FI64175B - LATEX BESTAOENDE AV PARTIKLAR AV EN INTERNT PLASTICERAD ADDITIONSPOLYMER - Google Patents

Description

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Patent-och registerstyrelsen 'Aittökan utlagd och utUkrtftan pubikarad 30.06.83 (32) (33) (31) Pyydetty «uolkeu * —Begird prloritet 17-03.77 O9.O2.78 USA (US) 778819, 876285 (71) Rohm and Haas Company, Independence Mall West, Philadelphia,

Pennsylvania 19IO5, USA (72) David Richard Gehman, Harleysville, Pennsylvania, Joseph Michael Owens, Hatboro, Pennsylvania, Richard Edward Zdanowski, Fort Washington, Pennsylvania, USA (7M Berggren Oy Ab {5b) Internally plasticized addition polymer latex formed by particles -Latex best & ende av partiklar av en internt plasticerad additionspolymer

The present invention relates to novel polymer latexes useful in forming coatings, adhesives and binders. These latexes are very useful for replacing polymer combinations and are suitable for use in polishing and other coating compositions. The resulting polishes or coatings may be suitable for use on either hard or soft surfaces and on the surfaces of floors and walls to form clear and glossy coatings. The invention also relates to polishing compositions containing the latices according to the invention and their use.

The polymer in the film-forming latex must be soft enough to form a uniform film, but it must also be hard enough for the film to be strong, to bind little dirt, and to have many other similar advantageous properties depending on the application. It is known that if the glass transition temperature (Tg) of the polymer is below the temperature at which the film is formed, a film with good uniformity is usually obtained, i. which is not "cheesy" after drying the latex layer. However, the considerable softness of the latex particles, which results in good film formation, causes the fabricated film to be soft and sticky, and not strong, hard and wear-resistant and tough. A conventional way to avoid this problem is to add to the relatively hard polymer such cohesive (coalescing) agents that are volatile enough to leave the film after film formation. In view of air contamination, it is preferable to exclude volatile film-containing substances from the treatment. Excluding them also means cost savings.

Another way of preparing Tg polymers using a low minimum film formation temperature (MFT) has been to add a large amount of hydrophilic monomers (e.g., those having a hydroxyl, amine, or carboxyl function) to the polymer. This causes the latex particles to swell in the water which softens the particles in the latex. However, at normal polymer concentrations, swelling is associated with very high viscosity, especially if storage and the pH used cause the carboxyl groups or amine groups to be completely or partially neutralized. Another disadvantage is the sensitivity of the final film to water as well as acidic and alkaline solutions. Polymers of hydrophilic monomers prepared by solution polymerization processes and added to the solution are disclosed in U.S. Patent No. 3,935,368 for use in coating vinyl chloride-based floor materials.

Another solution to the problem of obtaining a hard film in the form of a highly cohesive film is disclosed in U.S. Patent No. 3,949,107, which proposes adding to the floor a polish having an aqueous dispersion of resin having a Tg of 30-80 ° C, wherein either the polish or the floor is preheated to a temperature above the Tg of the resin.

A latex formed of internally plasticized addition polymer particles of the present invention suitable for making coatings, adhesives and binders and comprising (A) an earlier stage polymer and (B) a later stage polymer formed by polymerizing in the presence of an emulsion of polymer particles containing the polymer ( A), wherein polymers (A) and (B) each contain at least 10% by weight of the amount of polymer contained in particles 3 64175, characterized in that polymer (A) contains at least 10% by weight of hydrophilic polymers, of which at least 10% by weight is nonionic, and the polymer (B) is less hydrophilic than the polymer (A), wherein either (1) the polymer (B) is such that it has a higher Tg value than the polymer (A), and the hydrophilic units of the polymer (A) at least 0.5% is ionic and the penetration parameter of the polymer (A) is not more than 8 units higher than that of the polymer (B), the polymer (A) containing monoethylene or (2) the Tg of the polymer particles exceeds 15 ° C and the viscosity of the latex is less than 5000 cP measured at a solids content of 20% by weight in the pH range of 4 to 10 and has a minimum film temperature of more than 5 ° C. C below the calculated Tg of the polymer particles. The effect of the later stage polymer on the first stage polymer is that it limits the swelling of the first stage polymer in water. Thus, the product may be considered to be a hydroplastic first stage polymer made more hydrophobic and usually cured by a second stage polymer, or alternatively a usually hard hydrophobic second subject polymer made more hydroplastic and generally softer by a first stage polymer. The internally plasticized polymer formed has properties that differ from the properties of each component polymer, and these properties do not simply form the sum or average of the properties of the ingredients. For example, if the first polymer is one that is completely soluble at high pH, it has been found that after the formation of an internally plasticized polymer, this first polymer part is no longer soluble even at very high pH values.

The strongly water-swellable polymer component can be expected to provide a high-viscosity latex, although the MFT value may then be low relative to the Tg value. According to the present invention, changing the properties of the water-swellable first stage polymer by the second stage results in a relatively low viscosity of the latex.

The most preferred polymers of the invention contain at least one acrylate, methacrylate, binyl ester or vinyl aromatic mer unit. The most preferred hydrophilic ionic mers (if used) in these polymers are those having carboxylic acid groups. The most preferred hydrophilic nonionic mers in the polymer include mers formed by hydroxyalkyl esters of carboxylic acids or vinyl alcoholimers.

The process according to the invention for preparing a latex from internally plasticized addition polymer particles is characterized in that (a) an emulsion of the polymer particles of the previous step (A) is formed by polymerizing, and (b) in the presence of this emulsion the polymer (B) of the later stage polymer is formed on the polymer-containing particles, the amount of monomer of each polymer (A) and (B) is selected so that each of them constitutes at least 10% by weight of the amount of polymer contained in the particles and the polymer (A) contains at least 10% by weight of hydrophilic polymers, of which at least 10% by weight % are non-ionic, and the polymer (B) is less hydrophilic than the polymer (A), wherein either (1) the polymer (B) is such that it has a higher Tg value than the polymer (A) and the hydrophilic content of the polymer (A). at least 0.5% of the units are ionic and the penetration parameter of the polymer (A) is not more than 8 units higher than that of the polymer (B), the polymer (A) containing monoethylene or (2) the Tg of the polymer particles exceeds 15 ° C and the viscosity of the latex is less than 5000 cP measured at a solids content of 20% by weight in the pH range of 4-10 and has a minimum film temperature of more than 5 ° C for the polymer particles. below the calculated Tg value.

The polymer formed by the first step is considered an emulsion even though it is swellable or water-soluble in water. By "water-soluble" in this specification we mean water-soluble when the pH of the water is adjusted by adding an acid or base to a value that completely or partially neutralizes the polymer. By "water-swellable" we mean in this specification that the polymer binds water or can be bound to water at such pH. It is preferred that the usable pH be about 4 to 10. The swelling ratio of the swelling polymer, i.e., the volume of polymer swollen in a large excess of water divided by the volume of dry polymer, is preferably greater than two, and more preferably greater than six.

It is apparent that we are aware of the mode of operation of the hydrophilic monomer used in amounts of about 10 to 100 parts per 100 parts of the first charge monomer, but the invention is not limited to such theoretical considerations. It appears that the hydrophilic monomer, when polymerized, can bind the amounts of water introduced into the mixture, for example in the form of water of hydration. Consequently, any monomer that can be polynerized in the mixture and is sufficiently hydrophilic to effectively bind water is useful. Suitable hydrophilic monomers include, for example, acrylonitrile, methacrylonitrile, hydroxy-substituted alkyl and aryl acrylates and methacrylates, polyether acrylates and methacrylates, alkyl phosphate alkyl / supercrylates, and alkyl methacrylates, acrylic acid, methacrylic acid, maleic acid, .naleic anhydride, N-vinylpyrrolidone, alkyl and substituted alkylamides derived from acrylic acid, methacrylic acid, maleic acid (mono- and diamides) and monoacidic acid, fumaric acid (fumaric acid) diamides), acrylamide methacrylamide, and also other half-acid forms of the above-mentioned dibasic acids, such as half-esters, amino monomers, such as amino-substituted alkyl acrylates and methacrylates, vinylpyridines, amino-alkyl vinyl ethers ureido. Also within the scope of the invention are variations in the amount of hydrophilic monomer in the monomer mixture, such as when the hydrophilic monomer units are formed in situ or subsequently formed. For example, the monomer may be incorporated into a polymerizable mixture which is not itself hydrophilic, but which is modified during or after the treatment step, for example by hydrolysis to provide hydrophilicity, and examples of these are anhydride- and epoxide-containing monomers.

Preferred suitable hydrophilic monomers are acrylic compounds, especially amides and hydroxyalkyl esters of methacrylic and acrylic acids, and amides and hydroxyalkyl esters of other acids can also be used, but are not as good as the corresponding methacrylates and acrylates, which polymerize more easily. Monomers containing carboxylic acid groups are also preferred, especially acrylic acid, methacrylic acid and itaconic acid. Another preferred group of hydrophilic monomers are those potential hydrophilic monomers that provide the actual hydrophilic meric units in the polymer after hydrolysis. Such monomers include vinyl alcohol esters such as vinyl formate, vinyl acetate, vinyl propionate, vinyl butyrate, and vinyl 6,641,75 versinate. Hydrolysis of these monomers provides hydrophilic vinyl alcohol polymer units in the polymer. The most preferred such monomer is vinyl acetate.

