DE19508530A1 - Flame retardant, aqueous polymer preparations - Google Patents

Abstract

An aqueous formulation comprises a polymer constructed of from 0 to 99.95% by weight of one or more principal monomers I selected from C 1 -C 20 -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 one or more 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 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 II, the phosphorus compound being or becoming bonded to the polymer via the functional group. The formulation can be used for consolidating fibrous materials, in particular fibrous webs, or in coatings, impregnants, cleaning or care agents or adhesives to provide flame proofing.

Description

The invention relates to aqueous preparations containing a polymer composed of
0 to 99.95 wt .-% of so-called main monomers I, selected from C₁-C₂₀-alkyl (meth) acrylates, vinyl aromatics with up to 20 C-atoms, vinyl esters of up to 20 C-atoms containing carboxylic acids, ethylenically unsaturated nitriles, vinyl ethers alcohols containing 1 to 10 carbon atoms and aliphatic hydrocarbons with 2 to 8 carbon atoms and 1 or 2 double bonds,
0.05 to 100 wt .-% of monomers II, which carry at least one functional group, meaning no ethylenically unsaturated group, and this functional group is reactive with the phosphorus compound below in such a way that the phosphorus compound by reaction with the functional group is bound to the polymer
and 0 to 80% by weight of other monomers III and I which differ from I and II
and a phosphorus compound reactive with the functional group of the monomer II, the phosphorus compound being able to be or being bound to the polymer via the functional group.

The invention further relates to processes for producing the aqueous preparation and uses of the aqueous preparation, in particular the use for consolidating nonwovens.

Flame retardants for polymers can be added or copolymerized of halogen compounds, optionally in combination with anti mon connections can be achieved. Halogen and antimony free flame So far, protective agents have generally been too low Effectiveness.

There are special requirements for flame retardants in In the case of aqueous polymer preparations, e.g. B. polymer dispersions.

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

When later using the dispersion z. B. as Beschich The flame retardant must be treated or impregnated Removal of water distributed as evenly as possible in the polymer be to achieve a satisfactory effect.

DE-A-24 11 738 discloses ethylenically unsaturated To use phosphorus compounds as comonomers and so the Improve flame retardancy of polymers. The polymers contain also mandatory vinylidene chloride.

In US-A-3 695 925 the flame retardant finish of textiles or Nonwoven fabrics using ethylenically unsaturated Phosphorus compounds, which are generally halogen atoms are described.

The subject of EP-A-476 644 is also flame retardant of non-woven fabrics, the non-woven fabrics with an aqueous accessory treatment from phosphorus salts and melamine-formaldehyde resins be delt.

The object of the present invention is aqueous preparations, which also without halogen compounds for later use, e.g. B. as a coating or impregnating agent, a good one Effect flame protection.

Object of the present invention are also aqueous preparations conditions that are also good for consolidating nonwovens own.

Accordingly, the aqueous preparations defined at the outset, Processes for their production and their use were found.

The aqueous preparation according to the invention contains a polymer, which is built up from the monomers I, II and optionally III is.

The main monomers are z. B. (meth) acrylic acid alkyl ester with a C₁-C₁₀ alkyl radical, such as methyl methacrylate, methyl acrylate, n-butyl acrylate, ethyl acrylate and 2-ethylhexyl acrylate.

In particular, mixtures of the (meth) acrylic acid alkyl esters suitable.

Vinyl esters of carboxylic acids with 1 to 20 carbon atoms are e.g. B. Vi nyl laurate, stearate, vinyl propionate and vinyl acetate.  

As vinyl aromatic compounds such. B. vinyl toluene, α- and p-methylstyrene, α-butylstyrene, 4-n-butylstyrene, 4-n-decylstyrene and preferably styrene.

Examples of nitriles are acrylonitrile and methacrylonitrile.

Suitable vinyl ethers are e.g. B. vinyl methyl ether, vinyl isobutyl ether, vinyl hexyl and octyl ether.

As non-aromatic hydrocarbons with 2 to 8 carbon atoms and one or two olefinic double bonds are butadiene, iso pren, and also called ethylene, propylene and isobutylene.

The main monomers are also preferably used in a mixture puts.

Vinyl aromatic compounds such as styrene are e.g. B. often in Mixture with C₁-C₂₀-alkyl (meth) acrylates, especially with C₁-C₈ alkyl (meth) acrylates, or non-aromatic hydrocarbons substances such as isoprene or preferably butadiene.

Styrene and butadiene are particularly preferred as main monomers.

The free-radically polymerized polymer is preferably present 40 to 98, particularly preferably 60 to 95% by weight of the Mo nomeren I.

Monomers II have at least one functional group through which phosphorus compounds, which with this functional Group z. B. by addition, condensation or substitution can react to be bound to the polymer.

Examples of such functional groups are acid groups, which may or may not be completely or partially neutralized NEN, especially carboxylic or sulfonic acid groups, acid hydride groups, amide, primary or secondary amino groups, Hydroxy or alkoxy groups, epoxy groups, ureido or isocya nate groups or keto or aldehyde groups.

