MXPA96005526A

MXPA96005526A - Production of aqueous compositions of polim

Info

Publication number: MXPA96005526A
Application number: MXPA/A/1996/005526A
Authority: MX
Inventors: Cornelis Overbeek Gerardus; Jean Paul Buckmann Alfred; Wilhelmina Smak Ivonne
Original assignee: Zeneca Resins Bv
Priority date: 1994-05-03
Filing date: 1996-11-12
Publication date: 1998-10-23

Abstract

The present invention relates to: A method for making an aqueous crosslinkable polymer composition free of organic solvent comprising a) preparing an aqueous acid-functional solution with a Tg of 10 to 125 ° C and having interlacing functional groups; conducting an aqueous emulsion polymerization to make an aqueous emulsion of an olefinic hydrophobic polymer in the presence of the aqueous solution of the oligomer, the hydrophobic polymer having a Tg at least 25øC below that of the oligomer and optionally crosslinking functional groups, and c) combining with an entanglement agent that reacts with the crosslinker groups of the oligomer and polymer, said composition having a Koenig hardness of > 40 sec and a minimum film forming temperature (MFFT) < _55øC. Also the aqueous composition thus formed and its use in various applications. The aqueous composition has excellent properties and in particular an advantageous balance of MFFT and Koen hardness

Description

PRODUCTION OF AQUEOUS POLYMER COMPOSITIONS DESCRIPTION OF THE INVENTION The present invention relates to a process for the production of certain aqueous crosslinkable polymer compositions useful for coating, to the aqueous compositions thus produced and to their use in coating applications. There is an increasing impetus to replace or supplement solvent-based polymer coating compositions with counterparts and water-based due to the problems of environmental toxicity and flammability possessed by the use of volatile organic solvents. However, even when polymer-based aqueous compositions are advised, their production usually causes the intermediate use of organic solvents, requiring subsequent removal, which is very time-consuming and expensive, or the incorporation of a certain amount of a solvent into the solvent. the final composition acting to ensure proper film formation on the coating (known as a coalescing solvent). Therefore, there is currently a growing pressure to reduce or significantly eliminate volatile organic contents (VOC's) in polymer-based aqueous composition synthesis. as components in their production (even if they are subsequently removed) and in the resulting composition as an aid to the coalescence of the film. In addition, even if a solvent-free aqueous polymer coating composition can be obtained, it has been found difficult to obtain one with a balance of good properties conventionally required in most coating compositions, particularly an acceptably high hardness and a low or Minimum film forming temperature (MFFT). It must also have good resistance to water and solvent, and good storage stability. A method has now been invented that allows the compositions to be prepared. In particular, the process of the invention produces in most cases, if not all, the resulting composition with an exceptionally advantageous combination of MFFT and hardness, where a given composition with an exceptionally high hardness opposite to the MFFT is obtained. particular of that composition. According to the present invention there is provided a process for the production of an aqueous, solvent-free, interlaxable organic polymer composition useful for coating, the process is free of organic solvent and comprises: a) preparing an aqueous solution of a functional oligomer with the acid, developed from olefinically unsaturated monomers, said oligomer having a number average molecular weight, Mn, within the range of 500 to 50,000 (preferably from 2,000 to 25,000), a glass transition temperature Tg in the range of 10 ° to 125 ° C (preferably 50 to 125 ° C), the oligomer being formed, using an aqueous emulsion free of organic solvent or an aqueous solution polymerization process, and the functionality of the acid making the oligomer soluble in water, per se, or by neutralization, and the oligomer also having functional groups to impart interlacing capacity, when the aqueous polymer composition is subsequently dried, b) conducting an emulsion polymerization process aqueous to form an aqueous emulsion of a hydrophobic polymer, from at least one olefinic monomer unsaturated in the presence of the aqueous solution of the oligomer, the hydrophobic polymer having a Tg that is at least 25 ° C higher than the Tg of said oligomer (preferably at least 40 ° C higher), and said hydrophobic polymer optionally having functional groups for imparting the interlacing capacity, when the aqueous polymer composition is subsequently dried, and c) combining the aqueous emulsion of b) with an entanglement agent by adding the entanglement agent after the polymerization of step b) and / or carrying out the polymerization in the presence of the entanglement agent, the entanglement agent is reactable with the functional groups of the oligomer interleaver and, (if present) of the hydrophobic polymer after the subsequent drying, to effect entanglement, wherein the entanglement agent is not an agent and in addition, said polymer composition upon drying has a Koenig hardness of at least 40 seconds (preferably within the range of 60 to 200 seconds) and the polymer composition has a minimum film-forming temperature of 55 ° C (preferably within the range of 0 to 30 ° C). An aqueous polymer composition is also provided, which can be formed by a method described above. In addition, the use of an aqueous polymer composition, as defined above, is provided in coating applications, and in particular in the protective coating of substrates such as wood, plastic, metal and paper. The prior art describes a number of processes, in which an aqueous emulsion in a polymer system containing a hydrophilic polymer of Low molecular weight and a hydrophobic emulsion polymer has been produced by a multi-step process and wherein (usually) the hydrophilic oligomer has been solubilized in the aqueous medium. US 4,151,143 calls for the production of surfactant-free emulsion polymer coating compositions using a process involving, (1) a first step wherein the carboxyl-functional polymer prepared from the organic solution is dispersed / solubilized in water by neutralization, Y (2) a second stage, wherein a mixture of polymerizable monomers is subjected to emulsion polymerization. The polymer of the first stage may be of relatively low molecular weight, the polymer of the first and / or second stage is optionally hydroxy-functional, and the emulsion may be optionally mixed with an interlayer of the amino type, such as hexametoxymethylmelamine. US 4,894,394 refers to the production of an inverted core / shell latex by (1) the preparation of a hydrophilic low molecular weight first stage polymer by aqueous emulsion polymerization; (2) conducting a second emulsion polymerization to produce a second hydrophobic step; and (3) the pH adjustment of the resulting core / shell emulsion to dissolve the first stage. The monomers of the first and Second stage may optionally include hydroxyalkyl methacrylates and glycidyl methacrylate although not much emphasis is given. US 4,845,149 relates to an emulsion polymer preparation (useful as a pressure sensitive adhesive) by the polymerization of monomer emulsion in the presence of an aqueous solution or dispersion of a carboxyl-functional support polymer (low molecular weight) ). US 4,904,724 (= EP 320865) discloses that a polymer system of organic solvent solution (a mixture of acid-functional and acid-free polymers) is dispersed in water with neutralization and used as the seed for polymerization of an aqueous emulsion. The solution polymers can be carbonyl-functional, in which case an interlayer such as polyhydrazide is added. CA 2,066,988 (_ = DE 4,113,839) refers to the free polymerization of emulsifier, polymerizing the ethylenic monomers, (A) in an aqueous medium containing a neutralized acid-containing polymer, (B) (preferably a water-soluble styrene / acrylic acid copolymer with a molecular weight of 1,000-5,000). The monomers of (A) are fed to the aqueous medium during the polymerization and monomers may be optionally included functional amino or glycidyl, although entanglement per se is not mentioned. EP 0,522,791 refers to redispersible polymer powders prepared by a sequential polymerization process of two-step aqueous emulsion, to make an emulsion of core / shell polymers, followed by optional spray drying. In the first step, a carboxy-functional, low molecular weight polymer, which may optionally include up to 30% hydroxyalkyl methacrylate, is polymerized in an aqueous emulsion to form the shell part; this is neutralized, and in the second step, the monomers, which again may optionally include up to 30% hydroxyalkyl ester, are polymerized to form the core part, and the aqueous core / shell polymer emulsion is optionally converted, by drying by spray to a redispersible polymer powder. The core and the shell are preferably grafted together in the emulsion by the use of polyfunctional compounds, such as halyl methacrylate. The description remains silent with respect to the use of an interlacing agent to effect healing after any coating formation. EP 0,587,333 is directed to aqueous emulsions of multistage polymer resistant to water which has an alkali-insoluble polymer and an alkali-soluble dissolved oligomer, functional to the acid. These are made by sequential aqueous emulsion polymerization of a monomer system for the oligomer, including an acid functional monomer and optionally a polyfunctional compound, followed by that of a monomer system for the alkali insoluble polymer optionally including an amino acid monomer. functional. The purpose of the polyfunctional compound, or the amine functionality of the alkali-insoluble polymer is to cause a physical or chemical interaction between the alkali-soluble oligomer and the alkali-insoluble polymer, while they are present in the emulsion, for example, by grafting the two together phases while the final emulsion is formed. In addition, the aqueous emulsion may incorporate metal ions such as that of Zn, Mg and Ca, in order to create metal / carboxylate entanglements, which could occur after the formation of the coating from the emulsion. The alkali-soluble oligomer is solubilized in the emulsion either by neutralizing it with a base after completing both polymerization steps or, less preferably, neutralizing it with a base before the start of the polymerization of the second stage to form the alkali-insoluble polymer. None of the descriptions mentioned above teaches a procedure that has the selected combination of aspects and integrates as defined in the process of the invention, which are used to produce a composition suitable for the coating, having such advantageous combination of properties as described above. The process of the invention results in an aqueous composition that provides a high hardness polymeric coating (as defined) on substrates such as wood, plastic, metal and paper, the aqueous composition having a low MFFT (as defined). It also obtains coatings with a good resistance to solvent and water. The process by itself is free of organic solvent, as is the resulting aqueous polymer composition. The composition also has good storage stability. In particular, the process of the present invention allows the production of compositions, which at least for the most part have an exceptionally advantageous equilibrium of MFFT and Koenig hardness, where an unusually high Koenig hardness is obtained for the particular value of MFFT of the composition. This is more surprising since the achievement of the MFFT low and the high hardness in a composition could normally work between them, that is, if the composition has a very low MFFT, it will tend not to have a particularly high hardness, or a hardness too high for the composition that will not go relative to the relatively high MFFT. Being aqueous based, the lower limit of the MFFT for the compositions of the invention will, of course, be the freezing point of the aqueous vehicle phase. This will usually be about 0 ° C (maybe slightly lower due to any dissolved constituent although not usually below -2 ° C). Therefore, the MFFT scale for the compositions of the invention will usually be from about 0 to 55 ° C, preferably from 0 to 30 ° C. The Koenig hardness will be = 40 sec., And more usually on the scale of 60 to 200 sec. As discussed above, a particularly advantageous aspect is that, for most (if not all) of the compositions of the invention, the combination of MFFT and Koenig hardness is surprising and exceptionally advantageous. In fact, it has been found that most of the compositions of the invention conform to the following empirical equation in terms of the MFFT ratio and the Koenig hardness, where H represents the Koenig hardness (in seconds) and T represents MFFT (in ° C): H > 1.5T + 70 So, for example, when T = 5 ° C, H is > 70 seconds; when T is 10 ° C, H is > 77.5 seconds; when T is 10 ° C, H is > 85 ° C second; when T is 20 ° C H is > 100 ° C, when T is 40 ° C, H is > 130 ° C and so on. Furthermore, in many of the compositions of the invention, although not all, the combination of MFFT and Koenig hardness is much more advantageous than that suggested above and conforms to the empirical relationship: H > 1.5T + 90 So, for example, when T is 0 ° C, H is > 90 seconds; when T is 10 ° C, H is > 105 seconds; when T is 40 ° C, H is > 150 seconds and so on. Not all the yields of the compositions for the process of the invention satisfy one or both of the empirical equations, but the majority do so, as illustrated for the examples (see below) The solubilization of the oligomer is carried out before carrying out the polymerization step b). Solubilization subsequent to polymerization to form the hydrophobic polymer, the preferred technique in the process of EP 0,587,333, could incur a poor MFFT / Koenig hardness equilibrium compared to the solubilization before making the hydrophobic polymer. By performing the grafting (or pre-interlacing) during the formation of the emulsion composition as described in EP 0,587,333, it could probably result in a lower balance MFFT and Koenig hardness compared to effecting covalent entanglement after coating formation, as is achieved with the compositions of the invention. Furthermore, by providing an ionic entanglement after coating formation, also as described in EP 0 587,333, the advantageous balance of MFFT and Koenig hardness could be decreased as is achieved by the process of the present invention. The process of the invention, including the step to make the oligomer, is free of organic solvent as is the resulting polymer composition. Since solvent-free usually means totally solvent-free, it will be appreciated that from a practical point of view, it can sometimes be difficult to exclude very small amounts of organic solvents, which otherwise could have no material effect on the process or composition. , for example, when a small amount of a commercially obtained additive is incorporated, which can be carried in a vehicle that is at least partially an organic solvent. Therefore, free of organic solvent is also intended to be extended to substantially free of organic solvent. In step a) of the process, an aqueous solution of an oligomer with an Mn of 500 to 50,000 is formed and developed from the polymerization of monomers olefinically unsaturated. The polymerization technique employed, which is free of organic solvent, may initially be a polymerization process of aqueous solution to directly produce an aqueous solution of the oligomer, but is more usually a conventional aqueous emulsion polymerization process to form a emulsion or aqueous polymer latex. The procedure is extremely well known and does not need to be described in great detail. Suffice it to say that the process involves dispersing the monomer in an aqueous medium and conducting the polymerization using a free radical initiator (normally water soluble) and (usually) appropriate heating (for example 30 to 120 ° C) and employing stirring ( waving). The aqueous emulsion polymerization can be carried out with conventional de-emulsification agents (surfactants) being used for example in anionic and / or nonionic emulsifiers such as salts of Na, K and NH4 of alkyl sulfosuccinates, salts of Na, K and NH4 of sulphated oils, salts of Na, K and NH4 of alkylsulfonic acids, alkyl sulfates of Na, K and NH4 such as sodium lauryl sulfate, alkali metal salts of sulfonic acids C12_24 »fatty acids of ethoxylated and / or amino-fats, salts of Na, K and NH4 of fatty acids such as sodium stearate and sodium oleate; aryl-containing analogs of the alkyl-containing surfactants they are also useful; other surfactants include phosphate. The amount used is preferably low, preferably from 0.3 to 2% by weight, usually from 0.3 to 1% by weight based on the weight of total monomer charged. The polymerization can employ conventional free radical initiators, for example, hydrogen peroxide, t-butyl hydroperoxide, eumenal hydroperoxide, per sulfates, such as NH 4 persulfates, potassium per sulfate and sodium persulfate; you can use redox systems; combinations such as t-butyl hydroperoxide, isoascorbic acid and iron EDTA are useful; the amount of the initiator, with initiator system, is generally 0.05 to 3% based on the weight of the total charged monomers.