When polymerized with a hydrophilic monomer, the first charge may contain another monomer carefully selected to impart other advantageous properties to the final polymer. Each polyethylenically unsaturated monomer, if present, is preferably of a species in which different ethylene groups, i. addition polymerizable unsaturated groups, participate in the polymerization at approximately the same rate. No such crosslinking or segment-forming polyethylene-unsaturated monomer is present in the first step of the monomer system. The term "segment-forming monomer" is defined in U.S. Patent No. 3,796,771, column 4, line 66, column 5, line 20, which is incorporated herein by reference. The first batch preferably contains a monoethylenically unsaturated monomer.

It is desirable that the polymer of the first batch be softer than the polymer of the second batch. The hardness of the first batch can be adjusted by selecting the hydrophilic monomer and the comonomer used with it. Suitable comonomers which form soft polymers in the presence of free radical catalysts include primary and secondary alkyl acrylates having up to 18 or more carbon atoms in the alkyl substituents, primary or secondary alkyl methacrylates having up to 18 or more alkyl substituents, e.g. even more carbon atoms, or other ethylenically unsaturated compounds that can be polymerized with free radical catalysts to form soft, solid polymers that include vinyl esters of saturated monocarboxylic acids having more than two carbon atoms. The most preferred ethylenically unsaturated compounds are said acrylates and methacrylates, and of these the most practical esters are those having up to 8 carbon atoms in the alkyl groups.

The most preferred monomers which, as such, provide soft polymers can be represented by the formula CH ~ = C-C00Rx

^ I

R '1: 7 64175 wherein R' is hydrogen or a methyl group and Rx is when R 'is methyl, a primary or secondary alkyl group having 5 to 18 carbon atoms, or when R' is hydrogen, an alkyl group having no more than 18 carbon atoms, preferably 1 to 8 carbon atoms, and even more preferably 1 to 4 carbon atoms.

Typical compounds as defined above are methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, butyl acrylate, isobutyl acrylate, sec-butyl acrylate, amyl acrylate, isoamyl acrylate, 3,5-acrylate, hexyl acrylate , 5-trimethylhexyl acrylate, decyl acrylate, dodecyl acrylate, cetyl acrylate, octadecyl acrylate, octade-senyl acrylate, n-amyl methacrylate, sec.amyl methacrylate, hexyl methacrylate, hexyl methacrylate, 2-ethyl butyl methacrylate, 2-ethyl butyl methacrylate, , octadecyl methacrylate and those having substituted alkyl groups such as butoxyethyl acrylate or methacrylate.

As the polymerized ethylenically unsaturated monomers, which in themselves form hard polymers, alkyl methacrylates having alkyl groups having up to 4 carbon atoms can also be used, including tert-amyl methacrylate, tert-butyl or tert-amyl acrylate or cyclohexyl, cyclohexyl, cyclohexyl methacrylate, acrylonitrile or methacrylonitrile, and these form the most preferred group of monomers, which as such form hard polymers. Styrene, vinyl chloride, chlorostyrene, vinyl acetate and p-methylstyrene, which also form hard polymers, can also be used.

The most preferred monomers, which as such form hard polymers, can be represented by the formula

CH 2 = C-X

^ I

R * wherein R 'is hydrogen or a methyl group, and wherein x is one of -CN, phenyl, methylphenyl and ester-forming groups, -COOR ", wherein R" is cyclohexyl, or when R' is hydrogen, a tert-alkyl group, having 4 to 5 carbon atoms, or when R 'is methyl, an alkyl group.

8,64175 having 1 to 4 carbon atoms. A few typical examples have already been presented above. Other specific compounds include 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 impart hardness to the copolymer.

These monomers may also contain other functional groups for other purposes, such as to provide crosslinking to the polymer upon curing and to provide improved attachment to the substrate. Examples of such functional groups include carboxyl in free acid or salt form, including amido-substituted amido such as alkoxyalkylamido and alkylolamido, including epoxy, hydroxy, amino, oxazolidinyl and oxazinyl, and ureido. In most cases, these functional groups are also hydrophilic groups and many of these monomers are hydrophilic.

Another group of monomers useful in the present invention that can be polymerized as such to form soft polymers are butadiene, chloroprene, isobutene, and isoprene. These are those monomers commonly used in rubber latices in combination with monomers which provide hard polymers and which are also useful in the invention, such as acrylonitrile, styrene and the other "hard monomers" mentioned above. Olefin monomers, especially ethylene and propylene, are suitable "soft monomers". Highly useful first stage copolymers include ethylene / ethyl acrylate copolymers and ethylene / vinyl acetate copolymers to which a hydrophilic monomer has been added.

Another group of polymers useful in the present invention are vinyl alcohol ester polymers such as vinyl formate, vinyl acetate, vinyl propionate, vinyl butyrate, and vinyl versinate. Most preferred are copolymers of poly (vinyl acetate) and vinyl isotate with one or more of the following monomers: vinyl chloride, vinylidoene chloride, styrene, virulyl toluene, acrylonitrile, methacrylonitrile, the above acrylate or methacrylate esters, and each functional acrylate ester, and In 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 most preferred. Prior to the completion of the polymerization of the vinyl alcohol esters, some hydrolysis to the vinyl alcohol polymer units usually occurs or is done intentionally. The vinyl alcohol polymer units thus prepared are hydrophilic and are considered to be derived from the vinyl alcohol monomer herein. The amount of hydrolysis can be adjusted by adjusting the reaction time, temperature and pH to obtain the desired amount of vinyl alcohol in the product. Longer times, higher temperatures, highly acidic or highly alkaline conditions all increase the amount of hydrolysis and thus the amount of vinyl alcohol in the final product. The amount of hydrolysis can be determined by acid-base titration methods in water or in a suitable solvent system.

The most preferred mixture according to the invention is one in which the monomers of the first stage contain 65-85% by weight of C 1-4 alkyl acrylate, (C 1-4) alkyl methacrylate and / or styrene, 5-10% acrylic acid, methacrylic acid and / or itaconic acid. and 10-25% hydroxy- (C 1-4) alkyl acrylate and / or hydroxy- (C 1-4) alkyl methacrylate, and the polymers of the downstream polymer comprise methyl methacrylate and / or styrene. Another preferred mixture is one in which the marine units of the first stage contain 50-85% by weight of vinyl acetate (for subsequent hydrolysis), 1-10% of acrylic acid, methacrylic acid, itaconic acid and / or maleic acid (derived from maleic anhydride) and 8-25% by weight. % vinyl alcohol, and the subsequent marine units contain 70-100% methyl methacrylate and / or styrene and 0-30%, preferably 10-20% by weight, of acidic mers such as acrylic acid, methacrylic acid and / or itaconic acid isomers.

It is desirable that the acidomers in the first stage always contain 5% by weight of the first stage polymer of maleic anhydride or maleic acid, and 0.2-2% is the most preferred amount. In this context, the term "mer" means a unit in an addition polymer derived from said monomer by the addition of a double bond.

In general, the most preferred hydrophilic monomers for use in accordance with the invention are monomers having a solubility of at least 6 g per 100 g of water, those having a solubility of at least 20 g per 100 g of water are even more preferred, and most preferred are those having a solubility of at least 50 g per 100 g of water. g of monomer is soluble in 100 g of water. The first stage polymer contains at least 10% hydrophilic polymers, with 10-70% being the most preferred, at least 25% being even more preferred, with the range being 25-35% being most preferred. It is preferred to use at least 0.5% of the amount of hydrophilic monomer in monomers containing at least 0.5% ionic hydrophilic mers, such as acidomers, e.g. carboxyl or basic groups, for example amino groups, in either unneutralized or neutralized form. It is also preferred that at least 10% of the hydrophilic mers are non-ionic, i. non-ionized, such as hydroxyethyl acrylate or methacrylate, which can be prepared in situ, such as nonionic sea units of hydroxyethyl ester and vinyl alcohol mer units.

The final stage polymer is more hydrophobic and preferably harder than the first stage polymer. By more hydrophobic is meant that the later stage polymer is as such less swellable in water than the first stage polymer. By hardness is meant that the modulus of the later stage polymer is higher than that of the first stage polymer, with measurements being performed using polymer samples immersed in water. It is preferred that the final stage monomer be monoethylenically unsaturated.

The internally plasticized polymers of the invention are conveniently prepared using known emulsion polymerization methods and using a multi-step technique. However, they can also be prepared using continuous polymerization, in which case the continuously fed monomer mixture is changed either batchwise or continuously during the polymerization. In such polymerization, any change in the composition of the monomer feed can be considered as the end of the previous step. If no such changes occur in the feed mixture corresponding to the change from one step to another, the first half of the polymer feed can be considered as one step and the second half as the second step thereof. In a simpler form of the latices of the invention, a hydrophilic polymer is formed in the first step and a more hydrophobic polymer in the second step. Each of these polymer parts can also be polymerized as such in succession, i.e. this involves several steps. The first stage monomers are formed together with the initiators, soap or emulsifiers, as well as the polymerization modifiers and chain transfer agents in the first polymerization mixture, and polymerized, for example by heating, mixing and, if necessary, cooling, using well known conventional methods until the monomers are substantially complete. The monomers of the second step and each subsequent step are then added together with other suitable materials so that the desired polymerization of each step occurs sequentially until the monomers are substantially depleted. It is preferred that at each stage after the first stage, the amounts of initiator and soap, if used, are maintained at such a level that the polymerization occurs in the available particles and no significant amount of new particles or "seeds" are formed in the emulsion.

