GB2299094A

GB2299094A - Flame-resistant aqueous polymer formulations

Info

Publication number: GB2299094A
Application number: GB9604983A
Authority: GB
Inventors: Robert Rupaner; Rainer Hummerich; Beer Lex De; Klemens Massonne; Andreas Northemann
Original assignee: BASF SE
Current assignee: BASF SE
Priority date: 1995-03-10
Filing date: 1996-03-08
Publication date: 1996-09-25
Also published as: GB9604983D0; DE19508530A1; FR2731429A1

Description

Flame-resistant aqueous polymer formulations 2299094 The present invention

relates to aqueous formulations comprising 5 a polymer constructed of from 0 to 99.95% by weight of principal monomers I selected from the group consisting of Cl-C20-alkyl (meth)acrylates, aromatic vinyl compounds having up to 20 carbon atoms, vinyl esters of carboxylic acids containing up to 20 carbon atoms, ethylenically unsaturated nitriles, vinyl ethers of alcohols containing from 1 to 10 carbon atoms and aliphatic hydrocarbons having from 2 to 8 carbon atoms and 1 or 2 double bonds, from 0.05 to 100% by weight of monomers II which carry at least one functional group, which is not to be understood as meaning an ethylenically unsaturated group, this functional group being reactive with the below-defined phosphorus compound in such a way that the phosphorus compound becomes thereby bonded to the polymer, and from 0 to 80% by weight of further monomers III which differ from monomers I and II, and a phosphorus compound which is reactive with the functional group of monomer II, the phosphorus compound being or becoming bonded to the polymer via the functional group.

The present invention further relates to processes for preparing the aqueous formulation and to uses for the aqueous formulation, in particular to the use for consolidating fiber webs.

Polymers can be flameproofed by addition or copolymerization of halogen compounds, if necessary combined with antimony compounds.

So far halogen- and antimony-free flame retardants generally are still insufficiently effective.

Flame retardants have to meet special requirements in the case of aqueous polymer formulations, for example polymer dispersions..

The flame retardants would have to be water-soluble or at least waterdispersible so as not to settle out of the dispersion.

2 In the later use of the dispersion, for example as a coating or impregnant, the flame retardant has to be very uniformly dispersed in the polymer after water removal to produce a satisfactory effect.

DE-A-24 11 738 discloses using ethylenically unsaturated phosphorus compounds as comonomers to improve the flame resistance of polymers. The polymers also have a mandatory vinylidene chloride content.

US-A-3 695 925 describes the flameproofing of textiles or fiber webs using ethylenically unsaturated phosphorus compounds which are generally substituted by halogen atoms.

EP-A-476 644 likewise concerns the flameproofing of fiber webs by treating the fiber webs with an aqueous formulation of phosphorus salts and melamine-formaldehyde resins.

It is an object of the present invention to find aqueous formulations which ensure good flameproofing in later use, for example as coating or impregnant, even without halogen compounds.

The aqueous formulations should also be highly suitable for consolidating fiber webs.

We have found that this object is achieved by the above-defined aqueous formulations and we have also found processes for the preparation thereof and a use thereof.

The aqueous formulation of the present invention comprises a polymer constructed from monomers I and II and optionally III.

Examples of suitable principal monomers are Cl-Clo-alkyl (meth)acrylates, such as methyl methacrylate, methyl acrylate, n-butyl acrylate, ethyl acrylate and 2-ethylhexyl acrylate.

More particularly, mixtures of alkyl (meth)acrylates are also suitable.

Examples of vinyl esters of carboxylic acids having from 1 to 20 carbon atoms are vinyl laurate, vinyl stearate, vinyl propionate and vinyl acetate.

Examples of suitable aromatic vinyl compounds are vinyltoluene, a- and p-methylstyrene, a-butylstyrene, 4-n-butylstyrene, 4-n- decylstyrene and preferably styrene.

3 Examples of nitriles are acrylonitrile and methacrylonitrile.

Examples of suitable vinyl ethers are vinyl methyl ether, vinyl isobutyl ether, vinyl hexyl ether and vinyl octyl ether.

Suitable nonaromatic hydrocarbons having from 2 to 8 carbon atoms and one or two olefinic double bonds are butadiene, isoprene and also ethylene, propylene and isobutylene.

The principal monomers are preferably used in a mixture.

is Aromatic vinyl compounds such as styrene are for example f requently used in a mixture with Cl-C20-alkyl (mpth)acrylates, in particular with Cl-C8- alkyl (meth)acrylates, or nonaromatic hydrocarbons such as isoprene or preferably butadiene.

Particular preference is given to styrene and butadiene as principal monomers.

Preferably the free-radically polymerized polymer contains from 40 to 98, particularly preferably from 60 to 95, % by weight of monomer I.

Monomers II have at least one functional group whereby phosphorus compounds which are capable of reacting with this functional group, for example by addition, condensation or substitution reaction, become bonded to the polymer.

Examples of such functional groups are acid groups, which may be solely or partly neutralized, in particular carboxylic acid or sulfonic acid groups, anhydride groups, amide groups, primary or secondary amino groups, hydroxyl or alkoxy groups, epoxy groups, ureido or isocyanate groups and keto or aldehyde groups.

Examples of monomers having acid groups are (meth)acrylic acid, maleic acid, fumaric acid and itaconic acid.

Examples of monomers with anhydride groups are maleic anhydride and methacrylic anhydride.

Examples of monomers II are acrylic, methacrylic, maleic and itaconic acids, acrylamide, methacrylamide, vinylformamide, Nmethylolmethacrylamide, N-methylolacrylamide, methacrylic anhydride, maleic anhydride, glycidyl. (meth)acrylate, trimethoxysilylpropyl methacrylate (MEMO), hydroxyethyl (meth)acrylate, dimethylamincethyl (meth)acrylate, N-ureidoethyl methacrylate, vinylimidazole, acetacetoxyethyl methacrylate 4 (AAEM), acrylamidoglycolic acid, diacetoneacrylamide, 2-acrylamido-2- methylpropanesulfonic acid and dimethyl meta-isopropenylbenzyl isocyanate (TMI).

