MXPA99010686A - Process for preparing reactive latex blendswhich are chemically and physically stable until film formation - Google Patents

Abstract

This invention provides the composition, preparation, and end-use of waterborne cross-linking technology based compositions prepared from water-based latexes. The invention provides a water-based latex comprising dispersed, waterborne amino-functional polymer particles;dispersed, waterborne pendant-functional polymer particles;and water. The waterborne pendant-functional polymer comprises at least one pendant amine reactive functional moiety selected from the group consisting of carbonate, epoxide, isocyanate, isopropenyl, carboxylic acid, and allyl groups. In a preferred embodiment, a latex of the invention comprises dispersed, waterborne polymeric (polyamino)enamine (PPAE) particles;dispersed, waterborne pendant-functional polymer particles;and water. The PPAE is the reaction product of a surfactant-stabilized acetoacetoxy-functional polymer (SAAP) and a poly(alkylenimine). The water-based latexes of the invention provide stable emulsions containing a blend of waterborne polymer particles which undergo cross-linking upon film formation. The latex films or coatings may be cured at ambient temperatures or may be thermally cured. The latex is useful in variety of coating compositions such as, for example, paints, inks, sealants, and adhesives.

Description

PROCESS TO PREPARE REACTIVE LATEX MIXTURES WHICH ARE CHEMICALLY AND PHYSICALLY STABLE UP TO THE INFORMATION OF A MOVIE Field of the Invention This invention belongs to the field of emulsion chemistry. In particular, it relates to a combination of different water-borne polymers which are useful in a variety of coating compositions.

Background of the Invention In a growing number of industries, aqueous coating compositions continue to replace traditional, organic solvent based coating compositions. Paints, inks, sealants, and adhesives, for example, previously formulated with organic solvents, are now formulated as aqueous compositions. This reduces the potentially harmful exposure to the volatile organic compounds (VOC's) commonly found in solvent-based compositions. Although the movement Ref.32146 of the compositions based on an organic solvent to the aqueous compositions, leads to health and safety benefits, the aqueous coating compositions must meet or exceed the expected performance standards of the solvent-based compositions. The need to meet or exceed such performance places a premium on the characteristics and properties of the waterborne polymeric compositions used in aqueous coating compositions. The polymers carried by the water having various functional groups have been used to impart and achieve desired properties to a particular coating composition. For example, a coating composition must exhibit good film formation, printing and blocking resistance, as well as good adhesion and tensile properties. Polymers having acetoacetoxy and enamine functional groups which represent an example of waterborne polymers which have such properties, can carry different functional groups, and are useful in aqueous coating compositions. The U.S. Patent No. 5,296,530 discloses a fast curing coating prepared from a polymer having acetoacetyl groups, in which substantially all of the acetoacetyl groups have been converted to enamine functional groups. This conversion occurs, for example, by treatment with ammonia or a primary amine. The coatings thus prepared cure more quickly under sunlight or ultraviolet light than the coatings containing the acetoacetyl polymer, but which have not been converted to an enamine form. The U.S. patents Nos. 5,484,975 and 5,525,662 describe the preparation of the polymers containing functional acetoacetate groups and then, following the polymerization, reacting the acetoacetate group with a functional amine to form an enamine. The resulting polymers are reported to have a variety of uses including coatings, sealants, adhesives, and saturation applications. The U.S. Patent No. 5,408,659 describes polymeric formulations comprising an aqueous carrier, at least one polymeric ingredient, a non-polymeric polyfunctional amine, and a base. The polymeric ingredient has functional portions of both the acetoacetoxy type and the acid function. The formulations Aqueous polymers produce cross-linked polymeric surface coatings on a substrate. Japanese Patent No. 61-21171 describes a fast curing adhesive consisting of two separate liquids. The first liquid is an aqueous solution and / or aqueous emulsion of a polymeric compound containing an acetoacetyl group. The second liquid consists of polyethylene imine. Even with the common waterborne polymeric formulations, there remains a need for improved aqueous coating compositions and waterborne polymers for use in these compositions. In particular, there is a need for waterborne polymeric compositions which can be formulated as a stable, unique composition, but which undergoes cross-linking during film formation, imparting one or more desired properties to the resulting coating. The present invention satisfies such needs.

Brief Description of the Invention This invention provides a water-based latex comprising polymer particles with a function of amino transported by water, dispersed; polymer particles with suspended function, transported by water, dispersed; and water. In a preferred embodiment, a latex of the invention comprises polymerized (polyamino) enamine (PPAE) particles transported by water, dispersed: polymer particles with pendant function, transported by water, dispersed, and water. PPAE is the product of the reaction of a polymer with acetoacetoxy function stabilized by a surfactant (SAAP) and a poly (alkyleneimine). The water-based latices of the invention provide stable emulsions containing a combination of water-borne polymer particles which undergo cross-linking during film formation. Latex films or coatings can be cured at ambient temperatures or can be thermally cured. The latex is useful in a variety of coating compositions such as, for example, paints, inks, sealants, and adhesives.

Brief Description of the Drawings Figure 1 shows constant contour plots of double rubs of methyl ethyl ketone as a function of the size of epoxy containing latices, and latices containing PEI.

Detailed description of the invention The present invention provides a water-based latex. In one embodiment, the latex produces a stable emulsion, which contains a combination (or a mixture) of dispersed water-transported polymer particles, which undergo cross-linking during film formation. The latices of the invention are stable when stored at temperatures above or moderately above the ambient temperature. Still, a film or coating formed from the latex of the invention can be cured at room temperature (curing temperature) or at elevated temperatures (thermal curing). A water-based latex comprises dispersed polymer-dispersed water-transported amino particles; polymeric particles with suspended functions, transported by water, dispersed, and water. In other words, a water-based latex of the invention is an aqueous dispersion containing polymeric particles with amino function transported by water, separated and particles polymeric with suspended functions, transported by water, separated. In the water-based latices of the invention, polymers generally exist as particles dispersed in water. The particles can be structured or unstructured. Structured particles include, but are not limited to, core / shell particles and gradient particles. The particle size of the polymers can vary from about 25 to about 500 nm. Preferred particle sizes for small particles vary from about 25 to about 100 nm, more preferably from about 45 to 80 nm. For large particles, the preferred particle sizes vary from about 110 to about 450 nm. The polymer particles generally have a spherical shape. In a preferred embodiment, the generally spherical polymer particle has a core portion and a shell portion. The core / shell polymer particles can also be prepared in a multi-lobular form, a shape configured as a peanut, an acorn form, or a raspberry shape. It is further preferred in such particles that the core portion comprises about 20 to about 80 of the total weight of the particles and the portion of the shell comprises about 80 to about 20 of the total particle weight volume. A preferred molecular weight of the polymer according to the present invention, is a weight average molecular weight (Mw) from 1,000 to 1,000,000 as determined by gel permeation chromatography (CPG). A more preferred range for the weighted average molecular weight is from 5,000 to 250,000. The glass transition temperature (Tg) of the polymer according to the present invention can be up to about 100 ° C. In a preferred embodiment of the present invention, wherein a formation of a film at ambient temperatures of the particles is desirable, the vitreous transition temperature may preferably be below 60 ° C.

The Polymer with Amino Function Polymers that have amino (NH) groups available to react with the acetoacetoxy-functional polymer during film formation can be used as a polymer with a function of amino in the water-based latex of the invention. The amino groups can be primary or secondary amines. In general, amino groups must be present at or near the surface of the polymer particles to react with the acetoacetoxy functional polymer. The amino-functional polymer must contain a sufficient number of amino groups to allow efficient crosslinking with the acetoacetoxy functional polymer. Exemplary amino functional polymers include, but are not limited to, polymeric (polyamino) enamines and polymers prepared by reacting aziridines with carboxylic acid containing latices such as those described in U.S. Pat. No. 3,261,796. The polymeric (polyamino) enamines represent a particularly preferred group of the amino-functional polymers for use in a water-based latex according to the invention. By reacting an acetoacetoxy functional polymer containing a surfactant (SAAP) with ammonia, a primary or secondary amine produces an enamine functional polymer containing the surfactant of the invention. A polymeric (polyamino) enamine (PPAE) results from the reaction of an SAPP with a poly (alkyleneimine). The (polyamino) enamines Polymers represent a particularly preferred group of the amino-functional polymers for use in a polymeric composition carried by water according to the invention. These various polymers according to the invention, their preparation, and the related preferred embodiments are described below. The SAAP can be prepared by the free-radical emulsion polymerization of a non-acidic vinyl monomer having an acetoacetoxy functionality such as those of the following formula (1) with at least one surface-active, non-self-curing vinyl monomer and others non-acidic vinyl monomers. This produces a water-based dispersion of the polymeric particles containing a surfactant, with the polymer having pendant acetoacetoxy groups. When used herein, a non-acidic vinyl monomer is a monomer containing no ethylenically unsaturated carboxylic acid. A pendant acetoacetoxy group is not strictly limited to those at the polymer terminals. The pendant acetoacetoxy groups also include groups attached to the polymer backbone and available for further reaction.

The SAAP preferably contains about 1 to about 40 weight percent of the acetoacetoxy-functional monomers such as those of the following formula (1), about 0.05 to 20 weight percent of at least one surface-active vinyl monomer, self-curing and about 60 to about 90 weight percent of other non-acidic vinyl monomers. The percentage by weight is based on the total amount of the monomer. More preferably, the SAAP has from about 10 to about 25 weight percent of acetoacetoxy monomers, about 0.1 to about 10 weight percent of at least one surface active vinyl monomer, not self-polymerizing and about 75 to about 90 percent by weight. weight of other vinyl monomers. The polymerization of the water-based emulsion to prepare the SAAP preferably occurs in the presence of a nonionic surfactant and an anionic surfactant. The nonionic surfactant may be present in amounts ranging from about 0.25 to about 5 phr, and the anionic surfactant in amounts ranging from about 0.1 to 1 phr. The unit "phr" it defines the grams of dry weight of the recited component, for example the surfactant, per 100 grams of dry weight of the resin, wherein the "resin" includes all the components of the polymerization excluding water. The aspects of this emulsion polymerization and the preferred embodiments are described below. Any non-acidic vinyl monomer having the functionality of the acetoacetoxy type can be used to prepare a polymer of the invention. Of such monomers, the preferred monomers are those of the formula (1): RX-CH = C (R2) C (O) -X1-X2-X3-C < 0) -CH2-C (0) -R3 (I! for a monomer of the acetoacetoxy type of the formula (1), R1 is a hydrogen or halogen. R2 is a hydrogen, halogen, alkylthio group with Ci-Cß, or alkyl group with C? -C6. R3 is an alkyl group with C? -C6. X1 and X3 are independently O, S, or a group of the formula -N (R ') -, where R' is an alkyl group with C? -C6. X2 is an alkylene group with C2-C2 or a cycloalkylene group with C3-C2. The alkyl and alkylene groups described herein and throughout the specification can be straight or branched groups. Preferred monomers of the formula (1) are acetoacetoxyethyl methacrylate, acrylate acetoacetoxyethyl, acetoacetoxy (methyl) ethyl acrylate, acetoacetoxypropyl acrylate, allyl acetoacetate, acetoacetamidoethyl (meth) acrylate, and acetoacetoxybutyl acrylate. Acetoacetoxyethyl methacrylate (AAEM) represents a particularly preferred monomer of formula (1). Suitable non-acidic vinyl monomers which may be used, for example, include, but are not limited to, methyl acrylate; methyl methacrylate; ethyl acrylate; ethyl methacrylate; butyl acrylate; butyl methacrylate; isobutyl acrylate; isobutyl methacrylate; ethylhexyl acrylate; 2-ethylhexyl methacrylate; octyl acrylate; octyl methacrylate; iso-octyl acrylate; iso-octyl methacrylate; trimethylolpropyl triacrylate; styrene; methyl styrene; glycidyl methacrylate; carbodiimide methacrylate; alkyl crotonates with C? -C? 8; di-n-butyl maleate, di-octylmaleate; allyl methacrylate; di-allyl maleate; di-allylmalonate; methoxybutenyl methacrylate; isobornyl methacrylate; hydroxybutenyl methacrylate; hydroxyethyl (meth) acrylate; hydroxypropyl (meth) acrylate; acrylonitrile, vinyl chloride; ethylene; ethylene vinyl carbonate; epoxy butene; 3, 4-dihydroxybutene; (met) acrylate hydroxyethyl; methacrylamide; acrylamide; butyl acrylamide; ethyl acrylamide; (meth) vinyl acrylate; isopropenyl (meth) acrylate; cycloaliphatic epoxy (meth) acrylates; and ethylformamide. Such monomers are described in "The Brandon orldwide Monomer Reference Guide and Sourcebook" Second Edition, 1992, Brandon Associates, Merimack, New Hampshire, and in "Polymers and Monomers", the 1996-1997 Catalog of Polyscience, Inc., Arrington, Pennsylvania . To increase the stability of the polymer, a small amount (approximately 0.4 phr) of AMPS, sodium 2-acrylamido-2-methylpropan sulfonate, and other stabilizing monomers, can be incorporated into the SAAP. By adding such stabilizing monomers to the shell or shell of the polymer, it helps prevent flocculation during the addition of a polyalkyleneimine to form a PPAE. The high levels of such stabilizing monomers can create aqueous membrane layers between the polymer particles in the latex or alter the formation of the film. The AMPS is available from Lubrizol Corporation under the registered name LUBRIZOL 2405. The vinyl esters of the general formula (2) represent additional examples of non-acidic vinyl monomers: RCH = CH-0-C (0) -C (R) 3 (2! In the formula (2), R is independently hydrogen or an alkyl group of up to 12 carbon atoms. The particular monomers of the formula (2) include CH2 = CO-0-C (0) -CH3, CH2 = CO-0-C (0) -C (CH3) 3, CH2 = CO-0-C (0) -CH (C2H5) (C4H9), and CH2 = C0-0-C (0) -CH2CH3. The vinyl ester monomers also include the vinyl esters of vinyl alcohol such as the VEOVA series available from Shell Chemical Company as the VEOVA 5, VEOVA 9, VEOVA 10, and VEOVA 11 products. See O.W. Smith, M.J. Collins, P.S. Martin, and D.R. Bassett, Prog. Org. Coatings 22, 19 (1993). As a further preferred embodiment, the SAAP may also incorporate non-acidic, nitrogen-containing vinyl monomers, which are known to promote adhesion in the wet phase. Exemplary wet phase adhesion monomers include, for example, t-butylaminoethyl methacrylate; dimethylaminoethyl methacrylate; diethylaminoethyl methacrylate; N, N-dimethylaminopropyl methacrylamide; 2-t-butylaminoethyl methacrylate; N, N-dimethylaminoethyl acrylate; N- (2-methacrylamido-ethyl) ethylene urea; and N- (2-methacryloyloxy-ethyl) ethylene urea. N- (2-methacryloyloxyethyl) ethylene urea is available from Rohm Tech as a 50% solution in water under the trade name Rohamere 6852-0 and as a 25% solution in water under the trade name Rohamere 6844. N- (2-ethacrylamido-ethyl) ethylene urea is available from Rhone- Poulenc under the registered name WAM. Small amounts of vinyl acid monomers can also be used to prepare an SAAP according to the invention. Such acidic vinyl monomers include, for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, and monovinyl adipate. Incorporating the monomers of the acidic vinyl into the SAAP can increase the viscosity of the resulting latex and can have a detrimental effect on the formation of an enamine-functional polymer according to the invention. Generally, these monomers are used in small amounts. Preferably, the amount of the acidic vinyl monomers may vary, for example, from 0 to 5 phr. Larger amounts can be used to achieve a desired effect, such as increased viscosity. The SAAP preparation reacts the non-acidic vinyl monomers, as described above, with at least one surface-active, non-self-curing vinyl monomer (also known as an ethylenically unsaturated surfactant, not self-curing or a reactive surfactant). A non-self-curing surfactant monomer, instead of polymerizing with itself to form a separate polymeric surfactant, is substantially (preferably completely) incorporated in the polymer of the invention. Accordingly, the surfactant becomes part of the polymer. Non-self-polymerizing surfactants possessing, for example, propenylphenyl or allyl groups, are preferred. Examples include the surface active monomers sold by PPG Industries, Inc., such as the MAZON® SAM 181, 183, 184, 211 surfactants which are anionic sulphates or sulphonates and the MAZON® SAM 185-187 surfactants which are nonionic surfactants. Other surface-active vinyl monomers, not self-polymerizing, include the macro-monomers sold by Daiichi Kogyo Seiyaku under the names of the surfactants NIOGEN RN, AQUARON or HITENOL. These include the polyoxyethylene alkyl phenyl ether compounds of the general formulas (3), (4), and (5): (3) In formulas (3), (4), and (5), R is nonyl or octyl and n and m are preferably integers from 15 to 50 and from 15 to 40, respectively. More preferably, n ranges from 20 to 40, and m from 15 to 25. The products HITENOL RN, HITENOL HS-20 and HITENOL A-10 are the surface-active, non-self-polymerizing monomers particularly preferred. Other such polymerizable surfactants include the alkyl allyl sodium sulfosuccinate sold by Henkel, under the tradename of the TREM surfactant LF-40. S7? AP (as well as other polymers useful in the invention) can be prepared using emulsion polymerization techniques known in the art. The polymer, as is known in the art, can be prepared using free radical emulsion polymerization techniques which produced particles structured or unstructured. As mentioned above, the structured particles include, for example, core / shell particles, raspberry particles, and gradient particles. Chain transfer agents, initiators, reducing agents, buffers, and catalysts, known in the emulsion polymerization techniques, can be used to prepare the polymers. Exemplary chain transfer agents are butyl mercaptan, dodecyl mercaptan, mercaptopropionic acid, 2-ethylhexyl 3-mercaptopropionate, n-butyl 3-mercaptopropionate, octyl mercaptan, isodecyl mercaptan, octadecyl mercaptan, mercaptoacetic acid, allyl mercaptopropionate, allyl mercaptoacetate, crotyl mercaptopropionate, crotyl mercaptoacetate, and the reactive chain transfer agents taught in U.S. Pat. No. 5,247,040, incorporated herein by reference. In particular, 2-ethylhexyl 3-mercaptopropionate represents a preferred chain transfer agent. Typical initiators include hydrogen peroxide, potassium or ammonium peroxydisulfate, dibenzoyl peroxide, lauryl peroxide, di-tertiary butyl peroxide, 2,2'-azobisisobutyronitrile, t-butyl hydroperoxide, benzoyl peroxide, and the like. Suitable reducing agents are those that increase the polymerization rate and include, for example, sodium bisulfite, sodium hydrosulfite, sodium sulfoxylate and formaldehyde, ascorbic acid, isoascorbic acid, and mixtures thereof. Polymerization catalysts are those compounds that increase the polymerization rate and which, in combination with the reducing agents described above, can promote the decomposition of the polymerization initiator under the conditions of the reaction. Suitable catalysts include the transition metal compounds such as, for example, ferrous sulfate heptahydrate, ferrous chloride, cupric sulfate, cupric chloride, cobalt acetate, cobaltous sulfate, and mixtures thereof. As described above, the emulsion polymerization to prepare the SAAP preferably occurs in the water and in the presence of a nonionic surfactant and / or an anionic agent. Suitable nonionic surfactants include the surfactants such as alkyl polyglycol ethers such as the ethoxylation products of lauryl, oleyl, and stearyl alcohols; the alkyl phenol polyglycol esters such as the ethoxylation products of octyl- or nonylphenol, diisopropyl phenol, and triisopropyl phenol. Preferred nonionic surfactants are TERGITOL 15-S-40 and TERGITOL NP-40 surfactants available from Union Carbide. The surfactant TERGITOL 15-S-40 (CAS # 68131-40-8) is a reaction product of a mixture of linear secondary alcohols, 11-15 carbons and ethylene oxide. The surfactant TERGITOL NP-40 is the product of the reaction of a nonylphenol and approximately 40 moles of ethylene oxide. Another preferred nonionic surfactant is SURFYNOL 485 and surfactant SURFYNOL 485W available from Air Products. Anionic surfactants which can be used in the invention include surfactants such as ammonium or alkali metal salts of sulphates, sulfonates, alkyl, aryl or arylalkyl phosphates, and the like. These anionic surfactants include, for example, sodium lauryl sulfate, octylphenol glycol ether sulphate and sodium, sodium dodecylbenzene sulfonate, sodium lauryl diglycol sulfate, and tributyl tertiary ammonium phenol and penta- and octaglycol sulfates, salts from sulfosuccinate such as the semi ester of nonylphenol ethoxylated disodium of sulfosuccinic acid, the n-octadecyl sulfosuccinate and disodium, sodium sulfosuccinate and dioctyl, and the like. The surfactant AEROSOL 18, a 35% solution of N-octyldecyl sulfosuccinimat in water and the surfactant AEROSOL 0T-75, a 75% solution of sodium dioctyl sulfosuccinate in water and the surfactant AEROSOL 501, a solution At 50% of the alkyl sulfosuccinate and disodium in water, Cytec Industries are the preferred anionic surfactants. Water-soluble and water-dispersible polymers can also be employed as surfactants / stabilizers in the water-based latices of the invention. Examples of such polymeric stabilizers include water dispersible polyesters as described in U.S. Pat. Nos. 4,946,932 and 4,939,233; water-dispersible polyurethanes as described in U.S. Pat. Nos. 4,927,876 and 5,137,961; and the alkali-soluble acrylic resins as described in U.S. Pat. No. 4,839,413. It is also possible to use cellulose materials and polyvinyl alcohols. To form a PPAE, a SAAP is reacted with a poly (alkyleneimine). In general, a Poly (alkyleneimine) contains primary, secondary, and tertiary amine groups. The primary and secondary amine groups of the poly (alkyleneimine) react with the pendant acetoacetoxy groups on the SAAP to form enamine bonds that produce a polymeric (polyamino) enamine or PPAE. A poly (alkyleneimine) for use in the invention can have a weight average molecular weight of from about 800 to about 750, 000 The poly (alkyleneimine) is preferably a poly (ethylene imine) (PEI) and more preferably the PEI having a weight average molecular weight of from about 800 to about 25,000. The PEI may contain primary, secondary, and tertiary amine groups in a ratio of 1.5: 1.4: 1.0, respectively. Such PEI compounds are commercially available from many sources and include the poly (ethylenimine) POLYMIN and the poly (ethylenimine) LUPASOL® available from the BASF Corporation. The reaction to form the PPAE can be effected by adding, with agitation, the appropriate poly (alkyleneimine) to an emulsion of the SAAP. Sufficient poly (alkyleneimine) must be used to achieve a molar ratio of the NH groups with respect to the acetoacetoxy groups of about 1 to about 8 and preferably a molar ratio of from about 2 to about 5. The amount of poly (alkyleneimine) added to the polymer having the pendant acetoacetoxy groups can vary from about 5 phr (grams per weight of poly (alkyleneimine) up to 100 grams of the dry weight of the resin) up to about 30 phr and preferably from about 8 phr to about 25 phr. The water-based emulsions of the polymers can be combined for about 15-30 minutes at room temperature. When PPAE is prepared in a direct process, the reaction mixture containing the polymer having pendant acetoacetoxy groups may need to be cooled before adding the poly (alkyleneimine).

