EP3387031A1

EP3387031A1 - Process for preparing an aqueous polymer dispersion

Info

Publication number: EP3387031A1
Application number: EP16801986.7A
Authority: EP
Inventors: Lucia JIMENEZ GARCIA; Carmen-Elena Cimpeanu; Marcus SEIBERT; Hermann Seyffer; Dirk Lawrenz; Juergen Blaul
Original assignee: BASF SE
Current assignee: BASF SE
Priority date: 2015-12-11
Filing date: 2016-11-15
Publication date: 2018-10-17
Also published as: CN108368208A; US20180362689A1; WO2017097545A1

Abstract

The invention relates to a process for the preparation of an aqueous dispersion of a polymer P (aqueous polymer P dispersion) by radically initiated aqueous emulsion polymerization.

Description

Process for the preparation of an aqueous polymer dispersion Description

The present invention is a process for the preparation of an aqueous dispersion of a polymer P (aqueous polymer P dispersion) by free-radically initiated aqueous emulsion polymerization, which is characterized in that the polymerization of

> 3 and -i 8 wt .-% of at least one monoethylenically unsaturated compound having at least one epoxy group and / or an N-methylol group and / or at least one compound having at least two non-conjugated ethylenically unsaturated groups (monomers A), and

92 and <97% by weight of further, different from the monomers A,

ethylenically unsaturated compounds, wherein one of these ethylenically unsaturated compounds in

polymerized polymer

Glass transition temperature in the range> 0 and ^ 50 ° C would have (monomers B), wherein the amounts of the monomers A and B to 100 wt .-%

(Total monomer), in the presence of> 25 and ^ 120 wt .-% of at least one lignin compound L, based on the total amount of monomers, takes place, and

wherein the monomers B no ethylenically unsaturated C3 to C6 monocarboxylic and / or C ₄ - to comprise C6-dicarboxylic acids and their salts and anhydrides or monoethylenically unsaturated compounds having at least one silicon-containing group, a hydroxyalkyl group or a carbonyl group.

The present invention furthermore relates to the aqueous polymer P dispersions themselves obtainable by the process according to the invention, their use in processes for the production of moldings and the moldings themselves.

The solidification of fibrous and / or granular substrates, in particular in sheet-like structures, such as fiber webs, fiberboard, chipboard or more complex non-surface moldings, etc., often takes place by chemical means

Use of a polymeric binder. To increase the strength, in particular the breaking strength and the heat resistance, many binders are used which contain formaldehyde-releasing crosslinkers. But there is the danger of unwanted formaldehyde emission. To avoid formaldehyde emissions, numerous alternatives to the previously known binders have already been proposed. For example, US Pat. No. 4,076,917 discloses binders which contain carboxylic acid- or carboxylic anhydride-containing polymers and .beta.-hydroxyalkylamides as crosslinkers. A disadvantage is the relatively complicated preparation of ß-hydroxyalkylamides.

From EP-A-445578 boards of finely divided materials, such as glass fibers are known in which mixtures of high molecular weight polycarboxylic acids and polyhydric alcohols, alkanolamines or polyhydric amines act as a binder.

From EP-A-583086 formaldehyde-free, aqueous binders for the production of fiber webs, in particular glass fiber webs, known. The binders contain a polycarboxylic acid having at least two carboxylic acid groups and optionally also anhydride groups and a polyol. These binders require a phosphorus-containing reaction accelerator to achieve sufficient strengths of the glass fiber webs. It should be noted that the presence of such

Reaction accelerator can be dispensed only when a reactive polyol is used. As highly reactive polyols, β-hydroxyalkylamides are mentioned.

EP-A-651088 describes corresponding binders for cellulose fiber substrates. These binders necessarily contain a phosphorus-containing reaction accelerator.

EP-A-672920 describes formaldehyde-free binding, impregnating or coating compositions which comprise a polymer which is composed of 2 to 100% by weight of an ethylenically unsaturated acid or an acid anhydride as comonomer and comprises at least one polyol. The polyols are substituted triazine, triazinetrione, benzene or cyclohexyl derivatives, the polyol radicals always being in the 1, 3,5-position of the mentioned rings. Despite a high drying temperature, only low wet tensile strengths are achieved with these binders on glass fiber nonwovens.

DE-A-2214450 describes a copolymer which is composed of 80 to 99% by weight of ethylene and 1 to 20% by weight of maleic anhydride. The copolymer is used, together with a crosslinking agent, in powder form or in dispersion in an aqueous medium for surface coating. As the crosslinking agent, an amino group-containing polyhydric alcohol is used. However, to effect cross-linking, it must be heated up to 300 ° C.

From US-A 5,143,582 the production of heat-resistant nonwoven materials is under

Use of a thermosetting, heat-resistant binder known. The binder is free from formaldehyde and is obtained by mixing a

Carboxylic acid groups, carboxylic anhydride groups or carboxylic acid salt groups having polymer and a crosslinking agent. The crosslinker is a β-hydroxyalkylamide or a polymer or copolymer thereof. The polymer which can be crosslinked with the β-hydroxyalkylamide is, for example, composed of unsaturated mono- or dicarboxylic acids, salts unsaturated mono- or dicarboxylic acids or unsaturated anhydrides. Self-curing polymers are obtained by copolymerization of the β-hydroxyalkylamides with

Carboxyl-containing monomers.

In US-A 2004/82689 formaldehyde-free aqueous binder for the production of fiber webs, in particular glass fiber webs, disclosed which consist essentially of a polymeric polycarboxylic acid, a polyol and an imidazoline derivative. The resulting bonded fiber webs should have a reduced water absorption. Nonspecifically, both nitrogen-containing and nitrogen-free polyols are disclosed, but in particular the nitrogen-containing triethanolamine is described as being preferred. As specific imidazoline derivatives are mentioned reaction products of a fatty acid with aminoethylethanolamine or diethylenetriamine. The disclosed aqueous

Binder compositions contain a phosphorus-containing reaction accelerator.

According to WO 99/09100 thermally curable compositions and their

Use as a formaldehyde-free binder for the production of moldings, which in addition to an alkanolamine having at least two OH groups, a polymer 1, which ^ 5 wt .-% and another polymer 2, which is a 15 wt .-% of an α, β- ethylenically unsaturated mono- or dicarboxylic acid in polymerized form.

Furthermore, WO 10/34645 discloses aqueous binder systems for granular and / or fibrous substrates which contain, as active constituents, a polymer 1 containing δ 5.5% by weight and 20 20% by weight of an α, β-ethylenically unsaturated mono- or

Dicarboxylic acid in copolymerized form, a polymer 2 containing ä 40 wt .-% of an α, β-ethylenically unsaturated mono- or dicarboxylic acid in copolymerized form and a polyol compound having at least two hydroxyl groups.

In EP-A 2487204 aqueous binders for granular and / or fibrous

Discloses substrates which contain a salt compound in addition to a carboxylic acid group-containing polymer and a polyol compound essential. These saline

Binder liquors have an advantageous effect on the wet tensile strength and the breaking strength at 180 ° C of the bonded fiber webs.

Furthermore, EP-A 2502944 discloses aqueous binders for granular and / or fibrous substrates which contain as essential components a polymeric polycarboxylic acid, a nitrogen-free polyol compound having at least two hydroxyl groups and a hydroxy group-free organic nitrogen compound having a pKa value <7.

With lignin-containing binder systems, the following state of the art can be assumed.

Thus, US-A 2009/170978 discloses binder systems based on a mixture of polysaccharides, vegetable proteins or lignin derivatives with a

Emulsion polymer containing 5 to 40 wt .-% of an ethylenically unsaturated Contains carboxylic acid in copolymerized form. The polysaccharides and plant proteins are advantageously used as non-dissolved particulate systems. details

Comments on the use of lignin derivatives are not found.

In US-A 201 1/159768 aqueous binder systems are disclosed which grafted with ethylenically unsaturated carboxylic acids lignin derivatives and

oxazoline group-containing polymers.

In contrast, EP-A 2199320 discloses binder systems based on

Emulsion polymers and defatted soybean meal and their use for the production of composite materials. In a specific embodiment, the binders may additionally contain lignin or lignin sulfonate.

WO 2013/120752 discloses aqueous binder compositions which in addition to a lignin compound also contain a dispersion polymer, wherein the

Dispersionspolymerisat> 0.1 and ^ 10 wt .-% of at least one monoethylenically unsaturated compound having at least one silicon-containing group, an epoxy, a hydroxyalkyl, an N-methylol or a carbonyl group and / or at least one compound which at least two non-conjugated ethylenically unsaturated groups and advantageously additionally contains> 0.1 and ^ 4 wt .-% of at least one monoethylenically unsaturated C3 to C6 mono- and / or C4-C6-dicarboxylic acid and their salts and anhydrides in polymerized form.

However, those with the disclosed in the aforementioned document

Moldings produced, in particular fiber webs, not always fully satisfy in all mechanical properties, in particular dimensional stability at elevated temperature. Furthermore, the market is increasingly seeking alternative formaldehyde-free or reduced binder systems based on renewable resources.

