HUE026211T2

HUE026211T2 - Poliglicerinek jelenlétében polimerizált asszociációs akrilpolimer-emulzió, és sûrítõszerként való alkalmazása vízalapú készítményben

Info

Publication number: HUE026211T2
Application number: HUE12781395A
Authority: HU
Inventors: Jean-Marc Suau; Denis Ruhlmann
Original assignee: Coatex Sas
Priority date: 2011-11-04
Filing date: 2012-10-15
Publication date: 2016-05-30
Also published as: BR112014010163A8; CN103906769A; WO2013064763A1; US8859656B2; FR2982266B1; FR2982266A1; EP2773677A1; BR112014010163A2; CN103906769B; EP2773677B1; DK2773677T3; US20130116368A1

Description

EMULSION <>E AN ASSOCIATIVE ACRYLIC POLY MER POLYMERIZED IN THE PRESENCE OF POLYGLYCEROLS AND USE OF SAME AS A THICKENING AGENT IN AN AQUEOUS COMPOSITION

The present indention relates to new emulsions containing sereik associative thickener agents which, when polymerked in the presence of particular polyglyeerols, have a thickening power which is retnarkahly stable over time. The viscosimetrie variance caused by this type of thickener agent,. which appears very rapidly after several days' storage, is notably reduced by this means, in particular in. paints with low VÖC (Volatile Organic Compound) rates, or paints without VOCs, The: user is thus guaranteed identical application, properties kr their paint, le, an unvarying rheological profile for the paint they formulate, and which they apply, independently of the storage time of the said paint, over a period which can be as long as Several months.

Controlling: the rheology of a paint both in the stage of its manufoeture, and during its transport, storage or use, remains a poority at tlie current tune. The wide variety of constraints observed in each of these steps relates to a multiplicity of different rheological properties. Nevertheless, it is possible to summarise the requirement of the skilled man in the art in obtaining an effect of the thickening of the said paint, both tor reasons of stability over time, and for a possible application to a vertical surface, lack of spattering during use, or of sagging after application, etc. As a consequence, the products which contribute to this regulation of foe rheological properties have been designated by the term "thickener agents".

Historically, since the 1950s cellulose-based gums and products have been used, one of the essential characteristics: of which is their high molecular weight:.

However, these compounds have a number of disadvantages, such as their instability over time (see document US 4 673 518), foe need to use a large quantity of them {see document ERŐ 250943 Al), and their production costs, notably in terms of waste treatment (see document US 4 284 096).

Thickener agents called ’’associative” thickener agents were then created: these are water-soluble polymers having insoluble hydrophobie groups. Such macromoleeules have an associating character; when introduced into water, the hydrophobic groups tend to assemble in the form of micellar aggregates. 'These; aggregates are linked together by the hydrophilic parts of the polymers: a three-dimensional network is then formed: which panses the viscosity of the medium to be increased:. The operating mechanism and their characteristics arc now well known and described, for example m the documents “Rheology modifiers for water-home palnpf’ (Surface; Coatings Australia, 1985, pp. 6-10) and' ’’Rheological modifiers for water-based paints: the most flexible tools for yow formulations” (Euroeoaf 9?, UÂTCM, vol 1, pp 423-442).

Among these associative thickener agents, a technological platform is known which contains particular emulsions known as "HASI" (Bydrophobically modi fled Alkali-Soluble Emulsions), These contain polymers of (meth) acrylic acid, of an ester of these acids and of an associative monomer consisting of an oxyalkylated chain mmhnated by a hydrophobic group.

In the case of these associative monomers, the choice of hydrophobic group determines the varied rheological properties. The following patent applications filed by Coatex™ may be elled with this regard: EP 0 57?526 A!, which describes a fatty chain with linear or branched units of the alkyl and/or aryl type, having 26 to 30 carbon atoms, to develop high viscosities under a low shearing gradient, and EP 1 778 797 A!, which describes a branched fenninal chain comprising 16 to 24 Carbon atoms, to improve the pigmentary compatibility, and: increase the viscosity generally.

