EP2401428A2

EP2401428A2 - Mineral wool fibre mats, method for the production thereof and use of same

Info

Publication number: EP2401428A2
Application number: EP10707211A
Authority: EP
Inventors: Christoph Deller; Martin Jakob; Paolo Bavaj
Original assignee: Celanese Emulsions GmbH
Current assignee: Celanese Sales Germany GmbH
Priority date: 2009-02-27
Filing date: 2010-02-23
Publication date: 2012-01-04
Also published as: WO2010097192A3; US20110287680A1; WO2010097192A2; DE102009010938A1

Abstract

The invention relates to mineral wool fibre mats that are stabilised by a binder consisting of polymers containing carboxyl groups and selected cross-linking agents. Said mats can be used as insulating material and are characterised by low fomaldehyde emissions or the absence thereof.

Description

description

Mineral wool fiber mats, process for their preparation and use

The present invention relates to mineral wool fiber mats impregnated with a selected binder. These mats can be used, for example, as insulation materials, for example for thermal insulation of roofs.

Aqueous polymer dispersions for use as binders for mineral wool fiber mats are known per se. So are mineral wool mats with crosslinked polymers as

Binders subject matter of various patent documents.

US-A-2008/0175997 describes binder compositions for glass mats comprising an emulsion of a carboxyl group-functionalized polymer and a crosslinker with aziridine groups. Compared to conventional systems is a formaldehyde-free dispersion. This has comparable or even improved strength and flexibility compared to known systems. This document mentions other known binder systems for glass mats derived from carboxyl group-functionalized polymers and having specific crosslinkers, for example, polyol compounds combined with phosphorus-containing accelerator, active hydrogen-containing compounds such as polyol, polyvinyl alcohol or polyacrylate combined with fluoroborate accelerator. or crosslinkers which promote the esterification between COOH and OH groups in the polymer, or epoxidized oils.

From DE-A-10014399 a mixture of two polymeric systems is known, one of which bears carboxyl and / or hydroxyl groups, while the second contains copolymerized functional groups capable of reacting with the carboxyl and / or hydroxy groups of the first Systems to undergo a reaction to form a covalent bond. In claim 5, a selection of possible copolymerized functional groups is mentioned, including oxazolines. This document gives no indication of the use of a crosslinking compound in the form of a water-soluble, non-disperse reaction component.

DE-A-2604544 describes binders for solidifying glass fiber mats in which a carboxyl group-containing polymer is reacted with a crosslinker which is selected from the group of polyepoxides or capped isocyanates. The polymer base used is limited exclusively to polymers which are composed of ethylenically unsaturated esters of acrylic or methacrylic acid. It also appears from the text that aqueous primary dispersions based on (meth) acrylate, which are prepared by aqueous emulsion polymerization, are not suitable for the binders according to the invention for technical reasons.

JP-A-2000/064167 describes a carboxyl group-modified epoxy resin which is crosslinked using oxazoline group bearing components and can be used to bind fibrous materials, especially short cut fibers.

From EP-A-1, 018,523 a polymer dispersion is known which contains a) dispersed polymer which contains 5-20% by weight of copolymerized carboxylic acid units, b) dissolved polymer which contains 60-100% by weight of copolymerized carboxylic acid units and c) alkoxylated long-chain amine crosslinker contains. This dispersion is useful as a binder for e.g. Mineral wool mats, usable.

DE-T-699 21 163 describes an insulating product based on mineral wool on the basis of special mineral fibers, which is provided with a size based on a thermosetting resin, wherein this is mixed with a latex to improve the mechanical strength after aging. In particular polymers with hydrophilic groups are used as latex, for example with carboxyl, hydroxyl or carboxylic acid ester groups. As the thermosetting resin is called phenolic resin. DE-A-197 38 771 describes a binder for mineral wool comprising a) a phenolic resin-crosslinkable thermoplastic polymer such as polyacrylate or polyvinyl ester, b) phenolic resin and c) flame retardant.