The Polymer with Hanging Function The pendant polymer for use in the latex blends of the invention include polymers with at least one reactive functional portion of pendant amine. The reactive amine pendant reactive portion may be a carbonate group, an epoxide group, an isocyanate group, an isopropenyl group, a carboxylic acid group, or an allyl group. The portion with Reactive amine pendant function should be at or near the surface of the polymer particles. By having the reactive amine functional portion pendant at or near the surface of the particle, crosslinking can be achieved during the formation of the film with the amino-functional polymer. The reactive amine reactive portion may be located at the polymer terminals as well as along the polymer backbone. The pendant functional polymer may be a homopolymer of a monomer containing at least a portion with reactive function of pendant amine, such as a carbonate group, an epoxide group, an isocyanate group, an isopropenyl group, an allyl group, a group of carboxylic acid, or other reactive amine groups. The polymer with pendant function can also contain a mixture of monomers with pendant function. Preferably, the pendant polymer is a copolymer of the pendant monomers and other vinyl comonomers such as, but not limited to, the non-acidic vinyl monomers described above. For example, vinyl comonomers with a different function of acetoacetoxy include ethylenically unsaturated compounds such as substituted or unsubstituted acrylates, esters of vinyl, styrenic derivatives and the like. Exemplary listings of such vinyl comonomers can be found in U.S. Pat. Nos. 5,539,073 and 5,371,148 which are incorporated herein by reference. In general, the polymers with pendant function are prepared by polymerization techniques initiated by conventional emulsion or suspension free radicals. The polymerization can be initiated by a water-dispersible or water-soluble free radical initiator, optionally in combination with a reducing agent, at an appropriate temperature, usually between 55 and 90 ° C. The polymerization of the monomers can be carried out in a batch mode, by semilots or in a continuous mode. The emulsion polymerization techniques described above and shown in the examples are preferably used to prepare the pendant polymer. The monomers with pendant function containing a hydrolyzable carbonate moiety according to the invention, include those of the general formula (6): R4CH = € H-0-C (0) -C (R *) 3 (6) wherein R 4 is independently hydrogen or an alkyl group with C 1 -C 12. The particular monomers of the formula (6) include: CH2 = C0-0-C (0) -C (CH3) 3, CH2 = C0-0-C (0) -CH (C2H5) (C4H9), CH2 = CO -0-C (0) -CH3 and CH2 = CO-0-C (0) -CH2CH3. During the copolymerization, the carbonate-functional monomer is present from 2 to 24% by weight based on the total amount of the monomer. Preferably, the carbonate-functional monomer is present from 6 to 12% by weight, based on the total amount of the monomers. Another preferred pendant hydrolysable functional portion according to the invention is an epoxide moiety. Suitable pendant amine reactive functional monomers containing a hydrolyzable epoxide moiety according to the present invention include those of the general formula (7): R5-R6-R7-R8 (7) where R is selected from wherein R10 is hydrogen or an alkyl group with Ci-C3; R6 is selected from a group -C (= 0) -0- or -0-C (= 0) -; R7 is selected from - (-CH2CH2-0) n-CH2CH2-0-C (= 0) - or an alkyl group with Ci-Cß, wherein n is an integer from 0 to 100; R8 is -CHR9 = CHR9, where they are the same or different and are selected from hydrogen or a methyl group. R8 can be connected or linked directly to R5, or R8-R7- can be directly linked to R5, or R8 can be attached to a group R5-R6. By way of example, the monomers of the formula (7) include glycidyl (meth) acrylate, allyl glycidyl ether, The weight percent of an epoxide-functional monomer is a copolymer can vary from 2 to 24% by weight based on the total amount of the monomers, preferably from 6 to 12% by weight. Another portion with a pendant hydrolysable function according to the present invention is an isocyanate group. Suitable monomers containing a hydrolyzable isocyanate moiety according to the present invention include those of the general formula (8): R1XH = C (R11) -R12- (CR13) 2-NC0 (8) wherein R11 is a hydrogen or a methyl group; R12 is an alkyl group with C? -C20, a cycloalkyl group with C3-C8, an aryl group, a group -C (= 0) -0-, or a group -C (= 0) -0-R14, in where R14 is an alkyl group with C1-C20; and R13 is independently hydrogen or an alkyl group with C1-C3. "Aryl" is defined as a phenyl, naphthyl, or anthracenyl group, in which each nitrogen atom can be replaced with an alkyl group with C1-C10, preferably with an alkyl group with C6-C6, and even more preferably with a methyl group. Consequently, a phenyl group can be substituted from 1 to 4 times and the naphthyl can be substituted from 1 to 6 times. When R12 is phenyl, the groups R1: LCH = C (R11) - and - (CR13) 2-NC0 of the formula (8) may be in the ortho, meta or para positions. "Alkyl" in this context refers to a straight or branched chain alkyl group. A "cycloalkyl" group can be an alkyl with substituted Ci-Cio. A preferred monomer containing an isocyanate moiety is isopropenyl-α, α-dimethylbenzyl isocyanate. Hanging monomers containing a carboxylic acid group include, but are not limited to, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, and monovinyl adipate.

Water Based Latices of the Invention In the water-based latex of the invention, the polymer particles with amino function, (preferably the PPAE particles) may be present from about 5 to about 50 weight percent based on the dry resin and more preferably from about 10 to about 25 weight percent. The pendant polymer may be present from about 50 to about 95% by weight based on the dried resin. The pendant function polymer, more preferably, is present from about 75 to about 90 weight percent based on the dry resin. The following examples illustrate the preparation of a water-based latex according to the invention. In general, the latex of the invention can be prepared by mixing the aqueous latices of the polymeric particles with amino function of the polymer particles with pendant functions. Accordingly, a water-based latex of the invention can be a ready-mixed latex of "one package" or a "two pack" for mixing prior to use. Due to the advantageous stability of the water-based latex of the invention containing the polymer particles with amino function and the polymer particles with pendant function, latices of "one package" are preferred. The surfactants described above are preferably components of these latices, providing stability prior to and after mixing. A latex of the invention it may also contain other known additives in the latex compositions and may use another emulsion mixing or polymerization methodology such as that described in U.S. Pat. No. 5,371,148, incorporated herein by reference. A preferred embodiment of the invention relates to a latex containing dispersed water transported amino polymer particles (preferably PPAE particles); polymer particles with suspended function, transported by water, dispersed; and a shock absorber, particularly an ammonium-based buffer. The pH of a water-based latex of the invention can be adjusted and / or buffered using, for example, sodium bicarbonate, ammonium bicarbonate, diacid ammonium phosphate, an ammonium salt of a polyacrylate, or a mixture of such shock absorbers. The cushioning compound, such as ammonium bicarbonate, can be added to an aqueous dispersion of either the polymeric particles with amino function or the pendent function polymer particles, prior to mixing or to the final latex. Preferably, the buffer is added to the final mixed latex. When an ammonium buffer is used, there is a balance between the ammonium ion and the groups of amine of the polymer particles with amino function. Latices having pH values in the range of about 7.0 to 9.2, preferably 8.4 to 9.2, can be achieved using ammonium buffers. In addition, the cushioned latices of the invention possess increased stability (shelf life) at elevated temperatures and for extended periods of time. The water-based latices of the invention are useful in a variety of coating compositions such as architectural coatings, maintenance coatings, industrial coatings, automotive coatings, textile coatings, inks, adhesives, and coatings for paper, wood, and plastics. Accordingly, the present process relates to such a coating composition containing a water-based latex of the invention. The latices of the invention can be incorporated in these coating compositions in the same manner as the known polymer latices and used with the conventional components and / or additives for such compositions. The coating compositions may be clear or pigmented. With the ability to crosslink, the properties of the adhesion, and the strength properties, the water-based latices of the invention impart new and / or improved properties to various coating compositions. During the formulation, a coating composition containing a water-based latex of the invention can then be applied to a variety of surfaces, substrates, or articles, for example, paper, plastic, steel, aluminum, wood, gypsum board , or galvanized sheets (either primed or unprimed). The type of surface, substrate, or article to be coated generally determines the type of coating composition used. The coating composition can be applied using means known in the art. For example, a coating composition can be applied by spraying or by coating a substrate. In general, the coating can be dried by heating but preferably it is allowed to dry with air. Advantageously, a coating composition employing a water-based latex of the invention can be thermally or environmentally cured. As a further aspect, the present invention relates to a shaped or shaped article which has been coated with coating compositions of the present invention. A coating composition according to the invention may comprise a water-based latex of the invention, water, a solvent, a pigment (organic or inorganic) and / or other additives and fillers known in the art. When a solvent is used, miscible solvents in water are preferred. For example, a latex paint composition of the invention may comprise a water-based latex of the invention, a pigment and one or more additives or fillers used in latex paints. Such additives or fillers include, but are not limited to, leveling, rheology control, and flow control agents, such as silicones, fluorocarbons, urethanes, or cellulosic materials; Extenders reagent coalescent adjuvants such as those described in U.S. Pat. No. 5,349,026; smoothing agents; wetting and pigment dispersing agents and surfactants; ultraviolet (UV) absorbers; UV light stabilizers; pigments for dyeing; Extenders defoaming and defoaming agents; anti-sedimentation, anti-bagging and body-building agents; antiforming agents of an external layer; anti-flood and anti-flotation agents; fungicides and molds; corrosion inhibitors; thickening agents; plasticizers; reactive plasticizers; curing agents; or coalescence agents. The examples Specific to such additives can be found in Raw Materials Index, published by National Paint & Coating Association, 1500 Rhode Island Avenue, N, Washington, D.C. 2005. A water-based latex of the present invention can be used alone or in conjunction with other conventional water-borne polymers. Such polymers include, but are not limited to, water-dispersible polymers such as those consisting of polyesters, polyesteramides, cellulose esters, alkyds, polyurethanes, epoxy resins, polyamides, acrylics, vinyl polymers, vinyl acrylic polymers, polymers of styrene-butadiene, vinyl acetate-ethylene copolymers, and the like. Used in combination with certain other water-dispersible polymers, the water-based latices of the invention carry a unique advantage up to the final composition, in addition to their cross-linking ability, adhesion properties, and strength properties. PPAE, when present as a polymer with a preferred amino function, has the ability to purify the monomer containing the carbonyl or electron withdrawing group, α, β-unsaturated, residual, which remains or remains in the polymer latex. In other words, the PPAE purifies, through a Michael addition reaction, residual monomers such as α, β-unsaturated acids, α, β-unsaturated amides, α, β-unsaturated esters, and nitriles a, ß-unsaturated. Removing these monomers can not only eliminate the odors associated with them, but also improve health and safety when the composition is used. The following compounds are proposed to illustrate, not to limit, the invention. Examples of various coating compositions of the invention use the following materials: DOWICIL 75 is a condom sold by DOW Chemical Company, Midland, MI. Poly (ethyleneimine) LUPASOL G35, PM 2000, sold by BASF as a 50% solution in water. TAMOL 1124 and ACRYSOL SCT-275 are dispersants sold by Rohm & Haas Company. The rheology modifier SCT 275 (thickener) sold by Rohm & Haas Company. FOAMASTER AP and FOAMASTER VF defoamers sold by Henkel. The titanium dioxide pigment TI-PURE R-900 sold by DuPont.

The TRITON CF-10 surfactant sold by Union Carbide. The rheology modifier CELLOSIZE 4400H sold by Union Carbide. The FC-430 Fluoro surfactant, (98.5% solids), sold by 3M, St. Paul, Minnesota. The products SULFYNOL 104, 104DPM, and 485W (50% Solids), sold by Air Products and Chemicals, Inc., Allentown, Pennsylvania. TEXANOL is an alcohol ester solvent produced by Eastman Chemical Company, Kingsport, TN. The t-butylhydroperoxide was used as a 70% solution in water. The following methods were used to evaluate coatings and films prepared according to the invention.