However, associative thickener agents - and notably BASE - have a tendency to cause viscosities which may increase over the storage time, from the time when they are introduced into a paint. It is, indeed, wed known that the thickening power which they develop tends to increase over time, when they are associated in the paint with binders which require no or little In the way of coalescence aid agents: this trend can generally be observed 8 days after formulation. Such vahariee is: not desirable, since it is synonymous with a loss of control of the paint’s rheological profile,

The Applicant has developed a pew method for pmnofoeluring aqueous emulsions containing HA$B~type thickener agents, involving the use of particular polyglycerols. The respiting products develop viscosities which are completely stable within the paint formulations in which they are incorporated; a simple and eieetive solution is therefore found to the problem of Éeufogícal variance as mentioned above.

One of the characteristics of the polyglyccroîs in question, in addition to their chemical pâture, is based on the fact that they are used during the synthesis of HASB-type thickener agents; hr this sense, these are "polymerization surfactants''. Conversely, "formulation suriactanis" are used alter the polymerization of the thickener agents, notably in order to use the finished product obtained after polymerization in water.

The Applicant states that the use of surfactants during polymerization of an acrylic associative thickener agent is already known; it is notably described in document WO 2DD$ 019225 A.1. Furthermore, it is already known to use glycerol during the same type of synthesis, as disclosed in document WO % Ö6757 AI. Nevertheless, nothing described or suggested that the use of polyglycerols, as polymerization surjetants, was likely to lead to new aqueous emulsions containing HASlhtype associative thickener agents, giving the paints into which they are introduced partleulariy stable viscosities. A first object of the invention therefore consists of an aqueous emulsion of an associative thickener agent obtained by polymerization; a) of at least one monomer which: is :(met!riaeryhc acid, and preferentially methaeryhc add, h) of at least one monomer which is an ester of (meth)aerylie acid, and preferentially ethyl acrylate, e) of at least one monomer baying at least one hydrophobic group, characterized in that d) at least one polygiyeerol of formula (I) is used during the said polymerization

(!) where R designates hydrogen, an ester group iimetionalised by an alkyl, group, having 8 to 22 carbon atoms, or an alkyl group having 8 to 22 carbon atoms, mi preferentially an alkyl group having 8 to 22 carbon atoms.

This emulsion Is also characterized in that, for the said associative thickener agent obtained by polymerisation, the sah! polymerization consists in accomplishing a first step of tittrodueiBg into water compounds d) and the said sm&clants other than the compounds dk followed by a second step of increasing the temperature of the medium, followed fey a third step of mirndoeing polymerization. initiators, and then monomers, possibly added m combination with water and surfactants other than compounds d). lids emulsion Is also characterized in drat for the said associative thickener agent obtained by polymerization, in the said polymerization the surfactants other than compounds d) are chosen from among the anionic surfactants, and preferentially from among sodium doieeyl sulphate, dioctyl sodium stilfosuctínaíe, sodium dodecylfeeozenesulibnate, the nonrionte surfactants, and: preferentially the ethers of fatty alcohols and of polyoxyethylene: glycol, the: esters of polyoxyethylene glycol and the blends of these surfactants .

This emulsion is also characterized in that, for the said associative thickener agent obtained fey polymerization, the mass % of surfactants other than: d}/polymer is between 1% and 5% in the said polymerization.

This emulsion is also characterized in that, for the said associative thickener agent obtained hy polymerization, the said polymerization uses, as a % by weight, relative to the total weight of the said associative thickener: agent: a) ftofo 20% to 60% by weight of at least one monomer which is (meih}acrylie acid, and preferentially methaoylie acid, b) fern 40% ίο 80% of at least -ùm fnoáomer which is gp ester of (nteih)acrÿbc add, and preferentially ethyl acrylate, ei írom 0,S% to 2S% of at least one monomer having at least one hydrophobie gmug, d) som 0.1 % to 10% by weight of at least one polyglyedol of foimuk (I),

(1) where R designates hydrogen, an ester group functionalised by an alkyl group, haying 8: to 22 carbon atoms, or an alkyl group having 8 to 22 carbon atoms, and preferentially an alkyl group having 8 to 22 carbon: atoms, where the sum of the percentages a), b), c) and d) is equal to 100%·

This emtdsson is also characterieed in that, for the said associative thickener agent obtained by polymerisation, the monomer containing at least one hydrophobie group has the genefal formula R - (OE)P · · lOP)q ~ R’, where: - p and q designate integers of less than or equal to 1 SO, M least one of whies is non-aero, with preferentially q:::: 0 and 0 <' p < 80, - BQ and PÖ designate respectively ethylene oxide and propylene oxide, positioned in a random or regular manner, - R designates a polymerisable group, and preferentially the methacrylate or nwihacrylmethane group, - R* designates a hydrophobic group having at least 6 and at:most ;tb carbon atoms.