DE-A-197 20 674 describes a binder for mineral wool comprising a) a phenolic resin-crosslinkable thermoplastic polymer such as polyacrylate or polyvinyl ester, b) phenolic resin and c) flame retardant.

From EP-A-1 164 163 a mineral wool binder is known which is prepared by mixing a carboxylic acid and an alkanolamine under reactive conditions. As the carboxylic acid, e.g. a polyacrylic acid, polymethacrylic acid or a polymaleic acid used.

WO-A-01/05, 725 describes a mineral wool binder prepared by reacting a mixture which contains no polymer but has an amine and first and second anhydrides. Typical representatives of the reaction mixture are diethanolamine, cyclic aliphatic anhydride, e.g. Maleic anhydride, succinic anhydride or hexahydrophthalic anhydride, and aromatic anhydride, for example, phthalic anhydride.

WO-A-2007 / 060,236 describes a formaldehyde-free mineral wool binder comprising a) an aqueous dispersion of a polymeric polycarboxylic acid, b) a selected alkanolamine, e.g. Ethanolamine, and c) an activated silane obtained by reacting a silane, e.g. of alkoxysilane, with an enolisable ketone containing at least one carboxyl group or with a ketone having at least one hydroxyl group, e.g. Dihydroxyacetone or acetylacetone, was prepared.

JP-A-2006-089,906 describes a formaldehyde-free mineral wool binder containing a vinyl copolymer having hydroxyl groups and groups derived from an organic acid. In WO-A-2004 / 085.729 a formaldehyde-free binder for mineral wool is described which contains a) a compound having at least 2 cyclic ether groups and b) a copolymer having nucleophilic groups.

WO-A-2006 / 136,614 discloses a binder for mineral wool comprising a) phenol-formaldehyde binder and b) a hydroxylamine or an aminoalcohol.

From DE-A-40 24 727 a means for hydrophilizing mineral wool fibers is known which comprises a) phenol-formaldehyde binder and as hydrophilizing agent a mixture of b) water-soluble nitrogen-carbonyl compound, e.g. Urea, c) acrylic resin and d) mixture of carboxyl-containing fatty acid condensation products with organic phosphoric acid esters.

Binder formulations have also become known which contain oxazoline compounds as crosslinkers.

Thus, US-A-4,056,502 discloses swellable articles for hygienic applications or for disposable towels or door mats. Described are aqueous, carboxyl-containing polymers which are crosslinked with bis-oxazolinen or bis-iminooxazolinen. As crosslinkable polymers are e.g. Acrylate-acrylic acid copolymers mentioned.

US Pat. No. 4,297,449 describes the crosslinking of polymers with incorporated maleic anhydride groups in the polymer backbone using selected oxazoline derivatives as crosslinking agents. The crosslinked products are characterized by their high heat and solvent resistance and can be used as adhesives, coatings and molding compounds.

From US-A-4,297,621 a moisture curable composition is known. This has a selected polymer with oxazoline groups and another polymer with, for example, incorporated maleic anhydride groups in the polymer backbone. The curable compositions can be used for coating various products, including glass, are used. Among other things, powder coatings containing these compositions are described.

GB-A-1 347,066 describes heat curable compositions comprising a) a polyoxazoline having at least 2 oxazoline rings and b) a selected polycarboxylic acid having a molecular weight of at least 600. The compositions are used for coatings, preferably as powder coatings.

JP-A-2005-126,562 discloses adhesives based on an aqueous-phase-dispersed thermoplastic resin and a crosslinking agent, e.g. an oxazoline compound known.

JP-A-2008-088,404 describes aqueous resin composition having improved substrate adhesion, solvent and water resistance based on a water-soluble or water-dispersible polymer having 2-oxazoline group incorporated and a second polymer having a built-in group which reacts with the 2-oxazoline group.

The market is increasingly demanding products that are formaldehyde-free in the formulation and emission during the application process while preserving the current property profile.

