene C1-C4-alkylene, C1-C4-alkylene-arylene-C1-C4-alkylene, C2-C4-alkylene-C2-C4, C2-C4-S-alkylene C2-C4-Iquinyl or C2-C4-0-C2-C4-C2-C4-C2-C4-C2-C4-C2-C4-C2-C4-C3-C4-C4-C4-C4-C4-C4-C4-C4; and p is equal to or greater than The dye containing the hydroxyl groups can be selected from various azo-based classes, including azo, metazoate, diazo, methine, or apldene, polymethine, azo-methine, anthraquinone, aza-etine, antrap ir idona '3H-d ? betz (f,?) isoqu inol? na-, 7- tona), anthrapi pi na (7H-d? benz? f,?) soqn inol i na-7-one), f taloi 1 feriot lacina (L4H- naphtho (2,3-a) phenotylan-8, 13-dione), benzatrone (7H (de) anthracen-7-one), anthrap, irimidine (7H-benzo 'and pepmid-7-one) ), ant rap i razol, anthra iso iazol, tp fenodioxacin, 11 axantene-9-one, flsupndin (5, 12-d ih i droquipoxa 1 ina (2,3-b) phenazine), qu i nof talon, f aloc íanina, naphtha loyenina, nickel dithiole, coumapna (2H-l-benzap iran-2-one, couplana (2H-l-benzo? iran-2? m? na), indophenol, permaná, neither troar i lamí na, benzod i furano, f ta loi 1 f nox ac ina (34H-naphtho (2,3-a1 phene, ac-n-8-13-d canvas), f taloi lacpdona (13H- fto (2m3-c> acpdina 5, 8, 14-tr-tar), anti-oxidant-exonxanthone (8H-naphtho (2,3-e) 11 a; > ar ten-5, 8-13-tp ona), antrap i pdazone, naphtho < 1 ', 2', 3 ': 4,5) quino (2,1-b) qu i noza 11 n-5, 10-di nase, lH-anthra (2,1-) (3,4) t? apn-7, 12-dPopa, indigo, thioindigo, i-antenna, acpdina, azina, oxazine, 1,4- and 1, 5-naf oquinones, acid dihydrogen chloride, diuretic acid naf alen-1, 4,5,8-tetracarbaxyl, acid diimide, 3,4,9,10-pep, lenscarboxy, ionic acid, ibepzafenone, benzo p zol, naf otriazole, nf toqu jone, I gave my noi soindol in, na f top irano (3H-naphs (2, 1-b) pran-3-ones and 3-? M? Ns) and aminonaf such imide.

The polyurethane of US Pat. No. 5,194,463 can be obtained by the reaction of one or more dye-containing dyes containing one diisocyanate and, if desired, another diol, using known procedures. Numerous modifications of the known prior processes are possible to obtain a polymeric colorant that can be employed in the erasable ink composition of this invention. For example, part or all of the diester monomer with ftisphenoxy functionality of U.S. Patent No. 4,778,742, the dye monomer is functionalized according to U.S. Patent No. 5,104,913 or the hydroxyl-containing dye monomer of the Patent. US Pat. No. 5,194,463 can be replaced with a polymeric polymer dye monomer of the general formula (R + a---P-?? Ob)) where R is a portion of dye that is readily attached to the residue of polymer P, X is a functional group, a, b and c each represents at least 1, provided that the. product of b x c is at least 2, when c is a 1 minus 2, a is 1 and where there are more than one R, P or X, each R, P or X can be identical or different. The portion of dye R can be derived between any of the abovementioned dyes of the dye and fluxes mentioned above, the polymer residue P can be of a polymer, polyester, polya ida, polycarbonate or the like, and X can include groups reactive to hydroxyl, sulph idil, carboxy, primary amine, secondary amine and isocyanate. For example, a dye-containing dye such as a dye described in US Patent No. 5,194,463 or another dye containing dihydroxyl may react with α: < of ethylene, or of propylene or a mixture thereof to provide a liquid polyether dye monomer with hydroxyl termination. Polyether dyes of this type are known from US Patent Nos. 3,157,633 and 4,284,729, the presentations of which are incorporated herein by reference. Similarly, the dihydroxy-containing dye can react with ido alpha, omega-hydra; Icarbon; - 1 ico or analog of cyclic ester thereof, for example epsi 1 ón-capprol BC tona, to provide a liquid polyester dye monomer finished with water;-?the. Both the polyether dye monomer and the polyester monomer can be reacted with a polyisocyanate or an isocyanate-terminated prepolymer to provide the water-soluble polymer dye component of the erasable ink composition herein. The ink monomers employed in the practice of this invention possess portions of pendant dye covalently bonded there. The dye portions can be of any type such as, for example, azo, trifold, anthraquinone and metma. Azo dye portions are generally preferred. Dye monomers especially useful for carrying out the present invention include amine dye monomers possessing structural units of formula 1: where each A independently can be an ester or amide link, n can be an integer of