This emulsion is also charaeterfoed in that, for the said assoe|ative polymer obtained by polymeriMtion, i t has an average molecular mass by weight of between 20,1)00 g/moi and l,00i$O0: gdnoi, as measured by GFC.

Another object of the present invention consists in the use of such an emulsion, as a thickener agent of an aqueous formulation or an adhesive, where the said aqueous formulation is preferentially a water-based paint, a render coating, or a putty.

Another object: of the present invention lies in the fact that in the aqueous formulât«*» or adhesive containing said emulsion, the said aqueous fbinrodafionds preferentially a. wafer-based paint, a render coating, or a putty. A final abject of the present invention concerns the use of the polyglycerol of formula (I) as a monomer to prepare by polymerfoation an associative thickener agent in the form of an aqueous emulsion.

The following examples will enable the present invention to he better apprehended, without however limiting its scope,

EXAMPLES in each of die following examples, the molecular masses of the associative thickener agents fire determined byLPC,

Synthesis of the said thickener agents is well known to the skilled man in the art, and reference may be made in particular to the various documents cited in tire Application as background concerning HASE technology.

The paints are formulated using the methods well known to the skilled man in the art-All the Brookfield™ viscosities of the paint formulations are determined at 25°C.

Example 1

This example illustrates the synthesis and use of the various associative thickener agents according to the invention (presence of polygiyeerol during the synthesis), or outside the invention (without additives, with glycerol used during the Synthesis or as a formulation agent, with polyglvcerol added as a formulation surfactant).

The use in question occurs in a watewhased paint formulation, the eonstifufion of which is given in table 1 ; the figures indicate the mass in grams of each consfifeent.

Tafele 1 * !h© value of 12 grams is equal the mass of mu emulsion eooiaming 30% fey dry -weight of polymer (except for test n° 4 which uses 3.0 grams by dry weight of a commercial thickener agent in powder form)

ImjLL·

This test illustrates a HASE thickener agent outside the invention, polymerised with a conventional surfactant

This thickener agent results .from the synthesis, expressed as a % by weight of the monomers, of: a) 37.4% of rnethaeryiio acid, fe) 54.3% of ethyl acrylate, Ú): § .3 % of a monomer of formula (1),, in which: where R. desipates the methacrylate group, q u: 0, p = 25, where R’ desipates the hydrophobie group resulting from oxo alcohol having 16 carbon atoms. fo. a 1-litre reactor- 485,4 grams of hipermuied water and 6.Ö6 grams of sodium dodecy! sulphate and i 15 g of non-ionic surfactant, which is isottidceyl alcohol condensed with 3 molécules of ethylene oxide- ana weighed. The base of the tank |s then heated to 72°€ ± 2°C.

During this time- a pre-emulsion is prepared by weighing the fallowing in a beaker: - 14# grams dfbipérmuted water, ~ 2,33 grams of sodium dodecyi sulphate, - 111.33 grains of meihacrylic acid, ~ 161 AS grams of ethyl acrylate, - 24.6 grams of maeromonomer of formula (1),

The mass of non-ionic surfactant therefore accounts in this case for 3 .1% of the total mass of the manufactured polymer. 0.95 gram of ammonium persulphate is then weighed, diluted in 10 grams of Mpertmited water for the first catalyst, and 0.095 gram of sodiumotetabtsulphite diluted m 10 grams of bipermuted water for the second catalyst When rim base of the tank is at the remured temperature, both catalysts are added, and polymerisation is: effected tor 2 hours at %*€ ± 25C, with simultaneous addition of the pie-emulsion, The pump is rinsed with 20 grams of bipermuted water, and is fired for 1 hour at 76SCI ±-2°Ç, Finally it is cooled to ambient temperature, and the dispersion obtained in this manner is filtered,

IfMiill;

This test illustrates a HASE thickener agent outside the invention, polpuerixed with a conventional surfactant.