It was an object of the present invention to provide a process for the preparation of a specific formaldehyde-free or formaldehyde-reduced aqueous binder system based on a lignin compound for fibrous and / or granular substrates, by means of which improvements were made in the case of shaped bodies, in particular fiber webs

Dimensional stabilities, improved force modules and reduced elongation at elevated temperature result.

Accordingly, the method defined above was found.

The implementation of free-radically initiated emulsion polymerizations of ethylenically unsaturated monomers in an aqueous medium has often been described above and is therefore sufficiently known to the person skilled in the art [cf. for this emulsion polymerization in Encyclopedia of Polymer Science and Engineering, Vol. 8, pages 659 et seq. (1987); DC Blackley, in High Polymer Latices, Vol. 1, pp. 35 et seq. (1966); H. Warson, The Applications of Synthetic Resin Emulsions, chapter 5, pages 246 ff. (1972); D. Diederich, Chemistry in Our Time 24, pages 135 to 142 (1990); Emulsion Polymerization, Interscience Publishers, New York (1965); DE-A 40 03 422 and dispersions of synthetic high polymers, F. Hölscher, Springer-Verlag, Berlin (1969)]. The free-radically initiated aqueous emulsion polymerization takes place

usually in such a way that the ethylenically unsaturated monomers, usually with the concomitant use of dispersants, such as emulsifiers and / or protective colloids, dispersed in an aqueous medium and polymerized by means of at least one water-soluble radical polymerization initiator. From this general

Procedure, the method of the invention differs only by the use of specific monomers A and B, which in the presence of a

Ligning compound L are polymerized.

It is also important that in the resulting aqueous polymer P dispersions the residual contents of unreacted ethylenically unsaturated monomers by the skilled person also known chemical and / or physical methods [see, for example, EP-A 771328, DE-A 19624299, DE-A 19621027 DE-A 19741 184, DE-A 19741 187, DE-A 19805122, DE-A 19828183, DE-A 19839199, DE-A 19840586 and

198471 15], the polymer solids content by dilution or

Concentration can be adjusted to a desired value or other customary additives, such as, for example, bactericidal, foaming or viscosity-modifying additives, can be added to the resulting aqueous polymer P dispersions.

As monomers A, it is possible to use all monoethylenically unsaturated compounds having at least one epoxy group and / or one N-methylol group and / or compounds which have at least two nonconjugated ethylenically unsaturated groups.

As monomers A, which have at least one epoxy group, in particular vinyloxirane, allyloxirane, glycidyl acrylate and / or glycidyl methacrylate may be mentioned, with glycidyl acrylate and / or glycidyl methacrylate being particularly preferred.

Further suitable monomers A are all monoethylenically unsaturated compounds which have at least one N-methylol group, for example N-methylolamide compounds based on α, β-monoethylenically unsaturated C3- to C6-mono- or dicarboxylic acid amides, in particular N-methylolacrylamide and N-methylolmethacrylamide.

The monomers A further include compounds which are at least two

nonconjugated ethylenically unsaturated groups such as vinyl, vinylidene or

Have alkenyl groups. Particularly advantageous are the diesters of dihydric alcohols with α, β-monoethylenically unsaturated monocarboxylic acids, among which acrylic and methacrylic acid are preferred. Examples of such two non-conjugated ethylenically unsaturated double bonds monomers are alkylene glycol diacrylates and dimethacrylates, such as ethylene glycol diacrylate, 1,2-propylene glycol diacrylate, 1,3-propylene glycol diacrylate, 1,3-butylene glycol diacrylate, 1,4-butylene glycol diacrylate and

Ethylene glycol dimethacrylate, 1, 2-propylene glycol dimethacrylate, 1, 3

Propylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, 1,4-butylene glycol dimethacrylate, tri-esters of trihydric alcohols with α, β-monoethylenically unsaturated monocarboxylic acids, such as glycerol triacrylate, glycerol trimethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, and divinylbenzene, vinyl methacrylate, vinyl acrylate,

Allyl methacrylate, allyl acrylate, diallyl maleate, diallyl fumarate, methylenebisacrylamide,

Cyclopentadienyl acrylate, triallyl cyanurate or triallyl isocyanurate. Particularly preferred are 1, 4-butylene glycol diacrylate, allyl methacrylate and / or divinylbenzene, wherein

Divinylbenzene in the context of this document 1, 2-divinylbenzene, 1, 3-divinylbenzene and / or 1, 4-divinylbenzene to be understood.

With particular advantage, the monomer A is selected from the group comprising N-methylolacrylamide, N-methylolmethacrylamide, glycidyl acrylate, glycidyl methacrylate, 1, 4-butylene glycol diacrylate, allyl methacrylate and / or divinylbenzene.

As monomers B can all differing from the monomers A ethylenically unsaturated compounds are used, wherein the monomers B, however, no ethylenically unsaturated C3 to C6 monocarboxylic and / or C ₄ - to C6-dicarboxylic acids and their salts and anhydrides or monoethylenically unsaturated Compounds having at least one silicon-containing group, a hydroxyalkyl group or a carbonyl group to include. The monomers B are selected in type and amount such that a polymer composed solely of these ethylenically unsaturated compounds in copolymerized form would have a glass transition temperature in the range> 0 and> 50 ° C.

Advantageously, the monomers B are selected from the group consisting of conjugated aliphatic C ₄ - to Cg-dienes, esters of vinyl alcohol and a C to C10 monocarboxylic acid, Cr to Cio-alkyl acrylates, Cr to Cio-alkyl methacrylates, ethylenically unsaturated C3 bis C6-Monocarbonsäurenitrile ethylenically unsaturated C ₄ - to C6 Dicarbonsäurenitrile, C5 to Cio-cycloalkyl acrylates and methacrylates, C to C 10 dialkyl maleates, and C to Cio-dialkyl fumarates and vinyl aromatic monomers.

In the context of this document, C 1 - to C 10 -alkyl groups are understood as meaning linear or branched alkyl radicals having 1 to 10 carbon atoms, for example methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert. Butyl, n-pentyl, iso-pentyl, tert-pentyl n-hexyl, 2-ethylhexyl, n-nonyl or n-decyl be understood. C ₅ - to C ₁₀ -cycloalkyl groups are preferably to be understood as meaning cyclopentyl or cyclohexyl groups

optionally substituted by 1, 2 or 3 C to C ₄ alkyl groups.

Examples of monomers B are, in particular, 1,3-butadiene, isoprene, vinyl acetate,

Vinyl propionate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, isobutyl acrylate, sec-butyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate, n-hexyl methacrylate, 2-ethylhexyl methacrylate,

Methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, n-butyl methacrylate, iso- Butyl methacrylate, sec-butyl methacrylate, n-hexyl methacrylate, 2-ethylhexyl methacrylate, di-n-butyl maleate, di-n-butyl fumarate, styrene, α-methylstyrene, o- or p-vinyltoluene, p-acetoxystyrene, p-bromostyrene, p tert-butylstyrene, o-, m- or p-chlorostyrene, acrylonitrile,

Methacrylonitrile, malononitrile and / or fumaronitrile.

The monomers B are advantageously selected from the group comprising 2-ethylhexyl acrylate, n-butyl acrylate, acrylonitrile, 1,4-butadiene, ethyl acrylate, vinyl acetate,

Methyl methacrylate, styrene and / or tert-butyl methacrylate.

It is essential that the monomers B are selected in type and amount such that one of these ethylenically unsaturated monomers in

copolymerized form polymer would have a glass transition temperature in the range ä 0 and -i 50 ° C and preferably> 5 and ^ 30 ° C.

With the glass transition temperature Tg, in the context of this document the limit value of the glass transition temperature is meant, to which these according to G. Kanig (colloid journal &

Journal of Polymers, Vol. 190, page 1, equation 1) tends to increase with increasing molecular weight. The Tg is determined in the context of this document by the DSC method

(Differential scanning calorimetry, 20 K / min, midpoint measurement, DIN 53 765). The Tg values for the homopolymers of most monomers are known and e.g. in Ullmann's Ecyclopedia of Industrial Chemistry, VCH Weinheim, 1992, Vol. 5, Vol. A21, p. 169; other sources of glass transition temperatures of homopolymers form e.g. J. Brandrup, E.H. Immergut, Polymer Handbook, I St Ed., J. Wiley, New York 1966, 2nd ed. J. Wiley, New York 1975, and 3rd Ed. J. Wiley, New York 1989).

It is essential, however, that the glass transition temperatures of non-crosslinked or only slightly crosslinked polymers according to Fox (TG Fox, Bull. Am. Phys. Soc. 1956 [Ser. II] 1, page 123 and Ullmann ^'s Encyclopadie der technischen Chemie, Vol , Page 18, 4th edition, Verlag Chemie, Weinheim, 1980) can be approximated by the following equation:

1 / Tg = x1 / Tg1 + x2 / Tg2 + .... xn / Tgn, where x1, x2, .... xn are the mass fractions of the monomers 1, 2, .... n and Tg1, Tg2, .. Tgn the glass transition temperatures of each of only one of the monomers 1, 2, .... n constructed polymers in degrees Kelvin.