about 1 to about; immately 50, preferably 1 to about 5, P e < an aliphatic hydrocarbon (straight-chain, branched or cyclic), or aromatic (single-ring or fused) with up to approximately 30 carbon atoms, -andb are, independently, from 1 to approximately 10, Z is a group apleno co or for example femleno, difenileno or naftileno, that apciana lmente contains one or more his listeners such as for example halogen, hydroxy lo, -CHD, alkoxy, allamino, d íalqu i lamino, amida, a Iqui lamid, -NH2, phenyl, carbamyl, -CN, carbalkoxy, sulfamyl, sulfamyl and sulfa or a single bond when Y is an anthraquinone group and Y is a portion of dye selected from (1) an azo group where Y can be ~ N = ND or -N = NGN = ND where D is an aromatic nucleus of 1 to 5 rings (fused or connected by single bonds) or a heterocyclic ring of 4.5 or 6 members containing from one to four or more atoms of -N-, -S- and non-peroxidic atoms - O- and optionally leading n one or more auxochromic groups such as -CI, -Br, -F, -OH alkyl, alkoxy, alkylaryl, dyalkylamine, -NH2, -N02, phenyl, carbayl, -CN, carbalkoxy, sulfonyl, sulfamyl and sulfamido and C is a phenylene or naphthylene group; (2) a group tricianov ini where Y can be CN \ / c * c / \ NC oí (3) a rachone group where Y can be where R1 can be -OH, -NH2, alkylamine, 1-aminoalkyl or arylamino where aryl is phenyl or bi-phenyl substituted by auxochromic groups as defined for use in D as defined in (1) above, R2 and R3 ir. may independently be auxochromic groups as defined for use in D as defined in (1) above; and (A) is a methine group where Y can be \ / C - C «'where P and Q are independently selected from cyano, carbalkoxy, carbar i lo:; i, earbaralqui lax i, carbamyl, carboxy, N-alkylocarbamyl, N-a 1-l-N-ary Icarbami lo, N, N-diaqu. Icarbami lo, N-ri Icarbami lo, i-iclohe and Icarbami lo, aryl, 2-benzo-azole, 2-benzothiozole, 2-benzimidazole, 1, 3, 4-tiadiazole-2 -i lo, 1, 3, 4-oxad iazol-2-i lo, alkyl of S02, aryl of S02 and acyl or P and Q can be combined : omo where R4 is alkyl, aryl or cycloalkyl, and R5 is CN, C00H, C02, alkyl, carbamyl or NaCl Icarbamide, wherein each alkyl, aryl or cycloalkyl portion or portion of a group or radical may be substituted with one or more aoxochromic groups in accordance with that defined for use in D as defined in (1) above. The amine dye monomer is advantageously produced by the reaction of an aromatic amine of the general formula: R * - (CHa) .- N- (CH,) > - 7 Z where P.6 and P.7 are independently COOH, C00R8 where R8 is an alkyl group of 1 to about 8 carbon atoms, NH2 and OH, a and b independently are within a range of approximately 10 and Z is an aryl group such as phenyl, diphenyla, naphthyl, said aryl group optionally contains 1 or more substituents such as, for example, halogen, hydroxyl, -CH0, alkyl, alkoxy, alkylamino, di-quilanu.no, amide, a lky lick , -NH2, -N02, phenyl, carbamyl, -CN "carbalkoxy, sulfonyl, sulphonyl and sulfamido with one or more reagents selected from the group consisting of polyhydric alcohol, polyamine and polycarboxylic acid under reaction conditions of condensation polymerization to provide a polyester or a polyamide containing polyemized units of the aromatic amine identified above and groups reactive with isocyanate groups. Then, a portion of dye is coupled to the polyester or to the polyamide through the aromatic pendant units derived from the aromatic amide using any suitable technique such as, for example, diazoation. In an alternative modality, the dye portion is coupled to the aromatic pendant units of the aromatic amine before forming the polyester or the paliamide. Suitable palihydric alcohols include those of the general formula: HO-R-OH where R can be an aliphatic hydrocarbon (straight chain, branched or cyclic) or aromatic hydrocarbon (single ring or fused) with up to 30 carbon atoms, polyamines suitable include those of the general formula H2N-R.-NH2 where R is as defined above for the palihydric alcohol and suitable polylic acid acids include those of the general formula 0 0 II II LC-R-CL where R is the same as defined above for the polyhydric alcohol and L is halogen, hydroxyl or alkoxy. In a preferred embodiment, feni Id ietanolamine, i.e. it is employed as the aromatic amine, an alkanediol as butandial or hexandiol is used as the polyhydric alcohol and adipic acid is used as the polycarboxylic acid to provide a polyester polyol dye monomer in accordance with this disclosure.