This is the same thickener agent as that of test rf 1, in which the non-ionic surfactant has been replaced, in mass terms, by nonylphenol condensed with 4 molecules of ethylene oxide.

This test illustrates a HASE thickener agent outside the invention, polymerized with a conventional surfactant

This is the same thickener agent as that of test nö 1, in'which the non-dome surfactant has been replacé ίο mass terms, by a surfactant sold by the company Clfariant™ unter the name Polygiykoi™ B11/150, XSIt.C.4;

This test itasfrates a thickener agent outside tie invention, formulated in water with the introduction of glycerol after polymerization.

The thickener agent is that of test n° I, polymerized according to the technique described in test n° 1.

In the final solution with 30% by dry weight of active matter, 3% by dry weight of glycerol from the company Oleon™ rel ative to the dry weight of polymer is introduced. IM.0ÜÍ

This test illustrates a thickener agent outside the invention, formulated in water with the introduction of polygiyeero! after polymerization.

The thickener agent is that of test n° I , polymerized according to the technique described in test xf I.

In the final solution with 303¾ by dry weight of active matter, 3% by dry weight, relative to the dry weight of polymer, of polyglyeenoI-3 of formula .(1), with R:::ί H, and n::: 3 sold by the company Solvay™, is introduced.

Test n* 6:

This test illustrates a thickener agent outside the invention, formulated in water with the infroduetinn of polygiyeero] after polymerization.

The fhiekener agent is that of test h*5 1, polymerized according to the technique described in lest χΐ 1,

In the final solution with 303¾ by dry weight of active matter* 13·% by dry weight, relative to the dry Weight of polymer, of hydrophobic polygiyeero], which is Chnnexane™ MB of formula (|) with R ™ CjgHjs and n ~ 2 sold by the company Chime#»* is introduced,

Iséjű;

This test illustrates a thickener agent outside l&e Invention* polymerized in the presence of glycerol.

The thickener agent is that of test n° 1, polymerized according to te technique described in test tf 1, except that the non-ionic polymerisation surfactant has been substituted, in mass terms, by glycerol IrOräi the company Oleon™, iM.lfJl litis test illustrates: a thickener agent according to the invention, polymerized in the presence of poiygiyeerol~3, which is the one used in test n° 6.

The thickener agent: is that of fest nf L j^lymerized accordingto the technique described in test ri* 1, except that the nonrionie polymerization surihetant has been substituted, in mass terms, by the polyglycerol-3 of test n" 5, lestjriJi

This test illustrates a thickener agent according to the invention, polymerized in the presence of Cbimcxane™ NB, which is the one used in test n° C>.

The thickener agent is that of test n® 1, polyinerized according to the technique described in test tri 1, except that the non-ionic polymerisation surfactant has been substituted, in mass terms, by the Chimexane™ NB of test n° 6,

For each of these tests the Brookfield™ viscosities were determined at 25¾ at 10 and 10Ö revolutions per nnmne, at instants t ::: 1 day (gio m> μ·οο m) sod t ? days (μ to: μ;οα ns), where instant t 0 is the time: of manufacture of the paint.

The results are shown in table 2.

Table 2

These results demonstrate thaï only the thickener agents polymerized in the presence of poiyglycerols according ίο the invention enable the changes of viscosity of the paint after ? days to he limited.:

With test n° 9, which represents the preferential Varient of the invention, it is even possible to stabilise the paint's viscosity almost perfectly one week after its manufecture.

For the latter test, the Brookfield^ viscosities meMuremonts at 10 and 1ÛÔ revolutions per minute were repeated after 2 months: a vari ation of the yiscositf es of less than 3 % of the initially measured values Was Observed, denoting excellent stability over time.

Example 2

This example illustrates the synthesis and «se of different associative thickener agents, according to the invention (presence of polyglyeerol timing the synthesis), or outside the invention (without addition of jmlygiyeeroi during the synthesis}.

The use in question occurs in a water-based paint ftmnulation, the constitution of which is peers in table 3; the figures indicate the mass in grams of each constituent.

