SE444441B - INTERNAL SOFT ADDITION POLYMER PARTICLES IN THE FORM OF A LATEX OR PARTICULAR PARTICLES OR AS A COMPONENT IN A WATER BASED POLISH COMPOSITION - Google Patents

Description

2 cures and applied in the form of a solution are described in U.S. Pat. No. 935,366 for use in coating vinyl chloride flooring materials. Yet another solution to the problem of obtaining a hard coating in the form of a well-cohesive film is that according to U.S. Pat. No. 3,949,107, which discloses the application of a polish containing an aqueous diaper of a resin having a Tg of 30-80 ° C. a floor, wherein either the polish or the floor is preheated to a temperature exceeding resin seat Tg.

A The internally softened addition polymer particles according to the invention in the form of latex or of finely divided particles or as a component of an aqueous polishing composition are characterized in that they comprise (A) early-stage polymer and (B) later-stage polymer formed by polymer action. in the presence of an emulsion of polymer particles comprising polymer (A), wherein the polymers: fA) and (B) each constitute at least 20% by weight of the polymers in the particles, the polymer (A) containing at least 10% by weight of hydrophilic mers, of which at least 10% by weight are nonionic, and further comprise units of one or more of the following monomers: acrylate esters, methacrylate esters, vinyl esters and vinyl aromatic Å monomers, and wherein the polymer (B) is less hydrophilic than polymer N (A), wherein either (i) polymer (B) has a higher Tg than polymer (Å) and of the hydraulic units in polymer (A) at least 0.51, Ionic and E polymerene (A) interpenetration parameters are greater than that of the polymer (B) m ed up to 8 units, wherein polymer (A) comprises V units of monoethylenically unsaturated monomer; or (ii) the polymer- N particles have a Tg exceeding 15 ° C and the latex has a viscosity below 5000 cP when measured at 20% by weight solids in the pH range 4 ~ 10 and has a minimum film temperature of more than 5 ° C below the calculated Tg of the polymer particles.

Although the invention comprises addition polymer particles in the form of latex and of finely divided particles and as a component in an aqueous polishing composition, in the following, for the sake of simplicity, the latex variant will mainly be described. In accordance with the present invention, by sequencing, polymerization forms an unusually hard (high "Tg) relatively hydrophobic polymer on preformed, usually relatively soft (low Tg), hydro-, felt-functionalized copolymer latex particles to form latex particles, which for convenience are called internal ~~ ------_-. ---- .-- 1-w.-.---- - ---- »10 15 20 25 30 3 78Û2931-'f1_ ~ softened polymer latex particles. A latex is formed with a low viscosity but which still forms a film at a temperature which is low in comparison with the calculated Tg of the polymer in the particles.The viscosity and minimum film formation temperature (MFT) are measured under normal conditions of use, i.e. neutral to high pH for acidic polymers and neutral to low pH for base-containing polymers The latex of internally softened polymer particles is preferably prepared by preparing a water-swellable addition polymer under normal emulsion polymerization conditions.

This water-swellable polymer may also be water-soluble at the appropriate pH and is normally soluble at high pH when it contains acidic groups or at low DH when it contains basic groups.

Under the polymerization conditions, however, it does not dissolve in the aqueous medium but is retained as a latex. A second polymer is then formed by polymerization in the presence of the latex and can interact with and possibly. penetrate the first. This is achieved by adding to the first latex monomer which forms a polymer which is less water sensitive, i.e. less hydrophilic, and usually harder than that of the original latex, and by subsequent polymerization. The second monomer system is selected so that it has sufficient compatibility with the original polymer so that this The second polymer in its interaction with the first polymer has the purpose of limiting the swellability of the first polymer in water. The product can thus be considered as a hydro-pk plastic first polymer which is made more hydrophobic and usually cured alt. made a usually hard, hydrophobic swells. through the second polymer; second polymer more hydroplastic and usually softer through the first polymer. The internally softened polymer that is formed has properties that are not similar to the properties of either of the constituent polymers, nor does it have properties that constitute the sum of or the average of the properties of the components. For example, if the first polymer is one that is completely soluble at high pH, it is found that after the internally softened polymer is formed, the first polymer moiety is no longer soluble even at very high pH values.

A component polymer with high swellability in water would be expected to give a latex with high viscosity, although MFT could be low. compared to Tg. According to the present invention, the modification of the properties of the water-swellable polymer from the first step through the second step results in a relatively low viscosity of the latex. The preferred polymers of the present invention are at least one of acrylate, methacrylate, vinyl ester and vinyl aromatic moieties. Preferred hydrophilic ionic mers (if present) in the polymers are mers with carboxylic acid groups. Preferred hydrophilic nonionic mers in the polymer are mers of hydroxyalkyl esters of carboxylic acids or vinyl alcohols. The internally softened polymer of the present invention can be formed by polymerizing a first ethylenically unsaturated monomer system comprising comparatively hydrophilic monomer, usually by emulsion polymerization, and then in the presence of formed latex, emulsion polymerizing a second batch of ethylenically unsaturated monomer, which as such would form a harder and hydrophobic polymer than the polymer from the first batch. The polymer formed by the first batch (or step) is obtained as an emulsion although it is swellable in water or water soluble. The term "water-soluble" as used herein means solubility in water, when the pH of the water is adjusted by adding acid or base so that the polymer is completely or partially neutralized. The term "swellable in water" as used herein means that the polymer absorbs water or can be made to absorb water by such pH adjustment.The pH range considered useful is from about 4 to about 10.

The swelling ratio of the swellable polymer, i.e. the volume of the polymer in a large excess of water swollen divided by the volume of the polymer in the dry state, is preferably greater than 2 and especially greater than 6.

It is believed that the hydrophilic monomer should be used in amounts ranging from about 10 to about 100 parts per 100 parts of the first batch monomer; but the present invention is not limited to such theoretical considerations. It seems that the hydrophilic monomer when polymerized can serve to bind the quantities of water transferred to the composition, e.g. In the form of hydrated water. Any monomer which can be polymerized in the mixture and which is sufficiently hydrophilic to effectively bind water is therefore useful. Among suitable hydrophilic monomers may be mentioned as examples: acrylonitrile, methacrylonitrile, S7so2931-1. hydroxy-substituted alkyl and aryl acrylates and methacrylates, polyetheracrylates and methacrylates, alkylphosphatoalkyl acrylates and methacrylates, alkylphosphonoalkyl acrylates and methacrylates, acrylic acid, methacrylic acid, maleic acid, maleic acid anhydride, N-vinylacrylic acid; mono- and di-amides), fumaric acid (mono- and di-amides), itaconic acid (mono- and di-amides), acrylamide, methacrylamide, and also other half-acid forms of the above dibasic acids, such as half esters, amino monomers, such as amino-substituted alkyl acrylates and methacrylates, vinylpyridines and aminoalkyl vinyl ethers and ureido monomers including those having cyclic ureido groups. The invention also includes within its scope variations. incorporation of the hydrophilic monomer into the monomer mixture, such as, for example, when the hydrophilic monomer units are formed in situ or subsequently formed. A monomer may, for example, be included in the polymerization mixture which is not hydrophilic as such but is changed during the treatment or in a subsequent step, for example by hydrolysis, so that it becomes hydrophilic; anhydride and epoxide-containing monomers are examples of this.

Preferred suitable hydrophilic monomers are acrylic compounds, especially the amides and hydroxyalkyl esters of methacrylic and acrylic acids, amides and hydroxyalkyl esters of other acids are also preferred but to a lesser extent than the corresponding methacrylates and acrylates which polymerize more readily. Monomers containing carboxylic acid groups are also preferred and especially acrylic acid, methacrylic acid and itaconic acid. Another preferred group of hydrophilic monomers is represented by concrete examples of potentially hydrophilic monomers which give the actual hydrophilic moieties in the polymer upon hydrolysis. These monomers include esters of vinyl alcohol, such as vinyl formate, vinyl acetate, vinyl propionate, vinyl butyrate and vinyl versitate. Hydrolysis of these monomers yields hydrophilic vinyl alcohol units in the polymer. The preferred monomer among these is vinyl acetate.

Another monomer carefully selected to impart other desirable properties to the final polymer Any polymeric unsaturated monomer, if present, is present with the hydrophilic monomer in the first batch. preferably of the type in which the various ether groups, i.e. the addition polymerizable unsaturated groups, participate in the polymerization to approximately the same extent. Preferably, no such crosslinking or grafting bond is polyethylenically unsaturated monomer. The term grafting monomer is defined in column 4, line 66 to column 5 radius 20 of U.S. Patent No. 5,796,771. The first batch preferably contains monoethylenically unsaturated monomer. present in the first stage monomer system.

It is desirable that the first batch of polymer be softer. The hardness of the first batch can be controlled by the choice of hydrophilic monomer and possibly thus using comonomer. Suitable comonomers that form soft polymers in than the second batch polymer. presence of free radical catalysts are primary and secondary alkyl acrylates with alkyl substituents of up to 18 or even more carbon atoms, primary or secondary alkyl methacrylates having alkyl substituents of at least 5, for example up to 18 or more carbon atoms, or other ethylenically unsaturated compounds which are polymerizable with free radical catalysts to form soft solid polymers comprising vinyl esters of saturated monocarboxylic acids with more than 2 carbon atoms. The preferred ethylenically unsaturated compounds are listed acrylates and methacrylates and of these the most suitable esters are those having alkyl groups having not more than 8 carbon atoms.

The preferred monomers, which as such give soft plyomers, can be summarized by the formula CH 2 = e-coon * __ R 'wherein R' is hydrogen or the methyl group and RX represents, when R 'is methyl, a primary or secondary alkyl group having -18 carbon atoms, or when R 'is hydrogen, an alkyl group having not more than 18 carbon atoms, preferably 1-B carbon atoms and especially 1-4 carbon atoms.