In addition, when the polymerization is carried out in succession in several steps, there may be steps which, on the basis of their composition and proportions, form a combination of two different steps and which provide polymers with properties in between. The hydrophilic first step is at least 10%, preferably 20-80%, even more preferably 30-70% and most preferably 40-60% of the total polymer. Of course, other steps may be used before or after these two main steps. These other steps are always smaller in weight than the whole polymer compared to the lower main steps if they cannot be considered as part of either of the main components of the polymer. It is preferred that the polymer of the invention is a biphasic polymer. One skilled in the art will usually prepare a few internally plasticized polymer latex samples that differ in the weight ratio between the first and second steps and select the one that has the best properties for the particular application. An equal weight ratio is a conventional starting point for such experiments, which generally comprise one higher and one lower ratio, this ratio being selected taking into account the desired final properties, e.g., hardness, MFT, latex viscosity and non-stick time.

The copolymer is suitably prepared by emulsion copolymerization using several monomers in suitable proportions. Suitable emulsion polymerization methods are disclosed in U.S. Patent Nos. 2,754,280 and 2,795,564. Thus, monomers can be emulsified using an anionic, cationic or nonionic dispersant, which is usually used in an amount of about 0.5-10% by weight of the total monomers. . When a water-soluble monomer is used, a dispersant is used to emulsify any other monomers. A free radical type polymerization initiator such as ammonium or potassium persulfate may be used alone or in combination with an accelerator such as potassium metabisulfite or sodium thiosulfate. The initiator and accelerators, commonly referred to as catalysts, may be used in amounts of 1 / 2-2% by weight of each of the monomers to be copolymerized. The polymerization temperature can range from room temperature to 90 ° C or even higher as desired.

Examples of emulsifiers or soaps which are suitable for use in the polymerization process of the invention include e.g. alkyl, ammonium and ammonium salts of alkyl, aryl, alkaryl and aralkyl sulfonates, sulfates and polyether sulfates, corresponding phosphates and phosphonates and ethoxylated fatty acids, esters, alcohols, amines, amides and alkylphenols.

Chain transfer agents such as mercaptans, polymercaptans and poly-halogen compounds are often preferred in the polymerization mixture.

Another way to describe and define the first and second stage monomers of the invention is to use a solubility parameter concept. In "Polymer Handbook", 2nd edition, J. Brandrup and E.H. Immergut (John Wiley and Sons, New York 1975), Chapter 4, Volume 15, entitled "Solubility Parameter Values", written by H. Burrell, from page 4-337 to page 4-359 defines the solubility parameter and describes how it is defined and calculated, it provides a table of solubility parameters and also refers to the literature on solubility parameters. The solubility parameter is the square root of the cohesive energy density, which in turn is a numerical value of the potential energy of a 1 ml material resulting from van der Waal attraction between molecules in a liquid or solid. Burrell describes several ways to calculate solubility parameters from experimentally determined physical constants and two ways to calculate them from the structural formula of a molecule. Structural formula methods are commonly used when the values of the i3 641 75 physical constants are not available for this calculation or are highly unreliable. When performing the calculation based on the structural formula, tables of the molar attraction constants of the groups are used, such as those shown on page IV-339 of the book "Polymer Handbook". The table presented by Small is the most advantageous.

The solubility parameter can be considered as a continuation of the old rule "similar dissolve similar", which was already established in the early years of chemistry. The non-crosslinked polymer is usually soluble in a solvent having a similar solubility parameter, and the crosslinked polymer usually swells in a solvent having a similar solubility parameter. On the other side of such solvents with solubility parameters of polymers are remote from the respective parameters do not dissolve or swell the polymers. As Burrell has shown, the solubility parameters of the polymers can be determined e.g. by measuring the swelling of the polymer in solvent series. The solubility parameters of the polymers can also be determined by calculating molar attraction constants from the group, as mentioned above. In the usual situation, it has been found that solvents with a set of solubility parameters close to the corresponding values of the polymer dissolve the non-crosslinked polymer. In addition, those skilled in the art have classified solvents as having poor, moderate, or strong hydrogen bonding. It has been found that the range of solubility parameters for dissolving a particular non-crosslinked polymer differs from one class to another, although considerable overlap can usually also be observed. Burrell's Table 4, beginning on page IV-349, gives the solubility parameter ranges for poorly, moderately, and strongly hydrogen-binding solvents used to dissolve various polymers. Table 5, starting on page IV-354, shows the solubility parameters for a number of polymers and has been determined by calculation or some other method.

To form the internally plasticized polymer of the invention, the first stage polymer and the subsequent stage monomers are selected to interact in a substantial manner. There are both upper and lower limits for the degree of compatibility desired between the first stage polymer and the subsequent stages (second or last, as described above) of the i4 64175 monomer charges. It has been found that the degree of compatibility can be expressed numerically on the basis of the solubility parameter and is referred to herein as the "penetration parameter" lp. · This penetration parameter can be considered as a solubility parameter adjusted to give strong, moderate or weak hydrogen-binding solvents on the same scale. For a given molecule, the penetration parameter is defined as the solubility parameter plus the hydrogen binding value added above. The solubility parameters of the various molecules and the number of monomers are shown in Tables 1 and 2 of Burrell, starting on page IV-341. These tables also show a hydrogen bonding group suitable for a particular molecule. Additional values that are a new consideration in this invention are 17.2 for strongly binding molecules, 7.2 for moderately hydrogen binding molecules, and 2.8 for poorly hydrogen binding molecules.

The following table shows the series of monomers, as well as their solubility parameters, penetration parameters, and water solubility values. It also shows the water binding class of the monomer. The solubility parameter values and water binding class of most of these monomers are shown in Table 1 of Burrell. Vinyl alcohol is a special case because, as is well known, the state of this monomer is not stable. Polymers containing grains corresponding to vinyl alcohol can be prepared by hydrolyzing a polymer containing a corresponding vinyl ester such as vinyl acetate mer unit. The solubility parameter of this hypothetical monomer has been calculated by the Small method described above. Values for other monomers not listed in the Burrell · 1in table have been determined or calculated using the methods mentioned in the above paper. The dimensions of the solubility parameters shown in the table are the standard square root of the quotient of calories and cubic centimeters. The penetration parameter has the same dimensions. Water solubility is expressed in grams of raonomer per 100 g of water at 25 ° C. The hydrogen bonding class, strong, moderate, or poor, is determined using C.M. Hansen's method, Journal of Paint Technology, Vol. 39, pp. 104-117 and 505-514 (1967).

is 64175

Monane Solubility Hydrogen penetration Water solubility Abbreviation parameter tcxnical misparameter

Acrolein 9.8 S 27.0 40 Acr.

Acrylic acid 12.0 S 29.2 CM AA

Acrylonitrile 10.5 P 13.3 25-30 AN

0-brmistyrene 9.8 P 12.6 BrSt 1,3-butadiene 7.1 P 9.9 Bd

t-butyl acrylate 8.5 M 15.2 0.2 iBA

n-butyl acrylate 8.8 M 16.0 0.2 BA

Butyl 1 imetacrylate 8.2 M 15.4 0.01 BMA

Chlorostyrene 9.5 P 12.3 ClSt

i-decyl acrylate 8.2 M 15.4 0.01 iDA

Dichloroethylene 9.1 P 11.9 0.01 DCE

Ethyl acrylate 8.6 M 15.8 1.51 EA

Ethylene oxide 11.1 M 18.3 CM EO

Etyleeniepikloori-

hydrin 12.2 S 29.4 EEPC

Dimethylaminoethyl

1 breast plate 7.0 S 24.2 CM DMAEMA

dihydroxypropyl

methacrylate 9.0 S 26.2 CM DHPMA

ethylhexyl

acrylate 7.8 M 15.0 EHA

Ethyl methacrylate 8.3 M 15.5 0.1 EMA-hexene 7.4 P 10.2 hex

Hydroksietyy1i-

methacrylate 8.0 S 25.2 HEMA

Isoprene 7.4 P 10.2 Ipn

Maleic anhydride 13.6 S 30.8 16.3 (79) 1 MAn

Methacrylic acid 11.2 S 28.4 CM LAND

Methyl acrylate 8.9 M 16.1 5.2 MA

Methyl imetacrylate 8.8 M 16.0 1.6 MlVR

2-methylstyrene 8.5 P 11.3 MeSt

Styrene 9.3 P 12.1 ST

Vinyl 1 acetate 9.0 M 16.2 2.3 VAc

Vinyl chloride 7.8 M 15.0 VCl

Vinyl itoluene 9.1 P 11.9 Vtol

(Vinyl alcohol) 8.4 S 25.6 (CM) VOH

S = strong P = poor M = moderate CM = fully miscible as maleic acid ie 64175

In the case of the latex polymer according to the invention, the penetration parameter of the first stage is higher than that of the second stage, preferably at least 1 unit (calories per cubic centimeter). However, the penetration parameter of the first stage must not be too much higher than that of the second stage. The difference is not greater than 8 and preferably not greater than 6, preferably 1 to 6 units. When the polymer of the first stage contains 65% by weight or more of N, N-alkyl acrylate, C 1 -C 4 alkyl methacrylate, styrene or a mixture thereof, it is desirable that the Ip value of the first stage is not more than 6 units higher than that of the subsequent stage. When the polymer of the first stage contains 50% by weight or more of vinyl acetate, it is desirable that the Ip value of the first stage is 1 to 8 units higher than that of the later stage, the difference of 1 to 4 units being more preferred. 2-6 units being the most preferred and 4-5 units being the most preferred In this context, it should be noted that the second or subsequent step may contain some hydrophilic monomers and still conform to the rules in force between the first and second step penetration parameters.

As mentioned above, according to a preferred embodiment, the first step contains acidic, preferably carboxylic mer units, as well as some other hydrophilic mer units. The carboxyl polymer units are preferably obtained from monomers formed by acrylic acid, methacrylic acid and itaconic acid. Other hydrophilic meric units are preferably hydroxy-C 1 -C 4 -alkyl methacrylate, hydroxy-C 1 -C 4 -alkyl acrylate or vinyl alcohol units.