As monomers with an acid group such. B. (meth) acrylic acid, Maleic acid, fumaric acid or itaconic acid.

Monomers with acid anhydride groups are e.g. B. maleic anhydride or methacrylic anhydride.  

Examples of monomers II are acrylic, methacrylic, maleic and Itaconic acid, acrylic and methacrylamide, vinylformamide, N-methylol methacrylamide and N-methylolacrylamide, methacrylic acid and Maleic anhydride, glycidyl (meth) acrylate, trimethoxysilylpro pyl methacrylate (MEMO), hydroxyethyl (meth) acrylate, dimethylamino ethyl (meth) acrylate, N-ureidoethyl methacrylate, vinylimidazole, Acetacetoxyethyl methacrylate (AAEM), acrylamidoglycolic acid, Diacetone acrylamide, 2-acrylamido-2-methylpropanesulfonic acid or Dimethyl meta isopropenyl benzyl isocyanate (TMI).

In addition to the reaction with the phosphorus compounds, monomers II can conditions simultaneously or in part instead of this implementation also have other functions.

So by a salary z. B. on monomers with acid groups Dispersion of the polymer can be stabilized.

The proportion of the monomers II in the polymer is preferably 2 to 60, particularly preferably 5 to 40 wt .-%, based on the bottom lymerisat.

As possible monomers III z. B. suitable, the Ge Increase total amount of phosphorus in the system and help burn disrupt the process. Monomers are particularly suitable for this. which already contains phosphorus in chemically bound form in the molecule hold. Such monomers are esters of acrylic and methacrylic acid, the phosphorus in the form of a phosphoric acid ester or Phosphonic acid esters in the side chain. Such structure structures are, for example, from B.Boutevi, J. Appl. Pole. Sci., 52 (1994) 449-456 or known from EP 530 692. As particularly good Structures such as

mean
R⁶:
(R⁷) _t -O _Hv - (R⁸) _u -,
R¹, R², R³, R⁴, R⁵, R¹⁰, R¹¹
Hydrogen, alkyl, cycloalkyl, aralkyl or aryl,
R⁷, R⁸, R⁹
Alkylidene, cycloalkylidene, aralkylidene or arylidene,
m, p, q, r, s, t, u, v
0 or 1,
n
0, 1 or 2
U
COO, O, S or NR⁹
V, W, X, Y
O, S or NR⁹ and
Z.
O, S or NR¹⁰R¹¹
proven that derive from acrylic acid or methacrylic acid esters. The preparation of the monomers is known (for example from EP 530 692, US 2 993 033). Furthermore, vinylphosphonic acid and Al lylphosphonic acid and their esters and salts, or also mono-, di- and triallyl phosphate are suitable.

In order to achieve satisfactory fire protection, but phosphorus-containing monomers III are generally not necessary agile.

In general, no monomers I to III are necessary Halogens, especially chlorine, or in any form need the addition of antimony. It is an advantage of the inventor sufficient fire protection even without halogens and Antimony can be obtained.

The polymer can by conventional methods of radical Po lymerization, e.g. B. the solution, substance, suspension or Emulsion polymerization can be produced.

The polymer is preferably in the form of an aqueous dispersion sion before, z. B. in solvent or in substance (Without solvent) polymer produced dispersed in water will.  

Emulsion polymerization, in which di right an aqueous dispersion of the polymer is obtained.

The emulsion polymerization can e.g. B. discontinuously, with or without the use of seed latices, with presentation of all or individually ner components of the reaction mixture, or preferably below partial submission and replenishment of the or individual stock parts of the reaction mixture, or according to the dosing process without Template.

The monomers can be used as usual in emulsion polymerization in the presence of a water-soluble initiator and an emulga tors are polymerized at preferably 30 to 95 ° C.

Suitable initiators are e.g. B. sodium, potassium and ammonium peroxodisulfate or peroxodiphosphate, tert-butyl hydroperoxide, Hydrogen peroxide or water-soluble azo compounds or Redox initiators, consisting of an oxidation component such as the peroxides, persulfates, perphosphates or hydroper mentioned oxides in combination with a reduced substance such as e.g. B. ascorbic acid, sodium disulfite, sodium hydroxymethanesulfine acid, formamidine sulfinic acid, hypophosphorous acid or their Alkali or ammonium salts. To speed up the reaction who the multivalent, which also has a catalytic effect on the redox initiators Metal salts such as B. iron-II sulfate or cobalt-II sulfate added puts.

As emulsifiers z. B. ethoxylated alkylphenols and fat alcohols with EO grades from 2 to 70 and alkyl groups from 7 to 18 carbon atoms, the alkyl metal salts of sulfated or sulfo nated derivatives of these ethoxylation products, the alkali metal salts of alkylsulfonic acids, alkylarylsulfonic acids, sulfonated Diaryl ethers or mono- or dialkyl esters of the sulfoberstein acid. A special class of emulsifiers are alkali or Ammonium salts of phosphoric acid esters, the alcohol compo nente from optionally ethoxylated fatty alcohols or alkyl phenols with 4 to 22 carbon atoms.