It is important that the monomers B no ethylenically unsaturated C3 to C6 monocarboxylic and / or C ₄ - to comprise up to C6-dicarboxylic acids and their salts and anhydrides or monoethylenically unsaturated compounds having at least one silicon-containing group, a hydroxyalkyl group or a carbonyl , such

Compounds are disclosed, for example, in WO 2013/120752, page 5, lines 1 to 11, 18 to 28 and 36 to 39 and page 6, lines 24 to 34, inter alia. For clarification It should also be noted that in the context of the present invention, the monomers A are no silicon-containing groups, hydroxyalkyl groups or carbonyl groups and

Carboxyl, carboxylate or anhydride groups should have.

According to the invention, for the polymerization, 3.5 and -i 7 wt .-% of monomers A, and

> 93 and <96.5 wt .-% monomers B used.

However, with particular advantage, for the polymerization, 3.5% by weight and 5.5% by weight of N-methylolacrylamide, N-methylolmethacrylamide, glycidyl acrylate,

Glycidyl methacrylate, 1,4-butylene glycol diacrylate, allyl methacrylate and / or divinylbenzene, and

94.5 and 96.5% by weight of 2-ethylhexyl acrylate, n-butyl acrylate, acrylonitrile, 1,4-butadiene,

Ethyl acrylate, vinyl acetate, methyl methacrylate, styrene and / or tert.

Butyl methacrylate used.

In a particularly advantageous embodiment, the monomers A are mixtures of ethylenically unsaturated compounds which have at least one epoxy group, and compounds which have at least two non-conjugated ethylenically unsaturated groups or combinations of ethylenically unsaturated

Compounds which have at least one N-methylol group, and compounds which have at least two non-conjugated ethylenically unsaturated groups, such as glycidyl acrylate and / or glycidyl methacrylate in combination with 1, 4-butylene glycol diacrylate, allyl methacrylate and / or divinylbenzene, preferably

Glycidyl methacrylate in combination with 1,4-butylene glycol diacrylate or N-methylolacrylamide and / or N-methylolmethacrylamide in combination with 1,4-butylene glycol diacrylate,

Allyl methacrylate and / or divinylbenzene, preferably N-methylolacrylamide in combination with 1, 4-Butylenglykoldiacrylat used.

According to the invention, the total amount of monomers A and B

(Total monomer) in the aqueous reaction medium before initiation of

Polymerization reaction are submitted. However, it is also possible, if appropriate, to initially introduce only a partial amount of the monomers A and / or B in the aqueous reaction medium before the initiation of the polymerization reaction and then after initiation of the reaction

Polymerization under polymerization conditions during the free-radical

Emulsion polymerization the total amount or any remaining

Residual quantities according to the consumption continuously with constant or itself adding varying amounts of flow or discontinuously. The dosage of the monomers A and B as separate individual streams, as inhomogeneous or homogeneous

(Part) mixtures or carried out as a monomer emulsion. Advantageously, the monomers A and B in the form of a monomer mixture, in particular in the form of an aqueous

Monomer emulsion dosed.

It is important, however, that within the scope of the present document, the seed, step and gradient methods familiar to the person skilled in the art should also be included.

In the process according to the invention, it is advantageous to use dispersing aids which keep both the monomer droplets and the polymer particles formed dispersed in the aqueous medium and thus maintain the stability of the aqueous

Ensuring polymer dispersion. Suitable dispersing agents are both the protective colloids commonly used to carry out free-radical aqueous emulsion polymerizations and emulsifiers.

Suitable protective colloids are, for example, polyvinyl alcohols, polyalkylene glycols,

Alkali metal salts of polyacrylic acids and polymethacrylic acids, gelatin derivatives or acrylic acid, methacrylic acid, maleic anhydride, 2-acrylamido-2-methylpropanesulfonic acid and / or 4-styrenesulfonic acid-containing copolymers and their alkali metal salts but also N-vinylpyrrolidone, N-vinylcaprolactam, N-vinylcarbazole, 1-vinylimidazole, 2-vinylimidazole, 2-vinylpyridine, 4-vinylpyridine, acrylamide, methacrylamide,

amine-group-containing acrylates, methacrylates, acrylamides and / or methacrylamides containing homopolymers and copolymers. A detailed description of other suitable protective colloids can be found in Houben-Weyl, Methods of Organic Chemistry, Volume XIV / 1, Macromolecular substances, Georg-Thieme-Verlag, Stuttgart, 1961, pages 41 1 to 420.

Of course, mixtures of protective colloids and / or emulsifiers can be used. Frequently, dispersants used are exclusively emulsifiers whose relative molecular weights, in contrast to the protective colloids, are usually below 1000. They may be anionic, cationic or nonionic in nature. Of course, in the case of using

Mixtures of surface-active substances, the individual components to be compatible with each other, which can be checked in doubt by hand on fewer preliminary tests. in the

Generally, anionic emulsifiers are compatible with each other and with nonionic emulsifiers. The same applies to cationic emulsifiers, while anionic and cationic emulsifiers are usually incompatible with each other. An overview of suitable emulsifiers can be found in Houben-Weyl, Methods of Organic Chemistry, Volume XIV / 1, Macromolecular Materials, Georg-Thieme-Verlag, Stuttgart, 1961, pages 192 to 208.

However, emulsifiers are used in particular as dispersing aids. Common nonionic emulsifiers are, for example, ethoxylated mono-, di- and tri-alkylphenols (EO degree: 3 to 50, alkyl radical: C ₄ to C 12) and also ethoxylated fatty alcohols (EO degree: 3 to 80, alkyl radical: Cs to C36). Examples are the Lutensol ^® A grades (C12CM- fatty alcohol ethoxylates, EO units: 3 to 8), Lutensol ^® AO-marks (C13C15- oxo alcohol ethoxylates, EO units: 3 to 30), Lutensol ^® AT-marks (CieCis- fatty alcohol ethoxylates, EO units: 1 1 to 80), Lutensol ^® ON brands (C10 oxo alcohol ethoxylates, EO units: 3 to 1: 1) and the Lutensol ^® tO brands (C13 oxo alcohol ethoxylates, EO units: 3 to 20 ) from BASF SE.

Typical anionic emulsifiers are e.g. Alkali metal and ammonium salts of

Alkyl sulfates (alkyl radical: Cs to C12), ethoxylated of sulfuric acid monoesters of alkanols (EO degree: from 4 to 30, alkyl radical: C12 to C ₈₎ and ethoxylated alkylphenols (EO units: 3 to 50, alkyl radical: _C4 to C12), of Alkylsulfonic acids (alkyl radical: C12 to Cie) and of

Alkylarylsulfonic acids (alkyl radical: C9 to Cis).

Other anionic emulsifiers further compounds of the general formula

wherein R ¹ and R ² hydrogen atoms or C ₄ - to C2 to ₄ alkyl and simultaneously hydrogen atoms are not, and M ¹ and M ² alkali metal ions and / or ammonium ions have been found to be suitable. In the general formula (I), R ¹ and R ^{2 are} preferably linear or branched alkyl radicals having 6 to 18 C atoms, in particular having 6, 12 and 16 C atoms or hydrogen, where R ¹ and R ^{2 are} not both simultaneously H and Atoms are. M ¹ and M ² are preferably sodium, potassium or ammonium, with sodium being particularly preferred.

Particularly advantageous compounds (I) are those in which M ¹ and M ^{2 are} sodium, R ^{1 is} a branched alkyl radical having 12 C atoms and R ^{2 is} an H atom or R ¹ . Often, technical

Mixtures used which have a proportion of 50 to 90 wt .-% of the monoalkylated product, such as Dowfax ^® 2A1 (trademark of Dow Chemical Company). The compounds (I) are well known, for example from US-A 4269749, and commercially available.

Suitable cationic emulsifiers are generally a primary, secondary, tertiary or quaternary C6- to Cis-alkyl, -alkylaryl or heterocyclic radical

Ammonium salts, alkanolammonium salts, pyridinium salts, imidazolinium salts,

Oxazolinium salts, morpholinium salts, thiazolinium salts and salts of amine oxides, quinolinium salts, isoquinolinium salts, tropylium salts, sulfonium salts and Phosphonium. Examples include dodecylammonium acetate or the corresponding sulfate, the sulfates or acetates of the various 2- (N, N, N-trimethylammonium) ethylparaffinsäureester, N-Cetylpyridiniumsulfat, N-Laurylpyridiniumsulfat and N-cetyl-N, N, N-trimethylammonium sulfate, N- Dodecyl-N, N, N-trimethylammonium sulfate, N-octyl-N, N, N-trimethylammonium sulfate, N, N-distearyl-N, N-dimethylammonium sulfate and the gemini surfactant Ν, Ν'-

(Lauryl) ethylendiamindisulfat, ethoxylated tallow alkyl-N-methyl ammonium sulfate and ethoxylated oleylamine (for example Uniperol.RTM ^® AC from. BASF SE, about 1 1

Ethylene oxide). Numerous other examples can be found in H. Stäche, Tensid-Taschenbuch, Carl-Hanser-Verlag, Munich, Vienna, 1981, and in McCutcheon's, Emulsifiers & Detergents, MC Publishing Company, Glen Rock, 1989. It is favorable if the anionic counterparts are as possible are low nucleophilic, such as perchlorate, sulfate, phosphate, nitrate and carboxylates, such as acetate, trifluoroacetate, trichloroacetate, propionate, oxalate, citrate, benzoate, as well as conjugated anions of organosulfonic acids, such as methylsulfonate, trifluoromethylsulfonate and para-toluenesulfonate Tetrafluoroborate, tetraphenylborate, tetrakis (pentafluorophenyl) borate, tetrakis [bis (3,5-trifluoromethyl) phenyl] borate, hexafluorophosphate, hexafluoroarsenate or

Hexafluoroantimonate.