Swelling / Fraction Ratio of Latex Gel The fraction of the latex gel (LGF) is obtained by determining the insoluble weight fraction of the polymer in a latex sample. The swelling ratio of the latex (LSR) is obtained by determining the proportion of the weight fraction of insoluble polymer swollen in the selected solvent (by weight) or the weight dry of the insoluble weight fraction in a latex sample. The average values are determined from triple or quadruple measurements with acetone as the solvent. The procedure used is as follows. For each determination of the sample, a centrifuge tube is baked in a vacuum oven at 120 ° C for 90 minutes, cooled in a P205 desiccator and weighed (Wl). Sufficient latex is added to the conditioned tube to make a solution at approximately 1% when the solvent is added and the weight of the latex is recorded (W2). The solvent is added to the tube until the tube is approximately three quarters of the total and the solution is allowed to settle overnight. The next day, the sample is centrifuged at 75,530 rpm for 30 minutes. The portion of the clear liquid in the tube is removed. The remaining polymer gel is washed with the additional solvent. The washing and centrifugation step is repeated twice more. Finally, the portion of the clear liquid is removed and the tube containing the wet gel is weighed (W3). The tube containing the wet gel is baked overnight in an oven with forced air at 80 ° C and then baked in a vacuum oven at 120 ° C for 3 hours and cooled in a desiccator over P205. The tube plus the dry solids are they weigh and the vacuum portion of the baking process is repeated until reproducible weights are obtained (W4). The calculations were made according to the following equations: LGF = (W4-W1) / (W2 * TS) LSR = (W3-W1) / (W4-W1) where TS = solids of the total weight fraction of the latex .

Room or Site of Humidity and Constant Temperature: The films were prepared and measurements of the film were made in a room or site of constant temperature and humidity (CTH) at the standard ASTM conditions for the laboratory test of 23 + 2 ° C (73.5 + 3.5 ° F) and relative humidity of 50 + 5%.

Minimum Resistant Film Formation Temperature: The minimum resistant film formation temperature (MFFT strength) is determined by melting or pouring a wet latex film with a 0.010 cm (4 mil) applicator cube on an MFFT bar set at a temperature range at which the film will coalesce during drying, pulling the edge of a bronze spatula blade through the film from the cold end to the hot end onto the MFFT bar after 30 minutes, and recording the temperature at which the sheet offers significant resistance to the experiment.

Traction: The traction tests were performed in a CTH room on a United Model STM-l-PC Traction Tester, which is at a constant speed of the stretching machine. Samples of the film are obtained by molding or emptying the sample on a release paper with an aerial or bird bar of 0.018 cm (7 mils), drying the film for the desired time under the established conditions, and cutting a sample thin-film dog-shaped film, with a wide die of 2.54 cm (1") .The film is measured to verify the thickness of the film, mounted on the tension tester clamps and tested at a speed of 2.54 cm (1") / minute crosshead using a load cell with a force of 2.27 kg (5 pounds). Ten samples are tested or operated and the five samples with the largest breakdown voltage are averaged for all voltage values reported in accordance with ASTM D2370.

Fraction of the Film Gel (FGF) and the Ratio of Swelling of the Film (FSR): The gel fraction of the film (FGF) is obtained by determining the insoluble weight fraction of the polymer in a dry film sample. The swelling ratio of the film (FSR) is obtained by determining the ratio of the weight fraction of insoluble polymer swollen in the selected solvent (by weight) with respect to the dry weight of the weight fraction insoluble in a dry film sample. The average values are determined from quadruple measurements with acetone as the solvent. The procedure used was as follows: for each determination of the sample, a 325 mesh steel mesh of 10.16 cm x 10.16 cm (4"x 4") and a pot-shaped cup for weighing the metal are baked in an oven under vacuum at 120 ° C for 90 minutes, it is cooled for 30 minutes on P20s and weighed (W1 and W2, respectively). After the latex film is dried the required number of days under temperature and humidity Constants or baking in the oven at the temperature and during the specified time, one piece of the film is cut, weighed (W3), placed in the aluminum pan, and placed to the side. Another sample of the film is cut, weighed (W4), and placed in a jar with a screw cap with excess solvent on a stirring bath for 16 hours at a constant temperature. The gel of the film is recovered by pouring the solution plus the wet solids from the jug through the grid and then weighing the grid plus the wet solids retained (W5). At this point, fill in the solids and sample the film in the aluminum cup-shaped cup, they are dried in an oven with forced air at 80 ° C all night and then in a vacuum oven at 120 ° C for 3 hours and cooled for 30 minutes in a desiccator over P2Os. The samples are weighed and the vacuum portion of the baking process is repeated until reproducible weights for the grid plus the dry solids (W6) and the film sample are obtained in the aluminum canister cup (W7). The calculations were made by the equations shown below: FGF = (W6-W1) / [(W4) * [(W7-W2) / W3]] FSR = (W5-W1) / (W6-W1) Yellowness Index: Wet films of 0.018 cm (7 mils) are poured or melted onto polyester sheets. The coated polyester sheet and an uncoated control polyester sheet are allowed to dry under the specified conditions. The yellowness index is measured on both the clear emulsion film and the control panel placed on the top of a white control panel using a colorimeter in the L, a, b mode.

Color.

Wet films of 0.018 cm (7 mils) are poured or melted onto polyester sheets. The coated polyester sheet and an uncoated control polyester sheet are allowed to dry under the specified conditions. The color is measured on both the clear emulsion film and on the control panel placed on top of a white control panel using a colorimeter in the L, a, b mode.

Resistance to Methyl Ethyl Ketone: The dried films at the specified conditions were constantly soaked with methyl ethyl ketone (MEK). The data were obtained using a color detachment meter with a weight of 1 kg placed on the arm for a total weight of approximately 1500 g. The test ended when the through break of the film on the panel was observed first. The data were reported as double rubs with MEK (one set bacds and one forward). All the data are in an average of three results.

Viscosity of the Painting; The viscosity of the paint (in Krebs Units) was measured after 24 hours using a Krebs-Stormer viscometer.

Brightness: The gloss was measured on films of 0.015 cm (6 mils) (wet) cast or cast on a paper opacity 2B of Leneta after 24 hours using a micro-tri brightness meter at 20 degree and 60 degree settings by BYK-Gardner according to ASTM method D 523 for Specular Brightness.

Resistance to Blocking Blocking resistance was determined using 0.015 cm (6 mil) films (wet) on a Lecta 2B opacity paper in accordance with ASTM Test Method 4946 for Block Resistance of Architectural Paints using a pressure of 0.07 kg / cm2 (1 psi) after the film dried at designated times. The hot block resistance was determined in a forced air oven at 48.88 ° C (120 ° F) with the painted surfaces facing under a pressure of 0.07 kg / cm2 (1 psi) for 30 minutes. The tests were evaluated numerically where an evaluation of 1 represents 100% pass where the painted surfaces are left without noise, an evaluation of 2 represents the noise when the painted surfaces are separated but no degradation of the film occurs, a evaluation of 3 represents some destruction of the painted surfaces when the two surfaces are separate and an evaluation of 4 represents 100% failure where the painted surfaces flow completely together and the complete destruction of the films occurs during separation.

Resistance to Printing: Resistance to printing was determined using 0.015 cm (6 mil) films on a 2B Leneta opacity paper in accordance with ASTM Test Method D 2064-91 for the Impression Resistance of Architectural Paints using a pressure of 0.28 kg / cm2 (4 psi) placed on top of a stopper or stopper of black rubber # 6 which was placed on four layers of cheesecloth after the film dried at designated times. Resistance to hot printing is determined in a forced air oven at 48.89 ° C (120 ° F) with folded cheesecloth (as above) under a pressure of 0.28 kg / cm2 (4 psi) for 30 minutes. The tests were evaluated numerically in which an evaluation of 1 represents 100% of pass without demarcation (lifting of the fabric without printing under it), an evaluation of 2 represents the demarcations (it was observed some impression), an evaluation of 3 represents 100% failure (the cheesecloth impregnates the film).

Resistance to rubbing: The rub resistance was determined by following Test Method ASTM D2486 for rubbing resistance of architectural coatings. The coating is applied to wet samples of 0.018 cm (7 mils) on Form P121-10N of the Chafing Test Letters and allowed to dry for the specified period of time. The panel is placed in a Gardco Rubbing Machine, Model D-10V, 10 g of the Standardized Rubbing Media (abrasive type) for the ASTM D2486 and D3450 are placed in the rubbing brush, the panel is moistened with 5 ml of DI water, the counter of the test machine is placed in zeros, and the test is run at the maximum test speed on the machine. After every 400 cycles before the failure, the brush is removed and 10 g more of the rubbing medium is added evenly on the bristles, the brush is replaced, 5 ml of DI water is placed on the panel and the test is continued. The test is stopped at 1000 cycles or the failure, whatever happens First. The fault is defined as the number of cycles to remove the film from the paint completely in a continuous line across the width of the wedge.

Adhesion Test in Humid _ This procedure tests the coating adhesion to an alkyd substrate, aged, under wet, rubbing conditions. This procedure is described in "VYNATE® (Union Carbide Chemicals and Plastics Corporation) - Vinyl Emulsion Vehicles for Semigloss Interior Architectural Coatings", M. J. Collins, et al., Filed on 19 / o. "Water-Borne High-Solids and Powder Coating Symposium" Annual, February 26-28, 1992, New Orleans, Louisiana, USA. A 0.0254 cm (10 thousandths of an inch) depression of a commercial glossy alkyd paint is made on a "Leneta" rubbing board (adhesion varies from alkyd to alkyd.) Glidden Industrial Glaze was used. The alkyd film is allowed to age one week at ambient conditions, then baked at 43.33 ° C (110 ° F) for 24 hours, and then aged at least one more week at ambient conditions. A 0.018 cm (seven thousandths of an inch) depression of the test paint is made then on aged alkyd and allowed to air dry for three days. (To differentiate between the samples that pass this test, the drying times can be shortened). Seven days is a common period, and occasionally 5 hours of drying time is used. Normally constant temperature / humidity conditions are used, 22.2 ° C (72 ° F) / 50%, for drying. The test paint is provided with transverse notches then with a shaving machine and immersed in water for 30 minutes. The film of the paint is inspected to verify the formation of blisters and scratches with the fingernail to measure adhesion. While it is still wet, the panel is placed on a "Gardner" rubbing machine. Ten ml of "LAVA ™" soap paste is added to five percent, and the Nylon rubbing brush (WG 2000NB) is passed over the area of the paint film with notches or marks. Water is added when necessary to keep the paint film wet (flooded). The number of cycles for brushing for initial detachment is noted and referred to as "through break". The number of cycles for the complete removal of the film is frequently noted as well and reference is made to a "total failure".

Low Temperature Coalescence and Desiccation Cracks: The low temperature coalescence (LTC) was determined using a 0.018 cm (7 mil) (wet) paint film on a 2B opacity paper from Léñete which was allowed to dry for 24 hours in a room maintained at room temperature. 4.44 ° C (40 ° F) and 50% relative humidity and another 0.018 cm (7 mil) (wet) paint film on a 2B opacity paper of Leneta which was allowed to dry for 24 hours in a room maintained at 21.11 ° C (70 ° F) and 50% relative humidity. The yellowness index (Yl) was determined on each dry coating using a colorimeter in the L mode, a, b before and after dyeing the paint for 5 minutes with a Special Test Compound K and N of 0.015 cm (7 mils) (wet). The test compound was removed by washing with a camel hair brush moistened with mineral spirits. The panel was hung vertically to air dry for at least 3 hours. The change of Yl (delta Yl) for each sample of the paint was calculated and the low temperature coalescence was assigned a value based on the difference between the change in Yl for the coatings of 21.11 ° C (70 ° F) and 4.44 ° C (40 ° F). The Drying cracks were labeled "yes" if the coating which was dried at 4.44 ° C (40 ° F) and 50% relative humidity developed cracks and the delta Yl for the sample could not be determined. While this invention has been generally described, further understanding can be obtained by reference to certain specific examples which are provided herein for purposes of illustration only and are not intended to be limiting unless otherwise specified.

Example 1 Preparation of Waterborne Particles Containing Core Epoxide / Large Coraza To a 3000 ml resin boiler equipped with a condenser, nitrogen purge, and an underground feeding tube are added 640 g of water, 4.05 g of TREM LF-40, 1.93 g of TERGITOL NP-40 (70%), 7.3 g of sodium carbonate, 44.24 g of methyl methacrylate, 8.26 g of styrene, 57.09 g of 2-ethylhexyl acrylate, and 0.252 g of trimethylolpropane triacrylate. A nitrogen purge was started, then the reactor content was brought to 80 ° C at 400 rpm. After reaching 80 ° C, a starter charge composed of 7.70 g of sodium persulfate dissolved in 43.6 g of water was added to the reactor. An emulsion feed composed of 355 g of water, 11.7 g of TREM LF-40, 10.21 g of TERGITOL NP-40 (70%), 271.78 g of methyl methacrylate, 128.12 g of styrene, 350.63 g of 2-acrylate. ethylhexyl, and 1.55 g of trimethylolpropane triacrylate were started at 8.38 g / min. Five minutes after the first emulsion feed was started, an initiator solution composed of 4.36 g of sodium persulfate dissolved in 112 g of water at 0.466 g / min was fed. After the first emulsion feed was completed, a second emulsion feed composed of 171 g of water, 12.79 g of AEROSOL 18, 5.09 g of TERGITOL NP-40 (70%), 180.88 g of styrene, 90.0 g was fed. of ethylhexyl acrylate, 143.92 g of glycidyl methacrylate, and 1.68 g of sodium 2-acrylamido-2-methylpropanesulfonate (50% in water) at 8.38 g / minute. Five minutes after the last feed, a starter solution of 1.34 g of t-butyl hydroperoxide, and 1.34 g of formaldehyde and sodium sulfoxylate dissolved in 40.2 g of water were charged and heating continued for 30 minutes. The latex is then filtered through a 100 mesh wire screen. Solids level, 46.6; pH, 8.4; amount of dry material (100 mesh screen), 10.31 g; particle size (Dw), 239 nm, ZETA potential, -48 mv.

Example 2 Preparation of Waterborne Particles Containing Nucleus / Coraza Grande Poly (ethyleneimine) (The Molar Ratio of the N-H Group with respect to the acetoacetoxy group was 5.2) To a 3000 ml resin boiler equipped with a condenser, nitrogen purge, and an underground feeding tube are added 640 g of water, 4.05 g of TREM LF-40, 1.93 g of TERGITOL NP-40 (70%), 7.3 g of sodium carbonate, 39.20 g of methyl methacrylate, 13.29 g of styrene, 57.09 g of 2-ethylhexyl acrylate, and 0.252 g of trimethylolpropane triacrylate. A nitrogen purge was started, then the reactor content was brought to 80 ° C at 400 rpm. After reaching 80 ° C, a starter charge composed of 7.70 g of sodium persulfate dissolved in 43.6 g of water was added to the reactor. An emulsion feed composed of 355 g of water, 11.7 g of TREM LF-40, 10.21 g of TERGITOL NP-40 (70%), 240.83 g of methyl methacrylate, 81.66 g of styrene, 350.63 g of acrylate 2- ethylhexyl, and 1.55 g of trimethylolpropane triacrylate was started at 8.38 g / min. Five minutes after the emulsion feed was started, an initiator solution composed of 4.36 g of sodium persulfate dissolved in 112 g of water at 0.466 g / min was fed. After the first emulsion feed was completed, a second emulsion feed composed of 171 g of water, 12.79 g of AEROSOL 18, 5.09 g of TERGITOL NP-40 (70%) was fed., 144.90 g of styrene, 90.0 g of 2-ethylhexyl acrylate, 179.99 g of acetoacetoxyethyl methacrylate, and 1.68 g of sodium 2-acrylamido-2-methylpropanesulfonate (50% in water) at 8.38 g / minute. Five minutes after the last feed, a starter solution of 1.34 g of t-butyl hydroperoxide, and 1.34 g of formaldehyde and sodium sulfoxylate dissolved in 40.2 g of water were charged and heating continued for 30 minutes. After cooling, 373.63 g of the poly (ethylene imine) (50% in water) are added in place of the ammonium hydroxide solution. The molar ratio of the N-H group to the acetoacetoxy group was 5.2 The latex is then filtered through a 100 mesh wire screen. Solids level, 46.9; pH, 10; amount of dry material (100 mesh screen), 3.11 g; particle size (Dw), 164 nm, ZETA potential, -23.9 mv (pH = 11.7). The analysis The infrared of the films cast on ZnZe showed an absorption at 1653 cm-1 and 1565 cm-1 and a disappearance of the absorbances at 1631 cm "1 and 1655 cm" 1 after the addition of the poly (ethylene imine). After reacting the poly (ethylenimine) with the pendant acetoacetoxy group, the latex was centrifuged and the water in the phase was analyzed. Elemental analysis of the aqueous phase showed that more than 98% of the poly (ethyleneimine) was fixed to the surface of the latex particles.

Example 3 Preparation of Waterborne Particles Containing Large Nucleus / Coal Poly (Ethyleneimine) (The molar ratio of the N-H group to the acetoacetoxy group was 6.1) The procedure for the preparation of the latex in Example 2 was similar to the latex preparation described in Example 1 except that 499.76 g of poly (ethylene imine) (50% in water) are added in place of the ammonium hydroxide solution . The molar ratio of the N-H group to the acetoacetoxy group was 6.1. The latex is then filtered through a 100 mesh wire screen. Solids Level, 47.2, pH, 10; amount of dry material (100 mesh screen), 5.32 g; particle size (Dw), 197 nm, ZETA potential, -24.5 mv (pH = 11.7). The infrared analysis of the clear films cast or cast on ZnSe showed an absorption of 1653 cm-1 and 1565 cm "1 and a disappearance of the absorbances at 1631 cm" 1 and 1655 cm "1 after the addition of the poly (ethyleneimine) After reacting the poly (ethylenimine) with the pendant acetoacetoxy group, the latex was centrifuged and the water in the phase was analyzed.The elemental analysis of the aqueous phase showed that more than 98% of the poly (ethylene imine) It was fixed to the surface of the latex particles.