Monomers II may also have other functions in addition to or else partly instead of the reaction with the phosphorus compounds.

For instance, the presence of monomers with acid groups can serve to stabilize the dispersion of the polymer.

The proportion of monomer II in the polymer is preferably from 2 to 60, particularly preferably from 5 to 40, % by weight, based on the polymer.

Examples of possible monomers III are monomers which enhance the total amount of phosphorus in the system and help to interfere with the combustion process. Suitable for this purpose are in particular monomers which already contain phosphorus in chemically bound form in the molecule. Such monomers indeed esters of acrylic and methacrylic acid which have phosphorus in the form of a phosphoric or phosphonic ester in the side chain. Such structures are known for example from B.Boutevi, J. Appl. Pol. Sci. 52 (1994), 449- 456, or from EP 530 692. Structures which have been found to be particularly suitable are such as R2 R3 C =-- C R1 (W) q 1 (U)m-(R6)n-(V)P- P- (X) r- R5 1 (Y) 5 R4 where R6 iS:

(R7)t-Ov-(R8)u-, R1, R2, R3, R4, RS, R10 and W' are each hydrogen, alkyl, cycloalkyl, aralkyl or aryl, p,7, R8 and R9 are each 45 alkylidene, cycloalkylidene, aralkylidene or arylidene, is mp p, q, r, s, t, u and v are each 0 or 1, n is 5 0, 1 or 2 U is COO, 0, S or NR9 V, W, X and Y are each 0, S or NR9, and Z is 0, S or NWOR11.

which are derived from acrylic or methacrylic esters. The preparation of the monomers is known (for example from EP 530 692, US 2 993 033). Also suitable are vinylphosphonic acid and allylphosphonic acid and their esters and salts or else mono-, di- or triallyl phosphate.

To obtain satisfactory fire protection, however, phosphorus-containing monomers III are generally not necessary.

Nor in general are monomers I to III necessary which contain halogen, in partiuclar chlorine, or necessitate the addition of antimony in some form. It is an advantage of the present invention that adequate fire protection can be achieved even without halogens and antimony.

The polymer can be prepared by customary methods of free-radical polymerization, for example solution, substance, suspension or emulsion polymerization.

The polymer is preferably present in the form of an aqueous dispersion, for which a polymer which has been prepared for example in a solvent or in substance (without solvent) can be dispersed in water.

Particular preference is given to emulsion polymerization where an aqueous dispersion of the polymer is obtained directly.

The emulsion polymerization can be carried out for example batchwise, with or without the use of seed latices, with initial charging of all or individual constituents of the reaction mixture, or preferably with partial initial charging and subsequent addition of the or individual constituents of the 6 reaction mixture, or by the metering method without initial charge.

The emulsion polymerization of the monomers can be carried out as usual in the presence of a water-soluble initiator and of an emulsifier at preferably from 30 to 95C.

is Examples of suitable initiators are sodium, potassium and ammonium peroxodisulfate or peroxodiphosphate, tert-butyl hydroperoxide, hydrogen peroxide or water-soluble azo compounds or else redox initiators consisting of an oxidizing component such as the aforementioned peroxides, persulfates, perphosphates or hydroperoxides, in each case combined with a reducing substance, for example ascorbic acid, sodium bisulfite, sodium salt of hydroxymethanesulfonic acid, formamidinesulfinic acid, hypophosphorus acid or alkali metal or ammonium salts thereof. To speed up the reaction, the redox initiators are used together with catalytically active, multivalent metal salts, for example iron(II) sulfate or cobalt(II) sulfate.

Examples of emulsifiers used are ethoxylated alkylphenols and fatty alcohols having EO degrees from 2 to 70 and alkyl groups of from 7 to 18 carbon atoms, the alkali metal salts of the sulfated or sulfonated derivatives of these ethoxylation products, alkali metal salts of alkylsulfonic acids, alkylarylsulfonic acids, sulfonated diaryl ethers or mono- or dialkyl esters of sulfosuccinic acid. A particular class of emulsifiers are alkali metal or ammonium salts of phosphoric esters whose alcohol components consist of free or ethoxylated fatty alcohols or alkylphenols having from 4 to 22 carbon atoms.

Preference is given to the sodium or ammonium salts of sulfated and ethoxylated fatty alcohols or alkylphenols.

The polymerization can be carried out with molecular weight regulators. Suitable are for example SH-containing compounds such as mercaptoethanol, mercaptopropanol, thiophenol, thioglycerol, ethyl thioglycolate, octyl thioglycolate and tert-dodecyl mercaptan.

The solids content of the polymer dispersion obtained is preferably from 40 to 80, particularly preferably from 45 to 75, % by weight.

The dispersed polymer particle size is preferably from 30 to 600, particularly preferably from 100 to 400, nm.

is 7 The formulations of the present invention, in addition to the polymer, comprise a phosphorus compound which is reacted with the functional groups of monomer II.

Preference is given to water-soluble phosphorus compounds which, per molecule, contain at least one phosphorus atom in chemically bonded form and which are capable of reacting with monomer II or the monomer units in the polymer which are derived from monomer II and hence have become part of the polymer.

The water solubility of the phosphorus compounds is preferably at least 5 g/1 of water at 25C.

Examples of suitable phosphorus compounds are a) addition products of dialkyl phosphite with (meth)acrylic acid and (meth)acrylamide or their N-methylol derivatives. The N-methylol derivatives are particularly preferred. Also possible is further reaction with a lower alcohol, for example with methanol, to form a hemiaminal, since a higher storage stability of the products can be achieved as a result. The general structure of such products is (R10) 2P X- CH2CHR - C- Z 11 Q 11 0 where the substituents have the following meanings:

Z = OR1,09140,NH2, NHRI, NBCH20R1,NE-CH-COOR1 1 OH M= alkali metal or ammonium and R1= H, Cl-Cs-alkyl, CS-Clo-aryl R= H or methyl X= a single bond or oxygen.