The emulsifiers preferably used as dispersants are advantageously in a total amount ä 0,005 and ^ 10 wt .-%, preferably 0.01 and ^ 5 wt .-%, in particular 0.1 and 3 wt .-%, each based on the total amount of monomers used.

The total amount of the protective colloids used as dispersing aids in addition to or instead of the emulsifiers is often> 0.1 and 40% by weight and frequently equal to 0.2 and 25% by weight, in each case based on the total amount of monomers.

According to the invention, however, preference is given to using anionic and / or nonionic emulsifiers and, with particular preference, anionic emulsifiers as sole dispersing aids.

According to the invention, the total amount of the dispersing aids in the aqueous

Reaction medium before initiation of the polymerization reaction are presented. However, it is also possible, if appropriate, to initially introduce only a subset of the dispersing aids in the aqueous reaction medium before initiation of the polymerization reaction and then to add continuously or discontinuously under polymerization conditions during the free-radical emulsion polymerization the total amount or any residual amount of the dispersing aids remaining. Preferably, the addition of the main (ie> 50 wt .-%) or the total amount of the dispersants in the form of an aqueous monomer emulsion. The release of the free-radically initiated aqueous emulsion polymerization takes place by means of a free-radical polymerization initiator (free-radical initiator). In principle, these can be both peroxides and azo compounds. Of course, redox initiator systems come into consideration. As peroxides may in principle inorganic peroxides, such as hydrogen peroxide or peroxodisulfates, such as the mono- or di-Alkalimetalloder or ammonium salts of peroxodisulfuric, such as their mono- and di- sodium, potassium or ammonium salts or organic peroxides such as alkyl hydroperoxides, for example, tert. Butyl, p-menthyl or cumyl hydroperoxide, as well as dialkyl or

Diarylperoxide, such as di-tert-butyl or di-cumyl peroxide can be used. When

Azo compounds used are essentially ^2,2-azobis (isobutyronitrile), ^2,2'-azobis (2,4-dimethylvaleronitrile), and ^2,2'-azobis (amidinopropyl) dihydrochloride (AIBA, corresponding to V-50 from Wako Chemicals) , Suitable oxidizing agents for redox initiator systems are essentially the abovementioned peroxides. Suitable reducing agents may be sulfur compounds having a low oxidation state, such as alkali metal sulfites, for example potassium and / or sodium sulfite, alkali hydrogen sulfites, for example potassium and / or sodium hydrogen sulfite, alkali metal bisulfites, for example potassium and / or

Natriummetabisulfit, Formaldehydsulfoxylate, for example, potassium and / or

Sodium formaldehyde sulfoxylate, alkali salts, especially potassium and / or sodium salts, aliphatic sulfinic acids and alkali metal hydrosulfides, such as potassium and / or sodium hydrosulfide, salts of polyvalent metals, such as iron (II) sulfate, iron (II) ammonium sulfate, iron (II ) phosphate, endiols, such as dihydroxymaleic acid, benzoin and / or ascorbic acid, and reducing saccharides, such as sorbose, glucose, fructose and / or dihydroxyacetone. In general, the amount of the radical initiator used, based on the total amount of monomers, 0.01 to 5 wt .-%, preferably 0.1 to 3 wt .-% and particularly preferably 0.2 to 1, 5 wt .-%.

In the process according to the invention, the total amount of the radical initiator in the aqueous reaction medium can be initially introduced before the initiation of the polymerization reaction. However, it is also possible, if appropriate, to initially introduce only a partial amount of the free-radical initiator in the aqueous reaction medium before initiation of the polymerization reaction and then under polymerization conditions during the free-radical emulsion polymerization, the total amount or the remaining amount remaining in accordance with the

Consumption continuously or discontinuously.

Initiation of the polymerization reaction is understood to mean the start of the polymerization reaction of the monomers present in the polymerization vessel after radical formation of the radical initiator. In this case, the initiation of the polymerization reaction by adding radical initiator to the aqueous polymerization mixture in the polymerization vessel can be carried out under polymerization conditions. However, it is also possible that a partial or total amount of the free radical initiator is added to the aqueous polymerization mixture containing the monomers present in the polymerization vessel under conditions which are not suitable for triggering a polymerization reaction, for example at low temperature, and then in the aqueous polymerization mixture Polymerization conditions are set. Under polymerization conditions are generally those temperatures and pressures to understand under which the free-radically initiated aqueous emulsion polymerization with sufficient

Polymerization proceeds. They are dependent, in particular, on the radical initiator used. The type and amount of the radical initiator, which are advantageous

Polymerization temperature and the polymerization pressure selected so that the

Radical initiator has a half life <3 hours, more preferably <1 hour and most preferably <30 minutes and there are always enough starting radicals are available to initiate and maintain the polymerization reaction.

The reaction temperature for the free-radical aqueous emulsion polymerization is the entire range from 0 to 170 ° C into consideration. In this case, temperatures of 50 to 120 ° C, preferably 60 to 1 10 ° C and particularly preferably 70 to 100 ° C are applied in the rule. The free-radical aqueous emulsion polymerization may be carried out at a pressure less than or equal to 1 atm [1.013 bar (absolute), atmospheric pressure] such that the polymerization temperature may exceed 100 ° C and may be up to 170 ° C. In the presence of monomers A to F having a low boiling point, the emulsion polymerization is preferably carried out under elevated pressure. The pressure may be 1, 2, 1, 5, 2, 5, 10, 15 bar (absolute) or even higher values. If the emulsion polymerization is carried out under reduced pressure, pressures of 950 mbar, often 900 mbar and often 850 mbar (absolute) are set. The free-radical aqueous emulsion polymerization is advantageously carried out at 1 atm with exclusion of oxygen, in particular under an inert gas atmosphere, for example under nitrogen or argon.

According to the invention, the aqueous reaction medium can in principle also in minor amounts (<5 wt .-%) of water-soluble organic solvents, such as

Methanol, ethanol, isopropanol, butanols, pentanols, but also acetone, etc. include. However, the inventive method is preferred in the absence of such

Solvent carried out.

In addition to the abovementioned components, it is also possible during the emulsion polymerization to optionally use free-radical chain transfer compounds in order to obtain the

To reduce or control the molecular weight of the accessible by the polymerization emulsion polymers. These are essentially aliphatic and / or araliphatic halogen compounds, such as, for example, n-butyl chloride, n-butyl bromide, n-butyl iodide, methylene chloride, ethylene dichloride, chloroform, bromoform, bromotrichloromethane, dibromodichloromethane, carbon tetrachloride, carbon tetrabromide, benzyl chloride,

Benzylbromid, organic thio compounds, such as primary, secondary or tertiary aliphatic thiols, such as ethanethiol, n-propanethiol, 2-propanethiol, n-butanethiol,

2- butanethiol, 2-methyl-2-propanethiol, n-pentanethiol, 2-pentanethiol, 3-pentanethiol, 2-methyl-2-butanethiol, 3-methyl-2-butanethiol, n-hexanethiol, 2-hexanethiol, 3 Hexanethiol, 2-methyl-2-pentanethiol, 3-methyl-2-pentanethiol, 4-methyl-2-pentanethiol, 2-methyl-3-pentanethiol, 3-methyl

3-pentanethiol, 2-ethylbutanethiol, 2-ethyl-2-butanethiol, n-heptanethiol and its isomers Compounds, n-octanethiol and its isomeric compounds, n-nonanethiol and its isomeric compounds, n-decanethiol and its isomeric compounds, n-undecanethiol and its isomeric compounds, n-dodecanethiol and its isomeric compounds, n-tridecanethiol and its isomeric compounds, substituted thiols, such as, for example, 2-hydroxyethanethiol, aromatic thiols, such as benzenethiol, ortho-, meta-, or para-methylbenzenethiol, and all others in Polymer Handbook 3rd Edtition, 1989, J. Brandrup and EH Immergut, John Wiley & Sons, Section II , Pages 133 to 141 described sulfur compounds, but also aliphatic and / or aromatic aldehydes, such as

Acetaldeyhd, propionaldehyde and / or benzaldehyde, unsaturated fatty acids such as oleic acid, dienes with non-conjugated double bonds, such as divinylmethane or vinylcyclohexane or hydrocarbons with easily abstractable hydrogen atoms, such as toluene, are used. However, it is also possible to use mixtures of non-interfering radical-chain-transferring compounds mentioned above.

The total amount of radical-chain-transferring compounds optionally used during the emulsion polymerization, based on the total amount of monomers, is generally <5% by weight, often <3% by weight and frequently <1% by weight.

It is advantageous if a partial or total amount of optionally used

radical chain transferring compound is added to the aqueous reaction medium prior to the initiation of free radical polymerization. In addition, a partial or total amount of the radical chain transferring compound may be aqueous

Reaction medium advantageously also be supplied together with the monomers A and B during the polymerization.