Example 4 Preparation of Waterborne Particles Containing Core Epoxide / Small Coraza To a 3000 ml resin boiler equipped with a condenser, nitrogen purge, and an underground feeding tube are added 1100 g of water, 49.0 g of HITENOL HS-20, 8.05 g of TERGITOL NP-40 (70%), 7.3 g of sodium carbonate, 44.24 g of methyl methacrylate, 20.85 g of styrene, 44.47 g of 2-ethylhexyl acrylate, and 0.252 g of trimethylolpropane triacrylate. A nitrogen purge was started, then the reactor content was brought to 80 ° C at 400 rpm. After reaching 80 ° C, a starter charge composed of 7.70 g of sodium persulfate dissolved in 43.6 g of water was added to the reactor. An emulsion feed composed of 273.5 g of water, 19.65 g of AEROSOL 18, 20.19 g of TERGITOL NP-40 (70%), 271.78 g of methyl methacrylate, 128.12 g of styrene, 273.23 g of 2-ethylhexyl acrylate, and 1.55 g of trimethylolpropane triacrylate was started at 8.38 g / min. Five minutes after the emulsion feed was started, an initiator solution composed of 4.36 g of sodium persulfate dissolved in 112 g of water at 0.466 g / min was fed. After the first emulsion feed was completed, a second emulsion feed composed of 147 g of water, 12.15 g of AEROSOL 18, 12.5 g of TERGITOL NP-40 (70%), 90.88 g of styrene, 180 g was fed. of 2-ethylhexyl acrylate, 143.92 g of acetoacetoxyethyl methacrylate, and 1.68 g of sodium 2-acrylamido-2-methylpropanesulfonate (50% in water) at 8.38 g / minute. Five minutes after the last feeding, a starter solution of 1.34 g of t-butyl hydroperoxide, and 1.34 g of formaldehyde and sodium sulfoxylate dissolved in 40.2 g of water were charged and continued heating for 30 minutes. The latex is then filtered through a 100 mesh wire screen. Solids level, 42.3; amount of dry material (100 mesh screen), 3.2 g; particle size (Dw), 67 nm, ZETA potential, -46.3 mv (pH = 8.4).

Example 5 Waterborne particles containing Poly (Ethyleneimine) Core / Small Shell (the molar ratio of the N-H group to the acetoacetoxy group was 5.43) To a 3000 ml resin boiler equipped with a condenser, nitrogen purge, and an underground feeding tube are added 1100 g of water, 49.0 g of HITENOL HS-20, 8.05 g of TERGITOL NP-40 (70%), 7.3 g of sodium carbonate, 39.20 g of methyl methacrylate, 13. 29 g of styrene, 57.09 g of 2-ethylhexyl acrylate, and 0.252 g of trimethylolpropane triacrylate. A nitrogen purge was started, then the reactor content was brought to 80 ° C at 400 rpm. After reaching 80 ° C, a starter charge composed of 7.70 g of sodium persulfate dissolved in 43.6 g of water was added to the reactor. An emulsion feed composed of 273. 5 g of water, 19.65 g of AEROSOL 18, 20.19 g of TERGITOL NP-40 (70%), 240.83 g of methyl methacrylate, 81.66 g of styrene, 350.63 g of 2-ethylhexyl acrylate, and 1.55 g of triacrylate of trimethylolpropane was started at 8.38 g / min. Five minutes after the emulsion feed was started, an initiator solution composed of 4.36 g of sodium persulfate dissolved in 112 g of water at 0.466 g / min was fed. After the first emulsion feed was completed, a second emulsion feed composed of 171 g of water, 12.15 g of AEROSOL 18, 12.5 g of TERGITOL NP-40 (70%), 144.90 g of styrene, 90.0 g was fed. of 2-ethylhexyl acrylate, 179.99 g of acetoacetoxyethyl methacrylate, and 1.68 g of sodium 2-acrylamido-2-methylpropanesulfonate (50% in water) at 8.38 g / minute. Five minutes after the last feed, a starter solution of 1.34 g of t-butyl hydroperoxide, and 1.34 g of formaldehyde and sodium sulfoxylate dissolved in 40.2 g of water were charged and heating continued for 30 minutes. The emulsion is cooled, and then 376.7 g of poly (ethylenimine) (50% in water) are added in place of the ammonium hydroxide solution. The molar ratio of the N-H group to the acetoacetoxy group was 5.2. The latex is then filtered through a sieve of 100 mesh wire. Solids level, 41.8; pH, 10; amount of dry material (100 mesh screen), 2.65 g; particle size (Dw), 66 nm, ZETA potential, -31.1 mv (pH = ll). Infrared analysis of clear films cast or melted on ZnSe showed an absorption of 1653 cm "1 and 1565 cm" 1 and a disappearance of the absorbencies at 1631 cm "1 and 1655 cm" 1 after the addition of poly (ethylene imine). After reacting the poly (ethylenimine) with the pendant acetoacetoxy group, the latex was centrifuged and the water in the phase was analyzed.

Elemental analysis of the aqueous phase showed that more than 98% of the poly (ethyleneimine) was fixed to the surface of the latex particles.

Example 6 Preparation of Waterborne Particles Containing Poly (Ethyleneimine) Core / Small Shell (The molar ratio of the N-H group to the acetoacetoxy group was 4.27) The procedure for the preparation of the latex in Example 6 was similar to the preparation of the latex described in Example 5 except that 506.33 g of poly (ethyleneimine) (50% in water) were added in place of the ammonium hydroxide solution. The molar ratio of the N-H group to the acetoacetoxy group was 6.2. The latex was then filtered through a 100 mesh wire screen. Solids level, 42.0; pH, 10; amount of dry material (100 mesh screen), 2.75 g; particle size (Dw), 71 nm; ZETA potential, -35.6 mv (pH = ll). Infrared analysis of clear films fused or cast on ZnSe showed an absorption at 1653 cm "1 and 1565 cm" 1 and a disappearance of absorbances at 1631 cm "1 and 1655 cm" 1 after the addition of poly (ethylene imine) ). After reacting the poly (ethylenimine) with the pendant acetoacetoxy group, the latex was centrifuged and the aqueous phase was analyzed. Elemental analysis of the aqueous phase showed that more than 98% of the poly (ethyleneimine) was fixed to the surface of the latex particles.

Example 7 Preparation of Particles Transported by Water Containing Epoxide, Unstructured To a 1000 ml resin boiler equipped with a condenser, nitrogen purge, and an underground feeding tube are added 293.6 g of water, 1.34 g of TREM LF-40, 1.79 g of TERGITOL NP-40 (70%), 7.3 g of sodium carbonate, 12.71 g of styrene, 4.3 g of isooctyl acrylate, and 0.252 g of trimethylolpropane triacrylate. A nitrogen purge was started, then the reactor content was brought to 80 ° C at 400 rpm. After reaching 80 ° C, a starter charge composed of 2.3 g of sodium persulfate dissolved in 13 g of water was added to the reactor. An emulsion feed composed of 120 g of water, 9.94 g of AEROSOL 18, 7.2 g of TERGITOL NP-40 (70%), 241.47 g of styrene, 81.62 g of isooctyl acrylate, 17.0 g of glycidyl methacrylate, and 0.52 g of trimethylolpropane triacrylate was started at 1.72 g / min. Five minutes after the emulsion feed was started, an initiator solution composed of 1.3 g of sodium persulfate dissolved in 33.5 g of water at 0.160 g / min was fed. Five minutes after the last feed, a starter solution of 1.03 g of t-butyl hydroperoxide, and 0.72 g of formaldehyde and sodium sulfoxylate dissolved in 12 g of water was charged and heating was continued for 30 minutes. The latex is then filtered through a 100 mesh wire screen. Solids level, 42.7; pH, 7.9; amount of dry material (100 mesh screen), 6.95 g; Electron Micrography, 180 nm.

Example 8 Evaluation of the Films Prepared from the Mixture of Particles Transported by Water, which contains Epoxide and which contain PEI to verify the resistance to the solvent The mixtures were prepared by adding the appropriate weight fraction of the latex containing PEI to the latex containing the enamine (dry resin on dry resin). Typically, to 100 g of the latex containing the epoxide (Example 1) is added the appropriate heavy amount of the latex containing the PEI (33.75 g of Example 2) such that the weight fraction of the latices containing the PEI represented a fraction by weight of 25% (dry resin on dry resin). All the formulations were prepared in a similar manner with fractions of variable weight of the latex containing the PEI. After the mixtures were prepared, 1 phr of SURFYNOL 104 DPM (1 g of active SURFYNOL 104 per 100 g of dry resin) was added as a wetting agent. Wet films were cast or cast on panels treated with aluminum chromate (0.0635 cm x 7.62 cm x 22.86 cm (0.025"X 3" X 9") then cured in a forced air oven or allowed to cure room temperature at a relative humidity of 50%. The thicknesses of the dry film were measured, and the solvent resistance was determined by measuring the resistance of the films to double rubs of methyl ethyl ketone. The results are reported in the tables and figures given below: Table 1 Examples Examples Fracc.Vol. Thickness Peí. Time Cure MEK DR (Latex #) (Latex #) (Late PEI) Dry (30 minutes) Temp.Cure / Temp.Cure (° C) 1 2 25 1.0 / 1.6 105/120 71/197 1 3 25 1.1 / 1.4 105/120 64/175 1 5 25 1.0 / 1.2 105/120 63/146 1 6 25 1.0 / 1.4 105/120 46/125 4 2 25 1.0 / 1.4 105/120 158/220 4 3 25 1.0 / 1.6 105/120 52/306 4 5 25 1.3 / 1.7 120 ° C 32/110 4 6 25 0.91 / 1.6 105/120 17/92 '1 7 38 1.3-1.8 150 ° C 143 The first 8 combinations in Table 1 were analyzed by the least squares analysis. The results are shown in Figure 1. Figure 1. Constant contour plots of double rubs with methyl ethyl ketone co or a function of the size of the epoxy-containing latices, and the latices containing the PEI. The latices containing the PEI were added to a volume fraction of 25% (dry resin on dry resin). The graphs were constructed assuming a one-to-one stoichiometric level of N-H with respect to enamine. The films were cured for 30 minutes in a forced air oven.

Table 2 Examples Examples Fracc.Vol. Thickness Peí. Time Cured MEK DR (Latex #) (Latex #) (Late PEI) Dry (30 minutes) (1.0 mil. (Mm X Temp Cured / in./ 10 ~ 2) Curing Temp 1.5 mil.! ° C) in. . 1 Í? J Z- • _ • • U 2 days 24/47 TA 1 3 25 2.5 / 3.8 2 days 28/53 TA 1 5 25 2.5 / 3.8 2 days 28/49 TA 1 6 25 2.5 / 3.8 2 days 29 / 51 TA 4 2 25 2.5 / 3.8 7 days 35/61 TA 4 3 25 2.5 / 3.8 j days 28/50 TA 4 5 25 2.5 / 3.8 2 days 38/65 TA 4 6 25 2.5 / 3.8 2 days 31/56 TA 1 2 25 2.5 / 3.8 21 days 22/47 TA 1 3 25 2.5 / 3.8 days 24/49 'TA 1 5 25 2.5 / 3.8 21 days 32/66 TA 1 6 25 2.5 / 3.8 21 days 24/46 TA 4 2 25 2.5 / 3.8 21 days 66/129 TA 4 3 25 2.5 / 3.8 21 days 34/56 TA 4 5 25 2.5 / 3.8 21 days 55/99 TA 4 6 25 2.5 / 3.8 21 days 36/57 TA Example 9 Preparation of Films from Mixtures of Waterborne Particles Containing Epoxide and Containing PEI The mixtures were prepared by adding the appropriate weight fraction of the latex containing PEI to the latex containing the enamine (dry resin on dry resin). Typically, at 100 g of the latex containing the epoxide (Example 1) the appropriate heavy amount of the latex containing the PEI (33.75 g of Example 2) was added in such a way that the weight fraction of the latices containing the PEI represented a fraction by weight of 25% (dry resin on dry resin). All the formulations were prepared in a similar manner with fractions of variable weight of the latex containing the PEI. After the mixtures were prepared, 1 phr of SURFYNOL 104 DPM (1 g of active SURFYNOL 104 per 100 g of dry resin) was added as a wetting agent. The combinations and their MFFT values are shown in Table 3 given below.

Table 3 Latex Latex Latex PEI MFFT Resist. Example contains contains Fracc. In Visual: MFFT: Epoxy PEI Volume (° C) (° C) 9A 1 2 0.25 10.6 15.6 9B 1 3 0.25 11.0 13.0 9C 1 5 0.25 1.2 7.0 9O 1 6 0.25 < 0 5.8 9E 4 2 0.25 3.0 10.7 9F 4 3 0.25 2.0 11.8 9G 4 5 0.25 < 0 12.4 9H 4 6 0.25 < 0 11.6 Example 10 Evaluation of Prepared Films from Examples 1-6 and 9 for Traction Properties The wet films were cast or cast on release paper then cured in a forced air oven at 120 ° C for 30 minutes or allowed to cure at room temperature for 8 days in the CTH room. The samples of the film Free samples were analyzed to verify the properties in the traction and the results of the thermal curing are shown in Table 4, below, while the results of the curing 8 days at environmental conditions are shown in Table 5, which is given later.

Table 4 Cured Ultima Alarg. Energy: Alarg Rupture Module. index at 120 ° C Rupture (%) (in Ib / Initial in (%) Yellowness by 30 (kg / cm2) in.3) (ksi) Traction minutes (kg / cm2) Code Example: 2 100.0 145.1 1242 3.4 21.7 17.9 .. 3 105.3 129.5 1012 2.5 21.2 20.5 ... 120.2 117.4 867 3.1 20.9 20.7 ._ 6 31.9 35.8 104 4.3 13.0 10.6 - 1 141.5 252.3 3134 31.2 54.6 8.2 0.89 9A 117.8 80.8 934 24.3 55.0 8.7 3.79 9B 123.4 85.2 986 21.4 50.4 8.9 4.85 9C 129.0 89.5 1056 25.7 52.8 8.5 3.47 9D 131.7 90.7 1054 19.4 45.8 9.5 4.44 4 96.1 329.5 2136 10.0 18.6 16.1 0.37 9E 137.5 70.9 860 24.2 53.1 8.7 4.52 9F 159.7 71.5 997 31.8 62.1 8.2 5.61 Table 4 (Cont.) 9G 154.4 83.2 1043 26.0 50.1 8.6 3.85 9H 183.4 86.2 1269 29.1 56.5 8.9 4.62 Table 5 8 days Last Alarg. Energy Module Rupture Alarg. Index Cured Rupture (%) (in Ib / Initial in (%) Yellowness Ambient. (kg (cm2) in.3) (ksi) Traction Code (kg / cm2) Example 2 48.0 168.6 767 4.3 11.3 11.2"3 34.9 110.2 328 3.0 8.4 11.5 - 5 81.1 102.4 590 4.5 17.5 14.3 - 6 57.8 87.7 341 2.5 11.9 15.4 ... 1 82.2 185.3 1585 20.3 43.9 8.7 0.59 9A 85.21 115.0 909 9.1 33.7 11.3 1.89 9B 83.9 116.0 895 11.9 31.3 9.7 2.38 9C 104.0 114.7 980 10.6 33.7 1 1.1 1.96 9D 86.5 107.5 780 7.2 28.9 11.6 2.21 4 73.4 265.0 1548 18.8 21.5 8.1 0.1 1 9E 133.4 140.3 1424 11.7 30.2 11.2 2.4 9F 133.7 138.7 1371 9.3 28.5 13.1 2.51 Table 5 (Cont.) 9G 144.8 126.3 1273 12.2 30.6 n.6 0.05 9H 124.0 116.7 1026 1 l.l 27.8 p.3 1 -57 Example 11 Evaluation of the Films prepared from Examples 1-6 and 9 and to verify the Properties of the Swelling Ratio and the Fraction of the Gel The wet films were cast or cast on release paper then cured in a forced air oven at 120 ° C for 30 minutes or allowed to cure environmentally for 8 days in the CTH room. Samples of the free film were analyzed to verify the Properties of the Fraction of the Gel (Table 6) and the Swelling Ratio (Tables 7 and 8) and the results of the thermal cure are shown below.