In another preferred embodiment, a substituted iodolane is used as the aromatic amine. The particularly preferred substituted phenylalanine radicals are those corresponding to the following f or rmu: which is commercially available at Hen el Corp (Emer 5752) and which can be obtained by, for example, the aromatic substitution or the Vilsmeier-Haack reaction. See, for example, U.S. Patent No. 4,757,130. The first substituted phentanolamine phene is useful as an intermediate product for blue dyes. It will be understood by those skilled in the art that a molar excess of polyhydric alcohol initial reagents can be employed to provide a polyether dye monomer with hydroyl termini that a molar excess of initial polymeric reactants can be employed to provide onerous polya dye monomer with amine termination. The amine dye monomers are preferably linear and preferably contain from 3 to 5 dye portions per chain length of dye monomer, more preferably 1 or 2 dye portions per chain length. Those molecules which range from about 500 to about 5000, preferably from about 2500 to about 5 imo! they have been found particularly useful in the practice of this invention. The amine dye monomer reacts under polymer formation reaction conditions cut in a? as presented herein with an isocyanate group containing opomer to provide polyurethane-urea carried in water. It will be understood by those skilled in the art that non-colorful monomers, for example uncoloured pal-ether polyol, may be combined with the dye monomer and the monomer containing the unsaturated group to provide the polyurethane-polymer dye. Urea ported in water presented here. Any suitable monomer without casting can be used. Any suitable monomer containing an isocyanate group can be used from the same aera. Typically, such a monomer will correspond to the general formula: 0CN-R-NC0 where P s is the same as defined above in relation to the polyhydropic alcohol. Examples of the isocyanate group-containing monomers are the isomers of aromatic diisocyanates, such as, for example, toluene diisocyanate (TDI), full diisocyanate, 1, 3-bis (1- isoc), to-1-met i) 1) benzene and the like, aliphatic isocyanates or cyclohexanes or funcides di fune 1 are having between 2 and 38 carbon atoms, preferably between 4 and 12 carbon atoms, with, for example, diisocyanate of isoferone and hexamethyl diisocyanate, as well as isomers and aligomers of di (4- isoc ia tof ni 1) methane (MDI). An especially preferred water borne polymer dye for use herein is a water-borne polyurethane-urea prepared by modification of any of the polymer processes described in Frisch et al., Ed. , "Advances in Urethane Science and Technology", (Advances in Urethane Science and Technology) volume 10, pages 121-162 (1987), whose content is incorporated by reference. The aforementioned modification includes the replacement of part or all of one or more of the reactive polymers functional to those employed in these processes with a functional monomer having a colorant covalently linked in accordance with the present invention. Therefore, for example, an amine dye monomer and a monomer containing an isocyanate group react under reaction conditions for the formation of polymer carried in water at a ratio between the hydroxy lo (or amine) and the isocyanate equivalent of imadamente 0.25: 1 to approximately 1: 0.25, respectively. When an excess of isocyanate is employed, the resulting polymer can be an extended chain in accordance with well-known procedures. The reaction conditions of polymer formation carried in water which can be used to advantage for preparing the polymer dyes carried in water according to this invention, respectively, solvent, melt dispersion, prepolymer mixing, processes of? quetamine / quetacin, can be summarized as follows: 1. The process of the solvent The process of the solvent includes the steps of: a) reacting a liquid polymeric diol with a di-isocyanate to provide a prepolymer terminated by an isocyanate group possessing either which needs enough hydrafieel groups for the prepolymer to be self-imposed; b) reacting the prepolymer terminated by an isocyanate group dissolved in organic solvent with an aliphatic diamine chain linker, and where the prepsylimer has no sufficient hydrophilic groups for a self-dispersing process to be carried out, an extender of aliphatic diamipa chain having at least one hydrophilic group, to provide a solution of an organic self-dispersing polyurethane-urea solvent; and c) adding a sufficient amount of water to the organic solids solution of the. polyurethane-urea to form a dispersion of polyurethane-urea particles, at least one of said liquid polymeric, diisocyanate and aliphatic diamine has a portion of dye covalently bonded therein. 2. The melt dispersion process The melt dispersion process includes the steps of: a) reacting a liquid palladium diol, an hydrolytic diol having at least one ionic group and a diisocyanate to provide a prepolymer terminated in isocyanate group having ionic groups; b) reacting the isocyanate-terminated prepolymer with an end-agent reactive to formaldehyde to close the isocyanate end groups; c) dispersing the closed prepolymer in water; and d) reacting the dispersed closed prepolymer with formaldehyde to provide dispersed polyurethane-urea particles, at least one of said liquid polymeric diol, aliphatic diamine diisocyanate possesses a portion of dye digging lens therein bonded therein. 3. The prepolymer mixing process The prepolymer mixing process includes the steps of: a) reacting a liquid polymeric diol, a diol containing a carboxylic group and an aliphatic diisocyanate to provide an isocyanate-terminated prepolymer having groups carboxyl; b) reacting the prepolymer with a tertiary amine to convert the carboxyl groups to ammonium carboxylate groups and make the prepolymer self-dispersing; c) dispersing the prepolymer of au.tod ispersion in water; and d) reacting the dispersed prepolymer with a diamine chain extender to provide an aqueous dispersion of polyurethane-urethane particles, at least one of said liquid palmeric diol, diol containing carboxyl group, aliphatic diisocyanate and diamine chain extender. aliphatic liquid possesses a covalently bound dye. 4. The ketamine / ketacin process The ketamine / ketacin process includes the steps of a) reacting a liquid polymeric diol, a diol containing a carboxylic group and a diisocyanate to provide an isocyanate terminated prepslimer having carboxyl groups free; b) reacting the prepolymer with a tertiary amine to convert the carboxyl groups to ammonium carbaxylate groups and make the pre-polymer is self-dispersing; c) reacting the self-dispersion prepolymer with at least one member of the group consisting of quet ina and qutatacin in the presence of water to provide an aqueous dispersion of polyurethane non-urea particles, at least one of said liquid polymeric diol , diol containing alkoxy diisocyanate, alkoxy diisocyanate and aliphatic liquid diamine chain extender possesses a covalently bound dye. In a preferred embodiment of these water borne processes, the liquid polymeric diol is a diol of the general formula R-fP0H) 2 where R is a covalently bonded dye chromium forum and each P is the same