It is essential that the free-radically initiated aqueous emulsion polymerization also in the presence of a polymer seed, for example in the presence of 0.01 to 3 wt .-%, often from 0.02 to 2 wt .-% and often from 0.04 to 1, 5 % By weight of a polymer seed, in each case based on the total monomer amount, can be carried out.

A polymer seed is used in particular when the particle size of the polymer particles to be produced by means of a free-radically aqueous emulsion polymerization is to be specifically adjusted (see, for example, US Pat. No. 2,520,959 and US Pat. No. 3,397,165).

In particular, a polymer seed is used whose polymer seed particles have a narrow particle size distribution and weight-average diameters Dw <100 nm, often> 5 nm to -50 nm and often> 15 nm to> 35 nm. The determination of the weight-average particle diameter is known to the person skilled in the art and is carried out, for example, via

Method of Analytical Ultracentrifuge. Weight-average particle diameter in this document is understood to mean the weight-average Dw50 value determined by the method of the analytical ultracentrifuge (cf., in this regard, S. E. Harding et al., Analytical

Ultracentrifugation in Biochemistry and Polymer Science, Royal Society of Chemistry, Cambridge, Great Britain 1992, Chapter 10, Analysis of Polymer Dispersions with an Eight Cell AUC Multiplexers: High Resolution Particle Size Distribution and Density Gradient Techniques, W. Mächtie, pages 147-175).

Within the scope of this document, a narrow particle size distribution is to be understood as meaning the ratio of the weight-average particle diameter Dw50 and the number-average particle diameter DN50 [Dw50 / DN50] <2.0, preferably <1.5, and particularly preferably <1, determined by the method of the analytical ultracentrifuge. 2 or <1, 1.

Usually, the polymer seed is used in the form of an aqueous polymer dispersion. The aforementioned quantities are based on the

Polymerisate solids content of the aqueous polymer seed dispersion.

If a polymer seed is used, it is advantageous to use a foreign polymer seed. In contrast to a so-called in situ polymer seed, which is prepared before the actual emulsion polymerization in the reaction vessel and which generally has the same monomeric composition as the polymer prepared by the subsequent free-radically initiated aqueous emulsion polymerization, a polymer seed is understood to mean a polymer seed, which has been prepared in a separate reaction step and whose monomeric composition is different from the polymer prepared by the free-radically initiated aqueous emulsion polymerization, but this means nothing other than that for the preparation of Fremdpolymersaat and for preparing the aqueous polymer dispersion different monomers or

Monomer mixtures are used with different compositions. The preparation of a foreign polymer seed is familiar to the person skilled in the art and is usually carried out by initially charging a relatively small amount of monomers and a relatively large amount of emulsifiers in a reaction vessel and adding a sufficient amount of polymerization initiator at reaction temperature.

According to the invention, preference is given to polymer foreign seed with a

Glass transition temperature> 50 ° C, often> 60 ° C or> 70 ° C and often> 80 ° C or> 90 ° C used. Particularly preferred is a polystyrene or a

Polymethylmethacrylatpolymersaat.

The total amount of foreign polymer seed can be presented in the polymerization vessel. But it is also possible, only a subset of Fremdpolymersaat in

Prepare polymerization and the remaining amount during the

Add polymerization together with the monomers A and B. If necessary, however, it is also possible to add the total amount of polymer seed in the course of the polymerization. Preferably, the total amount of foreign polymer seed prior to initiation of the

Polymerization reaction submitted in the polymerization.

The aqueous polymer P dispersions obtainable by the process according to the invention usually have a polymer P solid content of> 10 and> 70 Wt .-%, often ä 20 and 65 wt .-% and often> 25 and 60 wt .-%, each based on the aqueous polymer dispersion P on. The number-average particle diameter (cumulant z-average) determined by quasi-elastic light scattering (ISO Standard 13 321) is generally in the range> 10 and> 1000 nm, frequently in the range> 10 and> 700 nm and often in the range> 50 to < 250 nm.

It is essential to the process that the free-radically initiated aqueous emulsion polymerization of the monomers A and B in the presence of> 25 and> 120% by weight of at least one

Lignin compound L, based on the total amount of monomers, takes place.

By lignins, the skilled person understands a group of phenolic macromolecules, which are composed of various monomer building blocks, such as in particular p-cumaryl alcohol, coniferyl alcohol and sinapyl alcohol, which are interconnected substantially via ether groups. The lignins are solid biopolymers, which are incorporated into the cell walls of plants and thereby cause the lignification of a cell, the so-called lignification. Because lignin in nature over a

enzymatic radical reaction takes place, the composition and proportions of the individual building blocks are highly variable and a directed linkage according to a consistently same scheme does not exist. It is also important that the lignin

different wood or plant species by the percentage of the aforementioned main components. Thus, the lignin contains mainly of softwood

Coniferyl units which have a guaiacyl radical (3-methoxy-4-hydroxyphenyl radical). In contrast, the lignin from hardwood contains varying proportions of guaiacyl and Sinapyleinheiten containing a syringyl (3,5-methoxy-4-hydroxyphenyl).

In paper and pulp production, the interfering lignin must be released from the lignocellulose and removed from the paper and pulp production process. The degradation and separation of lignin from the lignocellulose is essentially by two methods, namely the sulfate process, also called Kraft process and the

Sulfite. The degradation and separation of the lignin takes place after the

Sulfate process at elevated temperature (about 170 ° C) by reacting the lignocellulose (in wood or other cellulosic plants) with alkali metal sulfides in strong

alkaline medium, in particular sodium sulfide and sodium hydroxide are used. After separation of the cellulose, the spent liquor from the sulfate process in their

Solid substance when using conifers about 45 wt .-% and when using deciduous wood about 38 wt .-% of so-called kraft lignin on. In the sulphite process, the degradation and separation of the lignin is carried out by reacting the lignocellulose with sulfurous acid and subsequent neutralization with a base, wherein as a chemically not exactly defined reaction product, so-called lignosulfonates are formed. After separation of the cellulose, the spent liquor from the sulfite process in their

Solid substance when using conifers about 55 wt .-% and when using deciduous wood about 42 wt .-% of lignosulfonate on. As lignin compounds L according to the invention, it is possible to use all lignin compounds, lignin reaction products and / or lignin degradation products which have a solubility of> 10 g, preferably> 50 g and more preferably> 100 g per 100 g at 20 ° C. and 1 atm (1, 013 bar absolute) have deionized water. According to the invention, however, such embodiments are also included, whose lignin compound L has a solubility <10 g per 100 g of deionized water at 20 ° C and 1 atm. Depending on the amount of these lignin compounds used L, they may then be present in the form of their aqueous suspension. If, according to the invention, lignin compounds L are used in the manner and amount such that they are present in aqueous suspension, it is advantageous if the particles of lignin compound L suspended in an aqueous medium have a medium molecular weight

Particle diameter <5 μηη, preferably <3 μηη and particularly preferably <1 μηη have. The average particle diameter is determined as in the case of the aqueous polymer P dispersions by the method of quasi-elastic light scattering (ISO standard 13 321). However, particular preference is given to using lignin compounds L which have a solubility of> 10 g per 100 g of deionized water at 20 ° C. and 1 atm.

Power lignins and lignin sulfonates are advantageously used according to the invention, with linosulfonates being particularly preferred. Although all salts of lignin sulfonic acid can be used in the invention, calcium lignin sulfonate (CAS No. 8061-52-7), sodium lignin sulfonate (CAS No. 8061-51-6), magnesium lignin sulfonate (CAS No. 8061 -54-9) and / or ammonium lignosulfonate (CAS No. 8061-53-8) are preferably used. Particularly preferred are sodium and calcium lignosulfonate, with calcium lignin sulfonate being particularly preferred. These compounds may, for example, commercially available under the names Borre Movement ^® CA 120, Borresperse ^® NA 200 or

Borresperse ^® NA 220 of Borregaard Germany GmbH or StarLig ^® Na 2420 the company LignoStar Germany GmbH are obtained. Or Sartax ^® product lines, in particular Bretax ^® CL, the Burgo Group, Italy, available on the market - Furthermore corresponding products such as the Bretax ^® are. Lignosulfonates are advantageously used, which were obtained from so-called softwood. Softwoods are understood as meaning woods which have a density of earth <0.55 g / cm ³ (density of wood at 0% moisture content of wood [DIN 52183]), in particular the woods of fast-growing willows, poplars, lime trees and conifer woods , as

especially pines, firs, Douglas firs, larches and spruces. With particular advantage lignosulfonates are used, which were obtained from softwoods.

It is essential to the invention that the total amount of lignin compound L can be added to the aqueous polymerization medium before and / or during the emulsion polymerization of monomers A and B. Advantageously, at least a subset of

Lignin compound L presented before the initiation of the aqueous emulsion polymerization in the aqueous polymerization and the remaining amount optionally added during the initiation of the emulsion, often together with the monomers A and B, added. In a preferred embodiment according to the invention, the total amount the lignin compound L in the aqueous polymerization medium before initiation of the

Submitted polymerization.

In a further embodiment, the total amount of the invention

Lignin compound L and ^ 10 wt .-% of the monomers A and B prior to the initiation of

Polymerization reaction in the aqueous polymerization medium submitted.