[It will be appreciated that it is not necessary to use the entire amount of the oligomer prepared from the polymerization, or an aqueous solution of this total amount, for the aqueous oligomer solution which is specified in two steps a) and b) of the process of the invention (although it may be if desired); only a portion of these may be necessary for the purposes of steps a) and b)]. The emulsion polymerization process when used for step a) can be carried out using an "all-in-one" intermittent process (i.e., a process wherein all the components to be employed are present in the medium of polymerization at beginning of the polymerization), or a semi-intermittent process, wherein one or more of the components used (usually at least one of the monomers) is fully or partially fed to the polymerization medium during the polymerization. Although it is not preferred, totally continuous procedures can also be used in principle. The polymerization technique employed must, of course, be that of a low molecular weight polymer (as defined) that has been formed, for example by using a chain transfer agent such as one selected from mercaptans (thiols) certain halohydrocarbons and -typical styrene, since it is absolutely conventional. By an aqueous solution of the functional acid oligomer, it can be understood herein that the oligomer is completely or substantially dissolved in the aqueous medium, so that it is present as a true solution. However, the term also extends (less preferably) to the oligomer that exists as a dispersion in the aqueous medium (the term "water-soluble" being similarly constructed). In such a case, the polymer dispersion is in particular a colloidal dispersion of the polymer particles (as in an emulsion or polymer latex). Sometimes, of course, the distinction between colloidal dispersions and true solutions is difficult to distinguish, an intermediate situation of these are established existing or some of the polymer can be dispersed in the aqueous medium and something can be dissolved. In this way, the term "aqueous solution" is also intended to encompass a disposition of the oligomer in an aqueous medium corresponding to said intermediate states. Preferably, the acid-functional oligomer contains a sufficient concentration of acid functionality to render the polymer partially or preferably completely soluble in aqueous media, if necessary by neutralization of the polymer acid groups, as could be achieved by adjusting the pH of the aqueous medium. (If the acid-functional oligomer only has sufficient acid functionality to make it partially soluble in the aqueous medium of the emulsion, it can exist as a colloidal or intermediate dispersion between a colloidal dispersion and a true solution or it can be partially dispersed and partially dissolved). In general, the medium in which the oligomer is found by itself will be acidic (pH < 7), and the acid groups will be carboxyl groups so that the solution will be effected by increasing the pH of the medium (usually the polymerization medium). aqueous wherein the oligomer has been prepared), in order to neutralize the acid groups by the addition of a base, such as an organic or inorganic base, examples of which include organic amines such as trialkylamines (for example triethylamine, tributylamine), morpholine and alkanolamines, and inorganic bases such as ammonia, NaOH, KOH, and LiOH. Of course, the aqueous medium containing the acid-functional oligomer can already be alkaline (or sufficiently alkaline), so that the acid groups (such as the carboxyl groups) are neutralized without the requirement of adding a base positively to increase the pH, or the acid groups can be or include very strong acid groups such as sulfonic acid groups (pK 1 to 2), so that neutralization may not be necessary to achieve dissolution. In addition, it is possible that the acid monomers are polymerized in salt form instead of free acid. The aqueous emulsion polymerization of step b) produces a hydrophilic emulsion polymer, this type of polymer being well understood by those skilled in the art. Generally speaking, it can be considered at present as a water-insoluble polymer whose insolubility in water is maintained across the entire pH scale. The hydrophobic nature of the polymer is achieved by virtue of the polymer containing a sufficient amount of at least one hydrophilic monomer (i.e., in polymerized form) to render the polymer hydrophobic and insoluble in water across the entire pH scale. Therefore, the emulsion polymer formed in the emulsion process from step b), it is insoluble in the aqueous medium of said polymerization process without considering any adjustment in the pH at which the medium can be subjected. The monomer system used for the preparation of the acid-functional oligomer is any suitable combination of olefinically unsaturated monomers, which has been subjected to copolymerization providing a monomer system that includes a comonomer carrying an acid (preferably in a sufficient concentration to make to the resulting polymer totally or partially soluble in the aqueous media as discussed above), or a comonomer carrying an acid-forming group which produces, or subsequently converts to, said acid group (such as an anhydride, for example methacrylic anhydride or maleic anhydride, or acid chloride), and also with comonomer or comonomers that impart interlacing capacity. Typically, the acid-carrying comonomers are carboxyl-functional acrylic monomers or other ethylenically unsaturated carboxyl-bearing monomers, such as acrylic acid, methacrylic acid, itaconic acid and fumaric acid. It is also possible to use monomers containing sulfonic acid, for example, such as styrene-p-sulfonic acid or correspondingly styrene-p-sulfonyl chloride). A monomer carrying an acid can be polymerized as the free acid or as a salt, by example, the alkaline mental salts of NH 4 of ethylmetacrylate-2-sulfonic acid or 2-acrylamido-2-methylpropanesulfonic acid, or the corresponding free acids. Other non-functional, non-functional, non-crosslinking monomers that can be copolymerized with the acidic monomer include acrylate and methacrylate esters and styrenes; also dienes such as 1,3-butadiene and isoprene, vinyl esters such as vinyl acetate and vinyl alkanoates. The methacrylates include normal or branched acrylic esters of Cl to C12 alcohols and methacrylic acids, such as methyl methacrylate, ethyl methacrylate, and N-butyl methacrylate, and cycloalkyl methacrylates (usually from C5 to C12) such as methacrylate. isobornyl and cyclohexyl methacrylate. Acrylates include normal and branched acrylic esters of Cl to C12 alcohols and acrylic acid, such as methyl acrylate, ethyl acrylate, N-butyl acrylate and 2-ethylhexyl acrylate, and cycloalkyl acrylates (usually from C5 to C12) , such as isobornyl acrylate and cyclohexyl acrylate The styrenes include the same styrene and the various substituted styrenes, such as Qf-methylstyrene and t-butylstyrene The nitriles such as acrylonitrile and methacrylonitrile can also be polymerized, as well as the halides olefinically unsaturated such as vinyl chloride, chloride vinylidene and vinyl fluoride. Functional monomers imparting interlacing capacity (short entanglement monomers) include epoxy (usually glycidyl) and hydroxyalkyl methacrylates and acrylates (usually Cl to C12 hydroxyethyl), as well as keto functional monomers and aldehydes such as acrolein, methacrolein and vinyl methyl ketone, acetoacetoxy esters of hydroxyalkyl acrylates and methacrylates (usually Cl to C12) such as methacrylate and acetoxyethyl acrylate, and also keto containing amides such as diacetone acrylamide. The purpose of using said functional monomers provides a subsequent entanglement capacity in the resulting polymer system as discussed. (In principle, the functional monomer used to impart the entanglement capacity may be a monomer carrying an acid, but this is not usual). Typically, the acid-functional oligomer is derived from a monomer system containing 1-45% by weight of comonomer or acid comonomers, preferably 3-30% by weight and more preferably 3-20% by weight; from 0.5 to 20% by weight, preferably from 1 to 15% by weight and particularly from 1 to 10% by weight of interlacing monomer or monomers; and 98.5-50% by weight of comonomer or comonomers without crosslinking and without functional acid, preferably 96-65% by weight, and more preferably of 96-75% by weight. He Comonomer or comonomers without interlacing, without acid-functional in some cases, it is useful to select them from one or more of methyl methacrylate, styrene, ethyl acrylate, n-butyl methacrylate, and n-butyl acrylate, while the monomer of Acid is for example metracrylic acid and / or acrylic acid. Useful oligomers of this type are derived from a monomer system containing 3-12% by weight of methacrylic acid and / or acrylic acid, from 1 to 10% by weight of diacetone-acrylamide and / or acetoacetoxyethyl methacrylate, and is 50-90% by weight of methyl methacrylate, 0-30% by weight of acrylate of one or more of ethyl acrylate, n-butyl methacrylate and n-butyl methacrylate and 0-40% by weight of styrene. The oligomer of step a) must have a number average molecular weight within the range of 500-50,000, preferably 2,000-25,000 and particularly 3,000-19,000. (The molecular weights of the polymer can be determined by gel permeation chromatography calibrated using a known polymer as appropriate as a standard). The Tg of the oligomer may be in the range of 10 to 125 ° C, more preferably 50 to 125 ° C, and particularly 70 to 125 ° C. The aqueous emulsion polymerization process employed in step b) to form the hydrophobic polymer can be, in addition to the incorporation of the functional acid oligomer of step a), that of a conventional aqueous emulsion polymerization process and basically as described above when discussing the use of the process for the preparation of the acid-functional oligomer. However, a preferred important aspect of the invention is that it is usually possible to eliminate or minimize the requirement for the addition of a surfactant to act as an emulsifier in the polymerization of step b), since the acid-functional oligomer by itself, it can cover this function (that is, act as an emulsifying agent). In this way, the aqueous emulsion resulting from step b) preferably contains a very low level of such added emulsifier (not counting the same oligomer), being usually used with less than 0.5% (preferably less 0.25%, and usually 0) based on the total weight of charged monomers and with the only surfactant present being preferably one remaining from the polymerization of the oligomer (without the same oligomer). In fact, the total level of surfactant (not counting the same oligomer) is preferably < 1%, more preferably < 0.5%, particularly < 0.35%, based on the total weight of charged monomers for the hydrophobic polymer. The monomer system used for the formation of the hydrophobic polymer must be such that the polymer resulting hydrophobic, as described. It is possible to use monomers without interlacing, without functional acid similar to those used to make the oligomer, and in particular styrenes, such as the same styrene, α-methylstyrene, o-, m- and p-methylstyrene, o-, m- and p -ethylstyrene, p-chlorostyrene and p-bromostyrene; normal and branched acrylic and metracrylic esters of alkanols (usually 1-12C) and cycloalkanols (usually C5-C12) such as methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, t-butyl methacrylate, 2-ethylhexyl methacrylate , isobornyl methacrylate and cyclohexyl methacrylate and the corresponding acrylates; vinyl esters such as vinyl acetate and vinyl alkanoates; vinyl halides such as vinyl chloride, vinylidenehalides such as vinylidene chloride; dienes such as 1,3-butadiene and isoprene, but, of course, their selection must be such as to provide a Tg that is resultant of at least 25 ° C above that of the oligomer. A functional monomer or monomers for imparting entanglement capacity (which is not normally an acid monomer) can optionally be included, examples of which include hydroxy and epoxy functional methacrylates such as hydroxyalkyl methacrylate (usually C1-C12), for example, 2-hydroxyethyl methacrylate, glycidyl methacrylate and the acrylates corresponding, as well as functional keto and aldehyde monomers such as acrolein, methacrolein and methyl vinyl ketone, acetoacetoxy esters of hydroxyalkyl acrylates and methacrylates (usually C1-C12) such as acetoacetoxyethyl acrylate and methacrylate, and also amides containing keto or aldehyde, such as diacetone-acrylamide. Functional acid monomers may also be included as comonomers (eg, acrylic or methacrylic acid), although at that level (depending on their nature) in order not to affect the hydrophobic chara of the resulting polymer. Generally speaking, the monomer system used to be the hydrophobic polymer will usually contain less than 5% by weight of any acidic