The sodium or ammonium salts of the sulfated are preferred and ethoxylated fatty alcohols or alkylphenols.

To adjust the molecular weight in the Polymerisa tion controller can be used. Are suitable for. B. -SH containing Compounds such as mercaptoethanol, mercaptopropanol, thiophenol, Thioglycerin, thioglycolic acid ethyl ester, thioglycolic acid octyl esters and tert-dodecyl mercaptan.  

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

The particle size of the dispersed polymer particles is before preferably 30 to 600, particularly preferably 100 to 400 nm.

The preparations according to the invention contain, in addition to the polymer sat a phosphorus compound, which with the functional groups the monomer II is reactive.

Water-soluble phosphorus compounds are preferably suitable, which per molecule have at least one P atom in chemically bound Contain form and which are able to with monomers II or the monomer units in the polymer, which differ from the monomers derive ren II, react and thus part of the polymer be sates.

The water solubility of the phosphorus compounds is preferred at least 5 g / l water at 25 ° C.

As phosphorus compounds are z. B.

• 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. The further implementation with a lower alcohol such as. B. with methanol to a semi-aminal is possible, as a higher storage stability of the products can be achieved. The general structure of such products is in which the substituents have the following meaning: Z = OR¹, O⊖M⊕, NH₂, NHR¹, NHCH₂OR¹, M = alkali metal or ammonium
  R¹ = H, C₁-C₅ alkyl, C₅-C₁₀ aryl
  R = H or methyl
  X = single bond or oxygen.
  The compound with R¹ = methyl, R = H or methyl, X = bond and Z = NHCH₂OH is preferred. It is commercially available from Pfersee under the name Pyro vatex® CP. The preparation and composition is known (A. Kapura, J. Fire Sciences, 12 (1994) 3-13 and Kirk-Othmer, Encyclopedia of Chemical Technology, 4th ed., Vol. 10, p. 1007.
• b) addition products of dialkylphosphite with aldehydes, especially 1- (dialkylphosphono) -1-hydroxyalkanes with the common structure (R¹O) ₂P (= O) -CH (-OH) -R, in which the radicals preferably have the following meaning Zen:
  R¹ = H or a C₁ to C₅ alkyl radical
  R = H or a C₁-C₂₂-alkyl, alkylaryl, cycloalkyl radical, which may be interrupted by oxygen atoms and / or contain further functional groups such as alcohols, esters, ketones, nitriles or acid amides.
  Particularly preferred compounds b) are reaction products of diethyl phosphite with formaldehyde, acetaldehyde, butyl aldehyde, glyoxal, glutaraldehyde, benzaldehyde, glyoxy acid, glyoxate and carbohydrates such as glucose.
• c) Also oligomerizates of vinylphosphonic acid esters have been found as suitable, the manufacture of z. B. in the German patent registration 43377831 is described. Oligomeri are preferred sate with sulfate end groups. The connections can also be made through subsequent implementation with one or more polyols 2-6 C atoms, such as glycerol, pentaerythritol, 2,2-bis (hydroxy methyl) propanol, tartaric acid or sugars such as glucose, sacca rose or galactose or polyvinyl alcohol or copolymers Sates of hydroxyethyl acrylate before use in the dispersions be partially networked. The oligomerizates can be easily dilute with water and mix in dispersions or as Protective colloid in the polymerization of other monomers in Use aqueous phase. You will do this by transesterification the reactive phosphonic acid ester groups in the side chain and partly also by grafting onto the polymer backbone anchored.  
• d) Other suitable additives are the phosphorous, pyrophosp horige-, Hypophosphorige and (Ohrtho) phosphoric acid or their Salts, e.g. B. alkali metal or ammonium salts, e.g. B. sodium pyrophosphate, ammonium (hydrogen) phosphate also low molecular, at least partially neutralized and therefore what Serum-soluble polyphosphates of the general formula (NH₄PO₃) n with n = 3 - 50 Such compounds are commercially available (e.g. Ho staflam® TP AP 420 from Hoechst AG with n approx. 5).
• e) Other phosphorus compounds are derivatives, in particular Salts or esters of methylphosphonic acid, e.g. B. Aflammit PE or Flovan CG, which is preferably in combination with the ge called P-containing compounds are used, the Her position and use from EP 245 207, 321 002 and 535 486 is known. Phenylphosphonic acid and Hydroxymethylphosphonic acid (AHPP) and their salts be set.

All these compounds have in common that they are phosphorus Heteroatom contained in chemically bound form. A high impact The level of additives leads to less required addition quantity. A high mass ratio of those present in the molecule Phosphorus to the combustible C and H content present in the molecule is advantageous.

Generally preferred are additives of type a) which are good Allow attachment by reaction with the monomer II. Be completely Pyrovatex CP is particularly preferred. Fer are also preferred ner low molecular weight homopolymers of vinylphosphonic acids star with sulfate end groups, due to their small molecule Largewes and the end group well water soluble, so fine ver are divisible. They are particularly preferred in combination with Connections a) used. Sole use of the Ty pen c) is recommended for applications where an additional Lich formaldehyde-free is desired. examples for this are Paints and varnishes for the interior of living rooms.