According to the invention, the amount of lignin compound L> 25 and ^ 120 wt .-%, preferably> 30 and ^ 80 wt .-% and particularly advantageously> 35 and ^ 75 wt .-%, each based on the total monomer.

It is important that, according to the invention, the aqueous polymer should also comprise P dispersions which are obtainable by the process according to the invention.

It is also important that according to the invention the use of the

aqueous dispersion of the invention P-dispersions are to be included as a binder for granular and / or fibrous substrates. In this context of

It is also important that according to the invention aqueous binder compositions should be included which contains as essential component an aqueous polymer P dispersion which is obtainable by the process according to the invention.

It is essential that the aqueous binder composition according to the invention, in addition to the aqueous polymer P dispersion and the lignin compound L, additionally contain other components known to the person skilled in the art, such as, for example, thickeners, pigment distributors, dispersants, emulsifiers, buffer substances, neutralizing agents, biocides, antifoams, Polyol compounds having at least 2 hydroxy groups and having a molecular weight <200 g / mol, film-forming agents, organic solvents, pigments or fillers, etc. may contain.

However, the aqueous binder composition advantageously contains <1% by weight, in particular advantageously <0.5% by weight, of a polyol compound having at least 2

Hydroxyl groups and having a molecular weight <200 g / mol, in particular ^ 150 g / mol, such as ethylene glycol, 1, 2-propanediol, 1, 3-propanediol, 1, 2,3-propanetriol, 1, 2-butanediol, 1, 4-butanediol, 1, 2,3,4-butanetetrol, diethanolamine, triethanolamine, etc., based on the sum of the total amounts of polymer P and lignin compound L.

Also of importance is that the present aqueous binder composition may contain defatted soy flour having a mesh size of <43 μm in amounts, however, that are at least 20% by weight below the amounts described in EP-A 2199320, Section [0035 ] are disclosed. However, the binder composition according to the invention does not contain any such defatted soybean flour with particular advantage.

The novel aqueous polymer P dispersions and a

Binder composition comprising an aqueous polymer P dispersion as contain essential component, are advantageously suitable for use as a binder for granular and / or fibrous substrates. The abovementioned aqueous polymer P dispersions and the binder compositions containing them can therefore advantageously be used in the production of moldings from granular and / or fibrous substrates. Furthermore, the abovementioned aqueous polymerizate P dispersions and the binder compositions containing them are suitable as binders in non-cementitious coatings, such as flexible roof coatings, for example.

Moisture-proof coatings or fillers, sealants, such as

Sealants and adhesives, such as assembly adhesives, tile adhesives, contact adhesives or flooring adhesives.

Granular and / or fibrous substrates are familiar to the person skilled in the art. For example, these are wood chips, wood fibers, cellulose fibers, textile fibers,

Plastic fibers, glass fibers, mineral fibers or natural fibers such as jute, flax, hemp or sisal, but also cork chips or sand and other organic or inorganic natural and / or synthetic granular and / or fibrous compounds whose longest extent in the case of granular substrates <10 mm, preferably <5 mm and

in particular ^ 2 mm. Of course, the term substrate should also include the fiber webs available from fibers, such as so-called mechanically bonded, for example needled or chemically pre-bonded fiber webs with.

The aqueous binder composition according to the invention is particularly advantageously suitable as a formaldehyde-free or formaldehyde-reduced binder system for the abovementioned fibers and mechanically bonded or chemically pre-bonded fiber webs.

The process for producing a shaped body from granular and / or fibrous substrates is carried out such that an aqueous binder composition comprising, as the essential component, an aqueous polymer P dispersion is applied to the granular and / or fibrous substrate (so-called impregnation),

optionally, the thus treated granular and / or fibrous substrate is brought into shape and then the granular and / or fibrous substrate thus obtained is subjected to a thermal treatment step at a temperature> 1 10 ° C.

Impregnation of the granular and / or fibrous substrate is typically accomplished such that the aqueous binder composition is uniformly applied to the surface of the fibrous and / or granular substrate. The amount of aqueous binder composition is chosen so that per 100 g of granular and / or fibrous substrate> 1 g and ^ 100 g, preferably> 2 g and ^ 50 g and particularly preferably> 5 g and ^ 30 g of binder (calculated as Sum of

Total amounts of polymer P and lignin compound L on a solid basis). The impregnation of the granular and / or fibrous substrate is the

Skilled in the art and takes place, for example, by impregnation or by spraying the granular and / or fibrous substrate with the aqueous binder composition. After impregnation, the granular and / or fibrous substrate is optionally brought into the desired shape, for example by introduction into a heatable press or mold. Thereafter, the shaped impregnated granular and / or fibrous substrate is dried and cured in a manner known to those skilled in the art.

Frequently, the drying or curing of the optionally shaped impregnated granular and / or fibrous substrate takes place in two temperature stages, wherein the drying stage at a temperature <100 ° C, preferably> 20 ° C and ^ 90 ° C and particularly preferably> 40 and ^ 80 ° C and the curing step at a temperature> 1 10 ° C, preferably> 130 and <150 ° C and particularly preferably> 180 ° C and <220 ° C.

Of course, it is also possible that the drying step and the

Curing step of the moldings in one step, for example in a

Molding press done.

The moldings obtainable by the process according to the invention have advantageous properties, in particular an improved dimensional stability, an improved force modulus and a reduced elongation at elevated temperature in comparison with the moldings of the prior art. Accordingly, according to the invention, the moldings obtainable by the aforementioned process are also included.

Particularly advantageous is the inventive aqueous

Binder composition therefore for the production of fiber webs on polyester and / or glass fiber base, which in turn for the production of

use bitumen roofing membranes.

The production of bitumen roofing membranes is familiar to the person skilled in the art and takes place in particular by applying liquefied, optionally modified bitumen to one or both sides of a polyester and / or glass fiber fleece bound with a binder composition according to the invention. Accordingly, according to the invention also includes the aforementioned bituminous roofing membranes.

The invention will be illustrated by the following non-limiting examples. Examples

Polymer dispersion D1

In a 2 l polymerization vessel equipped with a stirrer, a reflux condenser and metering devices, to 366.9 g of a 47.7 wt .- put under a nitrogen atmosphere% aqueous calcium Ligninsulfonatlösung (Bretax ^® CL, product of Burgo Group), 73.7 g of deionized water and 8.3 g of a 15 wt .-% solution of a

Fatty alcohol sulfate (Disponil ^® SDS 15; manufactured by BASF SE.) In front. The master mixture was heated with stirring to 70 ° C, then the same

Monomerzulauf, the N-methylolacrylamide feed and the Initiatorenzuläufe started and dosed over 120 minutes, each with constant flow rates while maintaining the temperature. The monomer feed consisted of 120.0 g styrene, 1 17.5 g n-butyl acrylate and 2.5 g 1, 4-butylene glycol diacrylate. The N-methylol acrylamide feed consisted of 28.6 grams of a 35 wt% aqueous solution of N-methylolacrylamide and 9.4 grams of deionized water. The first initiator feed consisted of 75.0 g of 10 wt% - aqueous tert-butyl hydroperoxide solution and the second initiator feed of 57.0 g of a 10 wt .-% aqueous solution of sodium hydroxymethylsulfinate (Rongalite ^® C. Product of BASF SE). After completion of the feeds, the polymerization mixture was stirred for a further hour at 70.degree. Thereafter, 25.0 g of a 10 wt .-% - aqueous tert-butyl hydroperoxide solution were added within 30 minutes with a constant flow rate and then the polymerization mixture for 90 minutes at 70 ° C stirred.

Subsequently, the obtained aqueous polymer dispersion was cooled to 20 to 25 ° C (room temperature).

The polymer dispersion D1 prepared in this way had a solids content of 47.8% by weight and an LT value of 78%. A bimodal particle size distribution was measured, each with a maximum at 85 and 300 nm.

The solids contents were generally determined by adding a defined amount of the respective aqueous polymer dispersion (about 5 g) at 140 ° C in a drying oven to the

Constant weight was dried. Two separate measurements were carried out in each case. The value given in each case represents the mean value of these two measurements.

A measure of the particle size of the dispersed polymer particles is the LD value. To determine the LD value (light transmittance), the particular polymer dispersion to be examined was measured in 0.1% strength by weight aqueous dilution in a cuvette with an edge length of 2.5 cm with light of wavelength 600 nm and with the corresponding permeability of deionized water under the same

Measurement conditions compared. The permeability of deionized water was assumed to be 100%. The finer the dispersion, the higher the LD value measured by the method described above. The average particle size can be calculated from the measured values, cf. B. Verner, M. Bärta, B. Sedläcek, Tables of Scattering Functions for Spherical Particles, Prague, 1976, Edice Marco, Rada D-DATA, SVAZEK D-1.

The number average particle diameters of the polymer particles were generally determined by dynamic light scattering on a 0.005 to 0.01 weight percent aqueous solution

Polymerisatdispersion at 23 ° C by means of an autosizer NC from Malvern Instruments, England, determined. The average diameter of the cumulant analysis (cumulant z average) of the measured autocorrelation function is given (ISO standard 13321).