The viscosity of the polymer emulsion prepared can be measured by any known method, preferably using a "Brookfield Synchro-Letric Viscometer", model LV 1, the spindle and speed preferably being selected so as to obtain a medium reading. Measurements at 20 ° C are made in the pH range 3-10 using emulsions adjusted with water to a solids content of 20%. The pII value of the acid-containing copolymer emulsion is generally adjusted using a mineral base, an organic base such as an amine, or ammonia, the latter being most preferred. In internally plasticized polymer latices containing basic groups such as amine groups or quaternary ammonium groups, the pH can be adjusted with mineral acids such as hydrochloric acid or organic acids such as acetic acid. The viscosity of the latex is in the pH range of 3 to 10, generally less than 5,000 cp, more preferably less than 500 cp, even more preferably less than 150 cp, even more preferably less than 40 cp, and most preferably less than 10 cp. Lower values are highly desirable for certain applications, such as floor polishes.

The minimum film temperature (MFT) must be measured on a film cast in a latex with a solids content of 20% and a pH of 7 1 / 2-9 for ammonia-neutralized acidic polymers and 3-4 for acetic acid-neutralized basic polymers. The method D2354-68 (The American society for Testing Materials) is used. The MFT value is more than 5 ° C below the calculated glass transit temperature (Tg) when the Tg value of the polymer is greater than 5 ° C. The most preferred MFT values are below 18 ° C for polymers having a Tg value greater than 25 ° C, calculated for the entire polymer blend. The term MFT, as used herein to define certain polymers, means this value as determined for latex at the pH and solids content set forth above. In a few of the examples below, the MFT values determined under other conditions are given for comparison only and do not refer to the MFT values used to determine the polymers of the invention.

The hardness is expressed as the Knoop hardness value (KHN) and determined with a "Tukon Microhardness Tester" using a film formed by casting a latex on a solid substrate such as a glass plate. It is preferred that the polymers have a KHN value greater than 3, with a value greater than 5 being even more preferred and greater than 8 being most preferred.

The calculated Tg value of each step and the corresponding value of the whole polymer are determined by a calculation based on the Tg value of the homopolymers of the individual monomers as reported by Fox in Bull. Am. Physics Soc. 1, 3, page 123 (1956). Tables of Tg arbos of homopolymers are shown in the Polymer Handbook, Block III, Part 2, written by W.A. Lee and R.A. Rutherford. The desired calculated Tg value of the first step is less than 40 ° C, with a value below 5 ° C being more preferred and below 18,641 75 -10 ° C being most preferred. The desired calculated second stage Tg value is greater than 35 ° C, with a value above 75 ° C being more preferred and above 100 ° C being most preferred. The calculated Tg of the polymer, based on the composition of the polymer, is greater than 15 ° C, preferably greater than 20 ° C, and a value greater than 30 ° C is most preferred for floor polishes and the like. For a few other uses, such as adhesives, binders, and paints, polymers having a calculated Tg of less than about 40 ° C are suitable, including those with less than zero.

The internally plasticized polymer emulsions according to the invention can have a remarkably advantageous combination of properties, in particular 1) a low minimum film temperature together with a high hardness and a high Tg and 2) a low viscosity of the polymer emulsion also when neutralized. Thus, relatively hard latex polymer systems can be used, and a much smaller amount of coalescing agent than usual or not at all. This is very valuable in situations where such a coalescing agent causes secondary disadvantages. Due to the fact that no or very little added coalescing agent has been added to the mixture, coatings can be prepared which cure very rapidly using the polymers according to the invention. Other benefits of eliminating the added plasticizer, coalescing agent, or organic solvent include reduced costs, reduced burning sensitivity during processing, and lower emissions of toxic and fouling gases during and after use. These properties are very valuable in the manufacture and use of water-based industrial coatings, both clear and pigmented. In ink technology, the very rapid drying and non-combustibility of internally plasticized polymers are important factors. In the coatings of goods, the combination of high hardness and minimum film temperature provides durable air-drying coatings. An additional advantage of the latices according to the invention is that they are very easy to handle, which results in considerable cost savings due to the smaller number of ingredients and the ease of carrying out the mixing in a factory-scale treatment. The ease of mixing is presumably due to the fact that the latex according to the invention is resistant to the so-called against "clumping phenomena", i.e. the latex does not readily flocculate or gel when mixed with other ingredients.

Thus, the ingredients can usually be mixed in any order; i9 641 75 in conventional factory equipment and in addition the equipment remains much cleaner than when using conventional latexes.

As mentioned above, the polymer latices of the invention are remarkably useful to replace latex plus plasticizers, or a latex plus coalescing agent system comprising a number of blends used in a wide variety of polymer latex applications. These latexes are useful for forming free films as well as for forming coatings such as paints, varnishes, varnishes, powder coatings, etc. The latices of the invention are also useful as impregnating agents and adhesives in both natural and synthetic materials such as paper, paper, for plastics, metals and leather, and binders for nonwovens. They can be used to lower the minimum film formation temperature or to aid film formation in other latex systems when used in conjunction with them. Pigments, dyes, fillers, antioxidants, ozone inhibitors, stabilizers, flow regulators, surfactants or other suitable ingredients can be used in the polymer blends of the invention.

The polymer blends according to the invention can be added, with or without a solvent, by permanently or removably casting on a suitable substrate, in particular for use as coatings, fillers and adhesives. Brushing, flushing, dipping, spraying and other known methods can be used to add the latex of the invention. A particular advantage of the invention is that the reactive polymers can be prepared for use as air-cured or thermoset coatings, fillers or additives without the need for organic solvents, coagulants or plasticizers, although small amounts of these materials may be used. This is very valuable because the omission of volatile solvents and other volatile substances, such as coalescing agents, greatly reduces ecological hazards.

It is very important that the acid groups, hydroxyl groups or other functional groups added in the first stage of the polymerization are available in a further reaction such as neutralization or crosslinking. This utility of these groups distinguishes an internally plasticized polymer latex from a latex in which the second or subsequent steps coat or affect the first step such that the ability of the first step functional groups to react thereafter is reduced or eliminated altogether. Said cross-linking may be any conventional method, such as coordination cross-linking, ionic cross-linking or covalent bond formation. In general, the reaction of these latexes can be an ionic or covalent reaction. The ionic reaction occurs, for example, when such latices are added to floor polishes as will be described later. The formation of covalent bonds by reaction with aminoplasts, epoxies, isocyanates and beta-hydroxyethyl esters is in this field1; ta well known.

The polymer latices of the invention are highly useful in forming floor polishes and are preferably used in the floor polishes disclosed in U.S. Patent Nos. 3,328,325, 3,467,610 and 3,573,239.

In general, polishing compositions, using the polymers of the invention, can be determined by the amount of the following major constituents:

Ingredient Amount (A) Water-insoluble internally plasticized addition polymer, 10 to 100 parts by weight (B) Wax, 0 to 90 parts by weight (C) Alkali-soluble resin, 0 to 90 parts by weight (D) Moisturizing and dispersing agents,% 0 .5-20 (E) Polyvalent metal compound,% 0-50 (F) Water so as to give a total solids content of 0.5-45%, preferably 5-30% (D) is by weight of A + B + C by weight (E ) is the percentage by weight of A.

The sum A + B + C should be 100. The amount of C, if used, can always be 90% by weight of copolymer A and is preferably about 5-25% by weight of copolymer A.

For the production of non-caking, self-polishing mixtures will? the amount of wax should be more than 35% by weight, preferably 0.25% by weight of the total amount of polymer and wax according to the table above. Satisfactory caking floors and floor polishing compositions have been made without the use of wax. Thus, wax is not an essential ingredient in a self-polishing mixture. In the dry polishing mixture, the amount of wax must be at least 35% by weight of the total mixture. Examples of wetting and dispersing agents are the time metal and amine salts of higher fatty acids having 12 to 18 carbon atoms, such as sodium, potassium, ammonium or morpholine oleate or castor oleate, as well as conventional nonionic surfactants. The additional amount of wetting agent improves the spreading effect of the polish.

When polishing floors, the coating obtained from the mixture has a Knoop hardness value of 0.5-20 as measured using its 0.012-0.063 mm thick film on glass. This hardness range provides good resistance to abrasion and wear and can be obtained by appropriately selecting the monomers to be polymerized.

The following examples illustrate some preferred embodiments of the invention in which parts and percentages are by weight unless otherwise indicated.

Example 1 Preparation of an internally plasticized polymer emulsion A latex with a first stage, a second stage and an average Tg of -14 ° C, 105 ° C and 34 ° C, respectively, was prepared as follows: A. Apparatus A 5-liter 4-necked flask is equipped with a condenser. with stirrer, thermometer and monomer addition pump. Heating, cooling and nitrogen supply equipment are also used.

B. Feeding the material

Raw Material Feed Monomer Monomer Batch Step 1 Step 2

Water 2008 g 400 g 400 g

Sodium lauryl sulphate (surfactant) 16 2 2

Butyl acrylate (BA) - 600

Methyl methacrylate (MMA) - 140 100

Methacrylic acid (MAA) - 60 - 22 6 4 1 75

Hydroxyethyl methacrylate (HEMA) - 212

Sodium persulfate in 100 g of water (catalyst) 12 - C. Procedure 1. Add water and surfactant to the flask, start mixing and introduce nitrogen.