Table 3 * the 24 grams are the mass of an emulsion comaming 30% 'fey <hy weight of polymer Test.nltO;

This test illustrates a liASE thickener agent outside the invention, polymerized with a conventional surfactant.

This thickener agent results from the synthesis, expressed as a % by weight of the monomers, of a) 33.7% ofmeihacrylie add, b) 59.43¾ of ethyl acrylate, c) 6.9% of a monomer of formula (l)s in which: R designates the methacrylate group q =* 0, p « 25, R! designates the branched hydtpphobie group with 16 carbon atoms, in a 1 Titre raaeior, 288 grams ofbiperrnuted waterfB.S grams of sodium dodeeyl sulphate and U-5 g of nomionie surfactant, which is isotrideeyl alcohol condensed with 3 molecules of ethylene oxide, are weighed, The base of the tank is then heated to 72¾ ± 2¾.

During fois time, a pre-emulsion is prepared by weighing; the following in « beaker; - 285 grams of bipetmuied water, - 3 .5 grama of sodium dodeeyi sulphate». ~ 102.0b grams of methaerylie acid, - 1fo) grams of ethyl aerylate, - 21 grams of macromonomer of formula {!}» - 0.64 g of dodecyimercaptan.

The mass of non-ionic surfactant therefore accounts in this ease for 3.6% of the total mass of the manufocfored polynm 0.9$ gmnrof arnnionium persulphate is then weighed, diluted in 10 grams ofbipemmted water for the first catalyst, and 0,095 gram of sodium metabisulphife diluted in 10 grams of bipertmUed water for the second catalyst. When the base of the tank is at the required temperature both catalysts are added and polymerisation is effected for .2 hours at 760€ é 2°C» with simultaneous addition of the pre-emulsion, lire pump is rinsed with 2(> grams of bipemiuted water, and is fired for 1 hour at 76*C ±- 2°C. Finally it is cooled fo ambient temperature, and the dispersion obtained in this manner is filtered.

Ibis test ilfostrates a thickener agent according to the indention, polymericed m the presen ce of poIyglyeerol-3 sold by the company So Nay™ .

The thiekener agent is that of test n° TO, polysncrfzed according to tbe technique described in test a? 10, except that tbe non-ionie polymerisation surfactant has been substituted, in mass terms, by the polyglyeerol-# of test # S.

Ic§!.nl!.2;

This test illustrates a thickener agent aeeordisg to the invention, polymerized in the presence of Chimexane™ NB.

The thickener agent is that of test ns Hi, polymerized according to foe technique described in test xr' 10, except that the polymerization surfactant has been substituted, in foass terms, by the Chimekane™ HE.

mj£M

This test illustrates a BASE thickener agent outside the Invention, polymerized with a conventional surfactant.

This thickener agent results iront the synthesis, expressed as a % by 'weight of the monomers, of: a) 35.57% ofmeihaerylieaeid, h) 52.43% of ethyl acrylate, cl 12% of a monomer of tormnla (1¾ in which; R designates the methacrylate group, q - 0, p - 30, II designates the hydrophobic group consisting of 12 carbon atoms and derived from ethoxyiati on of an oxo alcohol consisting of 12 carbon atoms.

In a 1-litte reactor 48Si.4 grams of hipermuted water and 6.66 grams of sodium dodecyl sulphate and 11.5 g of a surfactant sold by the company C!arianfrM under the name Polyglykol™1 SIT/lffi arc weighed* The base of the tank is then heated to 72°C ± 2¾.

During this time, a pe^emuision is prepared by weighing the following, in a beaker; • 149 grams of hipermuted water, - 0,3 3 gram of sodi urn dodecyl sulphate, - IÖ5.S grams of methaerylic acid, 1553 grams o f ethyl aery! ate, ~ 3:5.7 grants of macromonomer of formula (1).

The mass of surfactant therefore accounts in this ease for 3.87% of the total mass of the manufactured polymer, 0,95 gram of ammonium persulphate is then weighed, diluted in 10 grams of hipermuted water for the first catalyst, and 0,093 gram of sodium .metabisulphite diluted in HI grants of hipermuted water for the second catalyst. When the base of the tank is at the required temperature both catalysts are added, and polyrneriaatioo is effected for 2 hours at 76°€ ár 2;°C, with simultaneous addition: of the pre-emulsion, The pmnp is rinsed with 2-0 grains of hi permuted water, and is fired for 1 hoar at 7d"C ú 2°C, Finally it is cooled to ambient temperature, add the polymer obtained in this manner is filtered.