Typical compounds within the scope of the above definition are methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, butyl acrylate, isobutyl acrylate, sec-butyl acrylate, amyl acrylate, isoamyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, octylacrylate, 3,5-ethyl acrylate, acrylate, octadecyl acrylate, octadecenyl acrylate, n-amyl methacrylate, sec-amyl methacrylate, hexyl methacrylate, 2-ethylbutyl methacrylate, octyl methacrylate, 3,5,5-trimethylhexyl methacrylate, decyl methacrylate, dodecyl methacrylate and acrylate acrylate, substated, octadate fmethacrylate. A lf! As polymerizable ethylenically unsaturated monomers, which as such form hard polymers, alkyl methacrylates having alkyl groups having up to 4 carbon atoms can also be used, also tert-amyl methacrylate, tert-butyl or tert-amyl acrylate , cyclohexyl, benzyl or isobornyl acrylate or methacrylate, acrylonitrile or methacrylonitrile, these being a preferred group of monomers which themselves form hard polymers. Styrene, vinyl chloride, chlorostyrene, vinyl acetate and p-methylstyrene, which also form hard polymers, can be used. Preferred monomers which as such form hard polymers can be summarized by the formula 'CH 2 =? -X' R wherein R 'is hydrogen or the methyl group and wherein X represents one of the groups -CN; phenyl, methylphenyl, and ester-forming groups, -COOR ", where R" is cyclohexyl or when R 'is hydrogen a tert-alkyl group having 4-5 carbon atoms, or when R' is methyl, an alkyl group having 1-4 carbon atoms. Some typical examples of these have already been mentioned. Other concrete compounds are methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, isobutyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate and tert-butyl methacrylate. Acrylamide and methacrylamide can also be used as monomers to contribute to hardness.

These monomers may contain other functional groups for other purposes, such as to provide crosslinking in the polymer upon curing or improved adhesion to a substrate.

Ex. on such functional groups is carboxyl in the form of free acid or salt, amido including substituted amido, such as alkoxyalkylamido and alkylolamido, epoxy, hydroxy, amino including In most cases these functional groups are also hydrophilic groups and many of monooxazolidinyl and oxazinyl, and ureido. the more are hydrophilic.

Another group of monomers useful in the present invention and which upon polymerization as such yield soft polymers is butadiene; chloroprene, isobutylene and isoprene. are commonly used in rubber latex in addition to monomers which give hard These monomers are polymers and are also useful in the present invention, such as acrylonitrile, styrene and other "hard monomers" as set forth above. The olefin monomers, especially ethylene and propylene, are suitable "soft monomers". Particularly useful copolymers for the first step are ethylene / ethyl acrylate copolymers and ethylene / vinyl acetate copolymers containing added hydrophilic monomer. A further class of polymers useful in the present invention are polymers of esters of vinyl alcohol, such as vinyl formate, vinyl acetate, vinyl propionate, vinyl butyrate and vinyl versitate. Preferred are poly (vinyl acetate) and copolymers of vinyl acetate with one or more of the following monomers: vinyl chloride, vinylidene chloride, styrene, vinyltoluene, acrylonitrile, methacrylonitrile, acrylate or methacrylate esters and the monomers listed above. vinyl ester polymers It is preferred that the first stage polymers contain at least 10% and preferably at least 30% by weight of vinyl. acetate units, with at least 80% being especially preferred. Before the polymerization of vinyl alcohol esters is complete, some hydrolysis to vinyl alcohol units normally or intentionally takes place. The extent of the hydrolysis can be controlled by controlling the time, temperature and pH of the reaction to form the desired amount of vinyl alcohol in the product. Longer times, higher temperatures, 4 very acidic or very alkaline conditions serve all to the functional group to increase the extent of the hydrolysis and thus the amount of vinyl alcohol in the final product.The extent of the hydrolysis can be determined by acid-base titration in water or in suitable solvent systems.

A preferred composition of the present invention is one in which the meres from the first step comprise 65-85% by weight of (C1-C10) -alkyl acrylate, (C1-Cu) -alkyl methacrylate and / or styrene, 5-10% of acrylic acid, methacrylic acid and / or itaconic acid and 10-25% hydroxy (C 1 -C 6) -alkyl acrylate and / or hydroxy- (C 1 -C 6) -alkyl methacrylate, and the more from the latter stage polymer include methyl methacrylate and / or styrene. Another preferred composition is one in which the mer units in the first step comprise 50-80% by weight of vinyl acetate (for subsequent hydrolysis), 1-10% by weight of acrylic acid, methacrylic acid, itaconic acid and / or maleic acid (derived from maleic anhydride) and -25% by weight of vinyl alcohol and the mer units in the later stage contain TO ~ 100% of methyl methacrylate and / or styrene and 0 ~ 30, before ~ Preferably 10-30% by weight of acid-containing merers, such as acrylic acid, methacrylic acid and / or itaconic acids. It is desirable that the acid amers in the first step comprise up to 5% by weight of the polymer weight in the first step of maleic anhydride or maleic acid, with 0.2-2% by weight being preferred. In the present preparation, the term "merer" refers to the moiety in the addition polymer that can be derived from the named monomer by addition to the double bond. In general, the preferred hydrophilic monomers used in the present invention are monomers having a soluble content of. at least 6 g per 100 g of water, those with a solubility of at least 20 g per 100 g of water are more preferred and most preferred are those in which at least 50 g of the monomer is soluble in 100 g of water.

The polymer in the first step contains at least 10% of hydrophilic nutrients, with 10-70% being preferred, at least 25% being especially preferred and in particular the range 25-35%. Of the hydrophilic monomer content, it is desirable that at least 0.5% of ionic hydrophilic mers be acidic mers, such as mers containing carboxyl or basic groups, such as amino groups, in either unneutralized or neutralized form. It is also desirable that at least 10% of the hydrophilic merers be nonionic, ie non-ionic, such as hydroxyethyl acrylate or methacrylate, which may be formed in situ, such as nonionic hydroxyethyl ester and vinyl alcohol moieties.

The polymer in the last step is more hydrophobic and preferably harder than that in the first step. By more hydrophobic is meant that the polymer in the latter step alone is less swellable in water than the polymer in the first step alone. By harder is meant that the polymer in the latter stage has a larger modulus than that of the polymer in the first stage, whereby measurements are performed on polymer samples immersed in water. It is preferred that the monomer from the latter stage be monoethylenically unsaturated.

The internally softened polymers of the present invention are conveniently prepared by known emulsion polymerization procedures using multi-step sequencing techniques. However, they can also be prepared by continuous polymerization, in which the monomer composition fed is continuously changed, stepwise or continuously, during the polymerization. In such polymerization, abrupt or discontinuous change in co-V .-. Now, .. ....._ ~ _ .., .., __._. ~ - ---------- ~ The assembly of the monomer feed is considered to be the end of a step. If there were no such changes in the composition of feedstock indicating change from one step to another, the first half of the polymer additive can be considered as representing one step and the other half as representing a second step. In the simplest form of the latex according to the invention, the hydrophilic polymer is formed in a first step and the more hydrophobic polymer is formed in a second step. As such, either of the component polymers may also be sequence polymerized, i.e., consist of multiple steps. The monomers in the first stage, together with initiators, soap or emulsifier, polymerization modifier or chain transfer agent, are added to the original polymerization mixture and polymerized, for example by heating, mixing, cooling as required, in a well known and completely conventional manner until the monomers are mainly pre-V used. The monomers in the second and subsequent steps are then added with suitable other materials, so that the desired polymerization in each step occurs in sequence to substantially complete consumption of the monomers. It is preferred that in each step after the first the amounts of initiator and soap, if any, be maintained at such a level that polymerization occurs on existing particles and that essentially no new particles or "seed nuclei" are formed in the emulsion.

When polymerizations are carried out in multi-step sequence processes, additional steps may be present, which in composition and proportion constitute a combination of the two distinct steps, whereby polymers are formed which have properties which lie between them.

The hydrophilic first step is at least 10, preferably 20-80, especially 30-70 and in particular 40-60% of the total polymer.

Other steps may, of course, exist before, between or after the two steps of principle interest.

These second steps always constitute smaller weight proportions of the whole polymer than either of the polymers which constitute main components when they cannot be considered as a part of one or the other of these by their composition.

It is preferred that the polymer according to the invention consists of a two-step polymer. The person skilled in the art in a given field usually produces a few internally softened polymer latex samples which differ. the weight ratio in the first and second steps. selects the one that for a given application gives the best fa 3 and »in the xapers. 10 lx) Q fi 55 ._ 17802951-1 The same weight ratio is usually the starting point for these experiments, which usually include a higher and a lower ratio, the spread in the ratio being selected with regard to the desired final properties, eg hardness, MFT, latex viscosity - tet, kiibbffi nia. The copolymer is usually prepared by emulsion copolymerization of the individual monomers in the proper proportions.

Conventional emulsion polymerization techniques are described in U.S. Pat. Nos. 2,754,280 and 2,795,56H. can be emulsified with anionic, cathinic or nonionic dispersants. The monomers can be sieving agents, about 0.5% to 10% of which are usually used based on the total weight of monomer. When water-soluble monomer is used, the diluent has the function of emulsifying another monomer. A free radical polymerization initiator, such as ammonium or potassium persulfate, may be used alone or in combination with a thiocellulator, such as sodium metabisulphide or sodium thiosulfate. The initiator tower and accelerator, commonly referred to as a catalyst, may be used in proportions of 1/2 to 2%. each based on the weight of the monomer being copolymerized. The polymerization temperature can vary from room temperature to 9006 or higher in a conventional manner. .

Ex. on emulsifiers or soaps suitable for the polymerization process of the present invention are alkali metal and ammonium salts of alkyl, aryl, alkaryl and aralkyl sulfonates, sulphates and polyether sulphates; corresponding phosphates and phosphonates; and ethoxylated fatty acids, esters, Alcohols, V amines, amides and alkylphenols. n Chain transfer agents including mercaptans, polymeric captans and polyhalogen compounds are often desirable in the polymerization mixture. Another way of describing and defining the monomers of the present invention in the first and second steps is in use. of the concept of solubility parameters, "Polymer Handbook", second edition, J. Brandrup and EH Immergnt; publisher (John Wiley and Sons, New York 1975) section IV, part 15 called "Solubility Prameter Values" by H. Eurrell, on p. IV-337 to IV-359, define solubility parameters, describe how it is used and calculated, contain tables of solubility parameters and provide further references to scientific literature regarding solubility parameters. The solubility parameter is the square root of the cone energy density, which in turn is the numerical value of the potential energy of L cc. material, the potential deriving from the van der Waals attractive forces between the molecules in a liquid or solid. Burrell k describes a number of ways to calculate solubility parameters from experimentally determined physical constants and two ways to calculate them from the structural formula of a molecule; The structural formula methods are used normally when data for calculation based on physical constants are not available or are considered particularly uncertain; Calculation from the structural formula is based on the use of tables of molar attraction constants, such as those listed on p. IV-339 in the "Polymer Handbook". The table according to Small t is preferred. The solubility parameter system can be considered as an extension of the old "equal dissolves equal" rule known from the days of chemistry *. A non-crosslinked polymer normally dissolves in a solvent with the same solubility parameter and a crosslinked polymer normally swells under the action of a solvent with the same solubility parameter. Conversely, solvents with solubility parameters that are very different from those of polymers do not dissolve the polymer or cause it to swell. As stated by Burrell, the solubility parameter for polymers can be determined, inter alia, by measuring the swelling of the polymer in a series of solvents. The solubility parameter of polymers can also be determined by calculation from the group molar attraction constants as mentioned above. In a representative situation, it is found that solvents with a range of solubility parameters around it for the polymer cause dissolution of the non-crosslinked polymer. Those skilled in the art have further added the classification of solvents with the characteristics low, moderate and strongly hydrogen bonded. In the choice for dissolving a given non-crosslinked polymer differs from one class to another, although usually substantially superior. It is found that solubility parameter overlap can be observed. Burrell's Table 4 beginning on p.