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

The compounds are preferred in amounts of 0.5 to 20, preferably 1 to 10 parts by weight of phosphorus (corresponds to phosphorus content of the reactive phosphorus compound) to 100 parts by weight of the polymer used at risk.

The phosphorus compounds can be used for aqueous preparation at any time tion, in particular dispersion, which contains the polymer, be added.

The phosphorus compounds can be bound to the polymer e.g. B. done by increasing the temperature. However, it is by no means necessary such a connection before processing the aqueous Effect preparation.

The connection can also occur during processing, e.g. B. after Apply the preparation to substrates and remove the Solvent.

One embodiment of the invention is also the phosphorus compound already in the polymerization of the monomers of the polymer add sats. Is carried out under the conditions of the polymerization then at least partially a connection of the phosphorver bonds to the polymer backbone.

Through the chemical connection of the phosphorus compounds to the Po Lymerisat their washability by water or organi counteracted solvents and a permanent washing and receive flame retardant resistant to cleaning agents.

The preparations according to the invention also have no further ad good fire protection.

However, the preparation can contain other additives which are suitable for a individual intended applications or for further improvement of fire protection can be added.

As additives that further increase fire protection, z. B. called:

• - Melamine, tris (2-hydroxyethyl) isocyanurate (THEIC) or Mela minor derivatives such. B. melamine phosphate, melamine cyanurate or hydrophilized, d. H. ethoxylated or phosphonomethylated Melamine derivatives or higher condensed compounds such as Me lem and melon. These connections are characterized by spe target heteroatoms such as nitrogen, which synergistically Support phosphorus flame protection. Ethoxilerte Melaminderi vate are known from EP 225 433, phosphonomethylated Mela  minor derivatives z. B. from EP DE OS 39 33 546. It is also possible to phosphonomethylate other acid amide groups, such as. B. Urea, acrylamide or polyacrylamide. Such a verb are known from DE 05 39 33 549 and DE OS 41 28 510.
• - magnesium or aluminum hydroxide, zinc hydroxystannate, Calcium or zinc cyanamide, boric acid, zinc borate and others Boric acid salts are also insoluble, finely dispersed Bare aggregates are suitable during combustion process give off water vapor and / or an oxide crust leave.
• - Water-insoluble plasticizers based on low molecular weight, orthophosphoric acid esters are additives well known to the person skilled in the art, which can be added to a latex and penetrate into the polymer. Such preferred compounds are of the phosphoric acid type. They are condensation products from phosphorus pentoxide or phosphoric acid with alcohols, phenols or polyols. They are known from Ullmann's Encyclopedia of Industrial Chemistry, 4th Edition Vol. 18, p. 301 f, Verlag Chemie, Weinheim 1979. Preferred substituents of the general formula (O =) _m P (O _n R¹) (O _n R²) (O _n R³) are those with R1 = R2 = R3 and m, n = 0 or 1. The substituents R1 to R3 can is methyl, ethyl, vinyl, allyl, propyl, butyl, octyl, ethylhexyl, phenyl, cresyl, chloropropyl, pentachlorophenyl, pentabromophenyl. When using polyols, depending on the reaction ratio, mixed or partially crosslinked or more condensed products are obtained, which often also have increased water solubility. Preferred polyols for this are those with 2 to 6 carbon atoms, such as glycerol, pentaerythritol, 2,2-bis (hydroxymethyl) propanol or glucose. Halogen-free compounds such as tributyl phosphate, tri allyl phosphate, tributoxyethyl phosphate, triphenyl phosphate, tricresyl phosphate, triphenylphosphine, triphenylphosphine oxide are very preferred. These are preferably low molecular weight compounds with a molecular weight below 1000 g / mol. The incorporation of such compounds takes place in the case of liquid compounds by stirring in, in the case of easily meltable compounds at elevated temperature and in the case of difficult-to-melt compounds in the form of a fine trituration.

Other additives that can be used are e.g. B. heat or light stabilizers, lubricants and mold release agents, film binding aids, plasticizers, colorants, pigments, reinforcements  kmittel, wetting and dispersing agents, hydrophilizing or Hy water repellents, waxes and thickeners.

Resins in particular have been found to be curing and crosslinking agents proven. Such resins are e.g. B. aminoplasts such as melamine or Urea resins or resols. Cyclic urea derivatives can also NEN are used, e.g. B. ethylene urea, 3,4-dihydroxy ethylene urea or N, N-dimethyl-3,4-dihydroxyethylene urea. The resins are, for example, from Encyclopedia of Polymer Science and Technology, Interscience Publishers 1965, Vol. 2, page 1 ff. or Volume 10, page 1 ff., or Ullmann's Encyclopedia of Techni chemistry, Verlag Chemie, 4th edition, volume 7, pp. 403-423 or Volume 18, pp 245-257 ago known. To be emphasized are connections, which are able to reak the proportion of free formaldehyde tion to lower. Examples include urea, polyurea, Ethylene urea, acetamide, guanidine, cyanguanidine, melamine as well Sulfonamides.