Table 6: Fractions of Latex and Film Gel in Acetone (THF) Example LGF: 2 Days 8 Days 21 Days 40 Days 120 ° C, 30 ' 1 87 89 90 91 (92) 2 84 93 3 83 95 4 83 86 87 87 (86) 89 94 6 85 93 9A 88 90 92 91 93 (95) 9B 87 90 93 92 94 (96) 9C 88 92 94 94 96 (95) 9D 88 91 92 93 94 (96) 9E 85 89 92 92 93 (93) 9F 86 89 91 92 93 (95) 9G 85 89 92 92 92 (92) 9H 83 89 92 91 92 (93) Table 7: Film Swelling Relations in THF E j em 2 Days 8 Days 21 Days 40 Days 120 ° C, 30 ' 1 12.4 12.2 12.0 10.8 11.6 4 15.3 13.0 12.5 10.6 12.2 9A 5.9 5.5 5.4 5.3 4.9 9B 5.5 5.0 4.9 5.7 4.4 9C 6.2 5.5 4.7 5.2 4.9 9D 7.1 4.8 5.4 4.7 4.7 9E 5.8 4.8 4.6 4.6 4.2 9F 6.3 4.6 4.6 4.2 4.2 9G 6.7 4.3 6.1 4.6 4.2 9H 6.0 6.2 4.9 4.7 4.4 Table 8: Latex and Film Swelling Ratios in Acetone Example LSR: 2 Days 8 Days 21 Days 40 Days 120 ° C, 30 ' 1 7.0 7.6 7.3 7.1 2 3.7 2.9 3 3.9 2.7 4 9.8 8.2 7.6 7.3 5 3.2 3.0 6 3.4 3.1 9A 5.8 4.9 4.6 4.4 4.3 9B 5.2 5.0 4.3 4.4 4.3 9C 5.6 4.8 4.3 3.9 4.7 9D 5.5 4.1 3.9 4.2 4.9 9E 3.9 4.6 3.4 4.0 3.7 9F 4.3 5.0 4.0 4.4 3.9 9G 6.8 3.9 3.3 4.5 3.8 9H 5.9 4.7 4.8 4.1 4.3 Example 12 Preparation of a particle with amino function (the molar ratio of the N-H group with respect to the acetoacetoxy group was 2.12) To a 3000 ml resin boiler equipped with a condenser, nitrogen purge, and an underground feeding tube are added 640 g of water, 4.05 g of TREM LF-40, 1.93 g of TERGITOL NP-40 (70%), 8 g of sodium carbonate, 55.23 g of methyl methacrylate, 4.03 g of styrene, 47.40 g of 2-ethylhexyl acrylate, 20.15 g of acetoacetoxyethyl methacrylate, and 0.336 g of trimethylolpropane triacrylate. A nitrogen purge was started, then the reactor content was brought to 80 ° C at 400 rpm. After reaching 80 ° C, a starter charge composed of 7.70 g of sodium persulfate dissolved in 43.6 g of water was added to the reactor. An emulsion feed composed of 355 g of water, 11.7 g of TREM LF-40, 10.21 g of TERGITOL NP-40 (70%), 339.33 g of methyl methacrylate, 24.8 g of styrene, 291.16 g of acrylate 2- ethylhexyl, and 2.06 g of trimethylolpropane triacrylate was started at 8.38 g / min. Five minutes after the emulsion feed was started, an initiator solution composed of 4.36 g of sodium persulfate dissolved in 112 g of water at 0.536 g / min was fed. After the first emulsion feed was completed, a second emulsion feed composed of 171 g of water, 12.79 g of AEROSOL 18, 5.09 g of TERGITOL NP-40 (70%), 211.03 g of styrene, 80.0 g was fed. of 2-ethylhexyl acrylate, 123.77 g of acetoacetoxyethyl methacrylate, and 1.68 g of sodium 2-acrylamido-2-methylpropanesulfonate (50% in water) at 8.38 g / minute. Five minutes after the last feeding, a starter solution of 1.34 g was loaded of t-butyl hydroperoxide, and 1.34 g of formaldehyde and sodium sulfoxylate dissolved in 40.2 g of water and heating was continued for 30 minutes. The emulsion is cooled, and filtered through a 100 mesh wire screen. Solids level, 46.64; pH, 8.2; amount of dry material (100 mesh screen), 24.65 g; particle size (Dw), 450 nm. The fraction of the latex gel in the acetone was 70.7% and the swelling ratio was 6.5. At 2500 of this latex, 115 g of poly (ethyleneimine) (50%) were added over 15 minutes. Solids, 46.6%, pH, 10.4; Particle Size (by Electron Microscopy), 450 nm. The fraction of the latex gel in the acetone was 84.6 and the swelling ratio was 5.4. Infrared analysis of clear films cast or cast on ZnSe showed an absorption at 1653 cm "1 and 1565 cm" 1 and a disappearance of absorbances at 1631 cm "1 and 1655 cm" 1 after the addition of poly (ethylene imine) ).

Example 12b Preparation of a particle with amine function To a 1000 ml resin boiler equipped with a condenser, nitrogen purge, and a tube of Underground feed is added 192 g of water, 1215 g of TREM LF-40, 0.58 g of TERGITOL NP-40 (70%), 13.55 g of methyl methacrylate, 1.21 g of styrene, 17.24 g of 2-ethylhexyl acrylate, 0.101 g of trimethylolpropane triacrylate, 6.05 g of acetoacetoxyethyl methacrylate, and 2.4 g of sodium carbonate. A nitrogen purge was started, then the reactor content was brought to 80 ° C at 400 rpm. After reaching 80 ° C, a starter charge composed of 2.31 g of sodium persulfate dissolved in 13.07 g of water was added to the reactor. An emulsion feed composed of 106.5 g of water, 3.51 g of TREM LF-40, 3.06 g of TERGITOL NP-40 (70%), 83.23 g of methyl methacrylate, 7.44 g of styrene, 105.91 g of 2-acrylate. ethylhexyl, and 0.62 g of trimethylolpropane triacrylate was started at 8.38 g / min. Five minutes after the emulsion feed was started, an initiator solution composed of 1.31 g of sodium persulfate dissolved in 33.67 g of water at 0.536 g / min was fed. After the first emulsion feed was completed, a second feed emulsion consisting of 51.3 g of water, 3.87 g of AEROSOL 18, 1.53 g of TERGITOL NP-40 (70%), 63.31 g of styrene, 24 g was fed. of 2-ethylhexyl acrylate, 37.13 g of acetoacetoxyethyl methacrylate, and 0.50 g of 2-acrylamido-2- Sodium methylpropanesulfonate (50% in water) at 8.38 g / minute. Five minutes after the last feed, a starter solution of 0.40 g of t-butyl hydroperoxide, and 0.40 g of formaldehyde and sodium sulfoxylate dissolved in 12.1 g of water were charged and heating continued for 30 minutes. The emulsion was cooled then 69.51 g of LUHYDRAN G35 (50% in water) were fed for 30 minutes. The emulsion is then filtered through a 100 mesh wire screen. Solids level, 46.57; amount of dry material (100 mesh screen), 0.40 g. Infrared analysis of clear films cast or cast on ZnSe showed an absorption at 1653 cm "1 and 1565 cm" 1 and a disappearance of absorbances at 1631 cm "1 and 1655 cm" 1 after the addition of poly (ethylene imine) ).

Example 12c Preparation of the particles with amine function (the molar ratio of the N-H group with respect to the acetoacetoxy group was 2.12) To a 1000 ml resin boiler equipped with a condenser, nitrogen purge, and an underground feeding tube are added 192 g of water, 1,215 g of TREM LF-40, 0.58 g of TERGITOL NP-40 (70%), 13.55 g of methyl methacrylate, 1.31 g of styrene, 17.14 g of 2-ethylhexyl acrylate, 0.101 g of trimethylolpropane triacrylate, 6.05 g of acetoacetoxyethyl methacrylate, and 2.4 g sodium carbonate. A nitrogen purge was started, then the reactor content was brought to 80 ° C at 400 rpm. After reaching 80 ° C, a starter charge composed of 2.31 g of sodium persulfate dissolved in 13.07 g of water was added to the reactor. An emulsion feed composed of 106.5 g of water, 3.51 g of TREM LF-40, 3.06 g of TERGITOL NP-40 (70%), 83.23 g of methyl methacrylate, 8.06 g of styrene, 105.29 g of 2-acrylate. ethylhexyl, and 0.62 g of trimethylolpropane triacrylate was started at 8.38 g / min. Five minutes after the emulsion feed was started, an initiator solution composed of 1.31 g of sodium persulfate dissolved in 33.67 g of water at 0.536 g / min was fed. After the first emulsion feed was completed, a second feed emulsion composed of 51.3 g of water, 3.87 g of AEROSOL 18, 1.53 g of TERGITOL NP-40 (70%), 62.59 g of styrene, 24 g was fed. of 2-ethylhexyl acrylate, 0.72 g of 2-ethylhexyl 3-mercaptopropionate, 37.13 g of acetoacetoxyethyl methacrylate, and 0.50 g of 2-acrylamido-2- Sodium methylpropanesulfonate (50% in water) at 8.38 g / minute. Five minutes after the last feed, a starter solution of 0.40 g of t-butyl hydroperoxide, and 0.40 g of formaldehyde and sodium sulfoxylate dissolved in 12.1 g of water were charged and heating continued for 30 minutes. The emulsion was cooled then 69.51 g of LUHYDRAN G35 (50% in water) were fed for 30 minutes. The emulsion is then filtered through a 100 mesh wire screen. Solids level, 46.59; amount of dry material (100 mesh screen), 0.15 g. Infrared analysis of clear films cast or cast on ZnSe showed an absorption at 1653 cm "1 and 1565 cm-1 and a disappearance of the absorbances at 1631 cm" 1 and 1655 cm "1 after the addition of poly (ethyleneimine) ).

Example 13 Preparation of waterborne, co-reactive particles containing the enamine functionality To a 1000 ml resin boiler equipped with a condenser, nitrogen purge, and an underground feeding tube are added 192 g of water, 1215 g of TREM LF-40, 0.58 g of TERGITOL NP-40 (70%), 2.19 g of sodium carbonate, 13.28 g of methyl methacrylate, 2.48 g of styrene, 17.12 g of 2-ethylhexyl acrylate, and 0.076 g of trimethylolpropane triacrylate. A nitrogen purge was started, then the reactor content was brought to 80 ° C at 400 rpm. After reaching 80 ° C, a starter charge composed of 2.31 g of sodium persulfate dissolved in 13.07 g of water was added to the reactor. An emulsion feed composed of 106.5 g of water, 3.51 g of TREM LF-40, 3.06 g of TERGITOL NP-40 (70%), 81.53 g of methyl methacrylate, 15.22 g of styrene, 105.19 g of acrylate 2- ethylhexyl, and 0.46 g of trimethylolpropane triacrylate was started at 8.38 g / min. Five minutes after the emulsion feed was started, an initiator solution composed of 1.31 g of sodium persulfate dissolved in 33.67 g of water at 0.536 g / min was fed. After the first emulsion feed was completed, a second feed emulsion composed of 51.3 g of water, 3.87 g of AEROSOL 18, 1.53 g of TERGITOL NP-40 (70%), 54.26 g of styrene, 27 g was fed. from '2-ethylhexyl acrylate, 43.17 g of acetoacetoxyethyl methacrylate, and 0.50 g of sodium 2-acrylamido-2-methylpropanesulfonate (50% in water) at 8.38 g / minute. Five minutes after the last feed, a starter solution of 0.40 g was charged of t-butyl hydroperoxide, and 0.40 g of formaldehyde and sodium sulfoxylate dissolved in 12.1 g of water and heating was continued for 30 minutes. The emulsion was cooled then 12.9 g of ammonium hydroxide (28% in water) was fed for 15 minutes. The emulsion is then filtered through a 100 mesh wire screen. Solids level, 46.05; pH, 10.05; amount of dry material (100 mesh screen), 0.74 g; Unimodal particle size (by laser light dispersion and TEM) 225 nm. The MFFT (visual) was 16.7 ° C. Infrared analysis of the clear films cast or cast on ZnSe showed an absorption at 1653 cm "1 and 1565 cm" 1 and a disappearance of the absorbances at 1631 cm "1 and 1655 cm-1 after the addition of the ammonium hydroxide.

Example 14 Preparation of water-borne, co-reactive particles containing a functionality of acetoacetoxy and enamine To a 1000 ml resin boiler equipped with a condenser, nitrogen purge, and an underground feeding tube are added 192 g of water, 1,215 g of TREM LF-40, 0.58 g of TERGITOL NP-40 (70%), 13.28 g of methyl methacrylate, 2.53 g of styrene, 17.07 g of 2-ethylhexyl acrylate, 0.076 g of trimethylolpropane triacrylate, and 2.19 g of sodium carbonate. A nitrogen purge was started, then the reactor content was brought to 80 ° C at 400 rpm. After reaching 80 ° C, a starter charge composed of 2.31 g of sodium persulfate dissolved in 13.07 g of water was added to the reactor. An emulsion feed composed of 106.5 g of water, 3.51 g of TREM LF-40, 3.06 g of TERGITOL NP-40 (70%), 81.53 g of methyl methacrylate, 15.53 g of styrene, 104.88 g of 2-acrylate ethylhexyl, and 0.46 g of trimethylolpropane triacrylate was started at 8.38 g / min. Five minutes after the emulsion feed was started, an initiator solution composed of 1.31 g of sodium persulfate dissolved in 33.67 g of water at 0.536 g / min was fed. After the first emulsion feed was completed, a second feed emulsion composed of 51.3 g of water, 3.84 g of AEROSOL 18, 1.53 g of -TERGITOL NP-40 (70%), 53.90 g of styrene, was fed. g of 2-ethylhexyl acrylate, 0.36 g of 2-ethylhexyl 3-mercaptopropionate, 43.17 g of acetoacetoxyethyl methacrylate, and 0.50 g of sodium 2-acrylamido-2-methylpropanesulfonate (50% in water) at 8.38 g g / minute. Five minutes after the last feed, a starter solution of 0.40 g of t-butyl hydroperoxide, and 0.40 g of formaldehyde and sodium sulfoxylate dissolved in 12.1 g of water were charged and heating continued for 30 minutes. The emulsion was cooled then 12.9 g of ammonium hydroxide (28% in water) was fed for 15 minutes. The emulsion is then filtered through a 100 mesh wire screen. Solids level, 45.82; pH 10.11; amount of dry material (100 mesh screen), 0.74 g. Infrared analysis of the clear films cast or cast on ZnSe showed an absorption at 1653 c "1 and 1565 cm" 1 and a disappearance of the absorbances at 1631 cm "1 and 1655 cm" 1 after the addition of ammonium hydroxide.

Example 15 Preparation of co-reactive waterborne particles containing the acetoacetoxy and enamine functionality To a 1000 ml resin boiler equipped with a condenser, nitrogen purge, and an underground feeding tube are added 192 g of water, 1,215 g of TREM LF-40, 0.58 g of TERGITOL NP-40 (70%), 13.28 g of methyl methacrylate, 2.58 g of styrene, 17.02 g of 2-ethylhexyl acrylate, 0.076 g of trimethylolpropane triacrylate, and 2.19 g of sodium carbonate. A nitrogen purge was started, then the reactor content was brought to 80 ° C at 400 rpm. After reaching 80 ° C, a starter charge composed of 2.31 g of sodium persulfate dissolved in 13.07 g of water was added to the reactor. An emulsion feed composed of 106.5 g of water, 3.51 g of TREM LF-40, 3.06 g of TERGITOL NP-40 (70%), 81.53 g of methyl methacrylate, 15.83 g of styrene, 104.57 g of 2-acrylate. ethylhexyl, and 0.46 g of trimethylolpropane triacrylate was started at 8.38 g / min. Five minutes after the emulsion feed was started, an initiator solution composed of 1.31 g of sodium persulfate dissolved in 33.67 g of water at 0.536 g / min was fed. After the first emulsion feed was completed, a second feed emulsion composed of 51.3 g of water, 3.84 g of AEROSOL 18, 1.53 g of TERGITOL NP-40 (70%), 53.54 g of styrene, 27 g was fed. of 2-ethylhexyl acrylate, 0.72 g of 2-ethylhexyl 3-mercaptopropionate, 43.17 g of acetoacetoxyethyl methacrylate, and 0.50 g of sodium 2-acrylamido-2-methylpropanesulfonate (50% in water) at 8.38 g. g / minute. Five minutes after the last feed, a starter solution of 0.40 g of t-butyl hydroperoxide, and 0.40 g of formaldehyde and sodium sulfoxylate dissolved in 12.1 g of water were charged and heating continued for 30 minutes. The emulsion was cooled then 12.9 g of ammonium hydroxide (28% in water) was fed for 15 minutes. The emulsion is then filtered through a 100 mesh wire screen. Solids level, 45.21; pH, 10.04; amount of dry material (100 mesh screen), 1.14 g. Infrared analysis of clear films cast or cast on ZnSe showed an absorption at 1653 cm-1 and 1565 cm "1 and a disappearance of the absorbances at 1631 c" 1 and 1655 cm "1 after the addition of the ammonium hydroxide.

Example 16 Preparation of particles transported by water, co-reactive, containing the enamine functionality To a 1000 ml resin boiler equipped with a condenser, nitrogen purge, and an underground feeding tube are added 192 g of water, 1215 g of TREM LF-40, 0.58 g of TERGITOL NP-40 (70%), 13.28 g of methyl methacrylate, 2.63 g of styrene, 16.97 g of 2-ethylhexyl acrylate, 0.076 g of trimethylolpropane triacrylate, and 2.19 g of sodium carbonate. A nitrogen purge was started, then the reactor content was brought to 80 ° C at 400 rpm. After reaching 80 ° C, a starter charge composed of 2.31 g of sodium persulfate dissolved in 13.07 g of water was added to the reactor. An emulsion feed composed of 106.5 g of water, 3.51 g of TREM LF-40, 3.06 g of TERGITOL NP-40 (70%), 81.53 g of methyl methacrylate, 16.14 g of styrene, 104.26 g of 2-ethylhexyl acrylate, and 0.46 g of trimethylolpropane triacrylate were started at 8.38 g / min. Five minutes after the emulsion feed was started, an initiator solution composed of 1.31 g of sodium persulfate dissolved in 33.67 g of water at 0.536 g / min was fed. After the first emulsion feed was completed, a second feed emulsion composed of 51.3 g of water, 3.84 g of AEROSOL 18, 1.53 g of TERGITOL NP-40 (70%), 53.18 g of styrene, 27 g was fed. of 2-ethylhexyl acrylate, 1.08 g of 2-ethylhexyl 3-mercaptopropionate, 43.17 g of acetoacetoxyethyl methacrylate, and 0.50 g of sodium 2-acrylamido-2-methylpropanesulfonate (50% in water) at 8.38 g / minute . Five minutes after the last feed, an initiator solution of 0.40 g of t-butyl hydroperoxide, and 0.40 g of formaldehyde and sodium sulfoxylate dissolved in 12.1 g of water were charged and heating was continued for 30 minutes. The emulsion was cooled then 12.9 g of ammonium hydroxide (28% in water) was fed for 15 minutes. The emulsion is then filtered through a 100 mesh wire screen. Solids level, 46.48; pH, 9.87, amount of dry material (100 mesh screen), 0.85 g. Infrared analysis of the clear films cast or cast on ZnSe showed an absorption at 1653 cm "1 and 1565 cm" 1 and a disappearance of the absorbances at 1631 cm "1 and 1655 cm" 1 after the addition of ammonium hydroxide.