IV-349 provides ranges of solubility parameters for weak, moderate and strongly hydrogen bonded solvents used to dissolve a large number of polymers. In table 5 starting on p. IV-354 discloses solubility parameters of a number of polymers determined by calculation in sol and by other methods. the hydrogen bond increment value given below. To form the internally softened polymer system of the present invention, the polymer in the first step and the monomers in the second step are selected to interact to an appropriate extent, depending on the degree of compatibility desired between poly. - more in the first step and the monomer rates in the subsequent steps Here are both upper and lower limits with off-_ (second step or later or last as previously described).

It is found that the appropriate degree of compatibility can be expressed> in numerical terms by a property based on solubility parameters and referred to herein as interpenetration parameters, Ip. the penetration parameter can be considered as a solubility parameter set so that strong; moderate and weakly hydrogen bonding solvents are transferred to the same scale. For a given molecule, the interpenetration parameter is defined as the solubility parameter plus detiwi Solubility parameter Inter- for different molecules including a number of monomers are given in Tables 1 and 2 of Burrel starting on page IV-341. These tables also give the hydrogen protecting group for a given molecule, Increment , a new term according to the present invention, is 17.2 for strongly hydrogen bonding molecules, 7.2 for moderately hydrogen bonding molecules and 2.8 for weak hydrogen bonding molecules.1 A The following table contains a list of monomers together with the values of their solubility parameters, interpenetration parameters and water solubility, as well as the hydrogen bonding class of the monomer.

The solubility parameter values and hydrogen bond class of most of these monomers are thus set forth in Table 1 of Burrell. Vinyl alcohol is a special case because, as is well known, this monomer does not exist in a stable state. Polymers containing mer units corresponding to vinyl alcohol can be prepared by hydrolysis of a polymer containing corresponding vinyl ester units, such as vinyl acetate. The solubility parameter of this hypothetical monomer is calculated by the method of Small as indicated above.

Values of other monomers not found in Burrell's table are determined or calculated in accordance with the instructions in Burrell's writings v.s. Dimensions of the solubility parameters given in the table are the usual square root of (calories per cmñ).

The interpenetration parameter has the same dimensions. Water solubility is given in g monomer per 100 g of water at 2500. The hydrogen bond class 10 strong, moderate or weak is determined using the procedure according to C, M. Hansen, Journal of Paint Technology, vol. 39, p. 104-117 and 5o5 ~ 514 (1967). , _ »Soluble- Interpene- = Hydrogen- trat1ons ~ Water- For- Monomer parameter bind. parameter solve. shortening Acrolein _ '9.8 S 27.0 40 - Aer.

Acrylic acid 12.0 S 29.2 CM AA Acrylonitrile- 10.5 P l§ .5 25 ~} O AN o-bromobyrene 9.8 P 12.6 8 BrSt '1,3-butadiene 7.1 P 9.9 “Bd” 1-Butylaxrylg fi -8.5 M 15.2 0.2 1BA n ~ butyl acrylate 8.8 M 16.0 0.2 BA Butyl methacrylate 8.2 M 15.4 0.01 'BMA Chlorostyrene' ^ 9.5 P 12.3 _ clsp 1 + dexy1axry1au 8.2 M 7 15.4 o, o1 1DA .Dichlorethylene 9.1 P 11.9. 0.01 DCE Ethyl acrylate 8.6 M 15.8, 1.51 EA Enylene oxide 11.1 M 18.3 cmM 2Eo Ethylene epichlorohynrin, 12.2 s 29.4 7 EEPC Dimethylamino-ethyl methacrylate 7.0 S 24.2 CM DMAEMA Dihydroxypropyl methacrylate 9.0 S 26.2 CM DHPMA Ethyl hexyl acrylate 7.8 M 15.0 EMA Ethyl methacrylate 8.3 M 15.5 0.1 EMA 1-hexene 7.4 P 1012 hex Hydroxyethyl methacrylate 8.0 S 25.2 HEMA Isoprene. 7.4 AP 10.2 Ipn Maleic acid- _ 8 _ 1 anhydride 13,6 -S_ 30,8 16,5 (79) MAn Methacrylic acid 11,2 "S 28,4 CM MAA Mecy1axry1a: 8,9 M _ 16, 1 5.2 MA Methyl 1-methacrylate 8.8 M 1 16.0 1.6 MMA “2 ~ methyl1StyPen 8.5 1 P 11.3 Mest Styrene 9.3 P 12.1 ST 10 15 20 25 30 35 78029ö1-1 * 15 vinyl acetate 9.0 M 16.2 2.3 lvia vinyl chloride 7.8 M 15.0 V01 Vi lt yltoluen 9.1 P 11.9 vcø1 = '(vinyliaconol) 8.4 s 25 , 6 (cm) von "'S = strong' P = weak M = moderate - CM: completely miscible 1 _ as maleic acid.

For a latex polymer according to the present invention, the interpenetration parameter for the first stage is greater than the V for the second stage, preferably at least one unit larger (however, the calorie interpenetration parameter in the first stage must not be too much larger than that for the second stage. not more than 8 and it is desirable that it is not more than 6, preferably 1 to 6. Units If the polymer in the first step contains 65% by weight or more of C 1-4 alkyl alkylate, C 1-4 alkyl, alkyl methacrylate, styrene or a mixture thereof, it is desirable that the IP for the first stage is not more than 6 units greater than that for the second stage, with a difference of 1-4 units being preferred and 2-3 units being especially preferred. 50% by weight or more of vinyl acetate, it is desirable that the IP for the first stage be 1-8 units_ greater than that for the second stage, with a difference of 2-6 units being preferred and 4-5 units especially for edragen. It should be noted in this context that the second or later stage may contain certain hydrophilic monomers and still adhere to these rules for the difference between the interpenetration parameter for the first stage and that for the second stage.

As stated above, in a preferred embodiment, the first stage contains acidic, preferably carboxylic acid moieties as well as the other hydrophilic moieties. Carboxylmer units are preferably obtained from the monomers acrylic acid, methacrylic acid or itaconic acid. The other hydrophilic moieties are preferably hydroxy-C 1-4 alkyl methacrylate; hydroxy-C1-C4-alkyl acrylate or vinyl alcohol units. e. The viscosity of the polymer emulsion formed can be measured by any of the known methods, preferably with Brookfield Synchro-Letric Viscometer model LV 1, the choice of spindle and speed being preferably made to combinations such as 10 15 20 25 30 years! '_11 7802931' -1 16 results in a reading within the intermediate range. Measurements at 20 ° C are made at pH values in the range of 10 ~ 10 on emulsions which have been adjusted with water to a solids content of 20%. The pH of the acid-containing copolymer emulsions is generally controlled by the use of a mineral base, an organic base such as an amine, or ammonia, the latter being preferred. Internally softened polymer latex containing basic groups, such as amine groups or quaternary ammonium groups, can be adjusted for pH by using mineral acids, such as hydrochloric acid, or organic acids, such as acetic acid. The latex viscosity in the pH range 3-10 is usually below 5000 centipois, preferably below 500 centipois, especially below 150 oentipois and in particular below 40 centipois and most preferably below 10 centipoisps. the values are especially desirable for certain applications, such as in floor polishes. The minimum film temperature (MFT) should be measured on a film cast from a latex with 20% solids and a pH of 7.5-9 for ammonium neutralized, acid-containing polymers and 3-4 for γ-acetic acid-neutralized base-containing polymers. The American Society for Testing Materials Method D2354-68 is followed.V * MFT is more than 5 ° C-below the calculated glass transition temperature (Tg) of the polymer when Tg is above 5oC. Preferred are MT values below 1800 with polymers with a Tg calculated for the whole polymer composition of more than 2500. The term MFT used herein to define certain polymers refers to the value determined on a latex at the solids and solids just specified. In some of the following examples, MFT values given under other conditions are given for comparison purposes only and do not refer to MFT values used in defining the polymers of the present invention. Hardness is expressed as Knoop Hardness (KHN) and is determined by Tukon Microhardness Tests on a film formed by casting the latex on a solid surface, such as a glass plate.

It is preferred that the polymers have a KH greater than 3, with greater than 5'¿ being preferred and greater than 8 being especially preferred.

Calculated Tg for each step and for the polymer as a whole is determined by calculation based on Tg of homopolymers of individual monomers as described by Fox, Bull.Am.Physics Soc. 10 15 20 30 35 lv i 7802931-1 1, 3, p. 123 (1956). ¶Tables of Tg of homopolymers are given in the "Polymer Handbook", Section III, Part 2 of w.A. Lee and R.A.

Rutherford. the desired calculated Tg for the first step is less than 4000, with less than 500 being preferred and less than -1000 being especially preferred. The desired calculated Tg for the second step is greater than 3500, with greater than 7500 being preferred and greater than 100 ° C being especially preferred. the whole polymer composition is greater than 1500, preferably greater Calculated Tg for the polymer calculated on than 2000 and especially greater than 3000 for floor polishing agents and similar uses. For certain other purposes, such as adhesives, adhesives and paints, polymers with calculated Tg values below about 40 ° C including values below 0 are suitable.

Internally softened polymer emulsions of the present invention may have a remarkable combination of properties, '_' (1) low minimum film temperature coupled with high hardness (2) low polymer emulsion viscosity up to and including i Comparatively hard latex polymer systems especially and high Tg and neutralized state. can thus be used with much less coalescence than is usually the case or no coalescence at all. This is especially valuable in situations where coalescence gives rise to secondary disadvantages.