In the preparations according to the invention, the more usual ones wise additives used antimony trioxide and chlorine and bromine-containing additives are dispensed with.

The preparations according to the invention are suitable, for. B. as Be layering agents, impregnating agents, care and cleaning agents medium or as adhesives.

Suitable substrates for this use are e.g. B. textile mate materials, metal, wood, paper, plastic in the form of foils or also moldings.

Another possible use is fiber called simple.

The preparations according to the invention are particularly suitable for Bind nonwovens made of synthetic or natural fibers (Fleece binder).

Fibers made of cotton, cellulose, Polyester, leather or glass.

The substrates treated with the preparation according to the invention receive fire protection equipment from the aqueous preparation stung.

The preparations according to the invention can be used alone or according to Zu mix other additives, such as fillers and / or pigments Impregnation, spraying, coating, splashing, foaming, loading  glue, brush, calender or laminate on the sub strate to be applied.

To increase the internal strength of the polymer and, if necessary. Completion of the reaction between the polymer and the reak Tive phosphorus compound is available after all types of application preferably carried out a drying process. In the case of fiber like substances and especially the nonwovens and textiles For this purpose, materials are treated with the preparations Raw materials in a higher temperature drying oven puts. Depending on the substrate, a temperature of 80-280 ° C is before drawn from 120-220 ° C and residence times of 2-30 min ge elects.

The substrates treated with the preparation according to the invention can be used in a variety of ways, e.g. B. as flame retardant and flame retardant cardboard, wrapping paper, wallpaper, mats, table cloth cher, heat and sound insulation materials, as electronic Components, foils, for the production of objects of the sanitary Hospital supplies, such as surgical clothing, capes or wipes towels.

Nonwoven fabrics bound with the preparations can e.g. B. as fut , upholstery and padding in upholstered furniture, pillow fillings, Fiber fillings, sleeping bags and lining for clothing be set. Textile applications are also possible, such as B. flame retardant impregnation of bed linen, curtains, Covers or upholstery fabrics. Flame retardant technical fleece fabrics are used to manufacture filter materials for air filters in the household, in automotive and technical applications rich, from flame-retardant roofing membranes, sun protection slats, Insulating and insulating materials, made of glass, mineral and wood fa ser. The preparations according to the invention are also suitable as adhesives and pressure sensitive adhesives, as sealants and fillers and as Part of paints, paints and plasters.

Examples Test methods Translucency

The decrease in light transmission in% of white is measured diluted to a solid content of 0.01% Dispersion sample with a layer thickness of 25 mm.  

viscosity

The dynamic viscosity in mPa · s (rotary viscometer, 23 ° C, Rheomat STV, Contraves, measuring cup III according to DIN 53778 at 400 s ^-1 .

I. Preparation of dispersions Dispersion 1

A mixture of 2.25 g of hydrogen peroxide in 180 g of water was heated to 65.degree. At 60 ° C., 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 after 15 minutes the rest of the monomer emulsion and the reducing agent solution were added continuously over 180 minutes. After 1 h of post-polymerization at 650, the mixture was cooled to 25 ° C. and 15 g each of tert-butyl hydroperoxide (10%) and ascorbic acid solution (10%) were added. A speck-free and coagulate-free dispersion with a polymer content of 49% and a pH of 2.8 was obtained. The light transmission was 63%, which corresponds to an average particle size of approximately 240 nm. The viscosity was 26 mPa · s. The residual monomer value determined by gas chromatography was 700 for EA, for MMA and AN in each case <10 ppm.
Composition of monomer emulsion 1:

585 g ethyl acrylate (EA)
60 g methyl methacrylate (MMA)
75 g acrylonitrile (AN)
90 g of N-methylolacrylamide, 25% solution in water
7.5 g acrylic acid
56 g emulsifier 1
32 g of emulsifier 2
330 g water

Dispersion 2

The preparation of dispersion 1 is repeated, with the sub decided that in addition to hydrogen peroxide, 75 g of Pyrovatex CP were submitted. The coagulate and speck-free dis persion had a solids content of 48% and a pH of 2.6 on. The light transmission was 38%, the middle one Particle size approx. 370 nm and the viscosity was 32 mPa · s.  

Dispersion 3

A mixture of 125 g of a 60% solution of Polyvi nylphosphonic acid dimethyl ester, 2% of a monomer emulsion as in Dispersion 1 and 210 g of water are heated to 85 ° C. With Er range of the internal temperature of 70 ° C was given 8.3 g of the solution 3.75 g sodium persulfate in 100 g water and led the rest the monomer emulsion and the initiator solution continuously in 180 min and allowed to polymerize for 60 min. After cooling to 25 ° C was with 0.2% tert-butyl hydroperoxide and ascorbic acid aftertreated (based on polymer mass) and filtered. It was a speck-free and coagulate-free dispersion with a polymer obtained part of 49% and a pH of 2.0. The light through casualness was 44%, the average particle size was approximately 310 nm.