Example 17 Preparation of particles transported by water, co-reactive, containing the enamine functionality To a 1000 ml resin boiler equipped with a condenser, nitrogen purge, and an underground feeding tube are added 192 g of water, 1215 g of TREM LF-40, 0.58 g of TERGITOL NP-40 (70%), 13.28 g of methyl methacrylate, 2.68 g of styrene, 16.92 g of 2-ethylhexyl acrylate, 0.076 g of trimethylolpropane triacrylate, and 2.19 g of sodium carbonate. A nitrogen purge was started, then the reactor content was brought to 80 ° C at 400 rpm. After reaching 80 ° C, a starter charge composed of 2.31 g of sodium persulfate dissolved in 13.07 g of water was added to the reactor. An emulsion feed composed of 106.5 g of water, 3.51 g of TREM LF-40, 3.06 g of TERGITOL NP-40 (70%), 81.53 g of methyl methacrylate, 16.45 g of styrene, 103.95 g of 2-acrylate. ethylhexyl, and 0.46 g of trimethylolpropane triacrylate was started at 8.38 g / min. Five minutes after the emulsion feed was started, an initiator solution composed of 1.31 g of sodium persulfate dissolved in 33.67 g of water at 0.536 g / min was fed. After the first emulsion feed was completed, a second feed emulsion composed of 51.3 g of water, 3.84 g of AEROSOL 18, 1.53 g of TERGITOL NP-40 (70%), 52.85 g of styrene, 27 g was fed. of 2-ethylhexyl acrylate, 1.44 g of 2-ethylhexyl 3-mercaptopropionate, 43.17 g of acetoacetoxyethyl methacrylate, and 0.50 g of sodium 2-acrylamido-2-methylpropanesulfonate (50% in water) at 8.38 g / minute . Five minutes after the last feed, a starter solution of 0.40 g was charged of t-butyl hydroperoxide, and 0.40 g of formaldehyde and sodium sulfoxylate dissolved in 12.1 g of water and heating was continued for 30 minutes. The emulsion was cooled then 12.9 g of ammonium hydroxide (28% in water) was fed for 15 minutes. The emulsion is then filtered through a 100 mesh wire screen. Solids level, 46.04; pH, 9.72; amount of dry material (100 mesh screen), 0.47 g, particle size (per TEM) 225 n. Infrared analysis of clear films cast or cast on ZnSe showed an absorption at 1653 cm "1 and 1565 cm" 1 and a disappearance of absorbances at 1631 cm "1 and 1655 cm" 1 after the addition of ammonium hydroxide.

Example 18 Preparation of water-borne, co-reactive particles that contain the functionality of acetoacetoxy To a 1000 ml resin boiler equipped with a condenser, nitrogen purge, and an underground feeding tube are added 293.8 g of water, 1.34 g of TREM LF-40, 1.79 g of TERGITOL NP-40 (70%), 12.71 g of styrene, 3.84 g of iso-octyl acrylate, 1.35 g of isocyanate of m-tetramethylxylene, 0.014 g of sodium 2-acrylamido-2-methylpropansulfonate (50% in water) and 2.05 g of sodium carbonate. A nitrogen purge was started, then the reactor content was brought to 80 ° C at 400 rpm. After reaching 80 ° C, a starter charge composed of 2.31 g of sodium persulfate dissolved in 13 g of water was added to the reactor. An emulsion feed composed of 120 g of water, 7.16 g of TERGITOL NP-40 (70%), 9.94 g of AEROSOL 18, 241.47 g of styrene, 73.02 g of isooctyl acrylate, and 25.61 g of acetoacetoxyethyl methacrylate, and 0.52 g of 2-acrylamido-2-methylpropansulfonate sodium (50% in water) was fed at 1.72 g / min. Five minutes after the first emulsion feed began, an initiator solution composed of 1.3 g of sodium persulfate dissolved in 33.5 g of water at 0.16 min was fed. After the last feed, the reaction was maintained for 10 minutes at 80 ° C then cooled to 65 ° C for the next 20 minutes. During the next 30 minutes, a solution of 1.03 g of t-butyl hydroperoxide (70% in water) was fed and 0.72 g of formaldehyde sulphoxylate and sodium in 12 g of water were fed to the reactor while continuing the heating. After cooling, the emulsion is filtered through a 100 mesh wire screen. The dried solids are collected on a 100 mesh screen = 3.26 g. Level of solids, 43.84%; The particle size was 151 nm per TEM and the pH was 7.41.

Example 18b Preparation of water-borne, co-reactive particles that contain the functionality of acetoacetoxy To a 1000 ml resin boiler equipped with a condenser, nitrogen purge, and an underground feeding tube are added 192 g of water, 1215 g of TREM LF-40, 0.58 g of TERGITOL NP-40 (70%), 13.50 g of methyl methacrylate, 4.20 g of styrene, 15.15 g of 2-ethylhexyl acrylate, 0.101 g of trimethylolpropane triacrylate, and 2.19 g of sodium carbonate. A nitrogen purge was started, then the reactor content was brought to 80 ° C at 400 rpm. After reaching 80 ° C, a starter charge composed of 2.31 g of sodium persulfate dissolved in 13.07 g of water was added to the reactor. An emulsion feed composed of 106.5 g of water, 3.51 g of TREM LF-40, 3.06 g of TERGITOL NP-40 (70%), 82.92 g of methyl methacrylate, 25.80 g of styrene, 93.06 g of 2-acrylate. ethylhexyl, and 0.619 g of trimethylolpropane triacrylate was started 8. 38 g / min. Five minutes after the emulsion feed was started, an initiator solution composed of 1.31 g of sodium persulfate dissolved in 33.67 g of water at 0.536 g / min was fed. After the first emulsion feed was completed, a second feed emulsion composed of 51.3 g of water, 3.84 g of AEROSOL 18, 1.53 g of TERGITOL NP-40 (70%), 41.96 g of styrene, 41.1 g was fed. of 2-ethylhexyl acrylate, 7.20 g of dimethylaminoethyl methacrylate, 34.18 g of acetoacetoxyethyl methacrylate, and 0.50 g of sodium 2-acrylamido-2-methylpropanesulfonate (50% in water) at 8.38 g / minute. Five minutes after the last feed, a starter solution of 0.40 g of t-butyl hydroperoxide, and 0.40 g of formaldehyde and sodium sulfoxylate dissolved in 12.1 g of water were charged and heating continued for 30 minutes. The emulsion was cooled. The emulsion is then filtered through a 100 mesh wire screen. Solids level, 46.08; amount of dry material (100 mesh screen), 2.03 g, particle size (per TEM) 225 nm.

Example 19 Preparation of particles transported by water, co-reactive, containing the functionality of epoxy.

To a 1000 ml resin boiler equipped with a condenser, nitrogen purge, and an underground feeding tube are added 192 g of water, 1.22 g of TREM LF-40, 0.579 g of TERGITOL NP-40 (70%), 13.28 g of methyl methacryl-ato, 2.15 g of styrene, 17.45 g of 2-ethylhexyl acrylate, 0.076 g of trimethylolpropane triacrylate, and 2.19 g of sodium carbonate. A nitrogen purge was started, then the reactor content was brought to 80 ° C at 400 rpm. After reaching 80 ° C, a starter charge composed of 2.31 g of sodium persulfate dissolved in 13.07 g of water was added to the reactor. An emulsion feed composed of 106.5 g of water, 3.51 g of TREM LF-40, 3.06 g of TERGITOL NP-40 (70%), 81.53 g of methyl methacrylate, 13.22 g of styrene, 107.19 g of 2-acrylate. ethylhexyl, and 0.46 g of trimethylolpropane triacrylate was started at 8.38 g / min. Five minutes after the emulsion feed was started, an initiator solution composed of 1.31 g of sodium persulfate dissolved in 33.67 g of water at 0.536 g / min was fed. After after the first emulsion feed was completed, a second emulsion feed was fed consisting of 51.3 g of water, 3.84 g of AEROSOL 18, 1.53 g of TERGITOL NP-40 (68% in water), 56.59 g of styrene, 49.5 g of 2-ethylhexyl acrylate, 18.35 of glycidyl methacrylate, and 0.51 g of sodium 2-acrylamido-2-methylpropanesulfonate (50% in water) at 5.25 g / minute. After the last feed, the reaction is maintained for 10 minutes at 80 ° C then cooled to 65 ° C for the next 20 minutes. During the next 30 minutes, a solution of 0.40 g of t-butyl hydroperoxide (70% in water) and 0.40 g of formaldehyde and sodium sulfoxylate in 12.06 g of water was fed into the reactor while heating is continued. After cooling, the emulsion is filtered through a 100 mesh wire screen. The dried solids were collected on a 100 mesh screen = 0.29 g. The level of the total solids of 46.24% and the pH was 8.54.

Example 20 Preparation of water-borne, co-reactive particles that contain epoxy functionality To a 1000 ml resin boiler equipped with a condenser, nitrogen purge, and an underground feeding tube are added 192 g of water, 1.22 g of TREM LF-40, 0.579 g of TERGITOL NP-40 (70%), 13.28 g of methyl methacrylate, 2.20 g of styrene, 17.40 g of 2-ethylhexyl acrylate, 0.076 g of trimethylolpropane triacrylate, and 2.19 g of sodium carbonate. A nitrogen purge was started, then the reactor content was brought to 80 ° C at 400 rpm. After reaching 80 ° C, a starter charge composed of 2.31 g of sodium persulfate dissolved in 13.07 g of water was added to the reactor. An emulsion feed composed of 106.5 g of water, 3.51 g of TREM LF-40, 3.06 g of TERGITOL NP-40 (70% in water), 81.53 g of methyl methacrylate, 13.53 g of styrene, 106.88 g of acrylate of 2-ethylhexyl, and 0.46 g of trimethylolpropane triacrylate was started at 5248 g / min. Five minutes after the emulsion feed was started, an initiator solution composed of 1.31 g of sodium persulfate dissolved in 33.67 g of water at 0.336 g / min was fed. After the first emulsion feed was completed, a second feed emulsion composed of 51.3 g of water, 3.84 g of AEROSOL 18, 1.53 g of TERGITOL NP-40 (68% in water), 56.23 g of styrene was fed. , 49.5 g of 2-ethylhexyl acrylate, 18.35 g of glycidyl methacrylate, 0.36 g of 2-ethylhexyl 3-mercaptopropionate, and 0.51 g of sodium 2-acrylamido-2-methylpropanesulfonate (50% in water) at 5.25 g / minute. After the last feed, the reaction was maintained for 10 minutes at 80 ° C then cooled to 65 ° C for the next 20 minutes. During the next 30 minutes, a starter solution of 0.40 g of t-butyl hydroperoxide (70% in water) and 0.40 g of formaldehyde and sodium sulfoxylate dissolved in 12.06 g of water while heating was continued. After cooling, the emulsion is then filtered through a 100 mesh wire screen. Dry solids collected on the 100 mesh screen = 1.49 g. The level of the total solids was 46.51% and the pH was 8.84.

Example 21 Preparation of water-borne, co-reactive particles that contain epoxy functionality To a 1000 ml resin boiler equipped with - A condenser, nitrogen purge, and an underground feeding tube are added 192 g of water, 1.22 g of TREM LF-40, 0.579 g of TERGITOL NP-40 (70%), 13.28 g of methyl methacrylate, 2.20 g of styrene, 17.40 g of 2-ethylhexyl acrylate, 0.076 g of trimethylolpropane triacrylate, and 2.19 g of sodium carbonate. A nitrogen purge was started, then the reactor content was brought to 80 ° C at 400 rpm. After reaching 80 ° C, a starter charge composed of 2.31 g of sodium persulfate dissolved in 13.07 g of water was added to the reactor. An emulsion feed composed of 106.5 g of water, 3.51 g of TREM LF-40, 3.06 g of TERGITOL NP-40 (70% in water), 81.53 g of methyl methacrylate, 13.53 g of styrene, 106.88 g of acrylate of 2-ethylhexyl, and 0.46 g of trimethylolpropane triacrylate was started at 5248 g / min. Five minutes after the emulsion feed was started, an initiator solution composed of 1.31 g of sodium persulfate dissolved in 33.67 g of water at 0.336 g / min was fed. After the first emulsion feed was completed, a second feed emulsion composed of 51.3 g of water, 3.84 g of AEROSOL 18, 1.53 g of TERGITOL NP-40 (68% in water), 56.23 g of styrene was fed. , 49.5 g of 2-ethylhexyl acrylate, 18.35 g of glycidyl methacrylate, 0.72 g of 2-ethylhexyl 3-mercaptopropionate, and 0.51 g of sodium 2-acrylamido-2-methylpropanesulfonate (50% in water) at 5.25 g / minute. After the last feeding, the reaction it was kept for 10 minutes at 80 ° C then cooled to 65 ° C for the next 20 minutes. During the next 30 minutes, a starter solution of 0.40 g of t-butyl hydroperoxide (70% in water) and 0.40 g of formaldehyde and sodium sulfoxylate dissolved in 12.06 g of water was fed to the reactor while heating was continued. After cooling, the emulsion is then filtered through a 100 mesh wire screen. Dry solids collected on the 100 mesh screen = 1.49 g. The level of the total solids was 46.51% and the pH was 8.84.

Example 22 Preparation of water-borne, co-reactive particles that contain epoxy functionality To a 1000 ml resin boiler equipped with a condenser, nitrogen purge, and an underground feeding tube are added 192 g of water, 1.22 g of TREM LF-40, 0.579 g of TERGITOL NP-40 (70%), 13.28 g of methyl methacrylate, 2.30 g of styrene, 17.30 g of 2-ethylhexyl acrylate, 0.076 g of trimethylolpropane triacrylate, and 2.19 g of sodium carbonate. A purge with nitrogen was started, then the content of the reactor was brought up to 80 ° C at 400 rpm. After reaching 80 ° C, a starter charge composed of 2.31 g of sodium persulfate dissolved in 13.07 g of water was added to the reactor. An emulsion feed composed of 106.5 g of water, 3.51 g of TREM LF-40, 3.06 g of TERGITOL NP-40 (70% in water), 81.53 g of methyl methacrylate, 14.14 g of styrene, 106.26 g of acrylate of 2-ethylhexyl, and 0.46 g of trimethylolpropane triacrylate was started at 5248 g / min. Five minutes after the first emulsion feed was started, an initiator solution composed of 1.31 g of sodium persulfate dissolved in 33.67 g of water at 0.336 g / min was fed. After the first emulsion feed was completed, a second emulsion feed composed of 51.3 g of water, 3.84 g of AEROSOL 18, 1.53 g of TERGITOL NP-40 (68% in water), 55.51 g of styrene was fed. , 49.5 g of 2-ethylhexyl acrylate, 18.35 g of glycidyl methacrylate, 1.08 g of 2-ethylhexyl 3-mercaptopropionate, and 0.50 g of sodium 2-acrylamido-2-methylpropanesulfonate (50% in water) at 5.25 g / minute. After the last feed, the reaction was maintained for 10 minutes at 80 ° C then cooled to 65 ° C for the next 20 minutes. For the next 30 minutes, a starter solution of 0.40 g of t-butyl hydroperoxide (70% strength) in water) and 0.40 g of formaldehyde and sodium sulfoxylate dissolved in 12.06 g of water while heating was continued. After cooling, the reactor is then charged with a solution of 0.52 g of isoascorbic acid in 16 g of water and 0.52 g of 0.5% iron (II) sulfate, and 0.52 g of t-butyl hydroperoxide (70% strength). in water). After sedimentation overnight, the emulsion is filtered through a 100 mesh wire screen. Dry solids collected on the 100 mesh screen = 0.71 g. The level of the total solids was 46.74% and the pH was 8.54.

Example 23 Preparation of water-borne, co-reactive particles that contain epoxy functionality To a 1000 ml resin boiler equipped with a condenser, nitrogen purge, and an underground feeding tube are added 192 g of water, 1.22 g of TREM LF-40, 0.579 g of TERGITOL NP-40 (70%), 13.28 g of methyl methacrylate, 2.35 g of styrene, 17.25 g of 2-ethylhexyl acrylate, 0.076 g of trimethylolpropane triacrylate, and 2.19 g of sodium carbonate. A purge with nitrogen was started, then the content of the reactor was brought up to 80 ° C at 400 rpm. After reaching 80 ° C, a starter charge composed of 2.31 g of sodium persulfate dissolved in 13.07 g of water was added to the reactor. An emulsion feed composed of 106.5 g of water, 3.51 g of TREM LF-40, 3.06 g of TERGITOL NP-40 (70% in water), 81.53 g of methyl methacrylate, 14.45 g of styrene, 105.95 g of acrylate of 2-ethylhexyl, and 0.46 g of trimethylolpropane triacrylate was started at 5248 g / min. Five minutes after the emulsion feed was started, an initiator solution composed of 1.31 g of sodium persulfate dissolved in 33.67 g of water at 0.336 g / min was fed. After the first emulsion feed was completed, a second feed emulsion composed of 51.3 g of water, 3.84 g of AEROSOL 18, 1.53 g of TERGITOL NP-40 (68% in water), 55.15 g of styrene was fed. , 49.5 g of 2-ethylhexyl acrylate, 18.35 g of glycidyl methacrylate, 1.44 g of 2-ethylhexyl 3-mercaptopropionate, and 0.51 g of sodium 2-acrylamido-2-methylpropanesulfonate (50% in water) at 5.25 g / minute. After the last feed, the reaction was maintained for 10 minutes at 80 ° C then cooled to 65 ° C for the next 20 minutes. During the next 30 minutes, a starter solution of 0.40 g of t-butyl hydroperoxide (70% in water) and 0.40 g of formaldehyde and sodium sulfoxylate dissolved in 12.06 g of water was fed into the reactor while heating was continued. After cooling, the emulsion is then filtered through a 100 mesh wire screen. Dry solids collected on the 100 mesh screen = 0.79 g. The level of the total solids was 46.66% and the pH was 9.0.