polymer residue or a residue of different polymer. Examples of such liquid polymeric diols include any of the dye monomers of pal. aforementioned dihydroxy terminated polyester or polyether ether containing a portion of a covalently bound dye such as, for example, the amine dye monomer. The polymer dye component of the erasable ink composition of this invention generally has an average particle size of from about 25 to about 5000 n meters and preferably from about 50 to about 2000 nanometers. When the polymer dye component is not obtained in a particle size suitable for its. use in the erasable ink composition of the present inventioncan be reduced to such a size by any known or conventional method to obtain polymer powders, for example by grinding, milling, or by any of several processes of "hot water" to produce powders polymer such as those described in US Pat. No. 3,586,654, the content of which is incorporated herein by reference. When employed, the polyurethane ano-urea component carried in water of the erasable ink base fields of this invention generally has an average particle size of about 0.01 per pound between 4 microns and preferably about 0.05. Approximately 0.20 microns. The fully formulated erasable ink composition, that is, the polymeric dye component in admixture with the evaporable liquid vehicle component and that any optional component (s), may possess a relatively low viscosity, for example, from about 2 to about 80,000 centipoise and preferably from about 3 to about 30,000 centipoise when the water is the vehicle, or a relatively high viscosity, for example at least 100.00 centipoise and preferably at least approximately 500,000 centipoise when the vehicle is an organic solvent or a mixture of organic solvents that swell or dissolve the polymer dye. Obviously it will be recognized that when the erasable ink composition possesses such a high viscosity, it no longer easily flows only under the influence of the gravity, and it becomes necessary to provide a supply system under pressure for any marker instrument containing the ink. In order to improve or optimize one or more functional characteristics of the barrable ink composition, one or several optional components in the usual amounts can be added to the composition, for example, one or several latexes of natural and / or synthetic polymers, Theological modifiers , organic solvents, humectants, emulsifiers, surfers, plastiferous, dispersing agents, drying agents, release agents, partitioning agents, preservatives, antimicrobial agents, anti-corrosion agents, antioating agents, combination aids, and the like . With a without the addition of optional component (s), the erasable ink composition when applied to a substrate, and particularly a porous substrate such as cellulosic paper, and when dried should (1) sufficiently adhere to the substrate in such a way that it resists peeling 1 and (2) being substantially erasable. In addition, the dry erasable ink composition of this invention applied to paper evaluated by the adhesion test described infra generally presents less than approximately 3% by weight of flaking, preferably less than approximately 20 * / 5 by weight. shelling weight 1 and with an even higher degree of preference less than about 10% by weight of shelled 1 shear. The delineating capacity values delta E * ab of the erasable ink composition here as measured by ASTM D-2244-89 will generally be of the order of less than approximately 4.0, and preferably less than approximately 3.5 and with even more degree. elevated preferably, less than about 3.0. It is preferred that the erasable ink composition of the present invention, when evaluated by the dipping capacity test described infra has a sub-eminently low level of dipping, e.g., a doubling value of two or less and preferably a Embarrassment value of 1 (ie essentially absence of dunking). The erasable ink composition of this composition has .8 the purpose of being used in any of several markers and particularly in a ball pen. The following examples illustrate the erasable ink composition of this invention. EXAMPLES ILLUSTRATING THE PREPARATION OF MONOMERS OF POLYESID COLORING OF POL IESTER Polyester polyols obtained by the reaction of adipic acid, hexandiol and feni Idietanolami na were obtained in Puco (Hicksv i 13., NY). These polyols of palester are identified in Table 1 below. TABLE 3. Radium Psyol Onomer Polyester Weight Index (Adipic Acid, Pheni Molecular Hydroxy Idiethanolamine: Average Hexanediol> A 3.3: 1: 13 44.2 2539 B 13: 1: 13 33.3 3369 C 13: 2: 12 35.1 33.97 A monomer of polyester polyol dyes (hereinafter "DM1") derived from the polyol of paleate A was formed as follows: A 3-caliber round bottom flask equipped with a mechanical stirrer and an addition funnel was they added 45 g of H3P04 at 85 * / .. The reaction bottle was cooled to -5 ° C and 26.3 g (0.083 mole) of acid or trosi sulic furic at 40 * 4 were added, drop by drop, to the phrasing of The reaction was maintained while maintaining a temperature between -5 ° C and 0 ° C with agitation, a paste of 11.2 g (0.069 mole) of 2-amino-4-met i 1-3, 5-dithiane and approximately 50 tautomers. g of H3P04 at 85 V. Gap was added dropwise to the reaction flask through the addition funnel over a period of 30 minutes and stirred at 0 ° C for 1.5 hours to provide a diazonium salt solution. After 1.5 hours, the presence of excess nitration species was determined using qualitatively starch / iodine paper and any excess traction species was removed by adding an aqueous solution of urea to the mixture or su.lfáico acid. The diazonium salt solution was transferred through cannula to a solution of acetoni rilo (400 ml) and 182.7 g (0.072 mol) of polyester A at 0 ° C with stirring. The reaction mixture was allowed to reach room temperature and stirred for 2 hours. The reaction mixture was neutralized using a caustic substance. The solvent was removed in vacuo and a red-violet solid was obtained. This manomer of polyester polyol dye was washed until it was free of salts and other soluble materials with hot water.

A polyester dye monomer. Polyester iol (hereinafter "DM2") derived from polyester polyol B was formed as follows: To a 3-neck round bottom flask equipped with a mechanical stirrer and addition funnel was added 45 g of H3P04 to the 85% The reaction flask was cooled to -5 ° C and 15.51 g (0.049 mole) of nitrosi luric acid at 40 'was added dropwise to the reaction bottle while maintaining a temperature between -5 and 0 ° C. with agitation. A paste of 6.88 g (0.042 mole) of 2-amino-4-me i 1-3.5-d ic iano iof no and approximately 20 g of 85% H3P04 was added photo by drop to the bottle of the rection a through the addition funnel over a period of 30 minutes and stirred at 0 ° C for 1.5 hours to provide a diazonia salt solution. After 1.5 hours, the presence of excess nitration species was quantitatively determined using starch / iodine paper and any excess nitration species was removed by adding an aqueous solution of urea or sulpha acid to the mixture. .monkey. The diazonium salt solution was transferred by means of a cannula to a solution of acetonitrile (400 ml) and 500 g (0.148 moles) of polyol B of paloster B at 0 ° C with stirring.