Dispersion 4

The preparation of dispersion 3 is repeated, with the sub decided that 125 g of an aqueous 60% solution of dimethyl polyvinylphosphonate and 75 g Pyrovatex CP were used, half of which submitted and half was added to the emulsion feed. It became a speck-free and coagulate-free dispersion with a solid fabric content of 47.5%, light transmission of 33%, an average particle size of 400 nm and a pH of 2.1 received.

Dispersion 5

The preparation of dispersion 1 is repeated, with the sub decided that in addition to hydrogen peroxide, 75 g of Pyrovatex CP was submitted and for the preparation of the monomer emulsion 3% (based. on polymer mass) of the emulsifier 3 was used.

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 85 ° C. and initiated by adding 31 g of a solution of 10.8 g of sodium persulfate in 200 g of water. After 15 minutes, the remainder of the monomer emulsion and the remainder of the initiator solution were started to be fed continuously in 120 and 135 minutes, after which polymerization was continued for 60 minutes. After cooling to 25 ° C, 12 g of tert-butyl hydroperoxide (10%) and 13.5 g of ascorbic acid solution (10%) were added, and a speck-free and coagulate-free dispersion with a solids content of 44%, a pH of 1.6 was obtained and a light transmission of 87%. 90 ppm EA and less than 10 ppm styrene were detected by gas chromatography.
Composition of monomer emulsion 6:

1060 g of ethyl acrylate
240 g styrene
27 g acrylic acid
14 g of 2-acrylamido-2-methylpropanesulfonic acid
225 g of dimethyl polyvinylphosphonate, 60% in water
95 g of emulsifier 4
885 g water

Dispersion 7

200 g of a 60% solution of polyvinylphosphonic acid dimethyl ester, 1.2 g sodium acetate in 600 g water are heated to 85 ° C and with 5 g of a solution of 2.4 g of sodium persulfate in 95 g of water he moved. Immediately afterwards a monomer was started mixture of 196 g styrene, 196 g butyl acrylate and 8 g acrylic acid continuously in 120 min and the rest of the initiator solution in Add 180 min. After filtration, a dispersion with a polymer content of 39%, pH = 1.9 and a translucent light 25% rate.

II. Mixtures with polyvinylphosphonic acid dimethyl ester (PVPE) and Pyrovatex (Py)

1000 g of dispersion 1 are at 25 ° C with stirring with the ent speaking amount of polyvinylphosphonic acid dimethyl ester (PVPE) or mixed with Pyrovatex CP (PyCP) within about 15 minutes. After the addition is complete, the mixture is stirred for a further 10 min and filtered through a 125 µm filter. It never was Coagulation formation observed. 200 g of the mixtures were mixed with 50 g Diluted water, with 0.5 g Agitan 703 and 1.0 g Latekoll AL ver sets, with 10 wt .-% sodium hydroxide solution to a pH of approx. 9 brought and then added a solution of Collacral HP until a viscosity of about 800-1000 mPa · s was obtained. The after The following table shows the mixtures, their pH and viscosity action:  

Table 1

Examination for glass fabric

Glass fabric from the company Hexel Genin, blue, basis weight 200 g / m², was coated on both sides with the paste obtained and after each order dried in a drying cabinet at 120 ° C in 5 min net. The average coating order was around 100-110 g / m². 4 identical test strips were made from the coated fabric cut out in the longitudinal direction (300 mm × 95 mm) and 24 h at 23 ° C and 50% rel. Air-conditioned humidity. The exam was carried out according to DIN 54332, but with two changes: Instead of propane, butane served as fuel gas and to protect the Asbestos plate (sample holder) was between the fleece pattern and As best plate an aluminum foil interposed. The samples were 30 sec Flamed with the blue glowing flame, the burner ent distant and afterburn time, smoldering time, reaching the upper measuring mark (MM) and the damaged area determined.

Blends and testing for cotton fabrics

1000 g samples of dispersion 1 are as in Example 2.1. under Stir with the appropriate amount of polyvinylphosphonic acid ester and Pyrovatex CP added (Tab. 3). The homogeneous and koa Gulate-free dispersions are used for pre-impregnation and double-sided coating of cotton fabric used.

1000 g of the dispersion were mixed with 0.2 parts of Laventin LBN sets, diluted to a liquor concentration of 20 wt .-% and with it pre-made cotton fabric (Hornschuch, white, 253 g / m²) garnished, dried for 7 min at 120 ° C and on both sides with the following Mixture coated: Sodium hydroxide solution, 100 g of dispersion, 1.0 g Latekoll AL and approx. 13-15 g Collacral HP added to approx a viscosity of about 2000 mPa · s was reached. The paste was applied to both sides of cotton fabric and after each Order dried for 4 min at 120 ° C. A total order of approximately 170 g / m² was discontinued. The results of the flame tests are shown in Table 4.

Table 3

III. Addition of additives

1000 g samples of dispersion 1 are mixed with the corresponding Amount of additives and with 75.5 g of a 60% aqueous solution of PVPE with stirring at the specified temperature and Stirred for 2 hours.