Example 24 Preparation of water-borne, co-reactive particles that contain epoxy functionality To a 1000 ml resin boiler equipped with a condenser, nitrogen purge, and an underground feeding tube are added 192 g of water, 1.22 g of TREM LF-40, 0.579 g of TERGITOL NP-40 (70%), 13.28 g of methyl methacrylate, 2.40 g of styrene, 17.20 g of 2-ethylhexyl acrylate, 0.076 g of trimethylolpropane triacrylate, and 2.19 g of sodium carbonate. A nitrogen purge was started, then the reactor content was brought to 80 ° C at 400 rpm. After reaching 80 ° C, a starter charge composed of 2.31 g of sodium persulfate dissolved in 13.07 g of water was added to the reactor. A compound emulsion feed of 106.5 g of water, 3.51 g of TREM LF-40, 3.06 g of TERGITOL NP-40 (70% in water), 81.53 g of methyl methacrylate, 14.76 g of styrene, 105.64 g of 2-ethylhexyl acrylate, and 0.46 g of trimethylolpropane triacrylate was started at 5248 g / min. Five minutes after the emulsion feed was started, an initiator solution composed of 1.31 g of sodium persulfate dissolved in 33.67 g of water at 0.336 g / min was fed. After the first emulsion feed was completed, a second feed emulsion composed of 51.3 g of water, 3.84 g of AEROSOL 18, 1.53 g of TERGITOL NP-40 (70% in water), 54.79 g of styrene was fed. , 49.5 g of 2-ethylhexyl acrylate, 18.35 g of glycidyl methacrylate, 1.80 g of 2-ethylhexyl 3-mercaptopropionate, and 0.51 g of sodium 2-acrylamido-2-methylpropanesulfonate (50% in water) at 5.25 g / minute. After the last feed, the reaction was maintained for 10 minutes at 80 ° C then cooled to 65 ° C for the next 20 minutes. During the next 30 minutes, a starter solution of 0.40 g of t-butyl hydroperoxide (70% in water) and 0.40 g of formaldehyde and sodium sulfoxylate dissolved in 12.06 g of water was fed into the reactor while the heating. After cooling, the emulsion is then filtered through a sieve of 100 mesh wire. Dry solids collected on the 100 mesh screen = 0.85 g. The level of the total solids was 46.64% and the pH was 8.75.

Example 25 Preparation of water-borne, co-reactive particles that contain epoxy functionality To a 1000 ml resin kettle equipped with a condenser, nitrogen purge, and an underground feeding tube are added 293.8 g of water, 1.34 g of TREM LF-40, 0.70 g of TERGITOL NP-40 (70%), 12.71 g of styrene, 4.30 g of iso-octyl acrylate, 0.895 g of m-tetramethylxylene isocyanate, 0.014 g of sodium 2-acrylamido-2-methylpropansulfonate (50% in water) and 2.05 g of sodium carbonate. A nitrogen purge was started, then the reactor content was brought to 80 ° C at 400 rpm. After reaching 80 ° C, a starter charge composed of 2.3 g of sodium persulfate dissolved in 13 g of water was added to the reactor. An emulsion feed composed of 120 g of water, 7.16 g of TERGITOL NP-40 (70% in water), 9.94 g of AEROSOL 18, 241.47 g of styrene, 81.62 g of isooctyl acrylate, and 17.0 g of methacrylate of glycidyl, and 0.52 g of the sodium 2-acrylamido-2-methylpropanesulfonate (50% in water) is fed at 1.72 g / min. Five minutes after the first emulsion feed was started, an initiator solution composed of 1.3 g of persulfate was fed. sodium dissolved in 33.5 g of water at 0.16 g / min. After the last feed, the reaction was maintained for 10 minutes at 80 ° C then cooled to 65 ° C for the next 20 minutes. During the next 30 minutes, a solution of 1.03 g of t-butyl hydroperoxide (70% in water) and 0.72 g of formaldehyde sulphoxylate and sodium in 12 g of water was fed into the reactor while heating is continued. After cooling, the emulsion is filtered through a 100 mesh wire screen. The dry solids collected on a 100 mesh screen = 6.95 g. The total solids level was 42.74%, the particle size was 144 nm per TEM and the pH was 7.90.

Example 26 Preparation of particles transported by water, co-reactive, containing the carbonate functionality To a 1000 ml resin kettle equipped with a condenser, a nitrogen purge, and a subsurface feed tube, 435.6 g of water, 13.8 g of sodium vinyl sulfonate, 11.43 of TERGITOL NP-40 (at 70 ° C) were added. %), 1.0 g of sodium carbonate, 40 g of a monomer solution composed of 80 g of vinyl acetate, 280 g of VEOVA-10, 20 g of VEOVA-5, and 20 g of vinyl carbonate and ethylene. A nitrogen purge was started, then the reactor content was brought to 65 ° C at 400 rpm. After reaching 65 ° C, a starter charge composed of 1.03 g of t-butyl hydroperoxide (70%) and 0.072 g of formaldehyde sulphoxylate and dissolved sodium is added to the reactor. After 5 minutes, the remaining monomer solution was fed for more than 200 minutes, an initiator solution composed of 2.5 g of t-butyl hydroperoxide dissolved in 80 g of water, and 1.68 g of formaldehyde and sodium sulfoxylate dissolved in 80 g, were fed to the reactor for more than 200 minutes. Fifteen minutes after the starter solutions were completed, the reactor is cooled to 40 ° C. Post-initiators and a catalyst composed of isoascorbic acid (0.53 g), and t-butyl hydroperoxide (0.53 g), and a solution of 1% iron sulfate (0.53 g) were sequentially charged to the reactor and the heating for 30 minutes. The solids, 383.7%, filterable dry solids (100 mesh sieve), 3.2 g, pH, 4.64; particle size, 225 nm (Electron Micrographs); IR (carbonate absorption), 1815 c "1.

Example 27 Preparation of particles transported by water, co-reactive, containing the carbonate functionality To a 1000 ml resin kettle equipped with a condenser, a nitrogen purge, and a subsurface feed tube, 435.6 g of water, 13.8 g of sodium vinyl sulfonate, 11.43 of TERGITOL NP-40 (at 70 ° C) were added. %), 1.0 g of sodium carbonate, 40 g of a monomer solution composed of 280 g of vinyl acetate, 40 g of VEOVA-10, 80 g of butyl acrylate, and 20 g of vinyl carbonate and ethylene. A nitrogen purge was started, then the reactor content was brought to 65 ° C at 400 rpm. After reaching 65 ° C, a starter charge composed of 1.03 g of t-butyl hydroperoxide (70% aqueous solution) and 0.72 g of dissolved formaldehyde and sodium sulfoxylate is added to the reactor. After 5 minutes, the remaining monomer solution was fed for more than 200 minutes, an initiator solution composed of 2.4 g of t-butyl hydroperoxide dissolved in 80 g of water, and 1.68 g of formaldehyde and sodium sulfoxylate dissolved in 80 g, were fed into the reactor for more than 200 minutes. Fifteen minutes after the starter solutions were completed, the reactor is cooled to 40 ° C. Post-initiators and a catalyst composed of isoascorbic acid (0.53 g), and t-butyl hydroperoxide (0.53 g, 70% aqueous solution), and a solution of 1% iron sulfate (0.53 g) were charged sequentially to the reactor and the heating was continued for 30 minutes. The solids, 38.7%, filterable dry solids (100 mesh screen), 3.2 g, pH, 4.64; particle size, 150 nm (Electronic Micrographs); IR (carbonate absorption), 1815 cm "1.

Example 28 Preparation of water-borne, co-reactive particles that contain isocyanate functionality To a 1000 ml resin boiler equipped with a condenser, nitrogen purge, and an underground feeding tube are added 293.8 g of water, 1.34 g of TREM LF-40, 1.79 g of TERGITOL NP-40 (70%), 2.05 g of sodium carbonate, 12.33 g of styrene, 4.30 g of iso-octyl acrylate, 1.27 g of TMI and 0.014 g of 2-acrylamido -2-methylpropanesulfonate sodium (50% in water). A purge with nitrogen was started, then the content of the reactor was brought up to 80 ° C at 400 rpm. After reaching 80 ° C, a starter charge composed of 2.3 g of sodium persulfate dissolved in 13 g of water was added to the reactor. An emulsion feed composed of 120 g of water, 7.16 g of NP-40 (70%), 9.94 g of AEROSOL 18, 234.33 g of styrene, 81.62 g of isooctyl acrylate, 24.15 g of isocyanate of m-tetramethylxylene and 25.61 g of acetoacetoxyethyl methacrylate, and 0.52 g of sodium 2-acrylamido-2-methylpropanesulfonate (50% in water) was fed at 1.72 g / min. Five minutes after the first emulsion feed began, an initiator solution composed of 1.3 g of sodium persulfate dissolved in 33.5 g of water at 0.16 min was fed. Five minutes after the last feed, an initiator solution of 1.03 g of t-butyl hydroperoxide, and 0.72 g of formaldehyde and sodium sulfoxylate dissolved in 12 g of water were charged and heating was continued for 30 minutes. The emulsion is cooled, and filtered through a 100 mesh wire screen. The level of solids, 39.29. A solution additional initiator consisting of 0.053 g of t-butyl hydroperoxide, 0.53 g of isoascorbic acid and 0.55 g of formaldehyde sulfoxylate and sodium was added and the emulsion allowed to harden for one hour. The total solids measured were 42.36%. The following day the total solids were 42.89% and the fragments collected on a 100 mesh screen were 3.90 g with a pH of 6.4.

Example 29 Curing and Evaluation of films prepared from the combination of a polymeric latex transported by water, PPAE with co-reactive latices by environmental and thermal curing The mixtures were prepared by adding the appropriate weight fraction of the PPAE latex with respect to the co-reactive latex (dry resin on dry resin). Typically, the appropriate heavy amount of the PPAE latex is added to 25 g of the co-reactive latex. After the mixtures were prepared, 1 phr of SURFYNOL 104DPM (1 g of active SURFYNOL 104 DPM per 100 g of dry resin) was added as a wetting agent. In some cases, the TEXANOL alcohol ester was added as a coalescing agent because the mixtures did not form a film at room temperature. Wet films were emptied or molded onto panels treated with aluminum chromate (0.06 cm X 7.62 cm X 22.86 cm) (0.025"X 3" X 9") then cured in a forced air oven or allowed to cure ambient temperature in the CTH room The results are reported in Tables 1 and 2. The samples combined with the co-reactive carbonate latex appeared yellow after baking.

Table 9 Co-reactive Co-reactive Grams PPAE Grams SURFYNOL TEXANOL Example: Chemistry: Example: 104 DPM (g) Ester Alcohol (g) 13 Eriarpiria 25 l 24.98 0.47 14 Enapriria 25 l 24.98 0.47 15 Enairaxia 25 1 24.98 0.47 16 Enamina 25 1 24.98 0.47 17 Enamiria 25 [24.98 0.47 18 Acetoacetoxy 25 1 14.34 0.35 1.35 18b Acetoacetoxy 25 l 17.21 0.40 18b Acetoacetoxy 25 1b 5.65 0.29 18b Acetoacetoxy 25 1c 5.65 0.29 19 Epoxy 25 I 15.99 0.39 20 Epoxy 25 1 15.99 0.39 21 Epoxy 25 1 15.99 0.39 22 Epoxy 25 1 15.99 0.39 23 Epoxy 25 1 15.99 0.39 24 Epoxy 25 1 15.99 0.39 25 Epoxy 25 1 14.28 0.35 1.35 26 Carbonate 25 1 14.40 0.33 27 Carbonate 25 1 14.40 0.33 28 Isocyanate 25 1 14.38 0.35 1.35 Table 10 - Example Double Double Shine Double Shine Brightness Co-reacFrotara. 20 ° on Frotara. 20 ° on Frotam. 20 ° on tivo mezde MEK films of MEK films of MEK films clade with per thousand. Cured by a thousand. Cured a thousand. Cured Ejemp. 1 in. At 120 ° C in. 150 ° C cure- in. Then 1 in Pelic Table. Cured of pelic. das during de pelic Day cura¬ 1: after during 30 minutes afterwards do ambien¬ 120 ° C with a cure time of 1 day in such a case: during cure of CTH: for 30 30 minutes biental in minutes CTH site: 13 143 68 - - 29 47 14 115 60 - - 36 39 75 59 - - 30 37 16 143 60 - - 38 42 17 99 51 - - 37 42 18 35 78 283 88 18b 54 70 ~ - 18b + 13b 97 100 - - 18b + 13c 143 97 - - 19 52 65 33 69 20 47 60 58 64 21 41 63 45 65 22 50 60 47 57 23 35 64 79 63 24 29 58 28 58 25 39 74 110 82 26 10 37 8 36 27 9 36 8 35 28 26 53 54 60 Example 30 Preparation of waterborne, co-reactive particles that contain epoxy functionality To a 2000 ml resin kettle equipped with a condenser, nitrogen purge, and an underground feed tube are added 230 g of water, 3.25 g of HITENOL HS-20, 4.20 g of SURFYNOL 485W, 11.48 g of methyl methacrylate. , 4.21 g of 2-ethylhexyl acrylate, 0.076 g of trimethylolpropane triacrylate, 6.75 g of butyl methacrylate, 0.07 g of trimethylolpropane triacrylate, 0.03 g of 2-ethylhexylmercaptopropionate and 2.75 g of sodium carbonate. A nitrogen purge was started, then the reactor content was brought to 80 ° C at 400 rpm. After reaching 80 ° C, a starter charge composed of 3.00 g of sodium persulfate dissolved in 15.0 g of water was added to the reactor. An emulsion feed composed of 125.0 g of water, 2.43 g of HITENOL HS-20, 3.20 g of SURFYNOL 485W, 103.28 g of methyl methacrylate, 37.87 g of 2-ethylhexyl acrylate, 60.75 g of butyl methacrylate and 0.61 g of trimethylolpropane triacrylate was started at 4.24 g / min. Five minutes after the first feeding began in emulsion, an initiator solution composed of 1.50 g of sodium persulfate dissolved in 50.00 g of water at 0.29 g / min was fed. After the first emulsion feed was completed, a second emulsion feed composed of 130 g of water, 2.43 g of HITENOL HS-20, 3.15 g of SURFYNOL 485W, 54.00 g of glycidyl methacrylate, 169.88 g of methacrylate was fed. of butyl and 0.34 g of 2-ethylhexyl 3-mercaptopropionate at 4.24 g / minute. After the last feed, the reaction was maintained for 10 minutes at 80 ° C then cooled to 65 ° C for the next 20 minutes. During the next 30 minutes, a solution of 0.40 g of t-butyl hydroperoxide (70% in water) and 0.40 g of formaldehyde and sodium sulfoxylate dissolved in 12.06 g of water is fed into the reactor while heating is continued . After cooling, the emulsion was filtered through a 100 mesh wire screen. The dried solids were collected on a 100 mesh screen = 2.55 g. The level of the total solids was 46% and the pH was 7.3.

Example 31 Preparation of particles transported by water, co-reactive, containing the functionality of epoxy.

To a 2000 ml resin kettle equipped with a condenser, nitrogen purge, and an underground feed tube are added 230 g of water, 6.27 g of HITENOL HS-20, 11.48 g of methyl methacrylate, 4.21 g of acrylate, 2-ethylhexyl, 6.75 g of butyl methacrylate, 0.07 g of trimethylolpropane triacrylate, 0.03 g of 2-ethylhexylmercaptopropionate and 2.75 g of sodium carbonate. A nitrogen purge was started, then the reactor content was brought to 80 ° C at 400 rpm. After reaching 80 ° C, a starter charge composed of 3.00 g of sodium persulfate dissolved in 15.0 g of water was added to the reactor. An emulsion feed composed of 156.0 g of water, 7.31 g of HITENOL HS-20, 103.28 g of methyl methacrylate, 37.87 g of 2-ethylhexyl acrylate, 60.75 g of butyl methacrylate and 0.61 g of trimethylolpropane triacrylate were started at 4.24 g / min. Five minutes after the first emulsion feed was started, an initiator solution composed of 1.50 g of sodium persulfate dissolved in 50.00 g of water at 0.29 g / min was fed. After the first emulsion feed was completed, a second feed in emulsion composed of 130 g of water, 7.30 g of HITENOL HS-20, 54.00 g of glycidyl methacrylate, 169.88 g of methacrylate were fed. butyl and 0.34 g of 2-ethylhexyl 3-mercaptopropionate at 4.24 g / minute. After the last feed, the reaction was maintained for 10 minutes at 80 ° C then cooled to 65 ° C for the next 20 minutes. During the next 30 minutes, a solution of 0.40 g of t-butyl hydroperoxide (70% in water) and 0.40 g of formaldehyde and sodium sulfoxylate dissolved in 12.06 g of water is fed into the reactor while heating is continued . After cooling, the emulsion was filtered through a 100 mesh wire screen. The dried solids were collected on a 100 mesh screen = 3.25 g. The level of the total solids was 46% and the pH was 7.9.

Example 32 Preparation of particles transported by water, co-reactive, containing the functionality of epoxy.