It was therefore the task of providing bonded mineral wool fiber mats, which are characterized in that they are connected by formaldehyde-free binders and are ideal as insulating materials. In the context of this description, "formaldehyde-free" is understood as meaning a composition whose content of formaldehyde is less than 10 ppm

The present invention relates to a mineral wool fiber mat bound with a binder comprising a polymer containing carboxyl groups and / or salts thereof and a crosslinker selected from the group of compounds having at least divalent metal ions, the bis- or polyoxazolines, the bis- or polyimino oxazolidines, carbodiimides, bis- or polyepoxides and capped isocyanates.

Another aspect of the present invention relates to a mineral wool fiber mat containing a bio-soluble fiber material which is free of formaldehyde

Binders is applied, which is applied in a pH range in which the fibers are not attacked. This area ideally moves around the neutral point. This pH range is preferably 4.5-9, in particular 6-7.

The mineral wool fiber mats according to the invention contain glass wool and / or

Rock wool, and may in principle contain further additives known to the expert and / or other fibers.

For the production of glass wool, all known from the glass industry raw materials can be used. Usually, silica sand, soda and

Limestone used; Waste glass may be added to these raw materials, for example up to 70% by weight of waste glass. The melt is spun in a conventional manner to fibers.

For the production of rock wool can be proceeded similar to the production of glass wool. Usually basalt, diabase, feldspar, dolomite, sand and limestone are used; These raw materials can also be mixed with waste glass. The melt is spun in a conventional manner to fibers. In addition to the usual raw materials for the production of rock wool and slags can be used as waste products

Burning or manufacturing processes incurred, for example, blast furnace slag. This form of rockwool called slag wool is also known to the person skilled in the art.

The glass or stone wool used are preferably selected so that they have a high biosolubility. This is the ability of the fibers to be dissolved and broken down in the body by the body's own substances. The resulting glass or stone wool fiber mats, the binder is added to ensure their dimensional stability. Subsequently, the fiber mat is cured by heat treatment, for example in a stream of hot air. In addition, volatile components are removed from the fiber mat. Web forming processes of this type are described, for example, in US 2008/0175997 A1.

In an alternative method of production, mineral wool fiber mats can also be produced by a wetlaying technique. For this purpose, fibers can be presented together with the binder in an aqueous slurry and on a moving

Storage device, such as a water-permeable conveyor belt, are stored to a fiber mat. After removal of the water, the fiber mats are cured by heat treatment, for example in a hot air stream. Production processes for mineral wool mats of this type are described for example in DE 601 23 177 T2.

The polymers which are used as polymer base in the mineral wool fiber mats according to the invention are essentially based on one or more ethylenically unsaturated compounds, where at least one of these monomers must have one or more carboxyl groups. These are preferably copolymers of vinyl esters and / or esters of α, ß-ethylenically unsaturated C ₃ -Ca mono- or dicarboxylic acids and / or of alkenyl aromatic, which have been polymerized in each case with carboxyl-containing ethylenically unsaturated comonomers.

As a basis for the polymer classes mentioned, in addition to the carboxyl-containing monomers, the following main groups of monomers are suitable:

One group is vinyl esters of one to eighteen carbon atoms

Monocarboxylic acids, for example vinyl formate, vinyl acetate, vinyl propionate, vinyl isobutyrate, vinyl valerate, vinyl valerate, vinyl pivalate, vinyl 2-ethylhexanoate, vinyl decanoate, isopropenyl acetate, vinyl esters of saturated branched Monocarboxylic acids having 5 to 15 carbon atoms in the acid radical, in particular vinyl esters of Versatic ™ acids, vinyl esters of long-chain saturated or unsaturated fatty acids such as vinyl laurate, vinyl stearate and vinyl esters of benzoic acid and substituted derivatives of benzoic acid such as vinyl p-tert-butylbenzoate. Among them, however, vinyl acetate as the main monomer is particularly preferable.