Due to the absence or minimization of added coalescence in the formulation, coatings which produce hardness for a very short time can be prepared from the polymers of the present invention.

Additional benefits associated with the elimination of added plasticizer, coalescing agent or organic solvent are reduced cost, reduced flame susceptibility during treatment and reduced emission of toxic and polluting fumes during and after application. These properties are of particular importance in the preparation and use of water-based industrial coatings, both clear and pigmented. In the paint technology, the advantages of extremely fast drying and non-flammability of internally softened polymers are of paramount importance. In the field of commercial coatings, the combination of high hardness and low minimum film temperature is important for a blocking-resistant and air-drying coating. A further advantage of the latex according to the present invention is that the preparation is very simple, which results in a significant saving of costs due to fewer ingredients and easy mixing in factory operation. The simplicity of the mixture probably stems from the fact that the latex prepared according to the present invention is resistant to so-called "shocking phenomenon"; ie the latex does not flocculate or gel easily when mixed with the second component of the preparation. The ingredients can thus be mixed in any order in traditional factory equipment and, in addition, the equipment as such is obtained in a much purer state than with ordinary latexes.

As described above, the polymer latex of the present invention is particularly useful in replacing systems with latex plus plasticizer or latex plus coalescer, which includes a number of formulations used in a variety of fields where polymer latex is present. These latexes are useful in the formation of free films as well as in the formation of coatings, such as in paints, varnishes, varnishes, powder coatings and the like. The latex of the present invention is also useful as an impregnating agent and binder for both natural and synthetic materials, such as paper, textiles, wood, tiles, metal and leather, and as a binder for non-woven products. They can be used to lower the minimum film formation temperature or to facilitate film formation of other latex systems when used in combination with them. Pigments, dyes, fillers, antioxidants, antiozone agents, stabilizers, flow control agents, surfactants or other non-mandatory ingredients may be included in the polymer compositions of the invention.

The polymer compositions of the present invention can be applied with or without solvents by permanent or removable casting on suitable substrates, especially for use as a coating, filler or binder. Application by brushing, flowing, dipping, spraying or other known method can be applied to apply the latex of the present invention. One of the particular advantages of the present invention is that reactive polymers can be prepared for use as air-cured or thermo-cured coatings, fillers or binders without the need for organic solvents, coalescents or plasticizers, although small amounts of these materials may be desirable. This is especially valuable because the elimination of volatile solvents or other volatile materials, such as coalescents, reduces potential ecological risk. TS 20 25 _30 35 19 (7so29z1-1otl: It is of particular importance that the acid groups, hydroxyl groups or the other functional groups incorporated in the first stage of the polymerization remain available for further reaction, such as neutralization or crosslinking} This availability distinguishes the internally softened polymer latex from a latex in which a second or later step so overrides or interacts with the first step that the availability of the first step functional groups for subsequent reactions is reduced or eliminated.The crosslinking referred to may be any of the the usual types, such as coordination crosslinking, ionic crosslinking or covalent bond formation.In general, the reactions in these latexes can be ionic or covalent reactions.Ionic reactions are illustrated by the ionic crosslinking in the use of these latexes in floor polishes as indicated below. bonds through turnover with aminoplasts, epoxy resins, isocyanates and beta-hydroxyethyl esters are well known in the art.

A The polymer latexs of the present invention are particularly useful in the manufacture of floor polishes and are advantageously used in floor polishes disclosed in U.S. Patent Nos. 5,528 E25, 3,767,610 and 3,573,259.

In general, the polymer compositions utilizing the polymers of the present invention can be defined with respect to the following properties of the main constituents: Ingredient: AEQÉÄ (A) Water-insoluble, internally softened addition polymer, parts by weight 10-100 (B) Wax ditto o-90 (c) Aliquots o-90 (D) Wetting agents, emulsifying agents and dispersants% 0.5-20 (E) Polyvalent mecall stirring ditto o-50 (F) Water to a total amount of solid constituents 0.5-5%, preferably 5-30%.

(D) refers to weight percent on the weight of A + B + C (E) refers to weight percent on the weight of A.

A, B ooh C should together be 100.

The amount of C when present may be up to 90% by weight of the copolymer of A and preferably from about 5 to 25% by weight of the copolymer of A. For a non-polishable, self-polishing composition, the wax should not exceed 35 parts by weight. and is preferably 0 ~ 25 parts by weight per 100 parts by weight of total polymer plus wax according to the above table.

Satisfactory non-polishable floor polishes have been prepared without the use of a wax. The wax is not an essential ingredient in a self-polishing composition. For a dry polishable polishing composition, the wax should be at least 35 parts by weight of this total amount.

Ex. on hydrogen and dispersants are alkali metal and amine salts of higher fatty acids having 12 to 18 carbon atoms, such as sodium, potassium, ammonium or morpholinoleate or ricinoleate, as well as customary nonionic surfactants. Additional wetting agents improve the dispersing properties of the polish.

For polishing floors, the coating obtained from the composition should preferably have a Knoop hardness number of 0.5 ~ 20 when measured on a film thereof with a thickness of 1-3-6.3 .mu.m on glass. This hardness range provides good resistance to abrasion and wear and can be obtained by suitable selection of monomers for polymerization. Preferred embodiments of the invention will now be described by way of illustration in the following examples, in which parts and percentages are by weight unless otherwise indicated. A šëêmnslil Preparation of internally softened polymer emulsion A latex with first steps, second steps and average ~ Tg values of -14 ° c, 1o5 ° c resp. 54 ° c is prepared as follows; A. Equipment E A five-liter, four-necked piston is equipped with a radiator, agitator, thermometer and monomer auxiliary pumps. Heating, cooling and nitrogen purge means are provided.

B. Material supply Vessel- Monomer Charger ßseed material charge step 1 step 2 water 2oo8 g 400 g 400 g Sodium lauryl sulphate (surfactant) 16 2 2 Butyl acrylate (BA), - 600 + Methyl methacrylate (MMA) ~ 140 1000 Methacrylic acid (MAA) ~ 60 ' - Hyaroxyethylmecacrylac (HEMA) - 212 - Sodium persulphate in 100 g of water (catalyst) 12 «- 10 15 20, 25 30 21 78Q2951 ~ 1 C. Procedure ll Add carbonated water and surfactant to the vessel and start stirring and nitrogen purge. Combine the materials of each of the monomer batches and mix thoroughly to obtain stable monomer emulsions. V 3. Heat the vessel to 82-84 ° C with continuous mixing and nitrogen purge. 4. Add the catalyst solution to the vessel and start the addition of the monomer charge step 1 at such a speed that the addition is completed in about 50 minutes. Maintain the temperature at 82-8490 throughout the polymerization. 5. When the monomer charge step 1 has been added, maintain 82-84 ° C for 15 minutes. 6. After the hall period, start the addition of monomer charge step 2 at such a speed that the addition is completed after about 60 minutes. Maintain the temperature at 82-8400 during the polymerization. _ @ 7, When the addition of monomer charge, step 2 is complete, maintain 82-SÄOC for 50 min., Then cool and filter; A sample of the latex is neutralized to a pH of 9 with J ammonia; MFT is below 1500 and the viscosity is 15 centipois (Brookfield Viscosity, 20% solids). A film cast from the neutralized latex has a hardness of 12.1 KHN. ' In Exemgel 2 “Sequence charge ratio In accordance with the general procedure in ex. 1, three internally softened polymer latexes are prepared with the same composition in the first and second steps but with a different weight ratio between the first and the second step. The details are given in Table I.

It is found that the balance of properties low MFT and at the same time low viscous emulsion, is dependent on the weight ratio of hard hydfßf fl b andfas fi esscharee to soft hyarophilic forscastegsearge. ' This makes it clear that in a given monomer composition a few simple trial and error attempts may be required to determine the charge ratio required to obtain a product of the present invention. Table I shows the effects of 'change of charge ratio, where running as has low MT low viscosity at neutralization and high Tg. It can be seen from the table that run 2B gives a latex polymer according to the present invention, whereas run 2A has much too high viscosity at pH 9 and EC too high MFT. Runs 2A and EC are therefore given for comparison purposes only. Example 2 Polymerization Procedure The difference between a single emulsion copolymer, an internally softened polymer and a physical mixture of the two polymers is shown in the data set forth in Table II. All polymers were prepared by emulsion polymerization substantially in accordance with the procedure of e.g. 1 apart from the fact that at the time of the execution of runs 3A and BC there was no other charge, which are therefore stated only for comparison purposes. The total composition of each of the three examples is the same; estimated Tg is 4700.

TABLE II Pole erposition MFT / viscosity * driving BA / š fi n / MAA / HEMA / VMMA Description pa; pHA9 5A (cf.) 23/56/6/15 // o single charge, 52/3 46/55 single copolymer? 3Bb 23/6/6/15/750 internally meant 40/6 io / 140 polymer 3c (3sq.) 23/6/6 / äs / 750 physical 10 / io 1o / ge1- mixture image. arysikaiisk mixture 50:50 av (BA / MMA / MAA / HEMA = 46 / ia / 12 / Bo) than (MMA: 100). The polymer_ in run 5B is the same as in run 2B.

It can be seen from Table II that the single charge polymer from run 5A has an MFT in the vicinity of calculated Tg. The physical mixture, i.e. run} C: a mixture of an emulsion with the composition of the first stage of the run EB polymer with one with the composition according to the second step, run EB, is so viscous at high pH that the emulsion gels even if it is diluted to 20% solids before pH adjustment. Obs. that the internally softened polymer after neutralization to a pH of 9 has a much lower MFT and only moderately higher viscosity than the single batch copolymer.