2. The ingredients of each monomer charge are combined and mixed thoroughly to obtain a stable monomer emulsion.

3. Heat the flask to 82-84 ° C with constant stirring and conduction of nitrogen.

4. The catalyst solution is added to the flask and the addition of the step 1 monomer charge is started at such a rate that the addition is complete after about 50 minutes. The temperature is maintained at 82-84 ° C by polymerization.

5. After the addition of step 1 of the monomer charge is complete, maintain at 82-84 ° C for 15 minutes.

6. After this time, the addition of the step 2 monomer charge is started at such a rate that the addition is complete within about 60 minutes. The temperature is maintained in the range of 82-84 ° C during the polymerization.

7. When the addition of the step 2 monomer charge is complete, maintain the temperature at 82-84 ° C for 30 minutes, then cool and filter.

The latex sample is neutralized to pH 9 with ammonia. MFT value less than 15 ° C, viscosity 15 cp (Brookfield Viscosity; solids content 20%). The hardness of the film cast from neutralized latex is 12.1 KHN.

Example 2 Successive additions

Following the procedure described in Example 1, three internally plasticized polymer latices having the same first and second stage composition but different weight ratios of the first and second stages are prepared. Details are shown in Table 1.

It has been found that the appropriate equilibrium, low MFT, and at the same time low emulsion viscosity are sensitively dependent on the ratio of the hard i: 23 6 4 1 75 hydrophobic second stage charge to the soft hydrophobic first stage charge. This makes it apparent that when a particular monomer mixture is used, a few simple experiments may be required to determine the batch ratio required to obtain the product of the invention.

Table 1 shows the effects of the change in batch ratios, with Experiment 2B having a low MFT value after neutralization, a low viscosity, and a high Tg value. It can be seen that Experiment 2B concerns the latex polymer of the invention, while Experiment 2A has a viscosity that is far too high at pH 9 and Experiment 2C has an MFT that is too high. Experiments 2A and 2C are therefore presented for comparison only.

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The difference between a single emulsion copolymer, an internally plasticized polymer, and a physical blend of two polymers is shown in the values in Table 2. All polymers were prepared by emulsion polymerization using mainly the method of Example 1, except that Experiments 3A and 3C had no other charge and these experiments are therefore presented for comparison purposes only. The composition of each of these three examples is essentially the same. The calculated Tg value is 47 ° C.

Table II

Experiment Polymer composition Test description MFT / vi skoset BA / MMA / MAA / HEMA / MMA pH 3 pH 9

3A

(comparison) 23/56/6/15 // 0 single batch 52/3 46/55 simple topolymer 3B * 3 23/6/6/15 // 50 internally plasticized 40/6 10/140 polymer 3C a (comparison) 23/6/6/15 // 50 physical mixture 10/10 10 / gelation physical mixture 50:50 (BA / MMA / MAA / HEMA: 46/12/12/30) and (MMA: 100).

^ The polymer of Experiment 3B is the same as the polymer of Experiment 2B.

It can be seen from Table II that the polymer charge of Experiment 3A has an MFT value close to the calculated Tg value. Physical mixture, i.e. Experiment 3C, an emulsion mixture containing the first stage of the polymer of Experiment 3B and one having the composition of the second stage of Experiment 3B is viscous at high pH so that the emulsion gels when diluted to a solids content of 20% before adjusting the pH. It should be noted that when neutralized to pH 9, the internally plasticized polymer has a much lower MFT and only a reasonably high viscosity compared to a single batch copolymer.

Example 4 Balance of hydrophilic and hydrophobic properties of the steps Using the polymer emulsion of Experiment 23 as a control, the ratio between the water-swollen first-stage polymer and the second-stage polymer assemblages was varied. The effect of the first stage polymer on the second stage polymer has been demonstrated by providing intrinsic plasticization and controlled viscosity by sequential addition of (1) a soft hydrophilic and functionalized and (2) a hard and hydrophobic copolymer. This intrinsic plasticization is considered to depend on the balance of hydrophobic and hydrophilic nature between the two monomer charges, as shown in the values in Table III.

Table III

Test Composition Tg MFT / Viscosity (1) (2) Avg. pH 3 pH 9 4A * BA / M1A / MAA / HEMA / / MMA 4 100 47 40/10/23/6/6/15 // 50 6 140 4B BA / NWA / MAA / HEJ1V / MMA -13 105 35 30 / 10/29/0/6/15 // 50 10 70 4C EA / iftA / HEMA //) YiMA 14 105 53 55/10/29/6/15 // 50 lO 1400 4D BA / M «A / MAVHEMA // ST 4 100. 46 20/10 / (comparison) 22.5 / 6.5 / 6/15 // 50 10 30,000 The polymer emulsion of XEnulsion 4A is the same as in Experiment 2B.

The results in Table III show that, compared to Experiment 4A, it is more hydrophobic, i. less hydrophilic first stage polymer, good, 4B; the more hydrophilic first step 4C provides high viscosity; too hydrophobic the second stage 4D provides a very high viscosity at a high pH that is too high for most applications.

Example 5 Penetration parameter

According to Example 1, a number of emulsion polymers of different composition were prepared, the penetration parameter (lp) of which differed in both steps (Experiments 5A-5D, 5F-5H, 5J-5L and 5N-5R) or using the method of Example 8 below (Experiments 5E, 51 and 5M). Determinations of emulsion viscosity and MFT performed using an emulsion neutralized to pH 7.5-8.5 with ammonia and diluted to 20% polymer solids, and film hardnesses indicate which formulations are formed from internally plasticized polymers. Tables IV A and B show these values.

27 6 4 1 7 5

Table IVA

Experiment Composition Ratio 5A BA / MMA / COUNTRY / HEMA // MMA 23/6/6/15 // 50 5B BA / MMA / COUNTRY / HEMA // MMA 30/7/3/10 // 50 5C BA / MMA / MAA / HEMA // MMA 30.5 / 9/3 / 7.5 // 50 5D BA / MMA / MAA / HEMA // MMA 34.8 / 9.4 / 4.3 / 8.5 // 43 5E EA / VAc / VOH / MAn / AA // ST 5.5 / 37.8 / 5.6 / 0.4 / 0.7 // 50 5F BA / MMA / MAA / DHPMA // MMA 25 / 11.5 / 6/7 // 50 5G BA / MMA / MAA / VAC / VOH // MMA 23/6/6 / 13,5 / 1,5 // 50 5H BA / MMA / DMAEMA // MMA 18/17/15 // 50 51 EA / VAc / VOH // ST 23 / 23.9 / 2.1 // 50 5J BA / MMA / MAA // ST / AN 25 / 21.5 / 3.5 // 30/20 ( 5K BA / MMA / MAA / HEMA // ST 22,5 / 6,5 / 6/15 // 50 (ver.) 5L MMA // BA / MMA / MAA / HEMA 50 // 2,3 / 6/6/15 (trans) 5M BA / VOH / VAc // MMA 24 / 2.1 / 23.9 // 50 5N BA / MMA / MAA / DHPMA // MMA 25 / 11.5 / 6/7 , 5 // 50 50 BA / MMA / COUNTRY / HEMA // MMA 30/7/3/10 // 50 5P BA / MMA / COUNTRY / HEMÄ // MMA 30.5 / 8.25 / 3.75 / 7 , 5 // 50 5Q BA / MMA / MAA // ST / ΑΝ 25/19/6 // 30/20 (vert.) 5R EA / ST / MAA // ST 21/24/5 // 50 (vert. )

The meaning of the abbreviations is shown on page 15.

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Notes to Table IVB

1. The viscosity was measured at a solids content of 20% of the latex and was adjusted to pH 9 with ammonia except for Example 5H where the pH was adjusted to 3 with acetic acid.

2. MFT C grade, latex solids content 20% and adjusted to pH 9 with ammonia except for Example 5H (pH 3 as above).

3. Hardness = Knoop hardness number (KHN) as determined by the method set forth in Resin Review Vol. XVI No. 2, pp. 9 ff (1966); published by Rohm and Haas Company.

4. Tg calculated for "high polymer" by the method of Fox et al .; "(1)" and "(2)" mean the first and second or later stages and "average." value calculated for the whole mixture.

5. lp calculated for the first step (1) and the second step (2). The difference between the Ip values is in the table under "(1-2)".

The values in Table IVB indicate that an internally plasticized polymer is obtained as can be seen from the glass transition temperature, minimum film temperature, emulsion viscosity and hardness values when the fusion parameter of the first stage polymer is higher than, but not too much higher than that of the second stage polymer.

Experiment 5J, which shows a known polymer latex, does not contain internally plasticized particles as can be seen from the similarity of Tg and MFT values. As shown in Table IVA, the first stage polymer of this polymer contains only 7% hydrophilic sea units. Experiment 5K does not apply to the internally plasticized particles of the invention which can be seen from the high viscosity. As can be seen from Table IVB, its composition is such that there is too much difference in Ip values between the two-stage polymer. Experiment 5L is not in accordance with the invention; the viscosity is then so high that a gel is formed. It should be noted that the Ip difference between the polymers in these two steps is too low, it is less than O. In experiments 5Q and 5R, the known polymer latices have higher MFT than Tg values. Neither carbon contains a nonionic hydrophilic monomer in the first stage.

Example 6 Floor polish

The floor polish is prepared by mixing the ingredients together as follows (except for experiments 6A and 6E, as mentioned below): 3o 64175

Function Material Amount Medium Polymer emulsion 15% solids 100.0 parts

Wax "Poly EM-40" - 15% solid. (trademark;

Cosden Oil & Chemical Co.) 15.0 parts

Humidification- "Fluorad FC128" - 1% solid. (trademark; excipient 3M Co.) 0.5 parts

Application Tributoxyethyl phosphate - 100% active 0.5 parts excipient

Foam- "SWS-211" - 50% solid. (trademark; inhibitor Stauffer Wacker Silicone Corp.) 0.01 parts

Base Ammonia - 10% aqueous solution to pH 8

The floor polish is added and tested by the method described in detail in Resin Review Vol.