Test tri 14:

This test illustrates a thickener agent according to the irmerition, polymerized in the presence of polyglycerol-4 of the company Solvay™.

The thickener agent is that of test s° 13, polymerized according to the technique described in test n° 13, except that the non-ionic polymerization suriactani has been substituted, in mass terms, by poIyglyeerol-4.

Testű* 15:

This test illustrates a thickener agent according to the invention, polymerized in the presence of Chituexan#^ NB sold by the company CMmexm>

The thickener agent is that of test n° 13, polprerized according to the technique described in test if5' 13, except that the non-ionic polymerization surfactant has been substituted, in mass terms, by the Chimexane™ MB.

For each of these tests, the Brookfield™ viscosities were determined at 25°Cf at 10 and 1.00 revolutions per minute, at instants t ~ 1 day (μι?,.· :®f μιοο m) and t 7 days (bio m, μι·» -ο), where instant:: t::: 0 is the time of manufacture of the paint.

The results are shown in table 4,

Table 4

These results demonstrate that only the thickener agents polymerized in the presence of polyglycerols according to the invention enable the charges of viscosity of the paint after 7 days to be limited, and the best results are always obtained with the preferred variant of the invention.

The excellent result obtained with test n° 12 may be noted. For the latter test, the Brookfield™ viscosities measurements at 10 and 100 revolutions per minute were repeated after 1 .month: a variation of viscosities őrless than 5% of the initially measured values is observed,

Claims

pO&IGLJC&RÏNEK JILEmÉTÉBEN KÍUMEBIZÁET ASSZOCIÁCIÓS AKKILPOLIMEE-EMCLZIÓ, ÉS StmÍTésZEEtólVT VALÓ ALICALMäZÄSA vIzalàmi készítmenyien SMA1MLMÍ IGÉNYPONTOK 1* Így asszociációs sdrliőszer vizes emmziőia, melyei: a) : legalább egy monomer - mely akrilsav vagy metaíc.rli.sav (előnyöse» metakrílsav j - b) legalább egy monomer - mely az akrilsav vagy # metakrílsav egy észtere, előnyösen, etiTaMiát -> ej legalább egy monomer, mely legalább egy feároíob csoportot tartalmaz ·· a legalább egy Mdröfob csoportot tartalnw.o monomer hidrofor* csoportja legalább ;6 és legfeljebb 36 szénatontos -¾ poiimerízáeiójáv&i állítunk élő, azzal jellemezve, bagy a nevezett poíimerMetó soráni 4} legalább egy (1)