Example gel 4 Balance of a hydrophilic / hydrophobic character for the steps Using the polymer emulsion from run 23 as 7802931-1 .m> <; nwEhHom Hmuo »sno Amv umwmnm mnucm. ^« V uommpm mwmnmm uæv äwm oo fl mmcxmhwn w> u H »wpHmoxmH> \ oo H mmwnæ Hmä .uwwmum mn fl nm» mv zoo um fi nm fifi wë co fl nmnmnmm ww fl m »um hmm wmucmw fl m ^ \\ v Mumhuw fl mnnßnw 4n \ ww m \ @> \ m \ \ m. fi \:. wH ^ .MEm fi v om ø $ fi \ o fl m \ o: på mo fi q om \\ m fi \ w \ m \ nm mm ooo.m fi \ o «m \ mm mn mo fl 1 o # \\ w fi \ w. »\ ~.> \ m.» m ^. @ smwv m mm n ma .w> <Amv HV <2 ^ .ømu = mpmwn mpmmh & oNv @m »Hm @ xmH> \ amz wa AN mmßß fl momsw fi mwa fi ßøw a fi apom H nQmm In the control, the composition ratio between the water-swollen first stage polymer and that of the second stage is varied. The interaction of the first stage polymer with the second stage polymer is demonstrated by achieving internal softening with controlled viscosity through sequence-narrowed (1) soft, hydrophilic and functionalized and (2) hard and hydrophobic copolymers. This internal softening is shown to be dependent on the hydrophobic / thidrophil I balance of the two monomer charges in accordance with the data in Table III.

TêBELL III fí Tg MFT / viscose.

Driving Composition 1 '(1) (2) Avg. pH 5 pH 9 4A * sA / MMA / MAA HEMA // MMA 11 100 117 40/6 IO / UPO 23 / B / 6/15/50 _ 1113 BA / MMA / MAA HEMA // lwM / x 29/0 / ß / 15 / Bo -13 105 as 30/10 10/70 40 EA / MAA / HEMA // MMA 29/6/15 // 50 111 105 55 55/10 10/11100 4D (jamf) eA / MMA / MAA / HEMA / sT 4 100 116 20/10 10 / 22,5_ / 6,5 / 6/15/50 30,000 xThe polymer emulsion of emulsion ÅA is the same as of run QB.

The results in Table III show that betr. driving ÅA a more hydrophobic, ie less hydroiil, first stage polymer than ear, ÄB; In a more hydrophilic first step, 40, leads to high viscosity; an overly hydrophobic second stage, 4D, leads to_very high viscosity at high pH, too high for most uses.

Exemplary gel ä I I 'Interpenetration parameter Emulsion polymers of a number of compositions with different interpenetration parameters (Ip) in the two steps are prepared by the procedure according to ex. 1 (runs 5A-5D, 5F-BH, 5J-5L and 5N ~ 5R) or ex. 8 (runs 5E, 5I and SM) given below.

Determination of emulsion viscosity and MT performed on the emulsion neutralized to a pH of 7.5-8.5 with ammonia and diluted to 20% solid polymer constituents and by the film hardness shows that the formulations gave rise to internally softened polymers. Tables IV.A and B list these data. 25 'fjämf.) 79029z1 ~ 1 TABLE Iv.A' Kjgggß Komgosifqjggg Eërhàllande »5A kBA /» M / MAA / HEMA / MM 23/6/6/15 // 50 53 BAAum / MAA / HEMA // mm 30/7 / 3/10 // 50 5 :: BA / mm / MAA / nmMA // mm 30. 5/9 / 3/7. 5 // 50 sn nA / mfzA / raAA / HEMA // m 34, s / 9 “, 4- / 4, 3/8 ,, s // 43 _ ss EA / vAc / voH / MAn / AA // sr 5.5 / 37.8 / 5.6 / o, 4/0, f7 // 5o sF v BA / m / MAA / DHPMA // wm 2s / 11, s / 6/1 // so 5G BA / mm / MAA / vAc / voH // MM / xzs / s / s / m, 5 / 1,5 // 5o sn 'BA / mm / nMAEMA // mm 1s / 1I7 / 1 s // so I A51 EA / vAc / voH // sfr I 23 / 23,9 / 2, _1 // 50 _55 v kßA / r fl flA / MAA // sr / AN és / 21,5 / 3,5 // 3o / 2o> (Jämf-A) . - '~ 5_1 <ßA / maA / MAA / HEMA // ST, 22,5 / 6,5 / 6/15 // S0' (aämf) - '' sL _ maA // BA / ifmm / MAA / HEMA so // z, 3/6/6/15 f (cf. _._) - '5M lBA / voH / vAc // ßm 24 / 2,1 / 23.9 // 5o w BA / MMA / MAA / DmMA // mm 25 / 11, s / a / 'z, s / V / so so BA / MMA / MAA / HEMA // rm 30/7/3/10 // 50 - sp BA / »mA / mAA / nEm / A fl m 3o, 5 / a, 2s / 3,75 / 7, Vs / 1 / s @ so BA / »MA / MAA // ST / AN 25/19/6 // 50/20 cf. ) V 51: rEA / sT / MAA // sm '21/24/5 // 50 26 78Ü2931 ~ ï. @ HHm_, Nnmm mm Qom. mv, mm m w w.- m mmm mv mmm, m V om m. «o“ mH_ m.m fl mm mom. mm: .m mum, o fi m fi m.mH mm mom «H | m m vs m ow o.mH mv m mom 1: o.m o.mH o_mH mmw mom v mm «.o o.mH wmm fl mv mom m || Nm H. ~ H fi. O ~ mv com m mm _m. «M. ~ H m.mH vw mm W m mnv mßmm« ~ mH vw Qom m 1: «.m mmw fi m.mH mm oem mm mm m N o mm_ m.mH mw with m 1: mmm omwm m fi m fi mv mom m | vd omm øhw fi 0 mm mv mom. v mm m N o md m.m fl mm mom «fi | mm H.m omm fi H.mH vm mø fl em: mm m. ~ Q mm mmmm wm mom mm: NH Nmv omwm Nmow mw mom v m aà m; E ä, mmm mm å ww v m.> H nAmm mn om nav m fi v omv omv m fl v omv mv m fl v mmv m fi v Om UAV wa wa mmv omv Hßï vmßwmoxw fi b a .om Mm @. Fl x mm mm .M mmv am m mm .m øm Hmm ^ .mEmmv. gm mm zm om ~ .v. . zm ooo.om ^ .mswn ^. Mm ow _ M.memwv hm mm Hm ov mm omm mm owm, mm mm mm m mm m um m mm ow fl mm .mmm .wnmmmmw 10 15 20 25 30 35 40 21 7802931-1 Remarks re. Table IV.B. V 1. viscosity was measured on the latex at 20% solids and brought to a pH of 4 with ammonia apart from e.g. 5H, where the latex has a pH of 3 with acetic acid. 2. iver, i ° c, latex at 20% rest constituents and (adjusted to pH 9 with ammonia except eg 5H (pH 3 as above) 3. Hardness is Knoop Hardness Number (KHN) determined by the procedure. stated in Resin Review; vol.XVI, No. 2, page 9, ff (1966), a publication from Rohm and Haas Company. A li 4. Tg is calculated for a high polymer by the procedure according to Fox.vs "(1)" and " (2) "represents the first and second or later steps and" avg. "The value calculated for the composition as a whole. 5. Ip is calculated for the first step (1) and the second step., N _ ;; (2) The difference between these IP values is given under n (1_2) n_ b. The data given in Table IV.B show that an internally softened polymer is obtained, as shown by the glass transition temperature, minimum film temperature, emulsion viscosity and hardness values, when the interpenetration parameter value is greater than the maximum. secondly but not too much larger.

Run 5J, a polymer latex according to the prior art, does not refer to internally softened particles, as can be seen from the proximity between Tg and MFT.

As indicated in Table IV.A, this polymer has only 7% hydrophilic mer units in the first stage polymer. Run 5K does not refer to internally softened particles of the present invention, as evidenced by its high viscosity; as indicated in Table IV.B, its composition is such that an undesirably large difference 1 Run SL is not in accordance with the present invention, its viscosity is so high that a gel is formed; obs. in the two steps is too low, it is below zero. 5Q and 5R, prior art polymer latex, have MFT values neither containing nonionic hydro- Ip present between the polymers in the two steps. that the Ip difference between the polymers runs exceeding the Tg values; file monomers in the first step.

Example gel 6 gplvgolent A floor polisher is prepared by mixing the ingredients according to the following reoept (except runs 6A ooh 6E as indicated below): 10 15 20 30 35 '40 7802931 ~ 1 function Carrier Wax Wetting agent Compensating agent Defoaming agent:.

Base 28 Material Polymer emulsion-f 15% solids Poly EM ~ 4O - l5% solids (trademark- Cosden Oil & Chemical Co) Fluorad FCl28 - 1% solids' (trademark} M Co.) Tributoxyethyl phosphate - 100% active sws- 211 - 50% solids (trademark Stauffer Wacker Silicone Corp. Amount l00.0 parts 15.0 parts.) 0.5 ae1arÛ ~ '' 0.5 parts) 0.01 ae1ar Ammonia - 10% aqueous solution to pH 8 tdolvpolner ~ applied and tested by the procedure described in detail in Resin Review, vol. XVI, No. 2, 1966, published by Rohm and Haas Company, Philadelphia, Pennsylvania 19105 unless otherwise specified.

Polymer emulsions used and test results obtained are found in Tables V.A and V.B. eTABELL VA (comparison) Driving 6A 63 6c 6D 6E Polymer emulsion (note 1) grain.2B grain.5O grain.5P grain.5E (note.3) (note.4) Test (note 2) Visual gloss ,, _ One coating g-mg mg mg mg g-mg Two coatings mg mg-utm. mg-utm. mg-utm. mg Smoothing A coating utm. utm. utm. utm. utm.

Two coatings utm. utm. utm. utm. utm. 60 ° gloss 71 82 79 80 77 Hälmärkes- «'täml. resistance (TM 5) mg-utm. g-mg mg mg ~ utm. good Water Resistance (TM 4). »1 hour g utm, utm, utm, utm. 1 day g-mg utm. utm. utm. utm.