The reaction mixture was allowed to reach room temperature and was stirred for 2 hours. The reaction mixture was neutralized using a caustic substance. The solvent was removed under vacuum and a red solid was obtained. This polyester polyol dye monomer was Wash until it is free of salts of other solid materials with hot water. A monomer of polyester polyol dye (hereinafter "DM3") derived from polyester polyol C was formed as follows: To a round-bottomed flask equipped with a mechanical stirrer and with an addition funnel was added 45 g of H3P04 at 85%. The reaction flask was cooled to -5 ° C. and 21.30 g (0.067 moles) of 40% strength and 40% furanic acid was added dropwise to the prescription bottle while maintaining a temperature between -5 and 0. ° C, under agitation. A paste of 3.1.16 g (0.061 mole) of 2,4-dinitroani 1 ina and 30 g of 85% H3P04 was added dropwise to the phrasing of the reaction through the addition funnel over a period of 30 minutes and it was stirred at 0 ° C for two hours to provide a salt solution. of diazonium. After 2 hours, the presence of excess nitration species was qualitatively determined using amidon / iodine paper and any excess nitration species was removed by adding an aqueous solution of urea or sulphamic acid to the mixture. The diazonium salt solution was transferred through cannula to an aqueous paste (500 mL) of 300 g (O.093 mol) of finely ground polyester Plyol C at a temperature of 0 ° C with stirring. The reaction mixture was allowed to come to room temperature and was stirred for 2 hours. The reaction paste was neutralized using a caustic substance. A solid ro was obtained. This polyester psiol dye monomer was collected by filtration and washed several times with hot water to remove salts and other water-soluble material. A manure of Paliéster Doliol dye (hereinafter "DM4") derived from polyester polyol C: A 3-necked round bottom flask equipped with a mechanical stirrer and an addition funnel was formed in the following manner. they added 45 g of 85% H3P04. The reaction flask was cooled to a temperature of -5 ° C and 54.62 g (0.1721 mol) of 40% sulfuric acid was added dropwise to the reaction passage while maintaining a temperature between -5 and 0 ° C with agitation. A pulp of 28.86 g (0.156 moles) of 2-amin-4-chlorobenzothiazole and 30 g of 85% H3P04 was added dropwise to the passage of the reaction through the addition funnel over a period of 30 minutes. and stirred at 0 ° C for 2 hours to provide a diazonium salt solution. After 2 hours, the presence of an excess of nitration species was successfully removed using starch / induro paper and any excess nitration species was removed by the addition of an aqueous solution. of urea or sulfamic acid. The diazonium salt solution was transferred by means of a cannula to a 500 ml (500 ml) 500 gram paste (0.1564 moles) of polio! of polyester C finely milled at a temperature of 0 ° C with stirring. The reaction mixture was allowed to reach room temperature and was stirred for 2 hours. The reaction paste was neutralized using a caustic substance. A red solid was obtained. This polio dye monomer! Polyester was collected through filtration and washed several times with hot water to remove sa 3 es and another water-soluble material. A polyester polyol dye monomer <And then "DM5") derived from Pallial polyester C was formed as follows: To a round bottom flask 3-neck equipped with a mechanical stirrer and an addition funnel 45 g of H3P04 85% were added. The reaction flask was cooled to -5 ° C and 38.2 g (0.12 mole) of 40% strength sulfuric acid or trosium sulfo were added dropwise to the reaction bottle while maintaining a temperature between -5. and 0 * C, with agitation. A paste of 28.55 g (0.109 moles) of 2-bromo-4,6-d? N? rsam 1 ina and 30 g of 85% H3P04 was added dropwise to the reaction flask through the addition funnel over a period of minutes and stirred at 0 ° C for two hours to provide a solution of sl dihydrate. anio. After 2 hours, the presence of excess nitration species was qualitatively determined using amide / lodide paper and any excess nitration species was removed by adding an aqueous solution of urea or sulfamic acid to the mixture. The diazonium salt solution was transferred through the cannula to an aqueous paste (500 ml) of 500 g (0.156 moles) of polio! of finely ground polyester C at a temperature of 0 * C with stirring. The reaction mixture was allowed to come to room temperature and was stirred for 2 hours. Paste was neutralized from the reaction using a caustic substance. A red solid was obtained. This polyester polyol dye monomer was collected by filtration and washed several times with hot water to remove salts and other water-soluble material. dispersions pol íuretano-urea covers in water obtained from monomers dye polyester polyol DM3, DM2, DM3, DM4 and DM5, using the mixing of PREPOL í Eros, as follows: EXAMPLE 1 A perol resin 2000 L equipped with an addition funnel, a nitrogen inlet and mechanical stirrer DM5 (205.58 g), acid d Imeľ i lolpro i nico (DMPA) (8.99 g) (dissolve in 2 <added; "> g of IJ-met i lp i rol idona) and a catalyst of d 1111 nd i laura to (Fastea t 42 <" > 2) (0.3 g). The reaction mixture was heated to a temperature of 60-70ßC with stirring and isopherone diisocyanate (IPDI) (42.4 g) was added over a period of 20-30 minutes to form a group terminated ísacianato red prepolymer having free carboxyl groups. The prepolymer was stirred for 3-5 hours at temperature and the percentage of NCO was monitored. When the theoretical percentage of NCO was reached, tp-tilamine (5.91 g) was added to the color prepolymer and stirred at temperature for 3 minutes. The isodispersion polymer prepoly was dispersed in a sufficient amount of water using an impeller-type dispersing blade to provide a solid dispersion of 35-50%. The dispersed prepol then was then allowed to