XVI No. 2, 1966, published by Rohm and Haas Company, Philadelphia, Pennsylvania 19105, unless otherwise noted. The polymer emulsions and test results used are shown in Tables VA and VB.

Table VA

Experience (comparison)

6A 6B 6C 6D 6E

Polymer Emulsion (huan.l) Experiment 2B Experiment 50 Experiment 5P Experiment 5E

(huan.3) (hucnu 4)

Results (note 2)

Eye, gloss 1 top. h-eh eh eh eh h-eh 2 head. eh eh-erin. eh-perfect. eh-perfect. eh

Leveling 1 top excellent. excellent. excellent. excellent. excellent.

2 ch. excellent. excellent. excellent. excellent. excellent.

60 ° gloss (ΊΜ 3) 71 82 79 80 77 5) eh-erin. h-eh eh eh-erin. tyyä.

Water resistance (ΊΜ 4) 1 hour good difference. excellent. excellent. excellent.

1 day h-eh erin. excellent. excellent. excellent.

Tracer resistance (TM 6) 1 day eh good good eh 3 days eh-excellent. - - - Satisfied.

7 days eh-erin. eh eh-erin. eh-perfect.

Removability (TM 7) eh erin. excellent. excellent. sat.

Static friction coefficient (TM 1) 0.5 0.6 0.6 0.6 powder nood. (TM 2) a little O O O - 3i 64175

Notes to Table VA: 1. Experiment 6A illustrates known processing. It uses a floor polishing polymer emulsion with 1.65% zinc ion crosslinker. This polish is prepared by mixing the ingredients together as follows:

Function Material Quantity Medium BA / MMA / MAA copolymer emulsion - 15% solids 80 parts

Wax "Poly EM-40" - 15% solids (trademark Cosden Oil and Chemical Co) 15 parts

Alkali solution Low molecular weight acrylic resin - resin 15% solid. 5 parts

Coupling Diethylene glycol monomethyl ether 4 parts of the active ingredient

Coalescing Dibutyl Phthalate 1.0 parts substance

Moisturizer Fluorad FC-128 - 1% solid. (trademark 3M Co.) 0.4 parts

Leveling agent Tributoxyethyl phosphate - 100% active 1.0 parts

Foam - "SW-211" - 50% solid. (trademark Stauffer Wacker Silicone Co.) 0.01 part 2. The method of adding floor polishes is described in ASTM Method D1436-64, Method B (ASTM-American Society for Testing Materials, Philadelphia Pennsylvania). The test methods shown in parentheses are listed below.

3. Experiment 6D was performed using 1.25% zinc ion from emulsion polymer solids.

4. The composition of the polish of Experiment 6E differs from Experiments 6B, C and D in that the wax and antifoam are omitted and two parts of a coalescing agent, diethylene glycol monomethyl ether, are added.

The test methods in Table VA are shown in parentheses.

1. Lubrication: ASTM Method 02047-72; the plates were treated at 25 ° C and 55% relative humidity.

2. Powder Formation: ASTM Method D2048-69.

3. 60 ° Gloss: ASTM Method D1455-64 Vinyl Brick (Kentile No. 3-44 Kentile Floors, Inc.) was used in place of OTVA brick in this experiment.

4. Water resistance: ASTM method D1793-66 dynamic test method.

„64175 32 5. Durability of sensor traces: CSMA method 9-73 (Chemical Specialties Manufacturers Association, Washington D.C.); the experiment was modified by rotating for 15 minutes in each direction.

6. Detergent resistance was performed on black vinyl asbestos brick using 10 ml of 5% solution of Forward detergent (trademark S.C. Johnson) and 50 cycles in one day, 75 cycles in three days and 100 cycles in a 7-day experiment.

7. The removal test was performed using 75 cycles and 10 ml of 3% Spic and Span solution (trademark Procter & Gamble) and 1% aqueous ammonia on black vinyl asbestos brick.

Abrasion resistance tests were performed in a corridor with a vinyl asbestos brick floor with 3500-4000 pedestrians running daily. Part of this passage (3 m wide and 7.5 m long) was isolated and the residual polish was removed and polished by a conventional method as follows:

The floor was wiped to remove loose dirt using a commercially available cleaning solution in the form of an aqueous solution (1: 1) using Step-Off (S.C. Johnson & Sons, Inc. Racine, Wisconsin 53404) in a sweeping volume of about 5 2 liters / 100 m. After a 5 minute soak period, the floor was rubbed using a 40 cm black floor scrub disc (3M Company, St. Paul, Minnesota 55101; Scotch Brite Slim Line Floor Pad No. 61-6520-0105-0) in a scrubber with a rotation speed of 300 rpm. min (Mercury Floor Machines Inc., Englewood New Jersey, Model H-15-c) and the treated floor was thoroughly cleaned twice with a cloth with clear water and allowed to dry. The cleaned floor was divided into 1.8-meter zones perpendicular to normal corridor traffic. A coating of the test polish was added to each of these zones by means of a cloth using an amount of 2.5 1/100 m. After allowing the polish to dry for one hour, a second coating was added in the same manner. The appearance of gloss was tentatively assessed after 1 and 2 weeks of hard wear. The results of these observations, as well as the results of other experiments that followed the methods used to determine the results in Table VA, are shown in Table VB.

33 6 4 1 75

Table VB

Experiment 6A 6B 6C 6D

At first:

Gloss (visually) eh eh eh + eh +

Evenness is excellent. excellent. excellent. excellent.

Re-coating excellence. eh-perfect. eh-perfect. excellent.

1 week use:

Gloss (visually) h-eh eh eh eh +

Dirt adhesion resistance differs. excellent. excellent. excellent.

Durability of black rubber heel eh-erin. eh eh-erin. eh

Abrasion resistance eh-erin. eh + eh-erin. eh 2 weeks spend:

Gloss (visually) good good good + good

Lian adhesion response eh eh eh eh-

Durability of black rubber heel eh eh- eh eh

Abrasion resistance h-eh h-eh h-eh h-eh

The abbreviations used in Tables VA and VB are as follows: excellent. = excellent, eh = very good, h = good, + = plus, - = minus, except that if used between abbreviations it means "up to".

Example 7 Varnish and paint

The polymer latex of Example 1 was formed as follows:

Experiment 7A: A latex containing 40% solids is adjusted to pH 9 with 14% aqueous ammonia.

Experiment 7B: To 100 parts by weight of latex adjusted to pH 8.5 with 14% aqueous ammonia is added a mixture of 9.7 parts of water and 15.3 parts of butoxyethanol.

Experiment 7C: The ingredients were mixed together as follows:

Parts by weight

Water 4.7

Tamol 165 (22% water content) 1.3 (Rohm and Haas Co.)

Triton CF-10 (100%) 0.16 (Rohm and Haas Co.)

Nopco NXZ (Diamond Shamrock) 0.05

Zopaque RCL-9 (TiO pigment) 18.8 (SCM Corp; Glidden-Durkee Division)

Grind at high speed with dispersant (1200 m / min) for 15 minutes and add with stirring:

Polymer latex 70.4

Water 1.8

Butoxyethanol 2.8 total 100.0

The properties of the varnish and paint are determined by conventional methods. The results of these regulations, using films made from these alloys to coat metal sheets, are shown in Table VI.

Table VI

Feature ^ Experiment 7A Experiment 7B Experiment 7C

Touch dry / adhesive dry time (min 25 ° C, 40% relative humidity) 19/21

Hardness after air drying KHN, 1 h, 25 ° C, 40% rel. 6.5 about 1

Final hardness KHN 6.5 6.5 (hot. 30 min)

Fresh Printing (60 ° C / 16 h / 2g, 6 kPa) (heated 121 C / 60 min) none no minor traces

Flexibility test (0.04 mm / B-1000/1 h at 121 ° C) (12.7, 6.4, 3.2 mm mixtures) 0/1/1 // 1 // 7-8

Impact strength In-Lb (D / R)

Alodine 1200S * 50/16 U 'T-connection T -

Softening in water (16 h, 38 ° C) moderately moderately moderately rust, rust, rust, no cracks slightly cracks -i slightly cracks

Cleveland condensing Cabinet slightly rusty (16 h 40Qc) tea, no cracks 35,641 75

Feature ^ Experiment 7 A Experiment 7B Experiment 7C

Chemical and dirt resistance:

Alcohol (16 h) moderate moderate moderate effect effect effect

Ink (30 min) no effect

Mustard (30 min) no effect

Lipstick (30 min) no effect

Gasoline (30 min) affects the effect of a slight slight to moderate to moderate ^ "Results were obtained using 0.04 mm thick films heated for 1 hour at 121 ° C unless otherwise stated 2

The values of the air-dried films are 2/1.

The values in Table VIA show that the latex of Experiment 7A dries completely completely hard and forms a film that is both hard and flexible without a coalescing agent. The coalescing agent slows down the development of hardness and has a detrimental effect on a few resistance properties. Heating is required to maximize certain properties. The durability properties are generally good although the water and alcohol resistance results are not as good as the other results.