Deter entresistance (TM 6 - V 1 dysn ms ss ms - 3 days mg-utm, '- ~ - ~ - täml.g 7 days mg-utm, mg. Mg-utm. Mg-utm. - Removability ( TM 7) mg ütm. Utm. Utm. Täml.g Static friction coefficient (TM 1) 0.5 0.6 0.6 0.6 - Powder formation (TM 2) light zero zero zero - _. ...__ .., ...... _. Wu.-. 10 '_15 20 25 30 55 40 29 7802931-1 Note for table VA V 1. run 6A illustrates the state of the art / Here a floor polishing polymer emulsion with 1,65% zinc ion crosslinker This polishing agent is prepared by mixing the ingredients according to the following recipe: Function Material l 'Quantity Carrier BA / MMA / MAA copolymer emulsion _ V - 15% solids 80 parts Wax Poly EM ~ 40 - 15% solid constituents A ^ Adelar (trademark Cosden Oil and Chemical Com) - l5 parts Alkal1löel§ pagmelecular nelecrylnerte - 'resin l5% solids 5 parts Coalescer diethylene glycol monomethyl- Medium ether _ -. 4 parts Soft, meael aibutyl - 1. 0 parts hydrogen flour Fluered Fc-128; 1% solid '- _ constituents (goods. BM Co.) 0.4 parts Smoothing agent tributoxyethyl phosphate - 100% active 1.0 parts Foam inhibitor SW-211 - 50% solids - ~ 'In medium (trademark Stauffer Wacker Silicone Co.) 0.01 parts 2. Application of the floor polish is described in ASTM Method I Dl436-64, Method B. (ASTM - American Society for Testing 'Materials, Philadelphia, Pennsylvania). The specified test methods are listed below. Run 6D is performed with 1.25% zinc ion on emulsion polymer components. _ _ The recipe for the polish in run 6E differs from that for 6B, C and D excluding wax and defoamers and the addition of 2 parts coalescing agent, diethylene glycol monomethyl ether. '“3 Test methods for Table V.A - indicated in parentheses in the table. l.

Gl1an1ng = - ASTM method 02047-72; plate kenaitienerede § at 25 ° c a 55% relative humidity. '' Powdering: ASTM method D2048-69. 60 ° gloss: ASTM method 51455-64 - vinyl pletce (kentlle no. R ~ 44, Kentile Floors, Inc.), instead of OTVA plate in this experiment.

Water resistance: ASTM ~ method Dl793-66, dynamic test procedure. 'Resistance to rubber heels: CSMA Method 9-7) (Chemical Specialties Manufacturers Association, Washington D.C.) __ ... _ _ _ .. .___._.__..___ .. + ...._._.- 10 ia 20 925 ÉO 7802931 ~ 1 S0, test modified by rotation 15 min. in every direction. 6. Detergent resistance when driving on black vinyl asbestos board using 10 ml of 5% water detergent Forward (trademark S.C. Johnson), running 50 cycles in 1 day, in 75 during the third day and 100 cycles during the 7-day tests. 0 V g ~ 'U 7. Removability when driving for 75 cycles using 10 ml 3% Spic and Span (trademark Procter & Gamble) and 1% aqueous solution of ammonia on a black vinyl Å asbestos board. '' _l 'V Solution tests are carried out in a corridor with vinyl asbestos-tiled floors that are exposed to a daily traffic load of 3500-4000 pedestrian passages. A section of the corridor (3.5 m wide and 7.2 m long) is sanded off and freed of residual polish and re-polished in a typical gatekeeping procedure as follows: In the floor dust, a 1: 1 aqueous solution is removed to remove loose dirt of commercial stripper solution, Step-off (SC

-Johnson & Sons, Inc., Racine, Wisconsin 53404) is applied with a wire mop in an amount of about 25 m2 / liter; after a 5 min. drowning period, the floor is washed with a 40 cm black floor strip cushion (BM Co., St.Paul, Minnesota 55101; Scotch Brite Slim Line Floor Pad No. 61-6520-0105-O) in a floor machine operating at 500 rpm.

(Mercury Floor Machines Inc., Englewood, New Jersey, Model H-15-c); the treated floor is thoroughly rinsed twice by steam mopping with clear water and allowed to dry. The treated floor is divided into 1.6 m sections perpendicular to the normal direction of corridor traffic; On each of these sections a coating of polish is applied for testing with a wire mop in an amount of about 50 m2 / liter. After the original polish has been allowed to dry for 1 hour, a second coating is applied in the same way. The appearance of the polish is assessed from the beginning and after 1 and 2 weeks of heavy wear. The results of these observations and other tests in accordance with the procedures used in obtaining Table V.A are shown in Table V.B. . _ _. 'lOaM 15 20, 25 EO 35 31 _ TABLE V.B Driving I. 6A 6B .6C 6D yyâgrunglig: Gloss (visual), mg. mg mg + mg + Equalization '' ~ ~ utm. utm. utm. utm. Relocability V utm, mg-utm. mg-utm. utm.

One week wear: W Gloss (visual) _ g-mg mg mgA4 mg + Dirt absorption resistance utmà utm. utm. utm.

Resistance to black heel. mg-utmÅ mg mg ¥ utm. mg Abrasion resistance mg-utm; A mg + mg-utm. mg 2Xå_vgpkors abrasion: Gloss (visual) ag g _ g + - g + Dirt uptake resistance ___w_mg mg "5" * mg- 'W mg? Resistance to black heel A mg mg- mg mg Abrasion resistance 'g-mg g-mg g-mg g-mg The abbreviations used in Tables V.A and V.B are: utm. = excellent; mg = very good; g = god; + = plus; - = minus except for use between the abbreviations where the sign refers to "to". 'Exemgel Z Varnish and paint _ The polymer latex in ex; l is prepared as follows: Run IA: l Adjust 40% solid latex constituents to pH 9 with 14% aqueous ammonia solution.

Run TB: To 100 parts by weight of the latex adjusted to pH 8.5 with 14% aqueous ammonia solution is added a mixture of 9.7 parts of water and 15.3 parts of butoxyethanol.

Driving IC: The ingredients are mixed as follows: Weight parts Water _ _ 4.7 Tamol 165 (22% aqueous solution) (Rohm and Haas Co.) _ 1.3 Triton CF ~ 10 (100%) (Rohm and Haas Co.) 0 , 16 Nopco NXZ (Diamond Shamrock) 0.05 Zopaque RCL ~ 9 (@ iO-pigment) (SCM Corp.,, Glidden-Durkee Division) 18.8 - ~ ... t ..... ~ ... _l. ._ (_ ............_............._....-.-..... ....,,., ..... ~ ...,. .m _ 10 i5 25 50 35 7892931-1 i sz Weight grinder * Grinding 1 sufficient speed disperser (1200 m “/ min.) for l5 min. and setting while stirring with: Polymer latex 70, 4 water “1.8 V Butoxyethanol I * 2.8 Total 100.0 Key lacquer ~ and color properties are determined according to the usual paint industry procedures. The results of the determinations on films made from preparations by coating sheet metal are shown in Table VI. TABLE VI Properties2 (}) Driving 7A Driving TB Driving IC Testing for contact-free freedom (min. At 25 c and 40% relative humidity) 19/21 Air dry hardness KHN, 1 hour at 2500 and 40% rei. Humidity 6.5 final hardness KHN 6 5 (baking 30 min.) Hect pressure (6000/16 cm / 60 ') no 0.3 ass) (baking 122 ° c no Dornfiexibiiitet (1.5 mil /' B-iooo / 1 hr. At 122 ° c) (13, 6.5, 3 mm mixtures) O / 1/1 // In shock in-Le (D / R) Aioaine 12oosX_ 50 / ï6 (2) in T-bend - T-Tl Water rinsing (16 hours at 37 c) Cleveland condensed àp (16 hours at 4o ° c) Chemical and staining resistance: Alcohol (16 hours) light rust, no blisters moderate attack moderate attack Ink (30 min.) no attack Mustard (30 min.) Lipstick (ÉO min.) Petrol (50 min.) No attack no attack light attack light to moderate attack approx »l 6.5 mkt light track / 27-8 in moderate rust moderate rust moderate rust no blisters mad. blisters mod. blisters (moderate attack mild to moderate attack .a -..._ _ .. _.... f. ...- _ u-aw. 10 15 20 25 ÉO 35 MO 1.3 7802931-1 1 thick films baked for 1 hour at '' Results determined at 3.8 12200 for film tests unless other conditions are stated.

Air-dried films have values of 2 / l. ' The data given in Table VI.A show that the run YA gives a latex which dries very quickly to full hardness to form a film which is both hard and flexible without the aid of a coaicent. Such an agent retards the development of hardness and has a detrimental effect on certain resistance properties.

Resistance resistance ~ 2 Baking is required to maximize certain properties. The conditions are generally good, although the results are good. waterlogging and alcohol resistance are not as good as the other results.

Driving YC shows that the latex according to ex. coalescing agents can be used to form pigmented films with a comparatively small amount of l. The physical properties of the formed film are parallel to the properties of the unpigmented film. Other tests on the film formed in run 7C state: moderate i is rust of a sample exposed 5 days in a humidifier, signs of Q destruction after 5 days in a salt spray cabinet and change in gloss after 32 hours at 58 ° C in a Cleveland Condensing Cabinet as follows: 'Original (200/600 / B00) gloss final (2o ° / 6o ° / 8o °) gloss Example 8 Internally softened polymer emulsion based on vinyl acetate A latex with Tg values in the first step, second step and an average of 25 , 100 resp. 58 ° C and IP values of 17.5 and 1221 for the first resp. the second stage is prepared as follows: A. Equipment A five-liter, five-necked piston equipped with a radiator, effective 54/77/88 21/60/72 .. .. <~ .-- .., ....... stirrers, thermometers, funnels and means for heating, cooling and nitrogen purge.

B. Materialcharger Monomercharge. [Raw material »l lA- 2 Vessel charge § I Deionized water l66.3g 154 g 883.7g L octylphenoxylpoly (59) -; ethoxyethanol}; 4 5.1 1.7 5 Abex 185 (33%) '(Alcolae Inc) 8.5 12.8 4.3' sulfonate (23%) 6.8 10.2 3.4 Sodium dodecylbenzene II V10 15 20 25 50 55 40 78Û2931 ~ 1 34 Ethyl arylate 37.8 - “i 19.1 vinyl acetate '298.5 150.8 Styrene_ ~ 517.5 é Maleic anhydride #, l' - - Acrylic acid - - 7.2 - - : nir1at @ r = Fe + * - (0.15% »Feso4.6H2o) 6.4 ml of 0.26 g of ammonium persunate (APs) in 8 g of water. 0.26 g of sodium sulfoxylate formaldehyde in 8 g of water. Catalyst 1.92 g of APs and 0.52 g of t-butylhylax + peroxide (tBHP) in 110 g of water. Activator: 1.92 g NaHSO3 in 110 g water.