Another group of monomers form esters of α, ß-ethylenically unsaturated C ₃ -C 8 mono- or dicarboxylic acids with preferably Ci-Ci ₈ -alkanols and in particular CrCs- alkanols or C ₅ -C ₈ -cycloalkanols in question. The esters of dicarboxylic acids may be half esters or, preferably, diesters. Examples of suitable C 1 -C 6 -alkanols are methanol, ethanol, n-propanol, isopropanol, 1-butanol, 2-butanol, isobutanol, tert-butanol, n-hexanol and 2-ethylhexanol. Suitable cycloalkanols are, for example, cyclopentanol or cyclohexanol. Examples are esters of acrylic acid, methacrylic acid, crotonic acid, maleic acid, itaconic acid, citraconic acid or

Fumaric acid such as (meth) acrylic acid ethyl ester, (meth) acrylic acid ethyl ester, (meth) acrylic acid isopropyl ester, (meth) acrylic acid n-butyl ester, (meth) acrylic acid isobutyl ester, (meth) acrylic acid 1-hexyl ester, (meth) acrylic acid tert-butyl ester, (meth) acrylic acid 2-ethylhexyl ester, di-n-methyl maleate or fumarate, di-n-ethyl maleate or fumarate, di-n-propyl maleate or fumarate, di-n-butyl maleate or fumarate, Diisobutyl maleate or fumarate, di-n-pentyl maleate or fumarate, di-n-hexyl maleate or fumarate, dicyclohexyl maleate or fumarate, di-n-heptyl maleate or fumarate, di-n-octyl maleate or fumarate, di (2-ethylhexyl) maleate or fumarate, di-n-nonyl maleate or fumarate, di-n-decyl maleate or fumarate, di-n-undecyl maleate or fumarate, dilauryl maleate or fumarate, dimyristiyl maleate or fumarate,

Dipalmitoyl maleate or fumarate, di-stearyl maleate or fumarate and diphenyl maleate or fumarate.

Another group of monomers are the alkenylaromatics. These are monoalkenylaromatics. Examples include styrene, vinyl toluene, vinyl xylene, α-

Methylstyrene or o-chlorostyrene. Another group of monomers which mainly α together with Vinylestern and / or esters, beta-ethylenically unsaturated C ₃ -C ₈ mono- or dicarboxylic acids and / or alkenyl aromatics can be used form, aliphatic, monoolefinically or diolefinically unsaturated, optionally halogen- substituted hydrocarbons, such as ethene, propene, 1-butene, 2-butene, isobutene, conjugated C 1 -C 6 -dienes, such as 1,3-butadiene, isoprene, chloroprene, vinyl chloride, vinylidene chloride, vinyl fluoride or vinylidene fluoride.

The monomers mentioned usually form the main monomers, which are usually one in relation to the total amount of the monomers to be polymerized

Share of more than 50 wt.%, Preferably more than 75% combine.

The monomers are preferably to be selected so that a polymer or copolymer with good compatibility is formed in common formaldehyde-free binder formulations, which additionally has excellent binding properties in the production of mineral wool mats.

In addition to these copolymers, it is also possible to use homopolymers or copolymers which are derived completely or predominantly from carboxyl-containing ethylenically unsaturated monomers. Examples of these are polyacrylic acid or its salts, and also polymethacrylic acid or its salts, in particular the alkali metal salts of these polymers.

Preferred binder polymers are derived, in addition to the carboxyl group-containing monomers, from the following main monomers or combinations thereof:

Copolymers based on one or more vinyl esters, in particular vinyl acetate; Copolymers based on esters Vinylestern and α, ß-ethylenically unsaturated C ₃ -C ₈ - mono- or dicarboxylic acids with -C ₈ alkanols, especially esters of (meth) - acrylic acid and maleic / or fumaric acid; Copolymers based on vinyl esters, in particular vinyl acetate, with ethylene; Copolymers based on vinyl esters, ethylene and esters of α, β-ethylenically unsaturated C ₃ -C ₈ -mono- or dicarboxylic acids with Ci-C ₈ - Alkanols, especially esters of (meth) acrylic acid and maleic or fumaric acid; or copolymers based on esters of (meth) acrylic acid; Copolymers based on styrene, butadiene and / or esters of α, ß-ethylenically unsaturated C ₃ -C ₈ -MOnO- or dicarboxylic acids with d-Cβ-alkanols, in particular esters of (meth) acrylic acid.