chain-extend with water at a temperature of 40 ° C to provide a dispersion of p-urethane-urea particles having an average particle size of less than about 0.1 microns. The process described above was repeated to form Examples 2-8 which are summarized in Table 2 below: TABLE 2 Example Mop? ero dye of Isocyanate / DMPA polio! polyester / quantity (g) CÍ. nt i nity (g) DM1 / m-TMXDI * /, 61 1 7.43 42.0 DM1 / m-TMXDI / 8.60 194.79 42.0 DM2 / m-TMXDI / 8.25 82.44 42. DM3 / IPDI / 8.1 228.36 42.4 DM4 / IPDI / 8.59 205.58 42.4 DM4 / IPDI / 15.65 129.71 42.4 8 DM5 / IP I 3.0.60 249.86 42.4 E je p lo Triethylamine (g) Color 5.74 violet 6.48 violet 4 6.21 iolette 5 6.95 red 6 6.78 red 7 5.89 red 8 7.99 red * m-TMXDI = 1, 3-b? S (1-? Soc wool to-l- me i let 11) -benzene Polymer dyes of non-urine polymer =. in water used in the erasable ink composition are m * = > They are expensive to process, have superior stability to oxidation and superior thermal stability compared to polyurethane-urea polymer dyes manufactured from colorful polyether polyols such as, for example, the ppolyther pallaols described in American patent no. 5,231,135. In addition, the non-urea polyurethane dispersions manufactured from the polyester polyol dye monomers presented here possess superior properties, for example, water resistance, as compared to the poly-urethane-urea dispersions manufactured from the colorful polyester s shown in 1? American patent no. 5,231,135. EXAMPLES ILLUSTRATE THE PREPARATION OF PREPOL POLIFUNCTIONAL IMEPOS THAT HAVE PORTION OF COLORANTLY LINKED EXAMPLE 9 Di-ionolpropionic acid (8.25g) was dissolved in N-methylhydroquinone (13.8g /. itetramethylene glycol (TERETHANE T-2900 from DuPont) (208.2g), polyol dye (15. Og) corresponding to dye C of Table I of U.S. Patent No. ,231,135, isopherazone diisocyanate (42.40g) and catalyst of d ib t i 1 t ind i laur to f .72g). The solution was heated to a temperature of approx. It is preferably 60 to approximately 70 ° C for about 3 to approximately 5 hours with agitation. The color of the resultant isocyanate-terminated prepolymer having a covalently bound dye on it was red, EXAMPLE 10 Di-ethyl-lolpropic acid (7.37 g) was dissolved in N-met i-ipral idona (32.33 g). To this solution were added the iteration of the TEPETHANE T-2900 from DuPont (151.2 g and polyfluoroef: 0-48? 0 of Do »» Chemical) (84.0 g), polyol (5 . < * g) qu > Does ar respond to dye C of T bl? I from the P-? Tt »te Nortéame! icana No. 5,233,135, used by Ipanalo de I sofprona (42.40g) and catalyst of i bu i 1 1 n i laura o (0.48g). The solution was heated to a temperature from approximately 60 to approximately 70 ° C for approximately 3 hours at approximately 5 hours with agitation. The color of the resulting isocyanate group prepolymer resulting with covalently bound dye on it was red. EXAMPLE 13 D i and l-lolpropionic acid (3.50 g) was dissolved in N- and i-iprol idona 5.84 g). To this solution, an iteramethylene glycol (TERETHANE T-2900 from DuPont) (305. g), polyol dye (5.0g) corresponding to. dye U of Table I of U.S. Patent No. 5,231,135, polyol dye (5.0g) corresponding to dye G of Table I of U.S. Patent No, 5,231,135, isoferone diisocyanate (42.40g) and dibu catalyst. .ti 11 ind i laurato (0.12g). The solution was heated to a temperature of approximately 60 to approximately 70 ° C for about 3 to about 5 hours under stirring. The color of the resulting finished isocyanate group prepolymer having the. covalently attached dye there was violet-blue. EXAMPLE 12 D i and lolproponic acid (8.08 g) was dissolved in N i and i ip i rrol idona (13.5 g). To this solution, polytetramethylglycol (TEP.ETHANE T-2900 of DuPant) (184.5g) polyalclue (5.0g) corresponding to dye C of Table I of U.S. Patent No. 5,231,135, diisocyanate of isoferone (42.40g) and 1 i indi laurate catalyst (0.48g). The solution was heated to a temperature of approximately 60 to about 70 ° C for about 3 to approximately 5 hours with stirring. The color of the resulting isocyanate-terminated prepolymer with covalently bound dye there was red. EXAMPLE 13 D i et iolpropionic acid (8.08g) was dissolved in N- et i l? iRrol idana (13. g). To this solution, poly te tetragliol 'TERETHANE T-2900 from DuPont) (174.6g), polyol dye (5.0g) corresponding to dye C of Table I of U.S. Patent No. 5,231,135, isoferone diisocyanate ( 42.40g) and catalyst of d ibut i lt indi laurato (0.48g). The solution was heated to a temperature of about 60 to about 70 ° C for about 3 to about 5 hours with stirring. The color of the resultant isocyanate-terminated prepolymer with coexcessively bound dye there was red. EXAMPLE 34 Isoferonium diisocyanate (42.40g) and polymethylglycolol (TEPFTHANE T-2900 from DuPont) were mixed. (174.6g). To this mixture, polyol dye was added (5.0g. < corresponding to dye U of Table I of the U.S. Patent No. 5,231,135. The mixture was dissolved in methylene glycol 320) and the dibut catalyst 11 t indurars (0.24 g) was added to the solution which was stirred at room temperature overnight. The color of the resultant isocyanate-terminated prepolymer with covalently bonded dye therein was violet. EXAMPLES ILLUSTRATING THE PREPARATION OF POLYMER DYES EXAMPLE 15 The prepolymer mixing process was carried out in the following manner: the prepolymer of example 9 reacted with the tet i lamination agent (6.22 g) to convert the carba groups; in the prepolymer in ammonium carboxylate groups and make the prepolymer self-dispersing. Next, the autodispersing prepol was dispersed in water (241g) using an impeller-type dispersing blade. The prepolymer was then reacted at room temperature with a hydrazine chain extender (3.93g) to provide a polyurethane-urea particle dispersion of about 55.0 wt% solids. EXAMPLE 16 The process of prepolymer mixing was carried out in the following manner: the prepolymer of example 10 reacted with the tpeti lamination (5.60g) neut