Table 5

IV. Other flame retardants

100 parts of dispersion 1 were mixed with the following phosphorus containing reactive additives mixed, and to enable the The reaction was stirred for 2 hours at room temperature. The viscosity was with 25 wt .-% ammonia and the specified thickeners raised to a value of 1500-2000 mPa · s and thus a piece of furniture covering material (raw material 285-290 g / m² basis weight) coated, Dried at 100 ° C for 5 min and to complete the reaction post-condensed at 150 ° C for a further 3 min. The upholstery fabrics according to the British standard flame test (BS 5852) - butane flame and cigarette test checked.

Table 7

V. Production of further dispersions and blends Dispersion 8

A dispersion with the polymer composition 74 wt .-% ethyl acrylate, 20% by weight acrylonitrile, 4% by weight N-methylol methacrylamide and 1 wt .-% acrylic acid was based on dispersion 1, each but without polyvinyl phosphonic acid ester and without emulsifier 1, poly merized. The dispersion had a solids content of 49 % By weight, a light transmittance of 65% and a viscose from 20 mPa · s.

Dispersion 9

According to dispersion 3, a dispersion with the polymer set composition 81% by weight of vinyl acetate, 15% by weight of n-butyl acrylic lat, 3% by weight of N-methylolacrylamide and 0.5% by weight of sodium each vinyl sulfonate and acrylic acid. The solids content be contributed 50%, the light transmission 63%, the pH 4.9 and the Viscosity approx. 54 mPas.

Dispersion 10

A dispersion consisting of 50% by weight vinyl propionate, 40% by weight n-butyl acrylate and 10% by weight of versatic acid ester (VeoVa 10) by emulsion polymerization using sodium per sulfate as an initiator at 85 ° C. Served as emulsifiers 3% emulsifier 5 and 1% emulsifier 6, each based on the total monomeric. After the end of the polymerization, 10% calci umhydroxid slurry adjusted to pH = 8. It became a dis persion with a solids content of 47% and a medium Obtained particle size of 200 nm.

Dispersion 11

A dispersion with the polymer composition 80 wt .-% ethyl acrylate, 10% by weight acrylonitrile, 8% by weight methyl acrylate, 2.0 % By weight of N-methylolacrylamide was obtained by redox initiation with 0.2% Hydrogen peroxide and 0.2% ascorbic acid using 1.5% each of emulsifier 1 and 2 at 60 ° C. After treatment each with 0.15% tert-butyl hydroperoxide and ascorbic acid a speck-free and coagulate-free dispersion with a polymer obtained part of 49% and a pH of 2.7. The light through 0.01% solution was 53%. The gas chromato  graphically determined residual monomer value was for EA and AN each because <10 ppm.

Comparative dispersion 12

A dispersion was based on Example 1.3. through polyme Rization of a 1: 1 mixture of n-butyl acrylate and methyl meth made of acrylate. The dispersion contains no functional based monomers.

Mixtures with PVPE and PyCP

Analogously to II, the dispersions 8 to 12 with 5% by weight of Polyvi nylphosphonic acid dimethyl ester and 15 wt .-% Pyrovatex CP, each based on polymer mass, mixed with stirring and 2 hours after stirred, then in the manner described with water on uniformly diluted 40% with ammonia and thickener a viscosity of approx. 800-900 mPa · s and glass fabric coated on both sides (results in Table 9).

Dispersion 13

The production of dispersion 11 is like with the difference repeated that 10% ethyl acrylate was replaced by methacrylic acid the. After adding 10% by weight (based on polymer mass) of a Ge mix of mono-, bis- and tris-N, N ', N' '- (hydroxyethyl) melamine (= HOM) (weight ratio 1: 5: 4) with stirring 2 hours after stirred, the mixture divided and half with 10%, bez. on Polymer mass mixed with polyvinylphosphonic acid dimethyl ester. Then proceed as under II.

Dispersion 14

A mixture of 4% of a monomer emulsion, 24 g of emulsifier 4 and 570 g of water is heated to 85.degree. When he reached the internal temperature of 70 ° C, 32 g of the solution of 10.8 g of sodium persulfate in 200 g of water were added, the remainder of the monomer emulsion and the initiator solution were continuously added in 120 minutes and left to polymerize for 60 minutes. After cooling to 25 ° C., 0.2% tert-butyl hydroperoxide and ascorbic acid (based on polymer mass) were used and aftertreated and filtered. A speck-free and coagulate-free dispersion with a polymer content of 45% and a pH of 1.6 was obtained. The light transmission was 96%, the glass transition temperature approx. + 9 ° C (DSC).
Composition of monomer emulsion 14:

1066 g of ethyl acrylate
240 g styrene
27 g acrylic acid
13.5 g of 2-acrylamido-2-methyl-propanesulfonic acid
145 g emulsifier 4
800 g water

Dispersion 15

The preparation of dispersion 14 is like with the difference derholt that he 40 g of ethyl acrylate by acrylamidoglycolic acid were set.