To a 2000 ml resin kettle equipped with a condenser, nitrogen purge, and an underground feed tube are added 230 g of water, 12.16 g of AEROSOL 501, 11.48 g of methyl methacrylate, 4.21 g of 2-acrylate. ethylhexyl, 6.75 g of butyl methacrylate, 0.07 g of trimethylolpropane triacrylate, 0.03 g of 2-ethylhexylmercaptopropionate and 2.75g of sodium carbonate. A purge was started with nitrogen, then the contents of the ST reactor carried up to 80 ° C at 400 rpm. After reaching 80 ° C, a starter charge composed of 3.00 g of sodium persulfate dissolved in 15.0 g of water was added to the reactor. An emulsion feed composed of 156.0 g of water, 14.16 g of AEROSOL 501, 103.28 g of methyl methacrylate, 37.87 g of 2-ethylhexyl acrylate, 60.75 g of butyl methacrylate and 0.61 g of trimethylolpropane triacrylate were started at 4.24 g / min. Five minutes after the first emulsion feed was started, an initiator solution composed of 1.50 g of sodium persulfate dissolved in 50.00 g of water at 0.29 g / min was fed. After the first emulsion feed was completed, a second emulsion feed was fed consisting of 130 g of water, 14.16 g of AEROSOL 501, 54.00 g of glycidyl methacrylate, 169.88 g of butyl methacrylate and 0.34 g of 3- 2-ethylhexyl mercaptopropionate at 4.24 g / minute. After the last feed, the reaction was maintained for 10 minutes at 80 ° C then cooled to 65 ° C for the next 20 minutes. During the next 30 minutes, a solution of 0.40 g of t-butyl hydroperoxide (70% in water) and 0.40 g of formaldehyde and sodium sulfoxylate dissolved in 12.06 g of water is fed to the reactor while heating is continued. After cooling, the emulsion was filtered through a 100 mesh wire screen. The dried solids were collected on a 100 mesh screen = 1.21 g. The level of the total solids was 46% and the pH was 7.9.

Example 33 Preparation of particles transported by water, non-reactive, such as Control To a 2000 ml resin kettle equipped with a condenser, nitrogen purge, and an underground feed tube are added 230 g of water, 3.25 g of HITENOL HS-20, 4.20 g of SURFYNOL 485W, 11.48 g of methyl methacrylate. , 4.21 g of 2-ethylhexyl acrylate, 6.75 g of butyl methacrylate, 0.07 g of trimethylolpropane triacrylate, 0.03 g of 2-ethylhexylmercaptopropionate and 2.75 g of sodium carbonate. A nitrogen purge was started, then the reactor content was brought to 80 ° C at 400 rpm. After reaching 80 ° C, a starter charge composed of 3.00 g of sodium persulfate dissolved in 15.0 g of water was added to the reactor. An emulsion feed composed of 125.0 g of water, 2.43 g of HITENOL HS-20, 3.20 g of SURFYNOL 485W, 103.28 g of methyl methacrylate, 37.87 g of 2-ethylhexyl acrylate, 60.75 g of butyl methacrylate and 0.61 g of trimethylolpropane triacrylate it started at 4.24 g / min. Five minutes after the first emulsion feed was started, an initiator solution composed of 1.50 g of sodium persulfate dissolved in 50.00 g of water at 0.29 g / min was fed. After the first emulsion feed was completed, a second emulsion feed composed of 130 g of water, 2.43 g of HITENOL HS-20, 3.15 g of SURFYNOL 485W, 54.00 g of glycidyl methacrylate, 169.88 g of methacrylate was fed. of butyl and 0.34 g of 2-ethylhexyl 3-mercaptopropionate at 4.24 g / minute. After the last feed, the reaction was maintained for 10 minutes at 80 ° C then cooled to 65 ° C for the next 20 minutes. During the next 30 minutes, a solution of 0.40 g of t-butyl hydroperoxide (70% in water) and 0.40 g of formaldehyde and sodium sulfoxylate dissolved in 12.06 g of water is fed into the reactor while heating is continued . After cooling, the emulsion was filtered through a 100 mesh wire screen. The dried solids were collected on a sieve of 100 mesh = 2.55 g. The level of the total solids was 46% and the pH was 7.3.

Example 34 Curing and Evaluation of the films prepared by combining a polymeric latex transported by PPAE water with co-reactive latices by environmental curing.

The mixtures were prepared from the examples to 33 adding the appropriate weight fraction of the PPAE latex to the co-reactive latex (dry resin on dry resin). Typically, the appropriate heavy amount of the PPAE latex is added to 25 g of the co-reactive latex. After the mixtures were prepared, 1 phr of SURFYNOL 104DPM (1 g of SURFYNOL (104 active DPM per 100 g of dry resin) was added as a wetting agent.In some cases, TEXANOL (ester alcohol) was added as an agent of coalescence because the mixtures did not form a film at room temperature The wet films were cast or cast on panels treated with aluminum chromate (0.06 cm X 7.62 cm X 22.86 cm) (0.025"X 3" X 9" ) are then cured at room temperature at the CTH site, the results are reported in Table 11.

Table 11 Example CorreacChemistry Thickness of the double rubbings Mixed film Correactiva MEK mientos MEK samples with Example 1 (cm) then 1 after 2 in Table 1: dry week- weeks ambient environmental drying (temperature (ambient temperature) ambient ) 33 Non-reactive 0.003 17 72 30 Epoxy 0.0025 348 374 31 Epoxy 0.003 150 165 32 Epoxy 0.0025 105 248 Example 36 Coatings prepared from the polymeric latex transported with water, of PPAE, mixed with functional epoxy co-reactive latices.

The coatings were prepared and evaluated using the combined emulsions of examples 9D and 9H above.

Example 36a Preparation of Pigment Grinding A ground material of 56.77 liters (15 gallons) was prepared using a Premier distributor, as below, and a portion of the ground material was used to reduce each specific coating.

Material: Volume: Water 48.00 TAMOL 1124 4.00 TRITON CF-10 2.00 FOOAMASTER AP 2.00 DOWICIL 75 1.00 Disperse well when added under agitation: TI-PURE R-900 200. 00 Cowles until the ground material passes 7+ Hegman, add: Water 19. 00 Filter through a Fulfil filter and store.

Example 36b: Preparation of Coatings Material: Weight (g) Example: 1 2 (Mixture in emulsion used) (9D) OH) Material Ground 36a 137.5 137.5 Emulsion: 245 245 FOAMASTER AP Premix 1.0 1.0 FOAMASTER VF 1.5 1.5 SURFYNOL 104a 5.0 5.0 Water 54 54 Then add: ACRYSOL SCT-275 50.0 50.0 Example 36c: Evaluation of Coating properties The coating properties were evaluated at appropriate drying times. Damp paint, gloss, wet phase adhesion data and rubbing data are presented in Table 12 below. The value of the color "b", the paint drying cracks in a low temperature coalescence test, the properties of resistance to Blocking and printing are presented in Table 13 which is given below.

Table 12 - Sample of Coating Sample 1 Coating 2 pH 9.7 9.4 KU 89 83 brightness at 60 degrees 65 75 brightness at 20 degrees 24 32 1 day BT * 25 2600 1 day TF ** 3000+ 3000+ 8 days BT 19 3000+ 8 days TF 3000+ 3000+ 8 days rubbing 322 324 15 days rubbing 657 552 22 days rubbing 731 574 * TB = total break through adhesion in wet phase ** TF = total adhesion failure in wet phase Table 13 Sample of Coating Sample 1 Coating 2 color value "b '3.1 2.5 cracks drying if not 1 day drying - 1 day blocking FTF 1 day drying - 7 days blocking FTF 1 day drying - 6 1 day printing 1 day drying - 6 7 days printing 21 days drying - 9 1 day wet blocking FTF 21 days drying -7 days wet lock FTF 21 days hot and dry blocking 22 days rubbing 731 574 It is noted that in relation to this date the best method known by the applicant to carry out the aforementioned invention, is that which is clear from the present description of the invention.

Having described the invention as above, property is claimed as contained in the following

Claims (24)

1. A water-based latex, characterized in that it comprises polymeric particles with amino function, transported by water, dispersed, polymer particles with suspended function, transported by water, dispersed, and water, wherein the polymer with suspended function comprises at least a 'portion with reactive amine function, pendant.

2. A latex according to claim 1, characterized in that the reactive amine reactive function portion is selected from the group consisting of carbonate, epoxide, isocyanate, isopropenyl, carboxylic acid, and allyl groups.

3. A latex according to claim 1, characterized in that the polymer with amino function is a polymeric (polyamino) enamine comprising the product of the reaction of a polymer with acetoacetoxy function stabilized with a surfactant and a poly (alkyleneimine).

4. A latex according to claim 3, characterized in that the polymer with The acetoacetoxy function stabilized with a surfactant comprises about 1 to about 40 weight percent of a monomer of the Formula (1): R1-CH = C (R2) C (O) -X1-X2-X3-C (O) -CH2-C (O) -R3 (1) wherein R1 is a hydrogen or halogen; R2 is a hydrogen, halogen, an alkylthio group with C? -C6, or an alkyl group with C? -C6; R3 is an alkyl group with d-C6; X1 and X3 are independently O, S, or a group of the formula -N (R ") -, in which R 'is an alkyl group with C? -C6; X2 is an alkylene group with C2-C? 2 or a cycloalkylene group with C3-C2, about 0.1 to about 5 weight percent of a surface-active vinyl monomer, not self-polymerizing, and about 75 to about 90 weight percent of a non-acidic vinyl monomer; where the poly (alkyleneimine) is poly (ethylene imine).

5. A latex according to claim 4, characterized in that the monomer of the formula (1) is selected from acetoacetoxyethyl methacrylate, acetoacetoxyethyl acrylate, acetoacetoxy (methyl) ethyl acrylate, acetoacetoxypropyl acrylate, and acetoacetoxybutyl acrylate and the surface active, non-self-curing vinyl monomer is a polyoxyethylene alkyl phenyl ether of the formula (3), (4), or (5): CH2OCH2CH = CH2 r% "v © i i - OCH2CHO (CH2CH20) mS03NH4 (5) where R is nonyl or octyl, n varies from 5 to 50, and m varies from 15 to 40.

6. A latex according to claim 4, characterized in that it comprises from about 5 to about 50 weight percent of the polymer particles with amino function and about 50 to about 95 weight percent of the polymer particles with pendant function, based on the weight of the dried resin and wherein the particle size of the polymeric particles with amino function ranges from about 45 to about 500 nm and the particle size of the polymer particles with pendant function ranges from about 45 to about 500 nm.

7. A latex according to claim 6, characterized in that the particle size of the polymer particles with amino function ranges from about 25 to about 100 nm.

8. A latex according to claim 6, characterized in that the particle size of the polymer particles with amino function ranges from about 110 to about 450 nm.

9. A water-based latex, characterized in that it comprises polymer particles with amino function, transported by water, dispersed, polymer particles with suspended function, transported by water, dispersed, a buffer and water; the latex has a pH that varies from about 7.0 to about 9.2 and wherein the polymer with pendant function comprises at least a portion with reactive function of pendant amine.

10. A latex according to claim 9, characterized in that the reactive amine reactive function portion is selected from the group consisting of carbonate, epoxide, isocyanate, isopropenyl, carboxylic acid, and allyl groups.

11. A latex according to claim 9, characterized in that the amino-functional polymer is a polymeric (polyamino) enamine comprising the product of the reaction of a polymer with acetoacetoxy function stabilized with a surfactant and a poly (alkyleneimine) and the buffer is ammonium bicarbonate, diacid ammonium phosphate, or a mixture thereof.

12. A latex according to claim 11, characterized in that the acetoacetoxy functional polymer stabilized with a surfactant comprises about 1 to about 40 weight percent of a monomer of the formula (1): RX-CH = C (R2) C (O) -X1-X2-X3-C (O) -CH2-C (O) -R3 (1) wherein R1 is a hydrogen or halogen; R2 is a hydrogen, halogen, an alkylthio group with C? -C6, or an alkyl group with C? -C6; R3 is an alkyl group with C? -C6; X1 and X3 are independently 0, S, or a group of the formula -N (R ') -, in which R' is an alkyl group with C? -C6. X2 is an alkylene group with C2-C12 or a cycloalkylene group with C3-C2; about 0.1 to about 5 weight percent of a surface active vinyl monomer, not autopolymerisable; and about 75 to 90 weight percent of a non-acidic vinyl monomer; and wherein the poly (alkyleneimine) is poly (ethylene imine).

13. A latex according to claim 12, characterized in that the monomer of the formula (1) is selected from acetoacetoxyethyl methacrylate, acetoacetoxyethyl acrylate, acetoacetoxy (methyl) ethyl acrylate, acetoacetoxypropyl acrylate, and acetoacetoxybutyl acrylate and the monomer of Surface active vinyl, not self-curing, is a polyoxyethylene alkyl phenyl ether of the formula (3), (4), or (5): CH2OCH2CH = CH2 ~ ® - OCH2CHO (CH2CH20) mS03NH4 (5) where R is nonyl or octyl, n varies from 5 to 50, and m varies from 15 to 40.

14. A latex according to claim 12, characterized in that it comprises from about 5 to about 50 weight percent of the polymer particles with amino function and about 50 to about 95 weight percent of the polymer particles with pendant function, based on the weight of the dried resin and wherein the particle size of the polymer particles with amino function varies from about 45 to about 100 nm and the particle size of the polymeric particles with pendant function varies from about 45 to about 500 nm.

15. A latex according to claim 12, characterized in that the particle size of the polymer particles with amino function ranges from about 25 to about 100 nm.

16. A coating composition, characterized in that it comprises a latex according to claim 1 and an additive selected from a solvent, a pigment, a leveling agent, a rheology agent, a flow control agent, an extender, an adjuvant of the reactive coalescence, a crushing agent, a pigment wetting agent, a dispersing agent, a surfactant, an ultraviolet (UV) absorber, a UV light stabilizer, a defoaming agent, an antifoaming agent, an anti-settling agent , a bag antifoaming agent, a body-providing agent, an antiforming agent of an outer layer, an anti-flooding agent, an antiflating agent, a fungicide, a mold, a corrosion inhibitor, a thickening agent, a plasticizer, a plasticizer reagent, a curing agent, an agent for coalescence and a latex transported by water different from the latex according to claim 1.

17. A coating composition, characterized in that it comprises a latex according to claim 4 and an additive selected from a solvent, a pigment, a leveling agent, a rheology agent, a flow control agent, an extender, an adjuvant of the reactive coalescence, a crushing agent, a pigment wetting agent, a dispersing agent, a surfactant, an ultraviolet (UV) absorber, a UV light stabilizer, a defoaming agent, an antifoaming agent, an anti-settling agent , a bag antifoaming agent, a body-providing agent, an antiforming agent of an outer layer, an anti-flooding agent, an anti-floating agent, a fungicide, a mold, a corrosion inhibitor, a thickening agent, a plasticizer, a reactive plasticizer, a curing agent, an agent for coalescence and a latex transported by water different from the latex in accordance with the claim ication 4.

18. A coating composition, characterized in that it comprises a latex according to claim 9 and an additive selected from a solvent, a pigment, a leveling agent, a rheology agent, a flow control agent, an extender, an adjuvant of the coalescence, reactive, a crushing or smoothing agent, a pigment wetting agent, a dispersing agent, a surfactant, an ultraviolet (UV) absorber, a UV light stabilizer, a defoaming agent, an antifoaming agent, a anti-settling agent, a bag antifouling agent, a body-providing agent, an antiforming agent of an outer layer, an anti-flooding agent, an anti-floating agent, a fungicide, a mold, a corrosion inhibitor, a thickening agent, a plasticizer, a reactive plasticizer, a curing agent, an agent for coalescence and a latex transported by water different from the latex in accordance with claim 9.

19. A method for preparing a water-based latex, characterized in that it comprises the step of mixing a water-based latex containing polymeric particles with amino function, transported by the water, dispersed and water with a water-based latex containing suspended polymer particles, transported by water, dispersed and water, wherein the polymer with pendant function comprises at least a portion with reactive function of pendant amine.

20. A method according to claim 19, characterized in that the reactive functional portion of the pendant amine is selected from the group consisting of carbonate, epoxide, isocyanate, isopropenyl, carboxylic acid, and allyl groups.

21. A method for preparing a water-based, buffered latex characterized in that it comprises the step of mixing: an ammonium buffer, a water-based latex containing polymer particles with amino function, transported by water, dispersed and water, and a water-based latex containing polymeric particles with suspended function, transported by water, dispersed and water, wherein the polymer with suspended function comprises at least a portion with reactive function of pendant amine.

22. A method according to claim 21, characterized in that the reactive functional portion of pendant amine is selected from the group consisting of carbonate, epoxide, isocyanate, isopropenyl, carboxylic acid, and allyl groups.

23. A method according to claim 21, characterized in that the polymer with amino function is a polymeric (polyamino) enamine comprising the product of the reaction of a polymer with acetoacetoxy function stabilized with a surfactant and a poly. { alkyleneimine) and the buffer is the ammonium bicarbonate, the diacid ammonium phosphate, or a mixture thereof.

24. A method for purifying monomers containing an electron or carbonyl, α, β-unsaturated, residual extraction group of a polymeric latex, characterized in that it comprises the step of contacting a polymeric latex having monomers containing a group electron or carbonyl, α, β-unsaturated, residual extraction, with an effective amount of a latex according to claim 3. SUMMARY OF THE INVENTION This invention provides the composition, the preparation and the final use of compositions based on crosslinking technology, transported by water, prepared from water-based latices. The invention provides a water-based latex comprising polymer particles with amino function, transported by water, dispersed, polymer particles with suspended function, transported by water, dispersed; and water. The water-borne pendant polymer comprises at least one reactive amine reactive portion selected from the group consisting of carbonate, epoxide, isocyanate, isopropenyl, carboxylic acid, and allyl groups. In a preferred embodiment, a latex of the invention comprises polymeric (polyamino) enamine (PPAE) particles transported by water, dispersed; polymer particles with suspended function, transported by water, dispersed; and water. PPAE is the product of the reaction of a polymer with acetoacetoxy function, stabilized with a surfactant (SAAP) and a poly (alkyleneimine). The water-based latices of the invention provide stable emulsions containing a mixture of polymeric particles transported by water, which suffer from crosslinking during the formation of the film. Latex films or coatings can be cured at ambient temperatures or can be thermally cured. The latex is useful in a variety of coating compositions such as, for example, paints, inks, sealants, and adhesives.