Chaser: 0.52 g tBHP in 5 g water. 0.39 g of sodium sulfoxylate formaldehyde 5 in 5 g of water. Procedure I The monomer batches and vessel batches are weighed separately and each mixed to form an emulsion. The initiator mixture is prepared and transferred to the vessel. Efficient vessel agitation is carried out throughout the reaction sequence. The heat of reaction raises the vessel temperature from 2200 to a maximum (about 60 ° C for about 7 minutes.) At the temperature maximum, the addition of monomer charge 1 is started at a rate of 13 ml / min., And the addition of catalyst solution and activator solution is started as separate streams at a rate of 1 ml / min. The reaction temperature is kept ~ V at about 6200 at all times.When half of the monomer charge 1 is added (about 22 minutes), charge 1A is mixed with the remaining monomers in charge 1 and the addition is continued, after about 45 minutes this monomer addition (1 + 1A) and the vessel contents are kept at 62 ° C for 15 minutes The addition of monomer charge 2 is then started at a rate of 15 ml / min The second addition is terminated after about 1 hour and the vessel contents are kept at 6200 for 10 minutes, while the addition of catalyst and activator is completed.

The reaction mixture is kept at 6200 for another 15 minutes. and then allowed to cool to 5590. Chaser is now added rapidly and the reaction mixture is kept at 50-60 ° C for 15 minutes. The product is allowed to cool to room temperature and heated.

A sample of formed latex is neutralized to pH 8.5 with ammonia and is found to have a viscosity of # 0 centipois (20% solids Brookfield Synchro§Lectric Viscometer model LV1 spindle l at 60 rpm) and an MFT below 1500. One of these. ...___, ...... »_...._...._-....... ~ _ ~ _- ~ ---» ... a ..-.- .-.._. , _ ...___ 10 15 20 25 BO 40 35 7802931-1 sample cast film has a hardness of 17 KHN.

Exemgel_2 Internally softened polymer emulsion with an acid-containing final step A latex with Tg values in the first step, second step and on average of 28, 112 resp. 6500 in IP values of 17.5, and 14.5 for the first resp. the second step is prepared using the same equipment as 1 ex. 8 and the same procedure according to the following material chargef Monomercharge Raw material l 1A 2 Vessel deionizer Deionized water 154.0 g 64¶g 154.0 g 832 g Octylphenoxypoly (39) - ethoxyethanol 5.1 5.1 - Abex 26s (55%) (TM Aloolac Inc ) 12,8 12,8, - - Sodium dodecylbenzenesulfonate (25%) 10,3 10,5 ~ Ethyl acrylate 56,9 ~~ i. '- Vinyl acetate 449,5 - - Styrene - 440,0 - _ Methacrylic acid 7 , 2 77.6 - 4 Maleic anhydride - 4,1 - - 1n1t1acor = Fe ++ (0,15% Faso .6H 0) 6,4 m1 0,26 g ammonium persu fat (APS) in 8 g water. 0.26 g of sodium sulfoxylate formaldehyde in 8 g of water.

Catalyst: 1.92 g APS and 0.32 g t-butyl hydroperoxide (tBHP) in 110 g water. _.

Activator: 1.92 g NaHSO5 in 110 g water.

Chaser: 0.52 g tBHP in 5 g water. 0.39 g of sodium sulfoxylate formaldehyde in 5 g of water.

Procedure: 1. Material is added to the vessel and the temperature is adjusted to 2o ~ 22 ° c; flushing with N2.

Preparation of batch 1 and addition of 231 g to the vessel.

Addition of maleic anhydride 1 water and methacrylic acid (charge 1A) to the residue of monomer charge 1 and emulsification.

Addition of initiator; interrupt N2 flushing.

After several minutes of initiator addition, the exothermic reaction occurs at a maximum temperature of 55-6000. ___._...____._._._..-....__....__.._......: __ _ 10 15. 20 30 35 78Ü2931 ~ 1 w 6. When the maximum temperature is reached, the addition of monomer charge 1 is started and half of the catalyst and activator are added. _ooh kept at 6200 during the addition. 7. Addition of charge 1 takes H0-45 min .; half of the catalyst and activator are kept in the system at 62 ° for 20 minutes. V V, "8. After 20 minutes, the addition of batch 2 and of catalyst and activator is started.

The temperature tiliàces rise to 62 ° c when charge 1 and A addition of cata- 9. Addition of charge 2 takes about 55 min; lysator and activator take another 10 min. 10. The temperature is maintained at 62 ° C for 50 minutes. 0 ll. After a holding period, cool to 550, then add gases and hold for 10 minutes. for cooling to room temperature. 12. At room temperature, adjust the pH to 4.5-5.0 with 10% aqueous NH 4 CO 5.

A sample of the product latex has a viscosity of 19 centi¿_ pois (20% solids Brookfield Synchro-Lectric Visco ~ meter model Lvl One of this sample Zn ++ (which parts are mixed, 525 the film hardness is 15.5 KHN).

Example gel 10 Effect of hydrophilic monomer level In accordance with the procedure of Ex. 9, a group of poly-spindle 1 is prepared at 60 rpm and an MFT of 5790. Cast film has a hardness of 14 KHN; ZN (NH 5) 4 (HCO 3) 2 - based on solid polymer constituents as disclosed in U.S. Pat. No. 3,328 when 1% additional emulsions having the compositions and properties listed in Table VII. mixture of the ingredients according to the following recipe: Function Carrier Wax Wetting agent Corrosive agent Coalescing agent Base Material Polymer emulsion - 15% solids r AC 392- 15% solids (trademark Allied Chem.Corp.) Fluoride FC128 - 1% solids (trademark} M Co.) Tributoxyethyl phosphate - 100% active Methylcarbitol Ammonia - 10% aqueous solution Of these emulsions, floor polish is prepared by Charge 90.0 wt. 10.0 wt. 0.5 wt. 0.5 wt. 4.0 to PH 7: 5- ....._ .. ...___ ..._..--. ~ ._. 10 15 20 25 30 of 7802931-1 Each floor polish is applied and tested by in ex. 6 beg written procedure The results are given in Table VII, according to which superior polishing properties of IOD and I0E can be noted. V AC-592 is prepared at 55% solids as follows and diluted to 15% solids with water.o I IV 'Preparation Weight parts Ac polyethylene 392 - to' octylphenoxypoly (9) ethoxyethano1 IW 10 Kon (9095 Flame) 1.2 Sodium metabisulfic 0.4 water (1) to 50% solids 50 "water (2) to 35% solids _» 11.5 Transferring the first five components to a pressure vessel with stirring to give 50% concentrate. Stirring and stirring. heating to 9500 is started with the aeration open. Closing of valve and further heating to 15000 is carried out for half an hour. Water (45 parts) is added at 9500 to the reaction vessel while maintaining the temperature at 15000, after which it is cooled to room temperature with stirring. 500 ppm formaldehyde is added as a preservative.

Example ll Effect of acid variations In accordance with the procedure in ex. 9, a group of polymer emulsions according to Table VIII is prepared. Floor polishes are prepared from these emulsions and tested as described in e.g. 10. The results of the tests are given in Table VIII, which shows that ex. 11A does not have pronounced weaknesses and that the copolymers containing maleic anhydride do not show haze. _ 38 78029314 pwm fl .wosyßpm .sus .sßß now wow O fi š fi Nš fi wm mm H.NH H.m fl @. »H #.» H m fl »mums m fi wm .ßm ooñ .QQH om Hm @mx \ m \ wMm \ w «Wß \ oH @mx \ <\ O <> \ mo fi mo fifl n nmwøs nm> w1.UoE .wow .una Éw. Fi š» nm \ m .: w. Fi amm fi ß. @ Fl m fi nwøcß om oo fi vn OOH nm > m wow ..pxs w fifi mø o «m \ @. n 4%: Hwm fl m.mH MH hw fl â mm oo fi nn omš fi mëwßšàmåm Oåøäkhmxwnmà, åšmvwoæßmïm fi æmx \ <<: \ mo> \ 0 <> \\ @ <> @ «<2 \ mo> \ 0 <> Noa HH> A fl wmmë nm> m vom _. He? w flfi ww ~ fl m \ @. N H .: Hàw fl m. @ H m fl hmvcs Nm oo fl om omx \ m ~ ø \ m ~ m @ @mx \ mo> \ @ <> wn fl cw flfl n | fi wHw HHm: m fi> wn fi øsm fi pn mnm fl w> m fl \ ^ m0v ump «moxwH> nhwmmxwømwwhw fi about Amv QH | AHV QH fi wv QH A fl v QH oo .amä oo m fl mums I wa wo .A8 å. Oo .flfl v we wøamH ~ msnmmpx «> wn fi cupmmzßëëmm co fi m fi ßëmæwëm fl om zwmwmmmm 78Ü2931 ~ 1 39 w flfism w \ mø» h. om om 4 «: H.m fl m_ @ H n.wm oø fl mm àqbwwwgwm m fifl I, .lf i || ll | I1 || l | \ ¥ VI. .m> m ma w fifl mn w flfl wu .Euz | m.pxE .Eu: | w.uxë wow vow.pxa | Uow øow. »xE .Ep5 | w.uzE flfl ocv ppm fl m. ~ \«. n mM> \ æ. m øm w fi p om m .: ~ .m ~ V H.wH H.w fl o.wH wm: N H.mm m.mm øo fi oo fi m.wm: .®m O, .O _ ao BJ _ ï fi mmšw _ m \ m. nwm \. @ ßmæ \ <\ Q <> \ OHH maa HHH> A fl wmd fi »um noo hm fl mvmø fl mnwmn mpm fl m Ro: © H> K Éw.då @ w0m-w.Hem» wow wow .uxe .fi HOG m “b \ o ~ n: N mm H “mH m.> fi mm om oo fi» _> m Om NO # «O \ @ .. u \ w§ämm <fl M pmnnmnwwQ flfl wmm ~> <mcmpw fl wmnpcmwnmpmm w fl m fl w HHw§mH> wø fi nsmwp .nu fifl mnw fi H @ \ ^ @@ v »@pHmoxmH> nhmmmxwcwwwnm fl øm Amøv xump fl woxmH> t: - i; 3 Amv QH AHV QH Oo .ams 00 Q fi mwme - wa oo š .å oo AHV .wa .ø @ un @ fi Hmm »w @ pxH> mcwßpumw fl mëëmm co fl m fl ßswswëz fi om w flflfl hbvw ._ __... -._....___. ._..._._._ 10 15 20 25 BO 35 40 7ßozss1- »1 40 Egemgel 12 Variations of the ratio for first step / last step 'Polymer emulsions are prepared by the procedure in ex. 9 with variation of the ratios first step to last step regarding the weight as shown in Table IX. The composition of the first step of each is EA / vAo / voH / Mlxn / MAA = 1 "1 / 75.6 / 11.2 / 0.8 / 1.4 ooh has oo Tgu) of 27.7 ° c ooh an Ip (1) of 17.5., The last step in each is polystyrene with a Tg (2) of 10000 ooh an Ip (2) of 12.1. The Ip (1) -lp (2) value of each latex polymer Thus, floor polishing agents are prepared from these emulsions and tested as described in Examples 6 and 10. The test results are shown in Table IX.