functional monomer or monomers (regardless of what type), and preferably less than 2% by weight, and in some preferred embodiments nothing . The hydrophobic polymer is in some cases usually made of a monomer system comprising at least an alkyl methacrylate of 1-10 (such as n-butyl methacrylate), and C3_10 alkyl acrylate (such as n-acrylate). butyl), and usually diacetone-acrylamide and / or acetoacetoxyethyl methacrylate. The polymerization to make the hydrophobic polymer should be carried out using a chain transfer, but (different in the preparation of the oligomer) is usually effe without the use of such material. The number average molecular weight of the hydrophobic polymer is usually 50,000, more usually > 100,000 The upper limit does not usually exceed 5,000,000. The Tg of the hydrophobic polymer must be at least 25 ° C above, more preferably at least 40 ° C above the Tg of the oligomer. Usually, the Tg of the hydrophobic polymer will be within the range of -20 ° C to 50 ° C, more usually from 0 ° C to 40 ° C. The aqueous solution of the oligomer of step a) is present during the emulsion polymerization of step b) to make the polymer hydrophobic. The presence of the oligomer in the polymerization of step b) can be carried out in several ways, with the following being an example. In one embodiment, the aqueous solution of the oligomer is mixed with all the monomers to be used in the formation of the hydrophobic polymer and, on the other hand, a conventional "all at once" intermittent polymerization. (without any further addition of monomer or monomers) is carried out to be the latter. In another embodiment, the polymerization is basically still a batch, with all the oligomer solution being present in the polymerization vessel prior to starting the polymerization with some of the monomer system for the hydrophobic polymer, with the remainder of the monomer system for the hydrophobic oligomer being rapidly added in a single addition after the polymerization has begun. In a further embodiment, the polymerization is still basically a batch, with all the oligomer solution being present in the polymerization vessel before the start of the polymerization, but the monomer system for the hydrophobic polymer is now divided into several equal parts ( lots). These parts are added and polymerized consecutively with one another, in order to obtain more control over the polymerization; therefore, this is effectively a polyintermitting method. In other embodiments, semi-intermittent procedures are employed wherein part of (or none) of the monomer system for the hydrophobic polymer is present prior to the start of the polymerization in the polymerization reaction vessel and part (or the entire amount) is fed to the reaction medium in the polymerization vessel during the course of the polymerization. In such an embodiment, the aqueous oligomer solution is present (in part) in the reaction medium for the polymerization, while part of the aqueous solution of the The oligomer is mixed with the entire monomer system for the hydrophobic polymer (acting as an emulsifier) and the latter fed into the reaction medium in the polymerization vessel during the polymerization. In another embodiment, all of the oligomer solution is present in the reaction vessel prior to the start of polymerization and the entire monomer system for the hydrophobic polymer is fed to the vessel during the polymerization, i.e. there is no longer any oligomer present in the polymerization. the monomer feed. In a further embodiment, all of the aqueous oligomer solution is present in the reaction vessel before the start of the polymerization together with a part of the monomer system for the hydrophobic polymer, and the remainder of the monomer system is fed during the polymerization ( that is, without oligomer in the feed). In a further embodiment, part of the oligomer solution is present in the reaction vessel before the start of the polymerization together with a part of the monomer system for the hydrophobic polymer, and the remainder of the monomer system is mixed with the remainder of the monomer system. the oligomer solution being fed during the polymerization. In at least some of the embodiments of the invention, it is believed that the aqueous emulsion produced after formation of the hydrophobic polymer may be in the form of a "core / inverted shell" latex, in which the hydrophobic polymer has formed a core domain in the oligomer, the oligomer encapsulating the particles of the hydrophobic polymer by forming a shell around them, or carrying in the particles of hydrophobic polymer in its swollen matrix. Alternatively, it may be more real to speak of the oligomer simply in terms of being a seed for the polymerization process to form the hydrophobic polymer, without considering the actual structure of the resulting polymer system that is produced, of which it is not completely known. Accordingly, it has not been desired to join by any physical structure that can be assumed or proposed for the aqueous latex resulting from the polymer system of the invention. Preferably, the amount of crosslinking agent in step c) that is employed is such that the reaction of the number of crosslinking groups present in the oligomer and (if employed) in the hydrophobic polymer to the number of reactive groups (for purposes of interlacing) in the entanglement agent is within the range of 10/1 to 1/3, preferably 2/1 to 1 / 1.5. The interleaver in step c) is usually combined with the aqueous emulsion of step b) by adding thereto after the polymerization of step b) (sometimes just before use of the composition) although initially it can also be combined by carrying out the polymerization of step b) in the presence of an entanglement agent, that is, steps c) and b) are combined. Also, in principle, you can. use a combination of both incorporation records. It is a preferred aspect of the invention that the low molecular weight of the oligomer produced in step a) is achieved using a method that is different from that known in the art as catalytic chain transfer polymerization, the use of which is not usual in the process of this invention, although in principle it can be used. This process is one in which a low molecular weight polymer is produced using the radical polymerization technique, using a free radical initiator, in which the molecular weight is controlled using a catalytic amount of a transition metal complex, and in particularly a cobalt chelate complex, this technique being known in the art as a catalytic chain transfer polymerization (CCP). Such a technique has been fully described in the literature within the last decade. For example, several references in the literature such as N.S.Eni olopyan et al, J. Polym, Sci., Polym. Chem. Ed., Vol. 19, 879 (1981), describe the use of cobalt II porphyrin complexes as chain transfer agents in radical polymerization. free, while US 4526945 describes the use of cobalt II dioxime complexes for such purpose. Several other publications, for example US 4680354, EP-A-0196783 and EP-A-0199436, describe the use of other types of cobalt II chelates as chain transfer agents for the production of oligomers of olefinically unsaturated monomers by polymerization of free radical. WO-A-87/03605, on the other hand, claims the use of certain cobalt III chelate complexes for such a purpose, as well as the use of certain chelate complexes of other metals such as iridium and rhenium. Finally, co-pending application PCT / GB94 / 01692 (publication OA-95/04767, published on 16-2-95) describes a process for the preparation of an aqueous polymer emulsion, which in one embodiment comprises a) preparing an aqueous solution of a functional acid oligomer using a CCT polymerization process; and b) conducting an aqueous emulsion polymerization to form a hydrophobic polymer in the presence of the oligomer solution. Both the oligomer and the hydrophobic polymer may optionally include crosslinker groups and the composition may optionally include an entanglement agent. The description does not describe or teach a method having the selection of aspects and members as defined in the method of the invention. In particular, none of the compositions of the example include an oligomer with crosslinker groups, and none have oligomers with Tg within the range of 10-125 ° C and which are also at least 25 ° C higher than the Tg of the hydrophobic polymer. It will be appreciated that the oligomer and optionally the hydrophobic polymer possess functional groups for imparting latent entanglement capability to the composition (ie, so that entanglement takes place for example after the formation of a coating therefor), when combines with the entanglement agent in step c). For example, one or both polymers can carry functional groups such as hydroxyl groups and the composition subsequently formulated in step c) with an entanglement agent such as a polyisocyanate, melamine, or glycoluril; or the functional groups on one or both polymers can include keto or aldehyde-carbonyl groups and the interleaver subsequently formulated in step c) can be a polyamine or polyhydrazide such as adipic acid dihydrazide, oxalic acid dihydrazide, phthalic acid dihydrazide, terephthalic acid dihydrazide, isophorone diamine and 4,7-dioxadecane-1, 10 diamine. It will be observed that such entanglement agents affect the entanglement with the functional crosslinking groups of the oligomer and also of the hydrophobic polymer if present, by virtue of the formation of bonds covalent, and are not entanglement agents that could affect entanglement by virtue of the formation of nonionic bonds, as for example by the addition of metal ions to react with the carboxylate ions attached to the polymer. The minimum temperature of film formation (MFFT) of a composition, as used herein, is the temperature at which the composition forms a smooth and crack-free coating or film using DIN 53787 and applied using Sheen MFFT bar SS3000 copies. Koenig hardness as used herein, is a normal measure of hardness, being a determination of how the viscoelastic properties of a film formed from the composition reduce a deformation of tilting motion of the film surface, and it is measured in accordance with DIN 53157 NEN 5319. As is well known, the vitreous transmission temperature of a polymer is the temperature at which it changes from a brittle, vitreous state to a plastic, elastic state. The solids content of an aqueous composition of the invention is usually within the range of about 20 to 65% by weight based on the total basis weight, more usually 30 to 55% by weight. The content of solids it can be, if desired, adjusted by adding water or stirring water (for example by distillation or ultrafiltration). The relative amounts of the oligomer and the hydrophobic polymer in the aqueous polymer composition are preferably such that the weight percentage of the oligomer, based on the weight of the oligomer plus the hydrophobic polymer in the polymer composition, is preferably within the range of 1. to 70% by weight, more preferably from 5 to 50% by weight. The aqueous compositions of the invention can be used in various applications and for such purposes can be optionally combined additionally or formulated with other additives or components, such as defoamers, rheology control agents, thickeners, dispersing agents and stabilizers (usually surfactants) ), wetting agents, fillers, extenders, fungicides, bactericide, coalescence solvents and humectants (although solvents are not normally required), plasticizing agents, antifreeze agents, waxes and pigments. The aqueous compositions can be used, for example, appropriately formulated if necessary for the provision of films, polishes, varnishes, lacquers, paints, inks and adhesives. However, they are particularly useful and adequate to provide the basis for protective coating for wooden substrates (eg wood floors), and substrates made of plastics, paper and metal. The compositions once applied can be allowed to dry naturally at room temperature, or the drying process can be accelerated by heating. The entanglement can be developed allowing to be at rest for a prolonged period at room temperature (several days) or by heating to an elevated temperature (eg 50 ° C) for a much shorter period of time. The present invention will now be illustrated, but not in a limiting manner, by reference to the following examples. Unless otherwise specified, all parts, percentages and relationships are a basis in weight. The prefix C before an example indicates that it is comparative. The glass transition temperatures of the oligomers in the examples where the experimentally determined values in ° C use DSC differential scanning calorimetry, taking the peak of the derivative curve as Tg, or calculated from the Fox equation (as for the hydrophobic polymers , See later) . Sometimes, both methods are used and in such cases the values obtained were identical.