The compound with Rl=methyl, R=H or methyl, X=bond and Z=NHCH20H IS preferred. It is commercially obtainable from Ptersee under the name of PyrovatexOD CP. Preparation and composition are known (A.Kapura, J. Fire Sciences, 12 (1994) is a 3-13 and Xirk-Othmer, Encyclopedia of Chemical Technology, 4th ed., Vol. 10, p. 1007).

b) Addition products of dialkyl phosphite with aldehydes, especially 1(dialkylphosphono)-1-hydroxyalkanes having the common structure (R1 0) 2P (-0) _C3 (-011) -1 j, where the radicals preferably have the following meanings:

R1= H or Cj- to CS-alkyl R= H or a Cl-C22-alkyl, -alkylaryl or cycloalkyl radical with or without interruption by oxygen atoms and with or without the presence of further functional groups such as alcohols, esters, ketones, nitriles or amides.

Particularly preferred compounds b) are reaction products of diethyl phosphite with formaldehyde, acetaldehyde, butyraldehyde, glyoxal, glutaraldehyde, benzaldehyde, glyoxylic acid, glyoxylic esters and carbohydrates such as glucose.

C) It is also possible to use oligomers of vinylphosphonic esters whose preparation is described for example in German Patent Application 43377831. Preference is given to oligomers having sulfate end groups. The compounds can also be partially crosslinked by subsequent reaction with one or more polyols having 2-6 carbon atoms, such as glycerol, pentaerythritol, 2,2-bis(hydroxymethyl)propanol, tartaric acid or sugars such as glucose, sucrose or galactose or polyvinyl alcohol or copolymers of hydroxyethyl acrylate, before use in the dispersions. The oligomers are easy to dilute with water and mix into dispersions or to use as protective colloid in the polymerization of further monomers in aqueous phase. In this use, they end up attached in the side chain as a result of transesterification of the reactive phosphonic ester group and also, to some extent, to the polymer backbone as a result of grafting.

d) Further suitable additives are phosphorous acid, pyrophosphorous acid, hypophosphorous acid and (ortho)phosphoric acid or salts thereof, for example alkali metal or ammonium salts, for example sodium pyrophosphate, ammonium (hydrogen)phosphate, also low molecular weight, at least partially neutralized and hence water-soluble polyphosphates of the general formula 9 (NB4P03)n where n=3 - 50 Such compounds are commercially available (for example Hostaflam@ TP AP 420 from Hoechst AG with n about 5).

e) Further phosphorus compounds are derivatives, especially salts or esters, of methylphosphonic acid, for example Aflammit PE or Flovan CG, which are preferably used in combination with the aforementioned phosphorus- containing compounds, whose preparation and use is known from EP 245 207, 321 002 and 535 486. It is also possible to use phenylphosphonic acid and hydroxymethylphosphonic acid (AHPP) and salts thereof.

Common to all these compounds is that they contain phosphorus as a chemically bound hetero atom. High activity on the part of the additive minimizes the amount required. A high mass ratio of phosphorus present in the molecule to combustible carbon and hydrogen present in the molecule is of advantage.

Preference is generally given to additives of type a) which permit good attachment by reaction with monomer II. Very particular preference is given to Pyrovatex CP. Preference is also given to low molecular weight homopolymers of vinylphosphonic esters with sulfate end groups, which, owing to their low molecular weight and the end group, are readily water-soluble and hence finely dispersible. They are used with particular preference in combination with compounds a). The sole use of types c) is advisable for applications where the absence of formaldehyde is an additional requirement. Examples are paints and coatings for domestic interiors.

The amount of the reactive phosphorus compound depends essentially on the phosphorus content.

Preference is given to using the compounds in amounts from 0.5 to 20, preferably from 1 to 10, parts by weight of phosphorus (corresponds to phosphorus content of the reactive phosphorus compound) per 100 parts by weight of the polymer.

The phosphorus compounds can be added at any time to the aqueous formulation, especialy dispersion, which contains the polymer.

The phosphorus compounds can be attached to the polymer by raising the temperature, for example. However, it is certainly not necessary to bring about such attachment prior to processing the aqueous formulation.

Attachment may also occur in the course of processing, for example after application of the formulation to substrates and in the course of removal of solvent.

It is also an embodiment of the present invention to add the phosphorus compounds during the polymerization of the monomers of the polymer. The polymerization conditions are then usually enough to bring about an at least partial attachment of the phosphorus compounds to the polymer structure.

is Chemical attachment of the phosphorus compounds to the polymer counteracts their being washed off by water or organic solvents and produces a form of permanent flameproofing which is resistant to washing and cleaning.

The formulations of the present invention exhibit good fire protection even without further additive.

However, the formulation may include further additives which are desired for individual intended uses or for further improving the fire protection.

Examples of additives which further enhance the fire protection are:

Melamine, tris(2-hydroxyethyl) isocyanurate (THEIC) or melamine derivatives, for example melamine phosphate, melamine cyanurate, or hydrophilicized, ie. ethoxylated or phosphonomethylated, melamine derivatives or more highly condensed compounds such as melem and mellon. These compounds are notable for specific hetero atoms such as nitrogen which synergistically augment the phosphorus flame retardant. Ethoxylated melamine derivatives are known from EP 225 433, phosphonomethylated melamine derivatives for example from DE-A-39 33 546. It is also possible to phosphonomethylate other amide groups, for example urea, acrylamide or polyacrylamide. Such compounds are known from DE-A 39 33 549 and DE-A 41 28 510.

- Magnesium hydroxide, aluminum hydroxide, zinc hydroxystannate, calcium cyanamide, zinc cyanamide, boric acid, zinc borate and other boric acid salts are likewise 11 suitable for use as insoluble, finely dispersible aggregates which evolve water vapor and/or leave behind an oxide crust during the combustion process.