Experiment 7C shows that the latex of Example 1 can be used to form pigmented films using a relatively small amount of coalescing agent. The physical properties of the formed film are similar to those of the unpigmented film. Other experiments with films formed in Experiment 7C show moderate rusting of a sample that has been in a humid chamber for 5 days, signs of degradation after 3 days in a saline spray chamber, and a change in gloss after 32 hours at 38 ° C in a Cleveland condenser chamber as follows: 20 ° / 60 ° / 80 °) gloss 54/77/88

Final (20 ° / 60 ° / 80 °) gloss 21/60/72

Example 8 Internally plasticized polymer emulsion based on vinyl acetate

A latex with first and second stages and mean Tg values of 25, 100 and 58 ° C, respectively, and first and second stage Ip values of 17.5 and 12.1, respectively, was prepared as follows: 36 641 75 A. Apparatus 5 liters a 5-necked flask was equipped with a condenser, an efficient stirrer, a thermometer, addition funnels, and heating, cooling, and nitrogen feeders.

B. Materials used

Monomer charge Boiler charge

Raw materials 1 IA 2

Deionized water 166.3 g 154 g 883.7 g

Octylphenoxy-poly (39) ethoxyethanol 3.4 5.1 1.7 "Abex 18S" (33%) (Alcolac Inc) 8.5 12.8 4.3

Sodium dodecylbenzenesulfonate (23%) 6.8 10.2 3.4

Ethyl acrylate 37.8 to 19.1

Vinyl acetate 298.5 to 150.8

Styrene - 517.5

Maleic anhydride 4.1

Acrylic acid - 7.2 -

Initiator: Fe ++ (0.15% FeSO 4 · 61 ^ 0) 6.4 ml 0.26 g ammonium persulfate (APS) in 8 g water.

0.26 g of sodium sulfoxylate-formaldehyde in 8 g of water

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

Activator: 1.92 g NaHSO 3 in 110 g water.

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

C. Method of treatment

The amounts of monomer and the amounts fed to the kettle are weighed separately and each mixed to form an emulsion. The initiator mixture is prepared and fed to the boiler. Efficient mixing of the boiler is maintained throughout the reaction cycle. The heat of reaction raises the boiler temperature from 22 ° C to the maximum temperature (about 60 ° C in about 7 minutes). At the maximum temperature, the feed of the monomer charge 1 is started at a rate of 13 ml / million and the addition of the catalyst solution and the activator solution is started in separate additions at a rate of 1 ml / min. The reaction temperature is maintained at about 62 ° C throughout.

37 6 4 1 75

When half of the addition of monomer charge 1 has been completed (about 22 min), charge IA is mixed with the remaining monomers of charge 1 and the addition is continued. After about 45 minutes, the addition of this monomer charge (1 + IA) is complete and the contents of the pot are maintained at 62 ° C for 15 minutes. The addition of monomer charge 2 is then started at a rate of 13 ml / min. This second addition is complete in about an hour and the contents of the kettle are maintained at 62 ° C for 10 minutes at the time the catalyst and activator addition is completed. The reaction mixture is maintained at 62 ° for a further 15 minutes and then allowed to cool to 55 ° C. The additive is then added rapidly and the reaction mixture is maintained at 50-60 ° C for 15 minutes. The product is allowed to cool to room temperature and packaged.

A sample of the latex product is neutralized to pH 8.5 with ammonia and can be found to have a viscosity of 40 cp (20% solids, Brookfield Synchro-Lectric Viscometer Model LVI, spindle 1, 60 rpm) and an MFT below 15 ° C. The hardness of the film formed from this sample is 17 KHN.

Example 9 Internally plasticized polymer emulsion with an acid-containing final step

A latex with first stage, second stage and average Tg values of 28, 112 and 65 ° C, respectively, and first and second stage Ip values of 17.5 and 14.5, respectively, is prepared using the same equipment as in Example 8 and a similar procedure. as follows: 38 641 75

Material inputs.

Raw material Monomer charge Boiler charge 1 1Λ 2

Deionized water 154.0 g 64 g 154.0 g 832 g

Octyl Phenoxide (39) Ethoxyethanol 5.1 5.1 Abex 26S (33%) (TM Alcolac Inc) 12.8 12.8

Sodium dodecylbenzenesulfonate (23%) 10.3 10.3

Ethyl acrylate 56.9

Vinyl acetate 449.3

Styrene - 440.0

Methacrylic acid 7.2 77.6

Maleic anhydride - 4.1

Initiator: Fe ++ (0.15% FeSO 4 .6H 2 O) 6.4 ml 0.26 g ammonium persulfate (7iPS; in 8 g water. 0.26 g sodium sulfoxylate formaldehyde in 8 g water.

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

Activator: 1.92 g NaHSO 4 in HO g water.

Additive: 0.52 g tBHP in 5 g water.

0.39 g of sodium sulfoxylate formaldehyde in 5 g of water.

Procedure 1. The boiler temperature is adjusted to 20-22 ° C and nitrogen is introduced.

2. Prepare batch 1 and add 231 g to the pan.

3. Maleic anhydride is added to water and methacrylic acid (batch IA) to the remaining portion of monomer batch 1 and emulsified.

4. Add initiation, N ,, derivation is stopped.

5. Several minutes after the addition of the initiator, an exothermic reaction occurs when the temperature reaches 55-6G ° C.

6. At the peak temperature, the addition of monomer charge 1 is started and half of the catalyst and activator are added. The temperature is allowed to rise to 62 ° C and is maintained at this value during the addition.

39 6417 5 7. Addition of charge 1 takes 40-45 minutes, and after charge 1 and a half of catalyst and activator are added, the system is maintained at 62 ° C for 20 minutes.

8. After 20 minutes, start the addition of charge 2 and catalyst and activator.

9. The addition of charge 2 takes about 55 minutes and the addition of catalyst and activator takes an additional 10 minutes.

10. Maintain the mixture at 62 ° C for 30 minutes.

11. Cool to 55 °, then add additive and allow to stand for 10 minutes before cooling to room temperature. 12. At room temperature, adjust the pH to 4.5-5.0 with 10% aqueous NH 4 HCO 3.

The finished latex sample has a viscosity of 19 cp (20% solids content, Brookfield Synchro-Lectric Ciscometer Model HVAC, spindle 1, speed 60 rpm) and an MFT of 37 ° C. The hardness of the film cast from this sample is 14 KHN. When 1% Zn ++ (as ZN (NH 3) 4 (HCO 3) 2) is added based on the polymer solids as disclosed in U.S. Patent No. 3,328,325, the film hardness is 15.5 KHN.

Example 10 Effect of the amount of hydrophilic monomer

Following the procedure of Example 9, a group of polymer emulsions are prepared having the compositions and properties shown in Table VII. These emulsions are used to make floor polishes by mixing the ingredients together as follows:

Function of the substance Material Amount Medium Polymer emulsion - 15% solids 90.0 parts

Wax "AC 392" - 15% solids (trademark Allied Chem.Corp.) 10.0 parts

Moisturizer "Fluorad FC128" - 1% solids (trademark 3M Co.) 0.5 parts

Smoothing aid- Tributoxyethyl phosphate - 100% active ingredient 0.5 parts

Coalescing Methylcarbitol 4.0 substance

Base Ammonia -Ί0% aqueous solution to pH 7.5

Each floor polish is added and tested as described in Example 6, Figure 64175 40. The results are shown in Table VII, which shows the superior polishing properties of products 10D and 10E.

AC-392 is prepared at 35% solids as follows and diluted with water to 15% solids.

Composition Weight "A-C Polyethylene 392" 40

Octylphenoxypoly (9) ethoxyethanol 10 KOH (90% flakes) 1,2

Sodium metabisulphite 0.4

Water (1) to a solids content of 50%

Water (2) to a solids content of 35% 43

The first 5 components are fed to a stirred pressurized reactor to obtain a 50% concentration. Stirring is started and heated to 95 ° C with the valve open. The valve is closed and heating is continued to 150 ° C for 1/2 hour. Water (43 parts) is added to the reactor at 95 ° C while maintaining the temperature at 150 ° C, and then cooled to room temperature with stirring as quickly as possible. 500 mol of formaldehyde preservative are then added.

41 64175

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Example 11 Effect of acid content variations

Following the procedure described in Example 9, a number of polymer emulsions are prepared as shown in Table 8. These emulsions are used to prepare floor polishes and are tested as described in Example 10. The results of these experiments are shown in Table 8, which shows that the product of Example 11A is not of very poor quality and that the copolymers using maleic anhydride are not turbid.

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Example 12 Variations in the first stage / second stage Polymer emulsions are prepared by the method of Example 9, the ratios of the first stage and the last stage of which are shown in Table IX. The first stage composition in each is EA / VAc / VOH / MAn / MAA = 11 / 75.6 / 11.2 / 0.8 / 1.4 and the Tg (l) value is 27.7 ° C and the Ip (l) value 17.5. Both final steps are polystyrene with a Tg (2) of 100 ° C and an lp (2) of 12.1. Thus, each latex polymer has an Ip (1) to lp (2) value of 5.4. These emulsions are used to make floor polishes and are tested as described in Examples 6 and 10. The test results are shown in Table IX.

Table IX

Test 12A 12B 12C 12D 12E

The polymer emulsion

First // last step (by weight) 70 // 30 60 // 40 50 // 50 40 // 60 30 // 70 MFT ° C 19 ° 21 23 24 80

Viscosity * (cp) 22 21 24 20 17

Tg average ° C 46.3 53.0 60.0 67.3 75.0

Polishing properties Visible turbidity 0 0 0 low point 1.

Visible gloss good ladies good good satisfaction- good

Leveling eh fair eh eh eh

Detergent resistance is satisfactory. sat. sat. good eh

Removability is satisfactory. sat. sat. bad bad

Durability of interest traces good good good good good

Abrasion resistance good good ladies good good * Solid inep content 40% and pH 5.