The glass transition temperatures of the hydrophobic polymers in the examples were calculated in terms of the Fox equation. In this way the Tg, in degrees Kelvin, of a copolymer having copolymerized "n" comonomer is given by the fractions by weight W of each type of comonomer and the Tg of the oligopolymers (in degrees Kelvin) derived from each comonomer according to the equation: i - Hi + í? 2 + wn Tg Tg? Tg2 Tgn The Tg calculated in Kelvin can easily be converted to ° C. (If the hydrophobic polymer is a homopolymer, its Tg is simply that of the polymerized monomer, usually available from the literature). In two cases the TGs of the hydrophobic polymers were measured by DSC as well as being calculated; the values obtained were virtually identical. The following abbreviations are used in the examples MMA = methyl methacrylate ADAM = diacetone-acrylamide AAEM = methacrylate acetoacetoxyethyl MAA = methacrylic acid EA ethyl acrylate AP ammonium persulfate TM total monomer S / S solid / solids 3MPA 3-mercaptopropionic acid (chain transfer agent) LMKT dodecyl mercaptan (chain transfer agent) SA stoichiometric amount FM monomer content free dispersion disability (Mn / Mw when Mw = to weight average weight weight) BMA n-butyl methacrylate BA n-butyl acrylate S styrene DMEA dimethylethanolamine t-BHPO tert-butyl hydroperoxide 20 EDTA ethylenediamine tetraacetic acid ADH = adipic acid dihydrazide ALMA allyl methacrylate 25 RT room temperature A typical formulation and methods for the preparation of an aqueous solution of an acidic functional oligomer for use in the process of the invention is as follows: Formulation for the OLI olymeromer Composition EA / MMA / DAAM / MAA = 12.08 / 73.32 / 8 / 6.6 Surfagene FAZ 109 V (phosphate emulsifying agent): 0.5% in TM (s / s). 25% in the reactor; 75% in food. AP: 0.3% in TM (s / s). Added as a separate feed during polymerization of the emulsion (feed solids is 1.5% in demineralized water). LMKT: 4.5% in TM. NaHCO3: 0.3% in TM. 67% in the reactor; 33% in food. Neutralization: 2 SA NH3. Solids of the neutralized solution: 27%.