Polymer dispersion D2

The preparation of the polymer dispersion D2 was carried out completely analogously to the preparation of the polymer dispersion D1 with the difference that 314.5 g instead of 366.9 g of 47.7 wt .-% aqueous calcium lignosulfonate solution and 101, 1 g instead of 73, 7 g of deionized water were used.

The polymer dispersion D1 prepared in this way had a solids content of 48.1% by weight and an LT value of 74%. A bimodal particle size distribution was measured, each with a maximum at 250 and 935 nm.

Polymer dispersion D3

The preparation of the polymer dispersion D3 was completely analogous to the preparation of the polymer dispersion D1 with the difference that 209.6 g instead of 366.9 g of the 47.7 wt .-% aqueous calcium lignosulfonate solution and 156.0 g instead of 73, 7 g of deionized water were used.

The polymer dispersion D1 prepared in this way had a solids content of 48.4% by weight and an LT value of 63%. A bimodal particle size distribution was measured, each with a maximum at 1 10 and 360 nm.

Polymer dispersion D4

In a 1, 5 I-polymerization vessel equipped with a stirrer, a reflux condenser and metering devices, to 293.5 g of a 47.7 wt .- put under a nitrogen atmosphere% aqueous calcium Ligninsulfonatlösung (Bretax ^® CL, product of Burgo Group), 36.8 g of deionized water and 6.7 g of a 15 wt .-% solution of a

Fatty alcohol sulfate (Disponil ^® SDS 15) in front. The master mixture was heated with stirring to 70 ° C, then the monomer inlet and the Initiatorenzuläufe were simultaneously started and over 120 minutes, each with constant flow rates under

Maintaining the temperature metered. The monomer feed consisted of 96.0 grams of styrene, 96.0 grams of n-butyl acrylate, 6.0 grams of glycidyl methacrylate and 2.0 grams of 1,4-butylene glycol diacrylate. The first Initiatorzulauf consisted of 60.0 g of a 10 wt .-% aqueous tert-butyl hydroperoxide solution and the second initiator feed from 45.6 g of a 10 wt .-% aqueous solution of sodium hydroxymethylsulfinate (Rongalit ^® C). After completion of the feeds, 38.3 g of deionized water were added to the polymerization mixture and then the polymerization mixture was stirred for a further hour at 70.degree. Thereafter, 20.0 g of a 10 wt .-% - aqueous tert-butyl hydroperoxide solution were added within 30 minutes with a constant flow rate. Subsequently, 10.3 g of deionized water were added again and then the polymerization still 90 Stirred for minutes at 70 ° C. Subsequently, the resulting aqueous polymer dispersion was cooled to room temperature.

The polymer dispersion D4 prepared in this way had a solids content of 49.2% by weight and an LT value of 78%. A bimodal particle size distribution was measured, each with a maximum at 105 and 240 nm.

Polymer dispersion D5

The polymer dispersion D5 was prepared completely analogously to the preparation of the polymer dispersion D4 with the difference that 251.6 g instead of 293.5 g of the 47.7% strength by weight aqueous calcium lignosulfonate solution and 58.7 g instead of 36, 8 g of deionized water were used.

The polymer dispersion D5 prepared in this way had a solids content of 49.7% by weight and an LT value of 72%. The number average particle diameter was determined to be 265 nm.

Polymer dispersion D6

The polymer dispersion D6 was prepared completely analogously to the preparation of the polymer dispersion D4, with the difference that 167.7 g instead of 293.5 g of the 47.7% by weight aqueous calcium lignosulfonate solution and 102.6 g instead of 36, 8 g of deionized water were used.

The polymer dispersion D6 prepared in this way had a solids content of 49.1% by weight and an LT value of 55%. A bimodal particle size distribution was measured, each with a maximum at 85 and 340 nm.

Polymer dispersion D7

The preparation of the polymer dispersion D7 was carried out completely analogously to the preparation of the polymer dispersion D1 with the difference that the monomer feed of 120.0 g of styrene and 1 17.5 g of n-butyl acrylate and the N-methylolacrylamide feed from 35.7 g of a 35 wt % aqueous solution of N-methylolacrylamide and 9.4 g of deionized water.

The polymer dispersion D6 prepared in this way had a solids content of 48.0% by weight and an LT value of 76%. A bimodal particle size distribution was measured, each with a maximum at 95 and 235 nm.

Polymer dispersion D8 The polymer dispersion D8 was prepared completely analogously to the preparation of the polymer dispersion D4 with the difference that the monomer feed consisted of 96.0 g of styrene, 96.0 g of n-butyl acrylate and 8.0 g of glycidyl methacrylate.

The polymer dispersion D8 prepared in this way had a solids content of 49.0% by weight and an LT value of 75%. A bimodal particle size distribution was measured, each with a maximum at 90 and 300 nm.

Polymer dispersion D9

The polymer dispersion D9 was prepared completely analogously to the preparation of the polymer dispersion D4 with the difference that the monomer feed consisted of 97.0 g of styrene, 97.0 g of n-butyl acrylate and 6.0 g of 1,4-butylene glycol diacrylate.

The polymer dispersion D9 prepared in this way had a solids content of 48.9% by weight and an LT value of 77%. A bimodal particle size distribution was measured, each with a maximum at 100 and 245 nm.

Comparative dispersion V1

The preparation of the comparative dispersion V1 was carried out completely analogously to the preparation of the polymer dispersion D1 with the difference that 4.5 g of an aqueous

Polystyrene seed latex (solids content 33% by weight, with a weight average

Particle diameter of 28 nm) and 444.4 g of a 2.0% by weight solution of a

Fatty alcohol sulfate (Disponil ^® SDS 15) were used as a template.

The dispersion polymer coagulated about 30 minutes after the addition of 25.0 g of a 10 wt .-% - aqueous tert-butyl hydroperoxide solution.

Comparative dispersion V2

The preparation of the comparative dispersion V2 was carried out completely analogously to the preparation of the polymer dispersion D4 with the difference that 3.6 g of an aqueous

Polystyrene seed latex (solids content 33% by weight, with a weight average

Particle diameter of 28 nm) and 333.4 g of a 2.0 wt .-% solution of a

Fatty alcohol sulfates (Disponil ^® SDS 15) were used as a template.

The lignosulfonate-free comparative dispersion V2 prepared in this way had a solids content of 30.4% by weight and an LT value of 63%. The number average particle diameter was determined to be 155 nm

Comparative dispersion V3 The preparation of the comparative dispersion V3 was carried out completely analogously to the preparation of the polymer dispersion D4 with the difference that the monomer feed from 95.0 g of styrene, 95.0 g of n-butyl acrylate, 6.0 g of glycidyl methacrylate, 2.0 g of 1, 4-Butylenglykoldiacrylat and 2.0 g of acrylic acid.

The comparative dispersion V3 thus prepared had a solids content of 49.8% by weight and an LT value of 62%. A bimodal particle size distribution was measured, each with a maximum at 80 and 330 nm.

Comparative dispersion V4

The preparation of the comparative dispersion V4 was carried out completely analogously to the preparation of the polymer dispersion D4 with the difference that the monomer feed of 98.0 g of styrene, 98.0 g of n-butyl acrylate, 2.0 g of glycidyl methacrylate and 2.0 g of 1, 4-Butylenglykoldiacrylat duration.

The comparative dispersion V4 prepared in this way had a solids content of 50.1% by weight and an LT value of 68%. A bimodal particle size distribution was measured, each with a maximum at 105 and 355 nm.

Comparative Dispersion V5

The preparation of the comparative dispersion V5 was carried out completely analogously to the preparation of the polymer dispersion V3, with the difference that 48.0 g of deionized water and 3.6 g of an aqueous polystyrene seed latex (solids content 33% by weight, having a weight-average particle diameter of 28 nm) were initially charged , the monomer feed in the form of a homogeneous aqueous emulsion consisting of 103 g deionized water, 26.7 g of a 15 wt .-% aqueous solution of a fatty alcohol sulfate (Disponil ^® SDS 15), 95.0 g styrene, 95.0 g of n Butyl acrylate, 6.0 g of glycidyl methacrylate, 2.0 g of 1, 4-Butylenglykoldiacrylat and 2.0 g of acrylic acid was carried out as initiator feed 1 16.3 g of a 7 wt .-% aqueous

Sodium peroxodisulfate solution were used and the residual monomer removal using 4.0 g of a 10 wt .-% aqueous solution of tert-butyl hydroperoxide and 5.0 g of a 13.1 wt .-% aqueous solution of acetone bisulfite (1: 1 addition product from acetone and sodium hydrogen sulfite).

The comparative dispersion V5 thus prepared had a solids content of 50.0% by weight and an LT value of 63%. The number average particle diameter was determined to be 155 nm.

II Application-technical investigations

To produce the bonded fiber webs was a needled Rohvlies

Polyethylene terephthalate spunbonded fabric (400 cm length, 40 cm width) having a basis weight of 155 g / m ² used. For the preparation of the binder liquors were subsets of the aqueous

Polymer dispersions D1 to D9 and the comparative dispersions V2 to V5 diluted with deionized water to a solids content of 15 wt .-%. In the following, the binder liquors obtained are referred to as binder liquors BD1 to BD9 and BV2 to BV5.