In addition to the main monomers mentioned above, the binder polymers used according to the invention contain at least structural units which derive from monomers containing carboxyl groups.

This group includes mainly α, ß-monoethylenically unsaturated mono- and dicarboxylic acids having 3 to 10 carbon atoms and their water-soluble salts, eg. B. their sodium salts. Preferred monomers from this group are ethylenically unsaturated C ₃ -C ₈ carboxylic acids and C ₄ -C ₈ dicarboxylic acids, eg. Example, maleic or fumaric acid, itaconic acid, crotonic acid, vinylacetic acid, 2-carboxyethyl (meth) - acrylate, acrylamidoglycolic acid and especially acrylic acid, methacrylic acid, and the half esters of maleic and fumaric acid such as mono-2-ethylhexylmaleinat or monoethylmaleinate

These carboxyl-containing monomers are normally copolymerized in amounts, based on the total amount of the monomers to be polymerized, of less than 50% by weight, generally less than 20% by weight, preferably less than 10% by weight.

Of course, other comonomers which modify the properties in a targeted manner, be used in the polymerization. Such

Auxiliary monomers are normally copolymerized only as modifying monomers in amounts, based on the total amount of the monomers to be polymerized, of less than 10% by weight.

These monomers can have different functions; For example, they may serve to stabilize polymer dispersions or, by crosslinking during polymerization or during film formation, they may Improve film cohesion or other properties and / or react with the crosslinker through appropriate functionality.

Monomers which can serve for further stabilization are generally monomers which have an acid function and / or salts thereof. In addition to the carboxyl-containing monomers listed above, this group includes, for example, mers with other acid functions, such as ethylenically unsaturated sulfonic acids, ethylenically unsaturated phosphonic acids or dihydrogen phosphates and their water-soluble salts, eg. B. their sodium salts. Preferred monomers from this group are vinylsulfonic acid and its alkali metal salts,

Acrylamidopropansulfonsäure and their alkali salts, as well as vinylphosphonic acid and its alkali metal salts.

Examples of crosslinking auxiliary monomers are monomers having two or more vinyl radicals, monomers having two or more vinylidene radicals, and monomers having two or more alkenyl radicals. Particularly advantageous are the diesters of dihydric alcohols with α, ß-monoethylenically unsaturated monocarboxylic acids, among which acrylic and methacrylic acid are preferred, the di-esters of dibasic carboxylic acids with ethylenically unsaturated alcohols, other hydrocarbons having two ethylenically unsaturated groups or

Di-amides of divalent amines with α, ß-monoethylenically unsaturated monocarboxylic acids.

Examples of such two monomers having non-conjugated ethylenically unsaturated double bonds 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 or methacrylate and ethylene glycol diacrylate or methacrylates, 1,2-propylene glycol dimethacrylate, 1,3-propylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, 1,4-butylene glycol dimethacrylate, hexanediol diacrylate, pentaerythritol diacrylate and divinylbenzene,

Vinyl methacrylate, vinyl acrylate, vinyl crotonate, allyl methacrylate, allyl acrylate, diallyl maleate, diallyl fumarate, diallyl phthalate, methylenebisacrylamide, cyclopentadienyl acrylate, divinyl adipate or methylenebisacrylamide. However, it is also possible to use monomers having more than two double bonds, for example tetraallyloxyethane, trimethylolpropane triacrylate or triallyl cyanurate.