Example 13 Maleic Anhydride / Methacrylic Acid Amounts Polymer emulsions are prepared by the method of Example 9 using a set of maleic anhydride and methacrylic acid in the first step, as shown in Table X. Each final step is polystyrene and is present in an amount of 50% by weight of polymer. The polymer in Experiment 13A is the same as in Experiment 11A. With relatively small differences in composition, the Tg and Ip values of the other three polymers at 45,641,75 are only slightly different from Experiment 13A. Polishes made from these emulsions were tested in Examples 6 and 10 to give the results shown in Table X. This results in very different polish removability and detergent resistance. This is notable given the vinyl acetate content of the polymer.

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Example 14 Acid in the last step

The polish of Experiment 14A is prepared from the same polymer latex as in Experiment 11A. The film of this polymer was found to have a Knoop hardness number of 10. The polish of Experiment 14B is prepared from the polymer latex of Example 9 and crosslinked with 1% of Zn ++ polymer solids added as Zn (MH 2) 2 (HCO 3) 2 * The polish of Experiment 14C is prepared from a polymer latex sample, Table VA, note. 1. The KHN value of this polymer film is 13. These polishes are tested as described in Examples 6 and 10 and the results are shown in Table XI. A balance between removability and detergent durability while providing other good properties is noteworthy.

Table XI

Test 14A 14B 14C

Polishing properties

Leveling eh-excellent. eh eh-erinom.

χ

Gloss visually one coating h-eh / h h-eh / h-eh eh / h-eh two coatings eh-erinom./eh+ excellent./eh-erina. eh-erii om./erii relative

Visual turbidity 0 00

Detergent resistance is satisfactory. eh eh-erinc

Removability good eh-erinom. excellent xFound results on vinyl brick / OTVA brick; see Test Method 3 in Example VA, Table VA.

Claims (20)

48 6 4 1 75 A latex formed by internally plasticized addition polymer particles suitable for making coatings, adhesives and binders and comprising (A) an earlier stage polymer and (B) a later stage polymer formed by polymerizing in the presence of an emulsion of polymer particles containing polymer (A) , wherein polymers (A) and (B) each comprise at least 10% by weight of the amount of polymer contained in the particles, characterized in that the polymer (A) contains at least 10% by weight of hydrophilic polymers, of which at least 10% by weight are nonionic, and polymer (B) is less hydrophilic than polymer (A), wherein either (1) polymer (B) is such that it has a higher Tg value than polymer (A), and at least 0 of the hydrophilic units of polymer (A), 5% is ionic and the penetration parameter of the polymer (A) is not more than 8 units higher than that of the polymer (B), the polymer (A) containing a monoethylenically unsaturated monomer in the form or (2) the Tg of the polymer particles exceeds 15 ° C and the viscosity of the latex is less than 5000 cP measured at a solids content of 20% by weight in the pH range of 4-10 and has a minimum film temperature greater than 5 ° C of the calculated Tg of the polymer particles. below. Latex according to Claim 1, characterized in that the calculated Tg value of the polymer particles is greater than 20 ° C. Latex according to Claim 1 or 2, characterized in that it has a viscosity of less than 500 cP, the polymer particles have a Tg value of more than 30 ° C and the latex polymer is such that the film formed therefrom has a Knoop hardness of at least 5 . Latex according to one of the preceding claims, characterized in that 0.5 to 90% by weight of the hydrophilic units are acid or base units and in that the viscosity is less than 150 cP. Latex according to one of the preceding claims, characterized in that the viscosity is less than 40 cP, that the latex polymer is such that the film formed therefrom has a Knoop hardness value of at least 8 and the polymer (A) contains ionic units having carboxyl group-containing units. Latex according to Claim 5, characterized in that the viscosity is less than 10 cP and that 50 to 90% of the hydrophilic mers are mers formed by the hydroxyalkyl ester of the α, β-unsaturated acid. Latex according to Claim 6, characterized in that the addition polymers form monomers of acrylate, methacrylate, vinyl ester and / or vinyl aromatic monomer. The latex according to claim 3, wherein the polymers (A) and (B) each comprise at least 30% by weight of the latex polymer and the viscosity of the latex is less than 150 cP, characterized in that. the polymer (A) contains 10 to 70% by weight of hydrophilic mers and the polymer (B) has a calculated Tg of at least 10 ° C above the calculated Tg of the polymer (A). Latex according to Claim 8, characterized in that the minimum temperature of the film is at most 18 ° C, that the film formed from this latex polymer has a Knoop hardness of at least 5, the calculated Tg of the polymer (A) is at most 40 ° C and that the polymer (B) is harder than polymer (A). Latex according to Claim 9, characterized in that the viscosity is less than 40 cP and the film formed from the latex polymer has a Knoop hardness number of at least 8, a polymer (A) having a Tg of at most 5 ° C and a polymer (B) having a Tg of at least 7 ° C. Latex according to Claim 10, characterized in that it has a viscosity of less than 10 cP, the dolymers (A) and (B) each form at least 40% by weight of the latex polymer, the polymer (A) has a Tg of at most -10 ° C and the polymer (B) Tg value of at least 100 ° C. Latex according to Claim 11, characterized in that at least 0.5% by weight of the hydrophilic polymers are carboxylic acid isomers. 50 641 75 Latex according to Claim 12, characterized in that the latex polymer contains units of one or more of the following monomers: acrylate esters, methacrylate esters, vinyl esters and vinyl aromatic monomers. Latex according to Claim 13, characterized in that the units of polymer (A) contain 65 to 85% by weight of (C 1 -C 4) alkyl acrylate, (C 1 -C 4) alkyl methacrylate and / or styrene units, 5 to 10 % acrylic acid, methacrylic acid and / or itaconic acid units, and 10-25% hydroxy (C 1 -C 4) alkyl methacrylate and / or hydroxy (C 1 -C 4) alkyl acrylate units, and that the polymer (B ) units include methyl methacrylate and / or styrene units. Latex according to Claim 13, characterized in that the units of polymer (A) contain 50 to 85% by weight of vinyl acetate units, 1 to 10% of acrylic, methacrylic, itaconic and / or maleic acid units, and 8 to 25% of vinyl alcohol units, and the units of polymer (B) contain 100-70% of methyl methacrylate and / or styrene units and 0-30% by weight of acidic units. Latex according to Claim 15, characterized in that the units of the polymer (A) contain, by weight, 1 to 4% of acid units, of which 0.2 to 2% by weight in the polymer (A) are maleic acid units, 0 to 20% (C C 1-6 alkyl acrylate, 65-80% vinyl acetate and 10-20% vinyl alcohol units, and the units of polymer (B) contain 10-20% by weight of acid units. Latex according to one of the preceding claims, characterized in that the fusion parameter of the polymer (A) is 1 to 6 units higher than that of the polymer (B). An aqueous polishing composition capable of forming a coating having a Knoop hardness of at least 0.5, characterized in that it comprises: (a) 10 to 100 parts by weight of a latex formed of internally plasticized addition polymer particles comprising (A) the prior art step polymer and (B) a subsequent step polymer formed by polymerizing in the presence of an emulsion of polymer particles containing polymer (A), wherein polymers si 6417 5 (A) and (B) each comprise at least 10% by weight of the amount of polymer contained in the particles, and the polymer (A) contains at least 10% by weight of hydrophilic polymers, of which at least 10% by weight are nonionic, and the polymer (B) is less hydrophilic than the polymer (A) wherein either (1) the polymer (B) is such that has a higher Τσ value than the polymer (A), and at least 0.5% of the hydrophilic units of the polymer (A) are ionic and the permeation parameter of the polymer (A) is not more than 8 units higher than polymer (B), the polymer (A) containing units of a monoethylenically unsaturated monomer, or (2) the Tg of the polymer particles exceeds 15 ° C and the viscosity of the latex is less than 5000 cP measured at a solids content of 20% by weight in the pH range of 4- 10 and has a minimum film temperature of more than 5 ° C below the calculated Tg of the polymer particles, (b) 0 to 90 parts by weight of time A fluffy resin in an amount of not more than 90% by weight of part (a), (c) 0 to 90 parts by weight of wax, (d) wetting, emulsifying and dispersing agents in an amount of 0.5 to 20% by weight of the total amount of components (a), (b) and (c), (e) polyvalent the metal compound in an amount of 0 to 50% by weight of the component (a), (f) water so that the total solids content is 0.5 to 45%. Use of a wedge mixture according to claim 18 for polishing a hard surface, characterized in that the surface is coated with the mixture and the coating is dried or allowed to dry. A process for preparing a latex from internally plasticized addition polymer particles, characterized in that (a) an emulsion of the polymer (A) particles of the earlier stage is formed by polymerization, and (b) a polymer of the later stage polymer (B) is formed on the polymer-containing particles in the presence of this emulsion. , wherein the amount of monomers of each polymer (A) and (B) is selected such that each constitutes at least 10% by weight of the amount of polymer contained in the particles and the polymer (A) contains at least 10% by weight of hydrophilic polymers, of which at least 10% by weight is non-ionic, and the polymer (B) is less hydrophilic than the polymer (A), wherein either (1) the polymer 52 641 75 (B) is such that it has a higher Tg value than the polymer (A) and the polymer (A) at least 0/5% of the hydrophilic units are ionic and the penetration parameter of the polymer (A) is not more than 8 units higher than that of the polymer (B), the polymer (A) containing monoethylenically units of unsaturated monomer, or (2) the polymer particles have a Tg value greater than 15 ° C and a latex viscosity of less than 5000 cP measured at a solids content of 20% by weight in the pH range 4-10 and a minimum film temperature greater than 5 ° C below the calculated Τσ value of the polymer particles. , l 53 64 1 75