TABLE Ix _ Driving 12A 1213 120 121) 123 Polymer emulsion First / Last step (based on weight) 70 // 30 60 // 40 5o // 5o 40 // 60 30 // 70 NLFT ° c 19 ° 21 25 24 8o viscosity * (op) 22 21 21+ _ '20 17 A 'rgmeaei ° c 46.5 55.0 6o, o 67.5 75.0 Polishing properties Visual veil zero zero zero light mod.

Visual gloss good good + good 'good täml.g-g Smoothing mkt. g mkt.g + mkt.g mkt.g mkt. g A Detergontrosistens tamrg tämrg tämrg goa mkt. g Removability täml.g täml.g täml.g bad bad Heel brand- 7 _ _ V resistance good good good good good Total fötslitzt- _ resistance, good good good + good good XWith 40% solids and a pH of 5.

Example gel Maleic anhydride / methacrylic acid levels - Polymer emulsions are prepared by the procedure of Ex. 9 with varying maleic anhydride and methacrylic acid levels in the first step as shown in Table X; Each final step is polystyrene and represents 50% by weight of the polymer. The polymer in run 13A is the same as that in run 11A. The differences in composition are small ooh the Tg values and the Ip values for the other three polymers are little different from those for run 13A. Polishes prepared from these emulsions have been tested in accordance with 4, 7802931-1l ex. 6 and 10, obtaining the results given in Table X. '= Various varying removability and detergent resistance are achieved; this is remarkable in view of the content of vinyl acetate in the polymer. _ - gggaELL x _ Driving »13A - IÜB '130- ~ l§D Polymer emulsion - _' Composition The first step is EA / VAC / VOH / MAn / MAA Waern-holding ^ sß / fv fifi / 'Ló / 55/31? 'ja / way sßfdy 0,4 0,7 6, o / o, 6,2 / o, 2 6,5 0,8,', 7 7 xvmfr, ° c 23 23 26 _ 24 viscosity * (up) 24 22 18 * V l 46 _ Polishing properties V Visual veil zero zero zero ~ zero visual gloss good _ good, goa _ tamlf.gV ^ = i “- good - 'Smoothing mkt. g 'mkt.g mkt.g god-; mkt; g - Detergent resistance täml.g- mkt.g- tämlßg- bad É good utm. good V § The distant child namrg bad tämrg- ~ utm. good 2 x at 40% solids and a pH of 5.

Example gel 14 Acid in the last step The polish from run 14A is prepared from the same polymer latex as that in run 11A. A film of this polymer is found to have a Knoop hardness number of 10. The polish from Run 14B is made of polymer latex from e.g. 9 and crosslinked with 1% Zn ++, based on solid polymer constituents, added as Zn (NH3) 4 (HCO3) 2.

The polish from run 140 is prepared from a sample of polymer latex from run 6A, Table V.A, note. 1 ;. a film of this polymer has a kHN of 13. These polishes are tested as in e.g. 6 and 10; the results are given in Table XI. Obs. the balance between removability and detergent resistance obtained while maintaining a high standard. other properties. 780293141 ëë2n¿§ fi_ Polishing properties Smoothing k Visual gloss x one coating two coatings Visual veil Detergent resistance Removability 42 ¶ABLE XI 14A mkt.g-utm. g-mkt.g / E mkt.g-utm./ mkt.g + zero täml. g god lnßv 14c ~ mkt. g Ü mkmg-utm. g-mkt.g / mkt.g/@- g-mkt.g mkt. g utm./hkt.g- mkt.g- utm. utm./htm. noll nell mkt. g mkt. g- 'utm. mkt.g-ütm. utm. x fi edovísat as a result on vinyl record / bá OTVA record see test method 5 in table V.A. Ex. 6., _- ..._.........., ..-............... «-". A ~ ...... ..- ~ ...... n. ._ ._.

Claims (18)

W ““ ¶ 43 7802951-1. gArENrrnAv 1. Internally softened addition polymer particles in the form of a latex or of finely divided particles or as a component of an aqueous polishing composition, characterized in that they comprise (A) early-stage polymer and (B) later-stage polymer formed by polymerization in the presence of an emulsion of polymer particles comprising polymer (A), wherein the polymers (A) and (B) each constitute at least 20% by weight of the polymer in the particles, the polymer (A) containing at least 10% by weight of hydrophilic mers, of which at least 10% by weight are non-ionic, and further comprise units of one or more of the following monomers: acrylate esters, methacrylate esters, vinyl esters and vinyl aromatic monomers, and wherein the polymer (B) is less hydrophilic than polymer (A), wherein either (i) polymer (B) has a higher Tg than polymer (A) and of the hydrophilic units in polymer (A) at least 0.5% are ionic and the interpenetration parameter of polymer (A) is greater than that of polymer (B) with not more than 8 units , wherein polymer (A) comprises units of monoethylenically unsaturated monomer; or (ii) the polymer particles have a Tg exceeding 15 ° C and the latex has a viscosity below S000 cP when measured at 20% by weight solids within the pH range 4-10 and has a minimum film temperature of more than 5 ° C below the calculated polymer particles Tg. Addition polymer particles according to claim 1, characterized in that they do not contain steps other than the polymers (A) and (B). Addition polymer particles according to any one of the preceding claims, characterized in that the calculated Tg of the polymer particles is above ZOOC. Addition polymer particles according to any one of the preceding claims, characterized in that the latex has a viscosity below 500 cP, wherein the polymer particles have a Tg exceeding 30 ° C and the latex polymer is such that a film formed therefrom has a Knoop hardness ratio. of at least 5. 5. Addition polymer particles according to any one of the preceding claims, characterized in that of the hydrophilic units 0.5-90% by weight are acid or base units and have a viscosity below 150 cP. Addition polymer particles according to any one of the preceding claims, characterized in that the viscosity of the latex is ._, .._... ~ .f ...-.._.. - ..-..._._ ~ .... »_. ~ .._.._. _ _ _w__ -mm-w »« «-.-...., .._. v .. ~ -« - 1 ~ w .... ......, ..., ... ........... »....--- ~ ---- v- - ~ - ~ 78Û2931 ~ = 1 44 below 40 cP and that the latex polymer is such; that a film formed therefrom has a Knoop hardness number of at least 8, and that the polymer (A) contains ionic units comprising units containing carboxyl groups, " Addition polymer particles according to claim 6, characterized in that the viscosity is below 10 cP and that S0-90% of the hydrophilic mers are mers of hydroxyalkyl ester V of α, β-unsaturated acid. Addition polymer particles according to claim 7, characterized in that the mers in the addition polymer comprise mers of acrylate, methacrylate, vinyl ester and / or vinyl aromatic monomer. ' Addition polymer particles according to claim 4, characterized in that the polymer (A) comprises 10-70% by weight of hydrophilic merers and that the polymer (B) has a calculated Tg of at least 10 ° C above the calculated Tg of the polymer (A) ; wherein the polymers (A) and (B) each constitute at least 30% by weight of the latex polymer and the viscosity of the latex is below 150 CP.) Addition polymer particles according to claim 9, characterized in that the minimum film temperature is at most 18 ° C, that a film formed by the latex polymer has a Knoop hardness number of at least 5, that the calculated Tg of the polymer (A) is at least 4D ° C and that The P0 'lymer (B) is harder than the polymer (A). , Addition polymer particles according to claim 10, characterized in that the viscosity is below 40 cP, that the Knoopë hardness number of a film formed by the latex polymer is at least 8, that the Tg of the polymer (A) is at most 5 ° C and that the polymer (B) ) Tg is at least 75 ° C « Addition polymer particles according to claim 11, characterized in that the viscosity is below 10 CP, wherein the polymers (A) and (B) each constitute at least 40% by weight of the latex polymer, the Tg of the polymer (A) is at most -10 ° C and the polymer (B)'rg is at least 100%. Addition polymer particles according to claim 12, characterized in that at least 0.5% by weight of the hydrophilic merers are carboxylic acid amers. 9 l Addition polymer particles according to any one of the preceding claims, characterized in that the units of polymer (A) comprise 65 to 85% by weight of (C1-C4) -alkyl acrylate, (C1-C4) -alkyl methacrylate and / or control units; 5-10 weight pro- V _. .-. uwnwwv-.pf- »vw-.w ~ - ~ - '45 - 7802951-1 cent acrylic acid ~, methacrylic acid and / or itaconic surface units§ and 10-25% by weight hydroxy- (C1-C4) -alkyl methacrylate ~ and / or hydroxy- (CT-C4) -alkyl acrylate units, and that the units of polymer (B) comprise methyl methacrylate ~ and / Oller Styrene units- Addition polymer particle board according to any one of claims 1-13, characterized in that the units of polymer> (A) comprise 50 ~ 85% by weight of vinyl acetate units, 1-10% by weight of acrylic acid, methacrylic acid, itaconic acid and / or maleic acid units ; and 8 ~ 25% by weight of vinyl alcohol units; and that the units of polymer (B) comprise 100 to 70% by weight of methyl methacrylate and / or styrene units and 0-30% by weight of acid units. - Addition polymer particles according to claim 15, characterized in that the units of polymer (A) contain 1-4% by weight of acid units, of which 0.242% by weight of polymer (A) are units of maleic acid, 0-20% by weight (C1-C4). -alkyl acrylate, 65-80% by weight of vinyl acetate and 10-20% by weight of vinyl alcohol units; and the units of polymer (B) comprise 10-20% by weight of acid units. . l Addition polymer particles according to any one of claims 1 to 8, characterized in that the polymers (A) and (B) each constitute at least 30% by weight of the latex polymer. Addition polymer particles according to any one of the preceding claims, characterized in that the interpenetration parameter of polymer (A) is larger than denier polymer (B) by 1-6 units. A ..... »_.-.- .. ~ __._..__.._ ..