- Water-insoluble plasticizers based on low molecular weight orthophosphoric esters are well known additives for addition to a latex, which penetrate into the polymer. Preferably such compounds are of the phosphoric acid type. They are condensation products of phosphorus pentoxide or phosphoric acid with alcohols, phenols or polyols. They are known from Ullmann's Encyclopidie der technischen Chemie, 4th edition, Vol. 18, p. 301 f, Verlag Chemie, Weinheim 1979. Preferred substituents of the general formula (0=)mP(OnRl) (OnR2) (OnR3) are those where Rl=R2=R3 and m and n are each 0 or 1. The is substituents R1 to R3 can be methyl, ethyl, vinyl, allyl, propyl, butyl, octyl, ethylhexyl, phenyl, cresyl, chloropropyl, pentachlorophenyl, pentabromophenyl. The use of polyols produces as a function of the reaction ratio mixed or partially crosslinked or more highly condensed products which frequently also exhibit enhanced water solubility. Preferred polyols for this purpose are those having from 2 to 6 carbon atoms, such as glycerol, pentaerythritol, 2,2-bis(hydroxymethyl)propanol or glucose. Particular preference is given to halogen-free compounds such as 2S tributyl phosphate, triallyl phosphate, tributoxyethyl phosphate, triphenyl phosphate, tricresyl phosphate, triphenylphosphine, triphenylphosphine oxide. These are preferably low molecular weight compounds having a molecular weight below 1000 g/mol. Such compounds are incorporated by stirring a liquid, at elevated temperature if readily meltable or in the form of a finely ground powder.

Further additives which can be used include for example heat or light stabilizers, lubricants, demolding agents, film-forming aids, plasticizers, colorants, pigments, reinforcing agents, wetting and dispersing agents, hydrophilicizing or hydrophobicizing agents, waxes and thickeners.

Suitable hardeners and crosslinkers include in particular resins.

Examples-of such resins are amino resins such as melamine or urea resins or resols. It is also possible to use cyclic urea. derivatives, for example ethyleneurea, 3,4-dihydroxyethyleneurea or N,N-dimethyl-3,4dihydroxyethyleneurea. The resins are known for example from Encyclopedia of Polymer Science and Technology, Interscience Publishers 1965, Vol. 2, page 1 ff. or Volume 10, page I ff., of Ullmann's EncyclopAdie der technischen Chemie, Verlag Chemie, 4th edition, Volume 7, pages 403-423 and Volume 12 is, pages 245-257. Emphasis must be given to compounds which are capable of reducing the proportion of free formaldehyde by reaction. Examples are urea, polyurea, ethyleneurea, acetamide, guanidine, cyanoguanidine, melamine and also sulfonamides.

The formulations of the present invention do not require the customary addition of antimony trioxide or of chlorine- and bromine-containing additives.

The formulations of the present invention are useful for example as coatings, impregnants, care and cleaning agents or as adhesives.

Suitable substrates for this use include for example textile materials, metal, wood, paper, plastic in the form of film/sheet or else molded articles.

Another possible use which may be mentioned is the use as a fiber size.

The formulations of the present invention are particularly useful for bonding webs made of synthetic or natural fibers (web bonders or binder).

Fibers made of cotton, pulp, polyester, leather or glass are particularly suitable.

The substrates treated with the formulation of the present invention are fireproofed by the aqueous formulation.

The formulations of the present invention can be applied to the substrates alone or after admixture of other additives, such as fillers and/or pigments, by impregnating, spraying, coating, padding, foaming, adhering, brushing, calendering or laminating.

To enhance the integrity of the polymer and, where applicable, complete the reaction between the polymer and the reactive phosphorus compound, each application step is preferably followed by a drying step. In the case of fibrous substances, especially fiber webs and textile materials, the raw materials treated with the formulations are exposed for this purpose to an elevated temperature in a drying oven. Depending on the substrate, a temperature of 80-280C, preferably 120-220C, and residence times of 2-30 min are used.

13 The substrates treated with the formulation of the present invention can be used in a wide range of ways, for example as low-flammability and flame-resistant paperboard, packaging paper, wallpaper, matts, tablecloths, thermal and acoustic insulating materials, as electronic components, film/sheet, for manufacturing sanitary hospital requisites, such as surgical clothing, gowns or wipes.

Fiber webs bonded with the formulations can be used for example as lining, cushioning and wadding in upholstery, cushion fills, fiber fills, sleeping bags and also garment interlinings. There are also possible textile applications, for example flame-retardant impregnation of bed linen, curtains, cases or furniture covers. Flame-retardant technical bonded fiber web materials are used for manufacturing filter materials for air filters in the home and in the automotive and technical sector, low-flammability roofing membranes, sunscreen lamellae, insulator and insulating materials, from glass, mineral and wood fibers. The formulations of the present invention are also suitable for use as adhesive and contact-adhesive materials, as sealing and filling materials and also as constituent of coatings, paints and polymer-bound plasters.

Examples

Test methods Transmittance Transmittance in % of white light at a path length of 25 mm by a sample diluted to a solids content of 0.01%.

viscosity Dynamic viscosity in mPa-s (concentric cylinder viscometer, 230C, Rheomat STV, from Contraves, measuring cup III according to DIN 53778 at 400 s-1).