Lamina and procedure for the preparation of the OLÍ oligomer Load 1,2 and 4 to the reactor. Heat the batch to 70 ° C and add 5% of the pre-emulsified feed 5-12. Heat the batch to 80 ° C, add 30% of 3 and wait 5 minutes. Start feeding the pre-emulsified feed 5-12 and the feed of initiator 3. The reaction temperature is 85 ± 2 ° C. The monomer feed should take 60 minutes; Initiator feeding should take 70 minutes. Rinse the feed tank with 15. Maintain the batch at 85-90 ° C for another 30 minutes after the feed has been completed. The oligomer dispersion is a white, low viscosity product. Cool to 80 ° C and add the solution of 13 and 14 slowly. Keep at 80 ° C for another 30 minutes. The oligomer dispersion will slowly change to a transparent, low viscosity solution. Cool to 25 ° C.

Specifications Solids 27-28% PH 10 viscosity (mPas @ 25 ° C) 150 sediment before sieving (%) < 0.2 sediment after sieving (%) 0.05-0.1 FM (ppm) < 100 ppm (typical values: <10 ppm EA, 35 ppm MMA, 115 ppm MAA Tg (DSC) (° C): 75 ° C Mn: 4100 d: 2.3-2.4 Example 1 A typical formulation and methods for the preparation of a composition of the invention, by the "pre-emulsified feeding method" is as follows. Formulation: Composition: Part of oligomer: (see above for OLI) Part of polymer: BMA / BA / DAAM = 74.1 / 22.9 / 3 Tg (part of polymer, calculated) (° C): 2.0 01igomer / Polymer (s / s ): 60/100 (= 37.5 / 62.5) 40% of the oligomer used in the reactor: 60% of the oligomer used to emulsify the monomer feed. AP: 0.3% in TM (s / s). Added as a separate feed (2.5% -of solids). 0.2% in TM in the reactor. Solids: 37% '_ = * - Lamina and procedure for the composition of Example 1 Load 1-3 to the reactor. Load 4 and 8 into the feed tank. Mix for 5 minutes. Add a mixture of 5 5-7 and 9 to the stirred solution of 4 and 8. Emulsify the feed. Add 10% of the pre-emulsified feed to the reactor. Heat the reactor to 85 ± 2 ° C. Start feeding the pre-emulsified feed in 90 minutes to the reactor. The initiator feed 10 and 11 10 should take 100 minutes. Rinse the feed tank with 12. Hold the batch at 85 ± 2 ° C for 30 minutes. Cool to 40-45 ° C. Add 13.1 g of ADH (solid) to the dispersion (0.9 SA). Rinse with 20 g of demineralized water. Keep the batch at 40-45 ° C for 30 minutes. Cool to room temperature.

Specifications Solids (%): 37-37.5% pH: 9.5 Viscosity (mPas @ 25 ° C): 50 sediment before sieving (%): < 0.2 sediment after sieving (%): 0.05-0.1 FM (ppm): < 300 ppm (typical values) < 10 ppm EA, < 25 ppm MMA, < 125 ppm BA, < 200 ppm BMA MFFT (° C): 4 Koening hardness: 76 sec.

Example 2 Formulation Composition: Part of Oligomer: (see previous for OLI) Part of Polymer: BMA / BA / DAAM = 74.1 / 22.9 / 3.

Tg (part of polymer, calculated) (° C): 0 Oligomer / Polymer (s / s): 100/100 All the oligomer in the AP reactor: 0.5% in TM (s / s); 40% in the reactor, 60% as a separate feed (2.5% solids in demineralized water). Solids: 37% Sheet and procedure for the composition of example 2 Charge 1 to the reactor and dissolve 3. Add 2. Charge 10% of monomers 4-6 to the reactor. Heat the batch to 85 ± 2 ° C. Start feeding the monomers 4-6 and feeding the initiator (8 dissolved in 7). The monomer feed should take 60 minutes, feeding the Initiator should take 70 minutes. Rinse with 9. Keep the batch at 85 ± 2 ° C for one hour. Cool to 40 ± 2 ° C. Add a solution of 11.55 g of dissolved ADH in 103.97 g of demineralized water (0.7 SA). Maintain the batch at 40 ± 2 ° C for 30 minutes.

Specifications .

Solids: 37-37.5% pH: 9.5 Viscosity (mPas @ 25 ° C): 60 sediment before sieving (%): 0.2 sediment after sieving (%): 0.1-0.2 FM (%): < 0.2 MFFT (° C). : 0 Koenig hardness: 96 sec.

Example 3 A typical formulation and procedures for the preparation of a composition of the invention by an "intermittent method" is as follows: Formulation. Composition: Part of Oligomer: (see above for OLI) Part of Polymer: BMA / BA / DAAM = 74.1 / 22.9 / 3 Tg (part of polymer, calculated) (° C): 0 Oligomer / Polymer (s / s): 60/100 All the oligomer in the reactor Initiation system: 0.26% t-BHPO in TM (s / s) in the reactor 0.05% i-ascorbic acid in TM (s / s) in the reactor 5.07% FeEDTA in t-BHPO (s / s) in the reactor 0.21% i-ascorbic acid in TM (s / s) fed to the reactor Solids: 35% Lamina and procedure for the composition of Example 3.

* Made from FeSO, EDTA, NaOH and water. Load 1 and 2 into the reactor. Mix during minutes. Add 3-6 to the reactor. Add 7 followed by 8. Heat the batch to 35 ° C. Keep the batch at this temperature for 1 hour. Add 9. The temperature will increase to Approximately 57 ° C. Maintain the peak temperature during minutes. Start feeding 10. The feeding should take 30 minutes. Let the temperature move.

Keep the batch at the reaction temperature for 15 minutes. Cool to 35 ° C. Add 11-14 to the reactor, followed by 15, 16 and 17. Keep the batch at 35 ° C for 1 hour.

Add 18. The temperature will increase to approximately 42 ° C. Maintain the batch at the peak temperature during minutes. Start the feed 19. The feed should take 30 minutes. Let the temperature move.

Cool to 40 ± 2 ° C. Add 12.53 g ADH to the dispersion (0.9 SA). Rinse with 10 g of demineralized water. Maintain the batch at 40 ± 2 ° C for 30 minutes. Cool to room temperature.

Specifications . Solids: 35-35.5% pH: 9.5 Viscosity (mPas @ 25 ° C): 80 Sediment before sieving (%): < 0.2 Sediment after sieving (%): 0.05-0.1 FM (%): < 0.2 MFFT (° C): 10 Koenig Hardness: 84 sec An additional 0L2 acid functional oligomer was prepared in the aqueous solution, as follows.

Formulation for Oligomer 0L2 Composition. MMA / MAA / DAAM / BMA = 36/8/8/48 Sodium lauryl sulfate (emulsifying agent): 0.5% in TM (s / s). 25% in the reactor; 75% in AP food: 0.3% in TM (s / s). Added as a separate feed during emulsion polymerization (feed solids are 1.5% in demineralized water). LMKT and 3MPA: 2.4% in TM Neutralization: 1.SA NH3 Solids of the neutralized solution: 27-28% Sheet and procedure for the preparation of Oligomer 0L2 Load 1 and 2 into the reactor. Charge 4-11 to the feed tank and pre-emulsify by stirring. Heat the batch to 70 ° C and add 5% of the pre-emulsified feed to the reactor. Heat the batch to 80 ° C and add 30% of 3. Wait 5 minutes and start feeding the rest of the pre-emulsified feed for 60 minutes and simultaneously feed the rest of 3 for 70 minutes to 85 ° C. Maintain at 85 ° C for 30 minutes and then add 12 and 13. Maintain at 80 ° C for another 20 minutes and cool to room temperature.

Specifications . Solids 27-28% pH 8.4 Viscosity (mPas @ 25 ° C) 130 Sediment < 0.1% Tg (DSC, ° C) 60 Mn 8,400 d 2.5 Example 4 A composition of the invention was prepared using a 2-step poly-intermittent method as follows: Formulation. Composition: Part of oligomer: (see above for 0L2) Part of polymer: MMA / BA / DAAM = 38/58/4 Part of polymer Tg, calculated (° C) = 0 oligomer / polymer (s / s): 100 / 100 All oligomer in the reactor Initiating system 0.26% t-BHPO in TM (s / s) in the reactor. 0. 05% of i-ascorbic acid in TM (s / s) in the reactor . 07% FeEDTA in t-BHPO (S / S) in the reactor. 0.21% of i-ascorbic acid in TM (s / s) fed to the reactor. solids: approximately 35% Sheet and procedure for the composition of example 4 (* See example 3) Load 1 and 2 into the reactor and 3-5 into the feed tank. Heat the contents of the reactor to 35 ° C. Add 50% of 3-5 to the reactor and mix for 30 minutes. Add 50% of 6, 7 and 8 to the reactor; the polymerization will start. Allow the temperature to move approximately 55 ° C. Maintain this temperature for 15 minutes. Feed 50% of 9 in 30 minutes. Cool to 35 ° C and repeat this procedure for the other 50% of the components, but now cool to 40 ° C instead of 35 ° C. Add 10 and 11 for 30 minutes. Cool to room temperature.

Specifications . Solids 35-36% pH 8.4 Viscosity (mPas @ 25 ° C) 180 Sediment before sieving (%) < 0.1% FM (%) < 0.1% MFFT (° C) 10 ° C Koenig Hardness 103 sec. An aqueous solution of an acidic oligomer OL3 lacking monomer was prepared as follows for the purpose of providing a subsequent covalent crosslinking monomer: Formulation for oligomer 0L3. Composition. MMA / MAA = 90/10 Sodium lauryl sulfate (emulsifying agent): 0.5% in TM (s / s). 25% in the reactor; 75% in food. AP: 0.3% in TM (s / s). Added as a separate feed during the emulsion polymerization (feed solids 1.5% in demineralized water) LMKT and 3MPA: 2.4% in TM Neutralization: 1 SA NH3 Solids of the neutralized solution: 25% Sheet and procedure for the preparation of 0L3 Load 1 and 2 into the reactor. Charge 4-9 to the feed tank and preemulsify by stirring. Heat the batch to 70 ° C and add 5% of the pre-emulsified feed to the reactor. Heat the batch to 80 ° C and add 30% of 3. Wait 5 minutes and start feeding the rest of the pre-emulsified feed for 60 minutes and simultaneously feed the rest of 3 for 70 minutes at 85 ° C. Maintain at 85 ° C for 30 minutes and then add 10 and 11. Maintain at 80 ° C for another 20 minutes and cool to room temperature.