Mixtures with PVPE and PyCP

1000 g of dispersions 14 and 15 are stirred at 25 ° C with 10 wt .-% based on polymer of a 60 wt .-%, aqueous Solution of polyvinylphosphonic acid and added 2 hours after the pH value (approx. 1-1.5) stirred and for the impregnation of glass fabric (Interglas, Qua white, 130 g / m²). After impregnation, bandage excess medium squeezed off with a doctor blade and at 10 min Dried 120 ° C.

Substances used

Emulsifier 1:
20% aqueous solution of an octylphenol ethoxylate with approx. 25 mol EO per mol octylphenol;
Emulsifier 2:
35% aqueous solution of a sulfated octylphenol ethoxylate neutralized with sodium hydroxide solution with about 25 moles of EO per mole of octylphenol;
Emulsifier 3:
C₁₂-C₁₄ fatty alcohol with approx. 3 mol EO per mol alcohol, esterified with phosphoric acid, mixture of mono- and diester (= MO3 acid from Hüls AG); 20% aqueous solution neutralized with ammonia;
Emulsifier 4:
28% solution of a sulphated and ethoxylated (EO grade approx. 2-3) neutralized with sodium hydroxide solution; lauryl alcohol;
Emulsifier 5:
35% solution of the sodium salt of a sulfated lauryl alcohol ethoxylate with approx. 30 mol EO per mol alcohol;
Emulsifier 6:
20% solution of an ethoxylated tallow fatty alcohol with approx. 18 mol EO per mol alcohol; C₁₆ alkyl;
Emulsifier 7:
20% solution of an ethoxylated tallow fatty alcohol with approx. 30 mol EO per mol alcohol; C1₆ alkyl radical;
Emulsifier 8:
40% solution of a neutralized C₁₆ paraffinsulfonate.

Agitan 703 and Laventin LBN are wetting agents, manufacturer BASF. Latekoll AL and Collacral HP are thickeners, solid share = 30%, manufacturer BASF.

Aflammit P, PE and KWB as well as Flammentin PS are reactive flames preservatives from THOR Chemie, Speyer.

Pyrovatex CP and Flovan CGN are commercial products from Pfersee Chemie GmbH, Langweid.

Hostaflam TP AP 420 is an ammonium polyphosphate, (NH₄PO₃) _n , n approx. 5; Manufacturer: Hoechst AG, Frankfurt.

Claims (11)

1. Aqueous preparation containing a polymer built up from
0 to 99.95% by weight of so-called main monomers I, selected from C₁-C₂₀-alkyl (meth) acrylates, vinyl aromatics, with up to 20 C-atoms, vinyl esters of carboxylic acids containing up to 20 C-atoms, ethylenically unsaturated nitriles, Vinyl ethers of alcohols containing 1 to 10 carbon atoms and aliphatic hydrocarbons with 2 to 8 carbon atoms and 1 or 2 double bonds,
0.05 to 100% by weight of monomers II, which carry at least one functional group, which means no ethylenically unsaturated group, and this functional group is reactive with the phosphorus compound below in such a way that the phosphorus compound is reacted with functional group is bound to the polymer
and 0 to 80% by weight of other monomers III and I which differ from I and II
and a phosphorus compound reactive with the functional group of the monomer II, it being possible for the phosphorus compound to be bonded or bound to the polymer via the functional group. 2. Aqueous preparation according to claim 1, wherein the proportion of reactive phosphorus compound 0.5 to 100 parts by weight, bezo gene per 100 parts by weight of polymer. 3. Aqueous preparation according to claim 1 or 2, wherein the reactive phosphorus compounds are a compound of the formula acts with Z = OR¹, O⊖M⊕, NH₂, NHR¹, NHCH₂OR¹, M = alkali metal or ammonium
R¹ = H, C₁-C₅ alkyl, C₆-C₁₀ aryl
X = single bond or oxygen. 4. Aqueous preparation according to claim 3, wherein it is in the reactive phosphorus compound around N-methylol-3,3-di (meth oxy) phosphoryl-propionamide (R = H, R¹ = methyl, Z = NHCH₂OH) or a derivative etherified with a C₁-C₄ alcohol. 5. Aqueous preparation according to one of claims 1 to 4, wherein Monomers II are acrylamidoglycolic acid or acrylic amido-2-methyl-propanesulfonic acid. 6. Aqueous preparation according to one of claims 1 to 5, wherein the polymer is in the form of an aqueous dispersion. 7. Process for the preparation of aqueous preparations according to one of claims 1 to 6, characterized in that to next, an aqueous dispersion of the polymer is prepared and the phosphorus compound is added to this dispersion becomes. 8. Process for the preparation of aqueous preparations according to one of claims 1 to 6, characterized in that the Monomers I to III in the presence of the phosphorus compound poly be merized. 9. Use of aqueous preparations according to one of the An sayings 1 to 6 as or in coating compositions, impregnation detergents, cleaning or care products or glue fabrics. 10. Use of aqueous preparations according to one of the An Proverbs 1 to 6 for solidifying fibrous materia lien, especially non-woven fabrics. 11. With an aqueous preparation according to one of claims 1 up to 6 consolidated nonwovens.