I. Preparation of dispersions Dispersion 1 An initial charge of 2.25 g of hydrogen peroxide in 180 g of water was heated to 65C. At 60C, 2% of the monomer emulsion and 8% of a solution of 1.5 g of ascorbic acid in 100 g of water were added, and 15 min later a start was made on the continuous addition over 180 min of the rest of the monomer emulsion and the 14 reducing agent solution. Following 1 h of postpolymerization at 65% the batch was cooled down to 25C and 15 g each were added of tert-butyl hydroperoxide (10% strength) and ascorbic acid solution (10% strength). A globule- and coagulum-free dispersion having a polymer content of 49% and a pH of 2.8 was obtained. The transmittance was 63%, which corresponds to an average particle size of about 240 nm. The viscosity was 26 mPas. The residual monomer value, determined by gas chromatography, was 700 for EA and <10 ppm for each of MMA and AN.

composition of monomer emulsion 1:

585 g 60 g 15 75 g 90 g water 7.5 56 g 20 32 g 330 g Dispersion 2 of ethyl acrylate (EA) of methyl methacrylate (MMA) of acrylonitrile (AN) of N-methylolacrylamide, 25% strength solution in 9 of acrylic acid of emulsifier 1 of emulsifier 2 of water The preparation of dispersion 1 is repeated with the difference that 75 g of Pyrovatex CP were included in the initial charge as well as hydrogen peroxide. The resulting coagulumand globule-free dispersion had a solids content of 481 and a pH of 2.6. The transmittance was 38%, the average particle size about 370 nm and viscosity at 32 mPas.

Dispersion 3 An initial charge of 125 g of 601 strength solution of poly(dimethyl vinylphosphonate), 2% of a monomer emulsion as in dispersion 1 and 210 g of water is heated to 85C. On reaching an internal temperature of 700C, 8.3 g of a solution of 3.75 g of sodium persulfate in 100 g of water were added, the rest of the monomer emulsion and the initiator solution were added continuously over 180 min, and the batch was postpolymerized for 60 min. After cooling down to 25C, the batch was aftertreated with 0.2% each of tert-butyl hydroperoxide and ascorbic acid (based on polymer material) and filtered. A globule- and coagulum-free dispersion having a polymer content of 49% and a pH of 2.0 was obtained. The transmittance was 44% and the average particle diameter about 310 rim.

Dispersion 4 is The preparation of dispersion 3 is repeated with the difference that the dispersion was prepared using in addition 125 g of an aqueous 60% strength solution of poly(dimethyl vinylphosphonate) and 75 g of Pyrovatex CP, half of each being included in the initial charge and the remainder being added with the emulsion. A globule- and coagulum-free dispersion having a solids content of 47.5%, a transmittance of 33%, an average particle size of 400 and a pH of 2.1 were obtained.

Dispersion 5 The preparation of dispersion I is repeated with the difference that 75 g of Pyrovatex CP were included in the initial charge as well as hydrogen peroxide and the monomer emulsion was prepared using 3%, based on polymer material, of emulsifier 3.

Dispersion 6 A mixture of 5.0 g of emulsifier 4, 100 g of monomer emulsion 6 and 580 g of water was heated to 85C and initiated by addition of 31 g of a solution of 10.8 g of sodium persulfate in 200 g of water. After 15 min a start was made on the continuous addition, over 120 and 135 min respectively, of the rest of the monomer emulsion and the rest of theinitiator solution, and subsequently the batch was postpolymerized for 60 min. After cooling down to 25C, 12 g of tert-butyl hydroperoxide (10% strength) and 13.5 g of ascorbic acid solution (10% strength) were added, affording a globule- and coagulum-free dispersion having a solids content of 44%, a pH of 1.6 and a transmittance of 87%. 90 ppm of EA and less than 10 ppm of styrene were detected by gas chromatography.

Composition of monomer emulsion 6: 1060 g 240 g 27 g 14 g 225 g g 885 g of ethyl acrylate of styrene of acrylic acid of 2-acrylamido-2methylpropanesulfonic acid of poly(dimethyl vinylphosphonate), 60% strength in water of emulsifier 4 of water Dispersion 7 16 g of a 60% strength solution of poly(dimethyl vinylphosphonate) and 1.2 g of sodium acetate in 600 g of water are heated to 85C and admixed with 5 g of a solution of 2.4 g of sodium persulfate in 95 g of water. Immediately thereafter a start was made on the continuous addition, over 120 min and over 180 min respectively, of a monomer mixture of 196 g of styrene, 196 g of butyl acrylate and 8 g of acrylic acid on the one hand 10 and the rest of the initiator solution on the other hand. Filtration afforded a dispersion having a polymer content of 39%, a pS of 1.9 and a transmittance of 25%.

II. Blends with poly(dimethyl vinylphosphonate) (PDMVP) and is Pyrovatex (Py) 1000 g of dispersion 1 are admixed at 250C with the corresponding amount of poly(dimethyl vinylphosphonate) (PDMVP) or Pyrovatex CP (PyCP) in the course of about 15 min with stirring. On completion 20 of the addition the batch is stirred for a further 10 min and filtered through a 125 pm filter. Coagulum formation occurred in no case. 200 g of each mixture were diluted with 50 g of water, admixed with 0.5 g of Agitan 703 and 1.0 g of Latekoll AL, adjusted to a pH of about 9 with 10% strength by weight sodium 2S hydroxide solution and thereafter admixed with a solution of Collacral HP until a viscosity of about 800-1000 mPas was obtained. The table below shows the mixtures and their pH values and viscosities:

Table 1 % by weight % by weight pH Visc.

of PDWP of PYCP based on based on polymer polyme Comparison 0 0 6.8 860 a b 0 10 7.2 1100 c 0 15 6.9 1060 d 5 10 7.0 844 e 8 10 7.0 950 f 10 0 --7. 5 810 Testing on glass fabric 17 Glass fabric from Hexel Genin, blue, basis weight 200 g/M2, Was coated on both sides with the paste obtained and dried after each application for 5 min in a drying cabinet at 120C. The average coating add-on was 100-110 g/M2. 4 equal test strips (300 mm x 95 mm) were cut out of the coated fabric in the longitudinal direction and conditioned for 24 h at 23C and 501 rel. humidity. The test was carried out similarly to DIN 54332, with two changes: butane was used instead of propane and a piece of aluminum foil was placed between the web sample and the asbestos plate specimen support to protect the latter. The specimens were flamed with a blue flame for 30 sec, the burner was removed, and the afterburn time, glow time, whether or not specimens burned up to the upper measuring mark (MM), and the damaged area were determined.