Another group of auxiliary monomers is capable of reacting under crosslinking either by self-crosslinking or with a suitable monomeric reactant and / or with the crosslinkers present under selected conditions:

This group includes monomers having N-functional groups, in particular (meth) acrylamide, allyl carbamate, acrylonitrile, methacrylonitrile, N-methylol (meth) acrylamide, N-methylolallyl carbamate and the N-methylol esters, alkyl ethers or Mannich bases of N-methylol (meth) acrylamide or N-methylolallyl carbamate, acrylamidoglycolic acid, methyl acrylamidomethoxyacetate, N-

(2,2-dimethoxy-1-hydroxyethyl) acrylamide, N-dimethylaminopropyl (meth) acrylamide, N-methyl (meth) acrylamide, N-butyl (meth) acrylamide, N-cyclohexyl (meth) acrylamide, N- Dodecyl (meth) acrylamide, N-benzyl (meth) acrylamide, p-hydroxyphenyl (meth) acrylamide, N- (3-hydroxy-2,2-dimethylpropyl) methacrylamide, ethylimidazolidone (meth) acrylate, N- (meth acryloyloxyethylimidazolidin-1-one, N- (2-methacrylamidoethyl) imidazolin-2-one, N- [3-allyloxy-2-hydroxypropyl] aminoethyl] imidazolin-2-one, N-vinylformamide, N-vinylpyrrolidone or, N-vinyl ethylene urea.

Another group of auxiliary monomers form hydroxy-functional monomers such as the methacrylic acid and acrylic acid CrCg hydroxyalkyl esters, such as n-hydroxyethyl, n-hydroxypropyl or n-hydroxybutyl acrylate and methacrylate and their adducts with ethylene oxide or propylene oxide,

Another group of auxiliary monomers form those which are crosslinkable via carbonyl groups or self-crosslinking. Examples are diacetone acrylamide,

Allyl acetoacetate, vinyl acetoacetate and acetoacetoxyethyl acrylate or methacrylate. Another group of Hilfsmonomeren consists of silane-containing monomers z. Vinyltrialkoxysilanes, such as vinyltrimethoxysilane, vinyltriethoxysilane, alkylvinyldialkoxysilanes or (meth) acryloxyalkyltrialkoxysilanes, e.g. B. (meth) acryloxy-ethyltrimethoxysilane, or (meth) acryloxypropyltrimethoxysilane.

Another group of auxiliary monomers consists of epoxy group-containing monomers such as allyl glycidyl ether, methacrylic glycidyl ether, butadiene monoepoxides, 1, 2-epoxy-5-hexene, 1, 2-epoxy-7-octene, 1, 2-epoxy-9-decene, 8-hydroxy 6,7-epoxy-1-octene, 8-acetoxy-6,7-epoxy-1-octene, N- (2,3-epoxy) -propylacrylamide, N- (2,3-epoxy) -propylmethacrylamide, 4 Acrylamidophenyl glycidyl ether, 3-acrylamidophenyl glycidyl ether, 4-methacrylamidophenyl glycidyl ether, 3-methacrylamidophenyl glycidyl ether, N-glycidoxymethylacrylamide, N-glycidoxypropyl methacrylamide, N-glycidoxyethyl acrylamide, N-glycidoxyethyl methacrylamide, N-glycidoxypropylacrylamide, N-glycidoxypropyl methacrylamide, N-glycidoxybutylacrylamide , N-glycidoxybutylmethacrylamide, 4-acrylamidomethyl-2,5-dimethylphenyl glycidyl ether, 4-methacrylamido-methyl-2,5-dimethylphenyl glycidyl ether, acrylamidopropyldimethyl- (2,3-epoxy) -propylammonium chloride, methacrylamidopropyldimethyl- (2, 3-epoxy) -propyl-ammonium chloride and glycidyl methacrylate.

It is preferred within the scope of the present invention that as far as possible no functional monomers are used which contain free or bound formaldehyde. If this is necessary in the context of specific product customization, a compound that acts as a formaldehyde scavenger is usually included. Relevant examples are N- or S-nucleophiles such as urea or

Sodium bisulfite and other compounds described in the literature.

The binders used according to the invention can be prepared by any method of radical polymerization. Examples of these are the bulk, solution, suspension or, in particular, the polymerization

Emulsion polymerization. Preferred binders comprise aqueous polymer dispersions with the carboxyl group-containing copolymers described above. The application of these dispersions on the mineral wool fiber mats is solvent-free or nearly solvent-free.