Specifications . Solids 25% PH 8.3 Viscosity 55 sediment < 0.1% Tg (DSC and calculated ° C) 110 ° C Mn 9,700 d 2.5 Example C5 In this comparative example, a composition without intended groups was prepared to provide a covalent entanglement, using the 0L3 oligomer to investigate the effect on the balance of MFFT / Koenig hardness of the ionic entanglement. A poly-intermittent method was used (as in example 4). (The composition had Tg values of oligomer / hydrophobic polymer according to the requirements of the method of the invention). Formulation Composition Part of Oligomer: (see above for OL3) Part of Polymer: BMA / BA = 74/26 Part of Polymer Tg, calculated (° C) = 0 Oligomer / polymer (s / s): 60/100 All oligomer in the reactor Initiating system 0.26% t-BHPO in TM (s / s) in the reactor 0.05% of i-ascorbic acid in TM (s / s) in the reactor 5.07% FeEDTA over t-BHPO in the reactor 0.21% of acid i- ascorbic in TM (s / s) fed to the reactor Solids: approximately 35% Sheet and process for the preparation of the composition of Example C5.

Nr Component Quantity (g) Water 198.4 Oltromer solution OL3 800 BMA 296 BA 104 tBHPO (30% sludge 3.5 in demineralised water) Fe EDTA (1% solution *) 5.2 i-ascorbic acid 1% 20.0 in demineralised water) acid i-ascorbic 1% 84.0 in demineralised water) Water 209.3 . { * See example 3) Load 1 and 2 into the reactor and 3 and 4 into the feed tank. Heat at 35 ° C. Add 50% of 3 and 4 to the reactor and mix for 30 minutes. Add 50% of 5, 6 and 7 to the reactor; the polymerization will start. Allow the temperature to move approximately 55 ° C. Maintain at this temperature for 15 minutes. Feed 50% of 8 in 30 minutes. Cool to 35 ° C and repeat this procedure for the other 50% of the components, but now cooling to 40 ° C instead of 35 ° C. Add 9 for 30 minutes. Cool to room temperature.

Specifications . Solids 35% pH 8.3 MFFT (° C) 10 Koenig hardness 80 sec Viscosity (mPas @ 25 ° C) 200 Sediment (%) < 0.1% FM (%) < 0.1% 100 g of latex was formulated with a mixture of 0.57 g of demineralized water, 0.27 g of zinc oxide, 0.34 g of ammonium carbonate and 0.49 g of a 25% solution of ammonium hydroxide in water. This provides a latex of Zn metal ion interlacing with the following values: MFFT (° C): 37 Koenig hardness: 63 sec In this way, the effect of ionic entanglement has been both to increase the MFFT and to reduce the hardness of Koenig. Additional acidófunctional oligomers 0L4 and 0L5 were prepared as follows in the aqueous solution having covalent crosslinker functionality: Formulation for oligomer 0L4 Composition. EA / MMA / DAAM / MAA = 27.4 / 58/8 / 6.6 The preparation procedure was exactly like that of the OLI oligomer (using Surfagene FAZ 109V as the emulsifying agent).

Formulation for the oligomer OL5 Composition MMA / DAAM / MAA = 84/6/10 The preparation procedure was exactly like that of the oligomer OL2 (using SLS as an emulsifier).

Lamina and procedure for the preparation of oligomers 0L4 v 0L5.

Load 1, 2 and 4, 5 into the polymerization reactor.

Heat the contents of the reactor to 70 ° C and add 5% of the pre-emulsified feed 6-15. Heat the contents of the reactor to 80 ° C and charge 30% of 3 to the reactor and wait minutes. Feed the rest of 6-15 and 3 at 85 ° C for periods of 60 minutes and 70 minutes, respectively. Rinse the feed tank with 17 and keep the contents of the reactor at 85 ° C for another 30 minutes. Slowly add 16 to the reactor and keep at 80 ° C for another 30 minutes. The oligomer will dissolve or partially dissolve during this time. Cool to 25 ° C.

Specifications for OL4 and OL5 oligomers. Solids: 27-28% pH: 10 for OL4, 10 for 0L5. Viscosity (mPas at 25 ° C): 150 for 0L4, 140 for OL5 Sediment: < 0.2% FM: < 100 ppm Mn: ca9000 for OL4 ca? OOO for 0L5 d: 2.3-2.4 Tg for OL4 (calculated ° C): 60 Tg for 0L5 (DSC and calculated ° C): 110 Oligomer solutions of OL4 and OL5 were employed in the preparation of the following compositions of the invention of examples 6, 7 and 8 using the poly-intermintent method described for examples 4 and C5.

Examples 6, 7 and 8 Formulations. Composition: BMA / BA / DAAM = 74.1 / 22.9 / 3 Ex. 6 Oligomer: 0L4 Part of polymer Tg, calculated (° C) = 3 Ex. 7 Composition: BMA / BA / S / DAAM = 23/31/39/4 Oligomer: OL5 Part of polymer Tg, calculated (° C) = 20 Ex. 8 Composition: BMA / BA / S / DAAM = 46.7 / 10.3 / 39/4 Oligomer: OL5 Part of polymer Tg, calculated (° C) = 39 Other procedures as for examples 4 and C5.

Lamina and process for the preparation of the compositions of examples 6. 7 v 8.

Charge 1-3 to the polymerization reactor and 4-7 to the feed tank. Heat at 35 ° C. Add 50% of 4-7 to the reactor and mix for 30 minutes. Add 50% of 8, 9 and 10 to the reactor and the polymerization will start. Let the temperature will move to approximately 55 ° C. Keep at this temperature for 15 minutes. Feed 50% of 11 in 30 minutes. Cool to 35 ° C and repeat this procedure for the other 50% of the components, but now cool to 40 ° C instead of 35 ° C. Add 12-13 in 30 minutes. Cool to room temperature. The hardness values of Koenig and MFFT were as follows: MFFT CC) Dur. of Koenig (sec) pH Vise. (mPas @ 25 ° C) Ex.6 6 100 8.3 150 Ex.7 28 132 8.2 170 Ex.8 45 157 8.4 190 The specifications for the sediment and FM were similar to those for example 4. The compositions of examples 1,2,3,4, C5,6,7 and 8 were analyzed for their resistance to water and solvent using conductive stain tests. as follows: A coating of an example was applied to a wet film with a thickness of 100μm to a test chart (Leneta Company, Form 2C). It was allowed to dry at room temperature for 4 hours and at 50 ° C for 16 hours.

A roll of cotton soaked in water or ethanol 48%, was placed on the coating and kept in a saturated state for 16 hours by placing a glass on the roll. The roll was removed and the coating was analyzed for its appearance (whiteness, cracking or dissolution). If no damage is observed, a number of 5 is obtained. If the coating that has been completely dissolved, a number of 0 is obtained. The numbers from 4 to 1 remain for the increase in damage to the appearance of the coating. The results of the spot test for the examples were as follows: It will be noted that all compositions of the invention possess excellent water resistance and reasonably good ethanol resistance. On the contrary, the comparative composition of Example C5 has a significantly poorer resistance to water and ethanol. An additional acid-functional oligomer was prepared OL6 without any interlacing monomer that is intended to affect covalent entanglement (in an oligomer / polymer composition) after formation of the coating, but having in place of a difunctional monomer (ALMA) to effect grafting (or pre-entanglement) during the formation of the oligomer / polymer composition.

Formulation for oligomer 0L6 Composition BA / MMA / ALMA / MAA = 34 / 45.4 / 0.5 / 20 SLS (emulsifying agent): 0.5% in TM (s / s) AP: 0.3% in TM (1.5% in demineralized water) LMKT : 5.5% in TM Neutralization: 1 SA NH3 Solids of the neutralized solution: 24% Sheet and procedure for the preparation of the 0L6 oligomer Load 1 and 3 to the reactor. Heat the contents of the reactor to 70 ° C and add 5% of the pre-emulsified feed 4-8. Heat the contents of the reactor to 80 ° C and charge 30% of 2 to the reactor and wait for 5 minutes. Start feeding, with the contents of the reactor at 85 ° C, 4-7 and 11, 12 for a period of 60 minutes and 2 for a period of 70 minutes. Rinse the feed tank with 10 and keep the contents of the reactor at 85 ° C for another 30 minutes. Slowly add 9 to the reactor and keep at 80 ° C for another 30 minutes. The oligomer will dissolve at this time. Cool to 25 ° C.

Specifications . Solids: 24% pH: 8.4 viscosity (mPas): > 1000 sediment: < 0.2% FM: < 100 ppm Tg (DSC and calculated ° C): 49 Example C9 In this comparative example, a polymer composition was prepared using the oligomer OL6 in order to produce a grafted product (pre-link) between the oligomer and polymer phases in the resulting emulsion composition (ie, as in the preferred method of EP, 0,587,333). A poly-intermintent procedure was used. (the composition had oligomer / hydrophobic Tg polymer values according to the requirements of the method of the invention).

Formulation Composition Part of oligomer OL6 Part of polymer BA = 100% (homopolymer) Part of polymer Tg (° C) -45 oligomer / polymer = 100/100 Initiating system 0.26% tBHPO in TM (s / s) in the reactor 0.05% acid i-ascorbic in TM (s / s) in the reactor 5.07% FeEDTA in tBHPO (s / s) in the reactor 0.21% i-ascorbic acid in TM (s / s) fed to the reactor All the oligomer in the reactor Solids: 30% Laminate and procedure for the preparation of example C9 Load 1 and 2 into the reactor and 3 into the feed tank. Heat the contents of the reactor to 35 ° C. Add 50% of 4, 5 and 6 to the reactor and the polymerization will start. Allow the temperature to move approximately 55 ° C. Maintain at this temperature for 15 minutes. Feed 50% of 7 in 3 minutes. Cool to 35 ° C and repeat this procedure for the other 50% of the components, but now cool to 40 ° C instead of 35 ° C. Add 8 in 30 minutes. Cool to room temperature.