Table 2

Exp. Add-on Burn time Glow time Damaged area Smoke evolution g/M2 average ceases to burn burns uP to MM sec along across in sec in sec mm KM Comp. a 109 4x 78 9 none 230 49 slight b 114 + 4x no none 126 26 none c 114 + 4x no none 126 25 slight d 113 + 4x no none 122 25 slight e 114 + 4x no none 125 24 none f 113 + no none 132 30 slight + no none 101 22 + no none 114 28 9 9 - 51 sec none.188 41 (+) does not continue to flame continues to flame 4x - tested on 4 specimens measuring mark 1 i i 1 t 19 Blends and testing on cotton fabric 1000 g samples of dispersion 1 are admixed with the corresponding 5 amount of poly(vinylphosphonic ester) and Pyrovatex CP as in Example 2.1. with stirring (Tab. 3). The homogeneous and coagulum-free dispersions are used for preimpregnating and for the both-sided coating of cotton fabric.

1000 g of the dispersion were admixed with 0.2 part of Laventin LBN, and diluted to a liquor concentration of 20% by weight and used to preimpregnate cotton fabric (from Hornschuch, white, 253 g/M2), and the preimpregnated fabric was dried at 1200C for 7 min and was then coated on both sides with the following mixture: 15 100 g of dispersion admixed with sodium hydroxide, 1.0 g of Latekoll AL and about 13-15 g of Collacral HP to a viscosity of about 2000 mPas. The paste was applied to both sides of the cotton fabric which was dried for 4 min at 1200C after each application. The total add-on was about 170 g/M2. The results of 20 the flaming tests are reproduced in Table 4.

Table 3 % of PDMW % of PyCP based PE Visc.

based on on polymer polymer a 0 0 8.1 2200 b 0 is 7.4 2020 c 0 20 7.4 2200 d 5 10 7.6 1900 e 5 15 7.6 2050 f 5 20 7.4 2000 9 8 10 6.8 2000 Table 4

Exp. Add-c;n Burn time Glow time Damaged area Smoke evolution g/M2 average ceases to burn burns up to KM sec along across in sec In sec mm nun Comp. a 186 4x 81 >60 sec 229 so slight b 169 + 3x no none 101 22 slight c 166 + 3x no none 121 23 slight d 169 + no none 245 40 strong + no 105 25 slight 118 20 slight e 171 + 3x no none 114 27 slight f 169 120 none 240 39 strong + no none 91 22 slight + no none 95 23 slight 171 120 none 245 40 slight + no none 105 25 slight + no none 110 20 slight does not continue to flame contin to flame 3x - tested on-3 -Bp-ec-1-mens 1 1 1 1 1 is 21 III.Addition of additives 1000 g samples of dispersion 1 are admixed with the appropriate amount of additives and with 75.5 g of a 60% strength aqueous solution of PDWP by stirring at the stated temperature and subsequently stirred for 2 h.

Table 5

Exp. PD % of additive T pH 1Viscosity c mPas comparison - 25 8.3 870 a b 10 5 triphenyl phosphate 60 8.2 930 c 10 5 ethyl phosphono- 25 8.0 940 acetate d 10 5 triphenylphosphine 60 8.0 1100 e 10 5 triphenylphosphine 25 8.4 1010 oxide f 10 5 (NH4)2HP04 25 7.2 870 9 10 5 neopenty1glycol 25 18.2 1 660 based on monomer finely suspended in the formulation Table 6

Exp. Add-on Burn time Glow time Damaged area Smoke Film specimen g/M2 average evolution ceases to burn burns up to sec along across Observation sec KM mm mm sec b ill + (4x) no none 133 22 slight continues to burn c 113 + (4x) no none 123 25 slight drips, continues to burn d 112 + no none 135 23 slight continues to 56 none 235 40 burn + no none 136 29 + no none 138 27 e 112 + (4x) no none 128 29 slight continues to burn f 117 + (4x) no none 117 22 slight 9 106 + no none 127 33 slight continues to + no none 113 37 burn 67 none 219 40 47 none 225 43 Comp. 120 - (4x) 56 2 none 231 48 + slight drips, continues a 1 1 1 1 20 @3 a to burn (+) does not continue to flame continuePto flame 4X = tested on 4 specimens m hi is IV. Further f lame retardants 23 parts of Dispersion 1 were mixed with the below-mentioned phosphorus- containing reactive additives and subsequently stirred at room temperature for 2 h to allow the reaction to take place. The viscosity was raised to a value of 1500-2000 mPas with 25% strength by weight ammonia and the stated thickeners and the resulting composition was used to coat an upholstery fabric (raw material 285-290 g/M2 basis weight), which was subsequently dried at 1000C for 5 min and postcured at 150C for a further 3 min to complete the reaction. The upholstery fabrics were tested according to the British Standard ignitability test (BS 5852) - butane flame and smoldering cigarette.

Table 7

Exp. Parts of additive added pH Visc.

Comp. a without 7.8 2000 b 14 Aflammit PE, 100 7.1 2000 melamine c 20 Aflammit PE 8.2 1500 d 20 Flovan CGN 9.4 1300 e 20 Hostaflam TP AP 420 8.4 1600 1 1 1 - Results in Table 8 Table 8

Exp. Add-on Butane Cigarette g/M2 flame test test goes out burnt hole classification cigarette burnt hole classitica see area burnt goes out area burnt tion through 1 after min (width) through Comp. 102 no large yes not flame 10 0.5 cm yes flame a retardant retardant b 105 at once small no flame 5 0.5 cm no flame retardant retardant c 99 at once small no flame burnt 6.5 cm yes not flame retardant through retardant d 110 at once small no flame 10 1.5 cm no flame retardant retardant e 105 at once small no flame 8 2.3 cm partly not flame 1 1 1 1 1 retardant Iretardant 1 V. Preparation of further dispersions and blends Dispersion 8 A dispersion having a polymer composition of 74% by weight of ethyl acrylate, 20% by weight of acrylonitrile, 4% by weight of N- methylolmethacrylamide and 1% by weight of acrylic acid was polymerized on the lines of dispersion 1 but without polyvinylphosphonic ester and without emulsifier 1. The dispersion had a solids content of 49% by weight, a transmittance of 65% and a viscosity of 20 mPas.

is Dispersion 9 The method used for preparing dispersion 3 was followed to prepare a dispersion having a polymer composition of 91% by weight of vinyl acetate, 15% by weight of n-butyl acrylate, 3% by weight of N-methylolacrylamide and 0.5% by weight each of sodium vinylsulfonate and acrylic acid. The solids content was 50%, the transmittance 63%, the pH 4.9 and the viscosity about 54 mPas.