Furthermore, subsets of the comparative dispersion V2 with a 47.7% wt .-% calcium-Ligninsulfonatlösung were (Bretax ^® CL) mixed so that mixtures were obtained, whose ratio of calcium to Dispensonspolymerisat Ligningsulfonat 100/70, 100/60 and 100 / 40. These mixtures were also diluted with deionized water to a solids content of 15% by weight. The binder liquors obtained in this way are referred to below as binder liquors BV2-1 to BV2-3.

To produce the bonded nonwoven fabrics, the raw nonwovens were impregnated in a HVF impregnating machine with foulard from Mathis (rubber roller Shore A = 85 ° / steel roller) in

Soaked longitudinally with the respective binder liquor binder liquors BD1 to BD9, BV2 to BV5 and BV2-1, BV2-2, BV2-3. In each case, the wet entry was set to 166.7 g binder liquor per square meter (corresponding to a solids content of 25 g / m ² ). Thereafter, the obtained impregnated fiber webs were dried in an industrial dryer of Fa. Fleissner for 3 minutes at 200 ° C and cured. The bonded fiber webs obtained after cooling to room temperature are referred to as fiber webs F1 to F9 and FV2 to FV5 and FV2-1, FV2-2, FV2-3, depending on the binder liquors used.

With the bonded fiber webs F1 to F9 and FV2 to FV5 and FV2-1, FV2-2, FV2-3, the following measurements were carried out: tensile force at 180 ° C and 15% elongation, thermal dimensional stability at 200 ° C and elongation at 180 ° C and 40 N / 5 cm.

Tensile force at 180 ° C and 15% elongation and elongation at a tensile force of 40 N / 5 cm

The determinations were carried out by means of a Zwick tapping machine (Model Z10) with integrated tempering chamber. For this purpose, 50 × 210 mm strips (longitudinal direction) were longitudinally punched from the fiber webs F1 to F9 and also FV2 to FV5 and FV2-1, FV2-2, FV2-3 and clamped in the pulling device with a clamping length of 100 mm. After introduction into the tempering chamber, the respective test strip was tempered for 60 seconds at 180 ° C and then stretched at this temperature with a take-off speed of 150 mm / min with increasing tensile force. When a tensile force of 40 N / 5 cm was reached, the elongation of the test strips was determined in percent. In addition, when the test strip elongation reached 15%, the respective tensile force was determined in N / 5 cm. The results obtained are listed in Table 1. The results obtained are all the better to evaluate the lower the elongation obtained or the higher the respective tensile force. In each case 5 separate measurements were carried out. The values given in Table 1 represent the average values of these measurements. Shrinkage in the transverse direction at 200 ° C.

The shrinkage in the transverse direction at 200 ° C. was determined on the basis of DIN 18192. To this end, the fiber webs F1 to F9 and also FV2 to FV5 and FV2-1, FV2-2, FV2-3 became 100 × 340 mm strips in the longitudinal direction punched out. On the

Non-woven fabric strips were each a marking attached from the two narrow sides at a distance of 120 mm, with a measuring distance between the markers of 100 mm resulted. In the middle of this measuring section, the width of the nonwoven strip was controlled by measurement. Subsequently, the narrow ends were clamped in clamping rails.

In parallel, the tripod required for the measurement and a 4 kg stainless steel cylinder were heated to 200 ° C in a drying oven. For testing, the marked and measured fiber fleece strips were now attached freely suspended by means of a clamping rail to the tripod located in the drying cabinet. Subsequently, the 4 kg heavy stainless steel cylinder was hung on the lower clamping rail, the drying cabinet door closed and the so clamped nonwoven fabric for 10 minutes at 200 ° C in

Leave drying cupboard. The laboratory stand was then removed from the drying cabinet together with the loaded nonwoven strip and cooled for 5 minutes at room temperature. Thereafter, the stainless steel cylinder was first detached from the lower clamping rail and then the upper clamping rail from the stand (tripod and stainless steel cylinder were again in the. For temperature control for the next measurement

Drying cupboard provided). After removing the upper and lower clamping rail, the fiber fleece strip was laid flat on the laboratory bench and the respective distance was measured at the narrowest point in the transverse direction of the fiber fleece strips. In each case measurements were carried out on 6 separate measuring strips. The values also given in the table represent the mean values of these measurements

The smaller the shrinkage in the transverse direction, the better the results.

Indicated is the change in the transverse direction in percent, based on the corresponding distances before the thermal treatment.

Measurement results of the applied technical tests

Tensile force at 180 ° C elongation at 180 ° C shrinkage in

and 15% elongation and 40 N / 5 cm transverse direction at 200 ° C

Non-woven fabric [N / 5 cm] [%] [%]

F1 71 4.0 -2.1

F2 65 4,6 -1, 7

F3 68 4.7 -2.5

F4 70 4.5 -2.9

F5 69 4.8-3.0

F6 76 4.9 -3.4

F7 68 4.2 -2.3

F8 67 4.7 -3.1

F9 66 4.6 -3.2

FV2 55 9.0 -12.8

FV2-1 47 8.0 -10.1

FV2-2 54 6.0 -7.7

FV2-3 56 6.0 -7.7

FV3 58 5.5 -4.3

FV4 51 6.0 -5.0

FV5 50 10.8 -14.0

From the results, it can be clearly seen that the nonwoven fabrics bonded using the binder compositions of the present invention show markedly increased tensile values at 15% elongation, lower elongation at 40 N / 5 cm tensile strength, and less lateral shrinkage.

Claims

claims

1. A process for preparing an aqueous dispersion of a polymer P (aqueous polymer P dispersion) by free-radically initiated aqueous

Emulsion polymerization, characterized in that the polymerization of

> 3% and <8% by weight of at least one monoethylenically unsaturated compound having at least one epoxy group and / or one N-methylol group and / or at least one compound having at least two nonconjugated ethylenically unsaturated groups (monomers A), and

> 92 and <97% by weight of further ethylenically unsaturated compounds which differ from the monomers A, one of these ethylenically unsaturated compounds alone being suitable for use in

copolymerized polymer would have a glass transition temperature in the range> 0 and> 50 ° C (monomers B), wherein the amounts of monomers A and B to 100 wt .-%

(Total monomer), in the presence of> 25 and ^ 120% by weight of at least one lignin compound L, based on the total amount of monomers, takes place, and

A method according to claim 1, characterized in that the at least one monomer A is selected from the group comprising N-methylolacrylamide, N-methylolmethacrylamide, glycidyl acrylate, glycidyl methacrylate, 1, 4-butylene glycol diacrylate, allyl methacrylate and / or divinylbenzene.

Process according to one of Claims 1 or 2, where the monomers B are selected from the group consisting of C ₄ -C 4 -conjugated aliphatic dienes, esters of vinyl alcohol and a C 1 -C -monocarboxylic acid, C 1 -C 4 -alkyl acrylates, C 1 -C 4 -cycloalkyl alkyl methacrylates, ethylenically unsaturated C3 to C6 Monocarbonsäurenitrile ethylenically unsaturated C ₄ - to C 6 Dicarbonsäurenitrile, C5 to Cio-cycloalkyl acrylates and methacrylates, C to Cio-dialkyl maleates and dialkyl fumarates and C to Cio-vinyl aromatic monomers.

Method according to one of claims 1 to 3, characterized in that for the polymerization

> 3.5 and <7 wt .-% of monomers A, and > 93 and <96.5 wt .-% monomers B are used.

5. The method according to any one of claims 1 to 4, characterized in that the

Polymerization of 3.5 and -i 5.5% by weight of N-methylolacrylamide, N-methylolmethacrylamide,

Glycidyl acrylate, glycidyl methacrylate, 1, 4-Butylenglykoldiacrylat, allyl methacrylate and / or

Divinylbenzene, and

Ethyl acrylate, vinyl acetate, methyl methacrylate, styrene and / or tert-butyl methacrylate can be used.

6. The method according to any one of claims 1 to 5, characterized in that as

Lignin compound L a lignosulfonate is used.

7. The method according to any one of claims 1 to 6, characterized in that the

Polymerization> 30 and ^ 80 parts by weight of lignin compound L can be used.

8. Aqueous polymer P dispersion obtainable by a process according to one of claims 1 to 7.

9. Use of an aqueous polymer P dispersion according to claim 8 as

Binder for granular and / or fibrous substrates.

10. A process for producing a shaped body of granular and / or fibrous substrates, characterized in that an aqueous

Binder composition containing as essential component an aqueous polymer dispersion P according to claim 8 is applied to the granular and / or fibrous substrate, optionally the thus treated granular and / or fibrous substrate is shaped and then the granular and / or fibrous substrate thus obtained a thermal treatment step at a temperature> 1 10 ° C is subjected.

1 1. A process for producing a shaped article according to claim 10, characterized

in that the amount of aqueous binder composition is chosen such that per 100 g of granular and / or fibrous substrate> 1 and> 100 g of binder (corresponding to the sum of the total amounts of polymer P and lignin compound L) are applied.

12. Shaped article obtainable by a process according to one of claims 10 or 11.

13. Use of moldings according to claim 12 for the production bitumierter

Roofing membranes.

14. bitumen roofing membranes produced using moldings according to

Claim 13.