Specifications . Solids 30% pH 8.4 MFFT (° C) 0 Koenig hardness 29 sec. Viscosity (mPas @ 25 ° C) > 1000 sediment (%) < 0.2% FM (%) < lOOppm Examples CÍO and Cll In these comparative examples, hydrophobic oligomer / polymer compositions were prepared, wherein the oligomer is solubilized by neutralization in the aqueous phase subsequent to the polymerization to form the hydrophobic polymer (instead of before carrying out this polymerization, as in all the preceding examples), this being the preferred technique of EP 0,587,333 to effect solubilization. In the Cll example, the monomer system does not contain any monomer intended for covalent entanglement, whereas in the CIO example, the monomer system includes said entangled monomer (i.e., as for the present invention but solubilizing the oligomer). after polymerization instead of before polymerization to form the hydrophobic polymer). (Both compositions had Tg values of oligomer / hydrophobic polymer according to the requirements of the method of the invention): Formulation for the CIO example Composition of oligomer phase EA / MMA / DAAM / MAA = 12.1 / 73.3 / 8 / 6.6 Tg (DSC and calculated ° C): 85 Polymer phase composition BMA / BA / DAAM = 74/1 / 22.9 / 3 Tg (DSC and calculated ° C): 3 0.5 SLS (s / s) in TM used as the surfactant agent 0.3 AP (1.5% solution in demineralized water) used as a separate initiator feed for both phases. oligomer / polymer (s / s): 60/100 Formulation for example Cll EA / MMA / MAA oligomer phase composition = 12.1 / 81.3 / 6.6 Tg (DSC and calculated ° C): 88 Polymer phase composition BMA / BA = 75.6 / 24.4 Tg (calculated ° C): 1 Tg (DSC ° C): O Otherwise identical to the CIO example Sheet and procedure for examples CIO and Cll Load 1 and 2 into the polymerization reactor and heat to 85 ° C. Pre-emulsify 4-10 and charge 10% to reactor. Then charge 20% of 3 to the reactor and wait for 5 minutes. Load the rest of the feed (4-10) in 50 minutes and load 40% of 3 for a period of 60 minutes to 85%. This forms the oligomer. Charge 11-13 to the feed tank and feed this to the reactor in an additional 50 minutes. Simultaneously charge the remainder of 3 to the reactor for a period of 60 minutes at 85 ° C. Maintain at 85 ° C for another 30 minutes. This forms the hydrophobic polymer. Then slowly charge 16 to the reactor and wait another 30 minutes. Cool to 25 ° C and add 15 to the reactor (only CIO example); rinse with 14.

Specifications .

PH: 9-10 solids: 37-38% viscosity (mPas at 25 ° C): 1500 for eg. 1570 for eg .Cll FM: < 100 ppm sediment: < 0.2% MFFT (° C): 0 for ex. CÍO 37 for ej.Cll Hardness of Koenig: 52 sec for ej.ClO 13 sec for ej.Cll The water and ethanol resistances of the compositions of examples C9, CIO and Cll were analyzed (procedure described above). These were as follows (the values for MFFT and Koenig hardness, previously given also included): Axis C9 Exem .CIO Ex em.Cll MFFT ° C 0 0 37 Hardness (sec) 29 52 13 Resis. water 4 3 5 Resis. Ethanol 0 2 0 It will be understood that the postneutralization properties of the CIO example with entanglement are extremely poor compared to those of the examples of the invention, both in terms of equilibrium of MFFT / Koenig hardness and resistance to water / ethanol. The properties of the post-neutralization of the Cll example without interlacing gives a balance of MFFT / Koenig hardness even worse and a very poor resistance to ethanol. The properties of the graft (or pre-entanglement) of Example C9 are also very poor in terms of equilibrium of MFFT / Koenig hardness and resistance to ethanol.

Claims

1. A process for the production of an aqueous composition of the crosslinkable polymer free of organic solvent useful for coating, said process is solvent free and comprises: a) preparing an aqueous emulsion of an acid functional oligomer developed from olefinically unsaturated monomers, the oligomer having a number-average molecular weight, Mn, within the range of 500 to 50,000, and a vitreous transition temperature (Tg) within the range of 10 ° C to 125 ° C, said oligomer is being formed using a polymerization process of aqueous emulsion free of organic solvent or aqueous solution, and functionality. of acid making the oligomer soluble in water per se, or by neutralization, and the oligomer also having functional groups to impart interlacing capacity when the aqueous polymer composition is subsequently dried, b) conducting an aqueous emulsion polymerization process to form a aqueous emulsion of a hydrophobic polymer from at least one hydrophobic monomer from an olefinically unsaturated monomer, in the presence of the aqueous solution of the oligomer, hydrophobic polymer having a Tg that is at least 25 ° C higher that the Tg of the oligomer, and the hydrophobic polymer optionally having functional groups to impart interlacing capacity when the aqueous polymer composition is subsequently dried, and c) combining the aqueous emulsion of b) with an entanglement agent by the addition of the crosslinking agent after polymerization in step b), and / or carrying out the polymerization in the presence of the entanglement agent, said entanglement agent may react with the crosslinking functional groups of the oligomer and (if present), the hydrophobic polymer in the subsequent dried for effecting entanglement, wherein the entanglement agent is not an entanglement agent by the formation of ionic bonds, and wherein, in addition, the polymer composition upon drying has a Koenig hardness of at least 40 seconds and the polymer composition have a film forming temperature m minimum of = 55 ° C.

2. The process according to claim 1, characterized in that the oligomer has a number average molecular weight of 2,000 to 25,000.

3. The process according to any of claims 1 or 2, characterized in that the oligomer has a Tg within the range of 50 to 125 ° C.

4. The process according to claim 3, characterized in that the oligomer has a Tg within the range of 70 to 125 ° C.

5. The process according to any of the preceding claims, characterized in that the hydrophobic polymer has a Tg that is at least 40 ° C above the Tg of the oligomer.

6. The process according to any of the preceding claims, characterized in that the polymer composition upon drying has a Koenig hardness of 60 to 200 seconds.

7. The process according to any of the preceding claims, characterized in that the polymer composition has a minimum film-forming temperature of 0 to 55 ° C.

8. The method according to claim 7, characterized in that the composition of Polymers have a minimum film-forming temperature of 0 to 30 ° C.

9. The process according to any of the preceding claims, characterized in that the resulting composition has a Koenig hardness and a minimum film formation temperature according to the following empirical relationship: H = 1.5T + 70 where H is the hardness of Koenig in seconds and T is the minimum temperature of film formation in degrees centigrade.

10. The method according to claim 9, characterized in that the empirical relationship is: H = 1.5T + 90

11. The process according to any of the preceding claims, characterized in that the oligomer is complete (or substantially and completely), or partially dissolved in the aqueous medium in step a).

12. The method according to claim 11 further characterized by the dissolution of the oligomer is effected by neutralization of the same acid groups using a base.

13. The process according to any of the preceding claims, characterized in that the oligomer is derived from an olefinically unsaturated monomer system, which includes a comonomer that carries an acid, or comonomers carrying an acid-forming group which produces, or is subsequently convertible to, said acid group, and a comonomer having a functional group to impart interlacing capacity.

14. The process according to claim 13, characterized in that the acid bearing monomer is selected from olefinically unsaturated carboxyl-containing monomers.

15. The process according to claim 14, characterized in that the monomer is selected from carboxyl-functional acrylic monomers.

16. The process according to any of claims 14 or 15, characterized in that the carboxyl-bearing monomer is selected from acrylic acid, methacrylic acid, itaconic acid and fumaric acid.

17. The process according to claims 13 to 16, characterized in that the monomer system from which the oligomer is formed includes a non-crosslinking comonomer, without functional acid selected from acrylate and methacrylate esters; styrene, dienes, vinyl esters, nitriles and olefinically unsaturated halides.

18. The process according to claim 17, further characterized in that the non-crosslinking comonomer, without functional acid is selected from normal and branched alkyl esters of Cl to C12 alcohols and acrylic acid or methacrylic acid such as methyl acrylate, ethyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate and N-butyl methacrylate; and cycloalkyl acrylates or methacrylates such as isobornyl or cyclohexyl acrylate or methacrylate; the same styrene, α-methylstyrene and t-butylstyrene; acrylonitrile and methacrylonitrile, vinyl chloride, vinylidene chloride and vinyl fluoride; vinyl acetate and vinyl alkanoates; isoprene and 1,3-butadiene.

19. The method according to any of claims 3 to 18, characterized in that the Functional groups for providing entanglement capacity are selected from epoxy, hydroxide, keto and aldehyde groups.

20. The process according to any of claims 13 to 19, characterized in that the comonomers with functional groups for imparting interlacing capacity are selected from glycidyl acrylate and methacrylate, methacrylates and hydroxyalkyl acrylates such as methacrylate and hydroxyethyl acrylate, acrolein, methacrolein and methyl vinyl ketone, the acetoacetoxy esters of hydroxyalkyl acrylates and methacrylates such as acetoacetoxyethyl methacrylate and keto containing amides such as diacetone acrylamide.

21. The process according to any of claims 13 to 20, characterized in that the functional acid oligomer is derived from a monomer system comprising from 1 to 45% by weight of a functional acid comonomer, from 0.05 to 20% by weight of a interlacing comonomer and from 98.5 to 50% by weight of comonomer without interlacing, without functional acid.