In addition to the polymer containing carboxyl groups, the dispersions preferably used according to the invention contain protective colloids and / or emulsifiers.

Protective colloids are polymeric compounds which are present during the emulsion polymerization and which stabilize the dispersion.

Suitable protective colloids are, for example, polyvinyl alcohols, polyalkylene glycols, cellulose, starch and gelatin derivatives or polymers derived from N-vinylpyrrolidone, N-vinylcaprolactam, N-vinylcarbazole, 1-vinylimidazole, 2-vinylimidazole, 2-vinylpyridine, 4-vinylpyridine , Acrylamide, methacrylamide, amine group-bearing

Acrylates, methacrylates, acrylamides and / or methacrylamides. A detailed description of other suitable protective colloids can be found in Houben-Weyl, Methods of Organic Chemistry, Volume XIV / 1, Macromolecular Materials, Georg Thieme Verlag, Stuttgart, 1961, pages 411-420.

Emulsifiers are low molecular weight and surface active compounds which are present during the emulsion polymerization and which stabilize the dispersion. In the dispersions used according to the invention, it is possible to use ionic and / or nonionic and / or amphoteric emulsifiers, very particularly preferably nonionic emulsifiers or combinations of nonionic emulsifiers and anionic emulsifiers. A list of suitable emulsifiers can be found in Houben-Weyl, Methods of Organic Chemistry, Volume XIV / I, Macromolecular substances, Georg Thieme Verlag, Stuttgart, 1961, p 192-208).

The proportion of protective colloids can be up to 10% by weight, based on the dispersion, preferably from 1 to 6% by weight. The proportion of emulsifiers may also be up to 10% by weight, based on the dispersion, preferably from 1 to 6% by weight.

The binders used according to the invention contain at least one selected crosslinker.

This is typically present in amounts of 0.5 to 10% by weight, based on the binder, preferably in amounts of 0.1 to 5% by weight.

One group of crosslinkers is selected from the group of compounds having at least bivalent metal ions. These are compounds that can form complexes or coordinate bonds with the carboxyl groups of the binder polymer. Typically, this group includes salts of Al ³⁺ , Zn ²⁺ , Sn ²⁺ , Sn ⁴⁺ , Ti ⁴⁺ , TiO ²⁺ , Hf ⁴⁺ , HfO ²⁺ Zr ⁴⁺ , ZrO ^2+, and other polyvalent ions. Ideally, these ions may also include other components of the binder in the cross-linking and thus increase the crosslink density. These include, for example, the poly (vinyl alcohol) commonly used as a protective colloid

Another group of crosslinkers is selected from the group of Bis or

Polyoxazolines. These are preferably compounds of the formula I or polymers containing the structural units of the formula II

(II) R ¹ is alkylene, cycloalkylene, arylene or aralkylene, especially C ^ _-C alkylene or

phenylene,

R ^{2 is} hydrogen or alkyl, preferably hydrogen or C 1 -C 6 -alkyl, and n is an integer from 1 to 50.

Yet another group of crosslinkers is selected from the group of bis or polyiminooxazolidines. These are preferably compounds of the formula III or polymers containing the structural units of the formula IV

in which R ³ and R ^4, independently of one another, denote hydrogen, alkyl, cycloalkyl or aryl, preferably hydrogen or C 1 -C 6 -alkyl,

R ¹ , R ² and n have the meanings defined above, and

R ^{5 is} alkyl, cycloalkyl, aryl or aralkyl, preferably d-Cβ-Alky! or phenyl.

Yet another group of crosslinkers is selected from the group of carbodiimides. These are preferably compounds of the formula V

R ⁶ N r. NR ⁷ (V), wherein R ⁶ and R ⁷ independently of one another are alkyl, N, N-dialkylaminoalkyl, cycloalkyl, aryl or aralkyl, preferably or C 1 -C ₆ -alkyl, N, N-dialkylaminopropyl, phenyl or cyclohexyl.