(D általános képieiü (melyben R jelentése hMrógénatonp egy <W2 szénatomok alkiIcsoportot funkciós csoportként tartalmazó észtercsoport, vagy egy §~z2 szenatomos adatcsoport, és előnyösen egy 8-22 szénatomos alki!csoport) poh#!tcefittt aikasmazt&k. X Az L szabadalmi Igénypont szetó emutól ázzál jmmrnrn, hogy a poümerízáclóvai elolillíoit nevezett asszoeiáelos snrfíőszer esetében a nevezett pöiimerízacío abban áll, hogy első lépésben a dl yegyníéiekei és a nevezett - a Φ vegynktektol különböző - lélülemkíiv vegyüleíeket vfcbft adagoltuk, majd második lépjen a reakeíóelegyet melegítjük, és Mt követő harmadik lépésben poUmerizáeiós inleiátorokat aduim a reakeiőelegyhez, maja pedig a monomereket -- adott esetben vízzel együtt, és a d) vegyületektől különböző felületaktív szerekkel együtt - adjuk hozzá.
3, .Az I . vagy 2. szabadalmi igénypontok egyike szerinti ©mniziö, azzal Jellemévé, bogy a polímeozáfeióvai előállított, nevezett asszociációs súrtőszer esetében a nevezett tx>innedzáeíós reakcióban a d) vegyületektől különböző felületaktív vegyületeket az anionos felületaktív anyagok (előnyösen náüínm--dodec|l-szulíat, nátriinn-dioktíkszulföszakeinát náíntím^dodeeíl-benzolsznlibtmt), a nemionos felületaktív vegyületek (előnyösen a zsíralkohol-éterek .ék a. polífoxi-eiiléngíikölj-éierek,, a poliíori-etilénglikülj-^szterek) és e feíöktakfív vegyületek keverékei közül választjuk ki.
4, .Az 1 -· 3. szabadalmi igénypontok egyiké szerinti emulzió, azzal jellemezve, feögy a pofimerízácíóval előállított nevezett asszociációs: süritőszer esetében, a nevezett: polímerizációban a „Öj vegyületektől különböző iélüietnkiiv vegyületek: / polimer" arány töntégszázaiékbmkilbjezve 1% és 5% között van,
5, Az 1 · 4. szabadalmi igénypontok egyike szerinti emulzió, azzal jellemezve* bogy a pol:im.e.rizi©iőval előállított nevezett asszociációs süritőszer esetében, a nevezett pölimedzáéióban a kővetkező vegyületek©! alkalmazzuk, a nevezett asszociációs sikitö&mr összes tömegére: vonatkoztatott tömegszázalékban kifejezve: a) 20 tÖm:eg% - 60 íömegtl arányban legalább egy monomer, mely akrilsav vagy metakrílsav Isbei (előnyösen metakfílsav), b) 40 tömeg'% - 80 tömeg0/« arányban legalább egy monomer, mely az akrilsav vagy a meiakrilsáv egyik észtere (előnyösen etil-akrilátf. e) 0,5 iÖmeg% - 25 iömeg% arányban legalább egy monomer, mely legalább egy hidrofőb csoportot tartalmaz* d) ö, i tömeg?/«· - 1Ö töm:eg% arányban legalább egy (1)

CD általános képleiíl (melyben R jelentése .'hidrogénatom vagy egy 8-22 szenaiomos alkilcsoportót fcikcios csoportként tartalmazó észteresöport, vagy £gy szénatomos alkiiesoporí, és .előnyösen egy 8-22 szénatomos alkilcsoporO pmigboerm, és az aj, b), e) és d) százalékok összege 1 00%. & Az I - 5. szabadalmi igénypontok egyike szériát! emulzió, azzal jellemezve, bogy a polimerízáeievai előállítóit asszociációs sözilőszer esetében, a legalább egy hldroíób csoportot tartalmazó- monomer BrCOß^OPVR’ általános képiéin, melyben; p és q jelentései I SO vagy annál kisebb egész számok, melyek közöl legalább m egyik nem nulla (előnyösen qK:0 és ö<p<80), OE és öb jelentései következetesen etilén-oxid és propilén-cxld, R jelentése egy polimerizálható funkciós csoport (előnyösen metakrílát- -csoport, vagy melákriburatán-csoport ), R* jelentése egy legalább 6 és legfeljebb 36 szénatomos, hidroíob csoport,
7, Az I - 6, szabadalmi' igénypontok egyike szerinti émulzlő, azzal Jellemezve, hogy a poiimerizácíóval előállított nevezett asszociációs snrnoszer átlagos molekulatömege 20 000 g/mol és 1 000 000 g/mol között van, géipermeácíós kromategráüával (GPCí mérve. $. Az 1 - 7. szabadalmi Igénypontok egyike szerinti emulzió alkalmazása egy vizalapu készítmény- vagy egy ragasztóanyag süríioszereként. 8,szabadalmi igénypont szerinti alkalmazás, mely szerint a nevezett vizáiapu készítmény egy vizalapú festék, egy glelíanyag vagy egy bevonat,
10. Vizalapú készítmény vagy ragasztóanyag, amely az 1-7, szabadalmi Igénypontok egyike szerinti emulziót tartalmaz:. ti, A IC), szabadalmi igénypont szerinti vizalapú készítmény, mely szerint a nevezett: készítmény egy vizalapú festék, egy giettanyag vagy egy bevonat
12. Az (f) általános képletu poil glicerin, monomerként való alkalmazása egy asszoeíaems sihitószerpoiimerizáeióval·', vizes emulzió: fiájában történő előállítására.