Dispersion 10 A dispersion consisting of 50% by weight of vinyl propionate, 40% by weight of n-butyl acrylate and 10% by weight of Versatic ester (VeoVa 10) was prepared by emulsion polymerization using sodium persulfate as initiator at 85C. The emulsifiers used were 3% of emulsifier 5 and 1% of emulsifier 6, each based on total monomer material. After the polymerization had ended, 10% strength calcium hydroxide slurry was used to set pH 8. A dispersion having a solids content of 47% and an average particle size of 200 nm was obtained.

Dispersion 11 A dispersion having a polymer composition of 80% by weight of ethyl acrylate, 10% by weight of acrylonitrile, 8% by weight of methyl acrylate, 2.0% by weight of N-methylolacrylamide was prepared_by redox initiation with 0.2% hydrogen peroxide and 0.2% of ascorbic acid using 1.5% each of emulsifier 1 and 2 at 60C. Aftertreatment with 0.15% each of tert-butyl hydroperoxide and ascorbic acid gave a globule- and coagulum-free dispersion having a polymer content of 49% and a pH of 2.7. The transmittance of a 0.01% strength solution was 53%. The residual monomer value 1.1 26 determined by gas chromatography was <10 ppm for each of EA and AN.

Comparative dispersion 12 A dispersion was prepared on the lines of Example 1.3. by polymerization of a 1:1 mixture of n-butyl acrylate and methyl methacrylate. The dispesion contains no functionalized monomers.

Blends with PMVP and PyCP Similarly to II, dispersions 8 to 12 were mixed with 5% by weight of poly(dimethyl vinylphosphonate) and 15% by weight of Pyrovatex CP, each based on polymer material, by stirring and subsequently stirred for 2 h, then diluted with water in the described manner to a uniform 40%, adjusted with ammonia and thickener to a viscosity of about 800-900 =Pas and used to coat both sides of a glass fabric (results in Table g).

Table 9

Exp. Solids pH Visc. Add-on Burn time Glow time Coated area Smoke average evolution Disp. mPas g/M2 ceases to burns up sec along across burn to MM mm mm 1 sec sec 8 50 6.3 990 101 + 4x no none 106 24 none 9 so 6.1 990 ill + 4x no none 112 26 none 1 46 6.7 1 1000 101 + 4x no none 150 32 slight 11 50 6.3 1800 1109 1+ 4x no none 25 none 12 49.5 Dispersion unstable, thickened does not continue to flame 4x - tested on 4 specimens m 4 1 1 Dispersion 13 28 The preparation of dispersion 11 is repeated with the difference 5 that 10% of ethyl acrylate was replaced by methacrylic acid. Following addition of 10% by weight (based on polymer material) of a mixture of mono-, bis- and tris-N,N',N''-(hydroxyethyl)melamine (= HOM) (weight ratio 1:5:4) with stirring, the mixture is subsequently stirred for 2 h, divided and one half is admixed 10 with 10%, based on polymer material, of poly(dimethyl vinylphosphonate). Thereafter method II is followed.

is Table 10

Exp. PDMVP HOM pH Visc. Add- Burn time Glow Coated area Smoke on time average evolution Disp. % mPas 9/M2 ceases to burns up to sec along across burn MM rm mm a 9 sec 13 5.5 720 110 no 57 + 6 none 217 + 9 4 8 + 2 none no no 13 to 6.1 800 99 yes no none 132 26 none no 40 218 41 no 40 250 45 13 to 10 6.0 980 99 yes no none 114 + 3 2 3 + 2 none 1 1 1 1 3 x 1 1 1 11 1 1 1 m W Dispersion 14 An initial charge of 4% of a monomer emulsion, 24 9 of emulsifier 4 and 570 g of water is heated to 85C. When the internal temperature had reached 70C' 32 g of a solution of 10.8 g of sodium persulfate in 200 g of water were added, the rest of the monomer emulsion and the rest of the initiator solution were continuously added over 120 min, and the batch was postpolymerized for 60 min. After cooling down to 25C, the batch was aftertreated with 0.2% each of tert-butyl hydroperoxide and ascorbic acid (based on polymer material) and filtered. A globule- and coagulum-free dispersion having a polymer content of 45% and a pH of 1.6 was obtained. The transmittance was 96%, the glass transition temperature about +9C (DSC).

Composition of monomer emulsion 14:

1066 g 240 g 27 g 13.5 g 145 g 800 g Dispersion 1 of ethyl acrylate of styrene of acrylic acid of 2-acrylamido-2- methylpropanesulfonic acid of emulsifier 4 of water The preparation of dispersion 14 was repeated with the difference that 40 g of ethyl acrylate was replaced by acrylaraido glycolic acid.

Blends with PDWP and PyCP 1000 g of dispersions 14 and 15 are admixed at 25C with 10% by weight based on polymer, of a 60% strength by weight aqueous solution of poly(dimethyl vinylphosphonate) and subsequently stirred for 2 hours at the autogenous pH (about 1-1.5) and used for impregnating glass fabric (from Interglas, white, 130 g/M2). After impregnation, binder excess is squeezed off with a roll knife and the fabric is dried at 120&C for 10 min.