liquor agent to convert the carbaphyl groups to the prepolymer. in carbo groups; Ammonium amide and make the prepolymer self-dispersing. Afterwards, the Autadi spers ion prepol was dispersed in water (300g) using an impeller-type dispersing blade. The dispersed prepolymer then reacted at a temperature of approximately 76 ° with a chain extender, hydrazine (5.76 g), to provide a dispersion of the polyurethane-urea particles of about 50.7% by weight solids. EXAMPLE 17 The prepolymer mixing process was carried out in the following manner: the prepol polymer of example 11 reacted with the neutralizing agent, triethylamine < 2.64g) to convert the carbaxy groups into the prepolymer into ammonium carboxylate groups to make the prepolymer self-dispersing. Then, the self-dispersion prepolymer was dispersed in water (436g) using an impeller-type dispersing blade. The dispersed prepolymer was then heated to room temperature with a chain extender, hydrazine (1.49g), to provide a dispersion of the polyurethane-urea particles of approximately 45.9% by weight solids. EXAMPLE 18 The prepolymer mixing process was carried out in the following manner: the prepolymer of example 12 reacted with the neutralizing agent, triethylamine C6.09g), to convert the carboxyl groups to the. prepolymer in ammonium carboxylate groups and make the prepol. number is self-dispersion. Then, the self-dispersing prepalímers in water (300g) was dispersed using a driving-type dispersing blade. The dispersed prepolymer then reacted at room temperature with hydrazine (5.82g), a chain extender, to provide a dispersion of polyurethane-urea particles of about 46.4% by weight solids. EXAMPLE 19 The prepolymer mixing process was carried out in the following manner: the prepolymer of example 13 reacted with the neutralizing agent, triethylamine (6.09 g), to convert the carboxyl groups in the prepolymer into ammonium carboxylate groups and make that the prepolymer is self-dispersing. Then, the self-scattering prepolymer was dispersed in water (300g) using an impeller-type dispersing blade. The dispersed prepolymer then reacted at room temperature with hydrazine (5.82g), a chain extender, to provide a polyurethane-urea particle dispersion of approximately 46.9% by weight solids. EXAMPLE 20 The solvent process was carried out in the following manner: the prepolymer of Example 14 dissolved in the reaction mixture at room temperature with hydrazine (2.15 g), a chain extender, to provide a solution of organic solvent of polyurethane. urea of approximately 64.9% by weight solids. The properties of the polymer dyes of examples 15-20 are shown in Table 3 below: average particle size Example (dry) (nm) color (dry) Tg (° C) 50 - 500 red < 60 16 250 ro or < 60 17 250 - 2000 violet-blue 60 18 150 red < 60 19 150 red < 60 N / A violet 60 (solution) The polymer dye compositions of Examples 15-20 can be used directly as erasable ink compositions or they can be combined with one or more optional components such as emulsion before being used as compositions of erasable ink. To further illustrate the erasable ink composition of the present invention, the polymer dye of Example 15 was combined with a silicone emulsion, ie, a Silicone Ertyulsion SWS-233 from Wac er Chemical. Corp), to provide a barrable ink composition (example 21) containing 90% by weight of polymer dye and 10% silicone emulsion. In another example, the. The polymer dye of Example 17 was combined with an emulsion containing 25.0 wt% of sorbitan sesqualeate, i.e., Lonzamal S0C of Lonza, 1.67 wt% of dadeci lbencensul sodium fonate, i.e. Rhodoeal DS4 of Rhone Poulenc, and 71.66% by weight of water to provide an erasable ink composition (example 22) containing 90% by weight of polymer dye and 10% by weight of the emulsion. The properties of the erasable ink composition of examples 21 and 22 were evaluated. In particular, the color intensity, viscosity, adhesion, erasability and stainability of the erasable ink composition were evaluated. The intensity of the color was evaluated by means of a subjective visual evaluation of the manuscript document. The adhesion was determined by making a drawing on a heavy line drawing paper in advance with approximately 0.8 g of sample (spread over an area of 0.635 cm x 3.81 cm) and drawn with a number 6 applicator. . \? dry completely (Approximately 5 minutes at room temperature) and the paper was weighed again. The paper was then hand wrinkled approximately to the same extent for each sample tested, then unrolled, the flakes removed and the paper weighed again. This test was also carried out with an erasable ink prepared in accordance with U.S. Patent Nos. 5,120,359 and 5,203,913 (comparison example 1). Erase capacity was determined by performing a "WRITING TEST" (similar to a spirograph where the ink is applied in a circular arrangement on paper with certain ink crosses) with ballpoint pen pens containing the erasable ink composition of Examples 21 and 22 and the following commercially available pens containing the erasable ink: Pen Ink color Comparison example Er s rmate blue 2 Erasermate 2 blue 3 Scppto blue 4 Scppto ro o 5 The writing samples of "WRITING TEST" were then erased and reflectance measurements were carried out on the erased part of the paper versus a part without affecting / not touched paper. A quantitative value was obtained, ie, delta E * ab from the CIÉ laboratory measurement (described in ASTM D-2244-89). Minor values, indicate more complete deletions. The immersion capacity was evaluated subjectively for the composition of tint? erasable from examples 23 and 22 and comparative examples 2-5, 1-2 seconds after the writing i ntempt to smear the ink with the fingers. A lock value of 1 essentially represents an absence of a lock and a lock value of 5 represents such a degree of lock that the legibility of writing is significantly affected.