22. The process according to claim 21, characterized in that the oligomer is derived from a monomer system comprising from 3 to 30% in weight of acid-functional comonomers, from 1 to 15% by weight of crosslinking comonomers and from 96 to 65% by weight of non-acid-functional crosslinking comonomers.

23. The process according to any of claims 21 or 22, characterized in that the acid comonomer is methacrylic acid and / or acrylic acid and the non-acid-functional crosslinking comonomers are selected from one or more of methyl methacrylate, styrene, Acrylate ethyl, N-butyl methacrylate, 2-ethylhexyl acrylate and N-butyl acrylate.

24. The process according to claims 21 to 23, characterized in that the oligomer is derived from a monomer system comprising from 3 to 12% by weight of methacrylic acid and / or acrylic acid, from 1 to 10% by weight of diacetone- acrylamide and / or acetoacetoxyethyl methacrylate, from 50 to 90% by weight of methyl methacrylate, from 0 to 30% by weight of one or more of ethyl acrylate, n-butyl methacrylate and n-butyl methacrylate of 0 to 40% by weight of styrene.

25. The process according to any of the preceding claims, characterized in that the polymerization of the aqueous emulsion of step b) is carried out using a quantity of emulsifying agent recently added to said step (excluding the oligomer) which is less than 0.5% by weight based on the total weight of the monomers charged for step b).

26. The process according to claim 25, characterized in that the amount of recently added emulsifying agent is 0, and the only emulsifying agent that can be present (excluding the same oligomer) is that which remains of the emulsifying agent used in the polymerization of the oligomer of the step a).

27. The process according to any of the preceding claims, characterized in that the oligomer formed in step a) is positioned to act as an emulsifying agent in the polymerization step of step b).

28. The process according to any of the preceding claims, characterized in that the polymerization processes in steps a) and b) are carried out in the same polymerization vessel.

29. The process according to any of the preceding claims, characterized in that said hydrophobic polymer is derived from an olefinically unsaturated monomer system, which includes a monomer without interlacing, and which does not carry acid.

30. The process according to claim 29, characterized in that the non-crosslinking monomer which does not carry acid is selected from one or more of acrylate and methacrylate esters of alkanols, styrenes, dienes, vinyl esters, nitriles, vinyl halides and vinylidene halides .

31. The process according to claim 30, characterized in that the esters of acrylate and methacrylate are normal and branched alkyl esters of alcohols of Cl to C12 and acrylic or methacrylic acid, the styrenes are the same styrene, α-methylstyrene, or-, m- and p-methylstyrene, p-chlorostyrene and p-bromostyrene, the dienes are 1,3-butadiene and isoprene, the vinyl esters are vinyl acetate and vinyl alkanoates, the vinyl halide is vinyl chloride, and the halide of vinylidene is vinylidene chloride.

32. The process according to any of claims 29 to 31, characterized in that the monomer system used in the preparation of the hydrophobic polymer includes an interlacing comonomer having a functional group to provide selected entanglement capacity of epoxy, hydroxy, ketone and aldehyde.

33. The process according to claim 32, characterized in that the crosslinking co-monomer is selected from one or more of glycidyl methacrylate and acrylate, hydroxyalkyl methacrylates and acrylates such as methacrylate and hydroxyethyl acrylate, acetoacetoxyethyl esters, and amides. containing keto such as diacetone-acrylamide.

34. The process according to any of claims 29 to 33, characterized in that the monomer system used for the preparation of the hydrophobic polymer contains less than 5% by weight, of any acid-functional comonomer.

35. The process according to claim 34, characterized in that the co-monomer system does not contain any acid-functional comonomer.

36. The process according to any of the preceding claims, characterized in that the hydrophobic polymer is made of a monomer system comprising at least one C 1 -C 10 alkyl methacrylate and C 3 -C 10 alkyl acrylate, and diacetone-acrylamide and / or acetoacetoxyethyl methacrylate.

37. The process according to any of the preceding claims, characterized in that said hydrophobic polymer has a number average molecular weight of at least 50,000.

38. The method according to claim 37, characterized in that said hydrophobic polymer has a number average molecular weight of at least 100,000.

39. The process according to any of the preceding claims, characterized in that the aqueous solution of the oligomer of step a) is mixed with all the monomers that are to be used in the formation of the hydrophobic polymer and the intermittent polymerization "all in one" of another Conventional form (without the addition of monomers) is carried out to make the hydrophobic polymer.

40. The process according to any of claims 1 to 38, characterized in that the oligomer solution of step a) is present in the polymerization vessel used to make the hydrophobic polymer before the start of the polymerization together with some of the monomer system for the hydrophobic polymer, the rest of the monomer system for the hydrophobic polymer being added in a single addition after the polymerization has begun.

41. The process according to any of claims 1 to 38, characterized in that all the oligomer solution of step a) is present in the polymerization vessel used to make the hydrophobic polymer before the start of the polymerization, and the monomer system for Hydrophobic polymer is separated into several equal parts (batches), these parts are added and polymerized consecutively with each other.

42. The process according to any of claims 1 to 38, characterized in that part (or none) of the monomer system for the hydrophobic polymer is present before starting the polymerization in the polymerization vessel used to make the hydrophobic polymer and part (or the whole amount) is fed to the reaction medium in the polymerization vessel during the course of the polymerization.

43. The process according to claim 42, characterized in that the aqueous oligomer solution of step a) is present in part in the reaction medium for the polymerization, to prepare the hydrophobic polymer while part of the aqueous oligomer solution is mixed with the complete monomer system for the hydrophobic polymer and the latter feeding the reaction medium into the polymerization vessel during the polymerization.

44. The process according to claim 42, characterized in that the complete oligomer solution of step a) is present in the polymerization vessel before the start of the polymerization and the complete monomer system for the hydrophobic polymer is fed to the vessel during the polymerization, the oligomer not being present in the monomer feed.

45. The process according to claim 42, characterized in that all the aqueous oligomer solution of step a) is present in the polymerization vessel before the start of the polymerization together with monomer system part for the hydrophobic polymer and the remainder of the monomer system for the hydrophobic polymer fed during the polymerization, being oligomer in the feed.

46. The process according to claim 42, characterized in that part of the oligomer solution of step a) is present in the polymerization vessel before starting the polymerization to prepare the hydrophobic polymer together with part of the monomer system for the polymer hydrophobic and the rest of the monomer system for the hydrophobic polymer mixed with the rest of the oligomer solution, is fed during the polymerization.

47. The method of conformity according to any of the preceding claims, characterized in that the crosslinking agent is selected, suitable for crosslinking functionality in the oligomer and (if present) in the hydrophobic polymer of a polyisocyanate, melamine, glycolate, a polyamine and a polyhydrazide.

48. The process according to any of the preceding claims, characterized in that the ratio of the number of crosslinker groups present in the oligomer and (if used) in the hydrophobic polymer to the number of groups of reagents (for crosslinking purposes) in the agent of Crosslinking is within the range of 10/1 to 1/3.

49. The process according to any of the preceding claims, characterized in that the solids content of the resulting aqueous composition is within the range of 20 to 65% by weight on a basis by total weight.

50. The method according to any of the preceding claims, characterized in that the relative amounts of the oligomer and the hydrophobic polymer in the resulting aqueous composition is such that the weight% of the oligomer based on the weight of the oligomer plus the hydrophobic polymer is within the range from 1 to 70% by weight.

51. The aqueous polymer composition that is formed by the process according to any of the preceding claims.

52. The aqueous composition of the crosslinkable polymer, characterized in that it is free of organic solvent and is useful for coating, said composition is formed by a process that is free of organic solvent and comprises: a) preparing an aqueous emulsion of a functional acid oligomer developed from olefinically unsaturated monomers, the oligomer having a number-average molecular weight, Mn, within the range of 500 to 50,000, and a vitreous transition temperature (Tg) within the range of 10 to 125 ° C, said oligomer is being formed using an aqueous emulsion polymerization process free of organic solvent or aqueous solution, and the functionality of acid making the oligomer soluble in water per se, or by neutralization, and the oligomer also having functional groups to impart interlacing capacity when the aqueous composition of the polymer is subsequently dried, b) an aqueous emulsion polymerization process for forming an aqueous emulsion of a hydrophobic polymer from at least one hydrophobic polymer from an olefinically unsaturated monomer, in the presence of the aqueous solution of the oligomer, the hydrophobic polymer having a Tg which is at least 25 ° C greater than the Tg of the oligomer, and the hydrophobic polymer having optionally functional groups for imparting entanglement capacity when the aqueous composition of the polymer is subsequently dried, and c) combining the aqueous emulsion of b) with an entanglement agent by adding the entanglement agent after the polymerization in step b), and / or performing the polymerization in the presence of the entanglement agent, said entanglement agent can react with the crosslinking functional groups of the oligomer and (if present), the hydrophobic polymer in the subsequent drying to effect entanglement, wherein the crosslinking agent it is not an agent that effect entanglement by the formation of ionic bonds, and wherein in addition the composition of the polymer to be dried has a Koenig hardness of at least 40 seconds and the composition of the polymer has a minimum film formation temperature of < . 55 ° C.

53. The composition according to claim 52, characterized in that the composition has a Koenig hardness and a minimum film-forming temperature according to the following empirical relationship: H = 1.5T + 70 where H is the Koenig hardness in the second and T is the minimum film formation temperature in ° C.

54. The composition according to claim 53, characterized by the empirical relationship is: H = 1.5T + 90

55. The use of a composition according to any of claims 51 to 54 in the provision of films, polishers, varnishes, lacquers, paints, inks and adhesives.

56. The use of a composition according to any of claims 51 to 54 for the protective coating of substrates of wood, plastics, paper and metal.