Table 11

Exp. pH Visc. Add-on Burn time Glow time Coated area average Disp. mPas g/M2 ceases to burns up to sec along across burn MM mm fin in sec in sec 14 1.4 35 68 35 no none 157 46 - so none 234 55 - 45 none 245 58 1 36 no none 157 54 is 1.5 43 70 + no none 105 23 52 none 235 54 48 none 229 53 68 none 229 50 14 1.2 30 61 + 4x no none 101 _+ 29 129 12 1 1.2 117_ 171 + 4x no none 93 + 19 -----12 - 3 + 1 (+) does not continue to flame (-) continues to flame 4x tested on 4 specimens with addition of PVPE 32 Substances used Emulsifier 1:

is Emulsifier 2:

Emulsifier 3:

Emulsifier 4:

Emulsifier 5:

20% strength aqueous solution of an octylphenol ethoxylate with about 25 mol of EO per mole of octylphenol; 35% strength aqueus solution of a sodium hydroxide neutralized sulfated octylphenol ethoxylate with about 25 mol of EO per mole of octylphenol; C12-C14 f atty alcohol with about 3 mol of EO per mole of alcohol, esterified with phosphoric acid, mixture of mono- and diester (=M03 acid from HUls AG); 20% strength aqueous solution neutralized with ammonia; 28% strength solution of a sodium hydroxide-neutralized, sulfated and ethoxylated (EO degree about 2-3) lauryl alcohol; 35% strength solution of the sodium salt of a sulfated lauryl alcohol ethoxylate with about 30 mol of EO per mole of alcohol; Emulsifier 6: 20% strength solution of an ethoxylated tallow fat alcohol with about 18 mol of EO per mole of alcohol; C16-alkyl radical:

Emulsifier 7: 20% strength solution of an ethoxylated tallow fat alcohol with about 30 mol of EO per mole of alcohol; C16-alkyl radical; Emulsifier 8: 40% strength solution of a neutralized C16-paraffinsulfonate.

Agitan 703 and Laventin LBN are wetting agents from BASF. Latekoll AL and Collacral HP are thickeners, solids contents = 30%, from BASF.

Aflammit P, PE and KWB and also Flammentin PS are reactive flame retardants from THOR Chemie, Speyer.

Pyrovatex CP and Flovan CGN are commercial products of Ptersee 45 Chemie GmbH, Langweld.

33 Hostaflam, TP AP 420 is an ammonium polyphosphate, (NH4PO3)nl n about 5; manufacturer: Hoechst AG, Frankfurt.

is - 34

Claims

CLAIMS An aqueous formulation comprising a polymer constructed of from 0 to 99. 95 % by weight of one or more principal monomers I selected from C,-C,,M, alkyl (meth)acrylates, aromatic vinyl compounds having up to 20 carbon atoms, vinyl esters 5 of carboxylic acids containing up to 20 carbon atoms, ethylenically unsaturated nitriles, 0 vinyl ethers of alcohols containing from I to 10 carbon atoms and aliphatic hydrocarbons having from 2 to 8 carbon atoms and 1 to 2 double bonds, from 0.05 to 100% by weight of one or more monomers Il which carry at least one functional group, which is not to be understood as meaning an ethylenically unsaturated 9:

1 group, this functional group being reactive with the below-defined phosphorus compound in such a way that the phosphorus compound becomes thereby bonded to the polymer, and from 0 to 80 % by weight of one or more further monomers III which differ from monomers I and II, and a phosphorus compound which is reactive with the functional group of monomer(s) II, the phosphorus compound being or becoming bonded to the polymer via the functional group.

01

2. An aqueous formulation as claimed in claim 1, wherein the proportion of the reactive phosphorus compound is from 0.5 to 100 parts by weight, based on 100 parts by C weight of polymer.

0

3. An aqueous formulation as claimed in claim 1 or 2, wherein the reactive phosphorus compound is a compound of the formula (R10)2p-X-CH,CHR-C-Z 11 11 0 0 1 where 25 Z is OW, O'M', NH2, N11RI, NHCH.,ORI or N11-CH-COOR', 1 OH M is an alkali metal or ammonium, R' is H, C,-C,-alkyl or C6-Clo-aryl, R is H or methyl, and X is a single bond or oxygen.

4. An aqueous formulation as claimed in claim 3, wherein the reactive phosphorus compound is N-methylol-3,3-di(methoxy)phosphorylpropionamide (R=H, 2 R' = methyl, Z = NHCH,OH) or a C, -C,-alcohol ether derivative thereof.

5. An aqueous formulation as claimed in any of claims 1 to 4, wherein monomer II is acrylamidoglycolic acid or 0 acrylamido-2-methylpropanesulfonic acid.

6. An aqueous formulation as claimed in any of cWins 1 to 5, wherein the polymer is present in the form of an aqueous dispersion.

7. An aqueous formulation as claimed in any of claims 1 to 6, in which the polymer is constructed of from 60 to 95 % by weight of monomer(s) I and from 5 to 40 % by weight of monomer(s) II.

0

8. A process for preparing an aqueous formulation as claimed in any of claims 1 to 7, which comprises first preparing an aqueous dispersion of the polymer and then adding the phosphorus compound to this dispersion.

9. A process for preparing an aqueous formulation as claimed in any of claims 1 to 7, which comprises polymerizing the monomers I, II and III in the presence of the phosphorus compound.

10. A process as claimed in claim 8 or 9 carried out substantially as hereinbefore described or exemplified.

claims 8 to 10.

11. An aqueous formulation when prepared by a process as claimed in any of

12. An aqueous formulation as claimed in claim 1 and substantially as hereinbefore described or exemplified.

13. The use of an aqueous formulation as claimed in any of claims 1 to 7, 11 or 12 as or in coating Pants, cleaning or care a.

Ps, impreg il.> gents or adhesives.

14. The use of an aqueous formulation as claimed in any of claims I to 7, 11 or 5 12 for consolidating fibrous materials, in particular fiber webs.

15. Fiber webs consolidated with an aqueous formulation as claimed in any of claims 1 to 7. 11 or 12.