Table 4 below shows the properties of the torrable ink compositions: Table 4 (% by weight of composition intensity viscosity of dry ink retained in Example of color (cps) paper 21 comparable to -3-5 100% examples compare ivos 22 comparable to -3-5 100% examples comp ra ti vos Example - 63% compa rat i vo 1 E je p lo - comp ati vo E j emp 1 o comp rat i vo E jemp 1 or compa rat i vo 4 E p e compares t i vo c value of capacity v lor of Example of erasing (delta E * ab) embedding 21 3.17 1 22 1.44 1 Comparative Example 1 - - Comparative Example 2 3.3 2 Comparative Example 3 3.63 2 Example compares ivo 4 5.38 3 Comparative Example 5 - 4 The data in Table 4 clearly demonstrate the superiority of the erasable ink composition of this invention compared to the erasable inks available therein. Commerce. The erasable ink composition of this invention is highly adherent on a substrate to resist scale formation and is substantially barourable. While this invention has been presented herein in relation to certain embodiments and certain procedural details, it is clear that changes, modifications or equivalents may be employed by those skilled in the art. Accordingly, such changes within the principles of this invention have the. purpose of being included within the scope of the following claims.

Claims (11)

1. CLAIMS 1. An erasable ink composition comprising (a) a water-insoluble polymer dye obtained by the polymerization of a polymer-forming reaction medium containing at least two co-reactive polymeric polymers with at least one of the monomers possessed by a portion of covalently bound dye and (b) an evaporable liquid carrier in which the polymer dye = e is dissolved, dispersed or swollen, the erasable ink composition when applied to a substrate and drying is (1) sufficiently adherent on the substrate to resist the formation of scales and (2) substantially erasable.
2. 2. The erasable ink composition of claim 1 having less than about 3 < "/% by weight of shell flaking and a value of debris removal capacity E ab less than approximately 4.0
3. 3. The erasable ink composition of the rei indication 1 wherein the monomer possessing a covalently bound dye portion it corresponds to the formula 1 (P -a- f -X) b)) c where R is a portion of dye cavalently bound to the polymer residue P, X is a functional group, a, b and c, each represent the minus 3, provided that the product of b: <c is at least 2, when c is a 1 minus 2, a is 1 and where there are more than one R, P or X, each of R, P or X may be identical or different
4. 4. The erasable ink composition of the reagent 1 wherein the polymer dye is a polymer carried in water
5. 5. The erasable ink composition of the reagent 1 where the polymer dye is a urethane pal-u.rea carried in water
6. 6. The erasable ink composition of claim 5 wherein the polyurethane-urea carried in water is obtained through the solvent process, the melt dispersion process, the prepolymer mixing process, or the process of mixing; ketamine / ketacin.
7. 7. The erasable ink composition of any of the rei indications 1 to 6, wherein the polymer dye includes structural units of the general formula: where each A independently can be an ester to a good amide bond, n can be an integer of approximately 1 to about 50, R is an aliphatic or aromatic hydrocarbon with up to about 30 carbon atoms, a and b independently. , from 1 to 10, 1 is an aplepo group substituted or unsubstituted or a single bond when Y is an anthraquone group and Y is selected from the group consisting of an azo group, tri- caine, apraquinone and methine.
8. The erasable ink composition of any of claims 1 to 7, wherein the composition further comprises at least one additional component selected from the group consisting of natural latexes, synthetic latexes, Theological modifiers, suspending agents, organic solvents, humectants emulsifier, surfactants, pesticides, expansion agents, drying agents, release agents, division agents, preservatives, agents; ant i ic rota to us, an anchor agents, ant i o: - idanles and auxiliary combination.
9. 9. An arc-idor instrument containing the erasable ink composition of any of claims 1 to 8.
10. 10. A polymer is not carried in water obtained by the polymerization of a polymer formation reaction medium containing at least two functional polymers 1 is reactive with at least one of the monomers possessing a portion of a dye cavantly attached thereto under polymer-forming reaction conditions carried in water. _
11. 11. U-'t polymer containing the structural units of the general formula: A (CHa) É-N- (CHa) where each A, independently, may be an ester or amide bond, n may be an integer from about 1 to about 50, R is an aliphatic or aromatic hydrocarbon with up to approximately 30 carbon atoms, a and b are, independently, from 1 to approximately 10, Z is a substituted or unsubstituted arylene group or a single bond when Y is an anthraquinone group and Y is selected from the group consisting of an azo, trieanovinyl, anthraquinone and metina.