Further possible crosslinkers are selected from the group of bis- or polyepoxides. These are preferably compounds of the formulas VI or VII

wherein R ⁸ is alkylene, cycloalkylene, arylene or aralkylene, especially C ₂ -C ₆ alkylene, phenylene, biphenylene, _C6 H4-C (CH 3) 2 C ₆ H4, -C ₆ H ₄ -CH ₂ - C ₆ H ₄ -, -C ₆ H ₄ -OC ₆ H ₄ - or -C ₆ H ₄ -SC ₆ H ₄ -.

Furthermore, it is also possible to use oligomeric or polymeric compounds having a higher number of epoxide groups as crosslinkers.

Still other possible crosslinkers are selected from the group of capped isocyanates.

These include, for example, the water-dispersible polyisocyanate preparations of EP-A-206,059 or, generally, adducts of alcohols, ethoxylates, lactams, ketoximes, activated methylene compounds, dimethylpyrazoles with diisocyanates, such as methylenebis (4-phenylisocyanate), 1,6 Hexane diisocyanate, dicyclohexane diisocyanate, meta-tetramethyl xylene diisocyanate or isophorone diisocyanate.

The binders used according to the invention may contain further customary additives. These include, for example, film-forming aids for lowering the

Minimum film-forming temperature ("MFT depressant"), plasticizers, buffers, pH modifiers, dispersants, defoamers, fillers, dyes, pigments, silane coupling agents, thickeners, viscosity regulators, solvents and / or preservatives.

In addition to the above-mentioned crosslinkers, the binders used according to the invention may contain further crosslinking agents for controlling the crosslinking density and reactivity, which may be present in low molecular weight form or as crosslinker resins.

The binder used according to the invention is to be used in a formulation in which a pH is adjusted within a range which is optimal for a suitable reactivity of the functional groups of the polymeric binder with the groups of the crosslinker. This pH range is preferably between 4 and 8, in particular between 6 and 7.5. A suitable pH can already after the emulsion to the

Preparation of the polymer dispersion can be achieved or he can be subsequently adjusted by addition of pH adjusters in the formulation.

The preparation of the polymer dispersions used with particular preference is carried out under the customary continuous or batchwise methods of free-radical emulsion polymerization.

The carrying out of a free-radically initiated aqueous emulsion polymerization of ethylenically unsaturated monomers has already been described in detail and is therefore sufficiently known to the person skilled in the art [cf. for example, Encyclopedia of Polymer Science and Engineering, Vol. 8, pp. 659-677, John Wiley & Sons, Inc., 1987; DC Blackley, Emulsion Polymerization, pp. 155-465, Applied Science Publishers, Ltd., Essex, 1975; DC Blackley, polymer latices, 2 ^nd Edition, Vol. I ₁ pages 33 to 415, Chapman & Hall, 1997; H. Warson, The Applications of Synthetic Resin Emulsions, pages 49 to 244, Ernest Bonn. Ltd. London, 1972; D. Diederich, Chemistry in our Time 1990, 24, pages 135 to 142, Verlag Chemie, Weinheim; J. Piirma, Emulsion Polymerization, pp. I-287, Academic Press, 1982; F. Hölscher, Dispersions of Synthetic High Polymers, pages I to 160. Springer

Verlag, Berlin, 1969 and the patent DE-A 40 03 422]. It is usually carried out by dispersing the ethylenically unsaturated monomers, frequently with the concomitant use of dispersants, in an aqueous medium and polymerizing them by means of at least one free-radical polymerization initiator.

Here, water-soluble and / or oil-soluble initiator systems such as peroxodisulfates, azo compounds, hydrogen peroxide, organic hydroperoxides or dibenzoyl peroxide are used. These may be used either alone or in combination with reducing compounds such as Fe (II) salts, sodium pyrosulfite, sodium hydrogen sulfite, sodium sulfite, sodium dithionite, sodium formaldehyde sulfoxylate,

Ascorbic acid can be used as a redox catalyst system.

The polymeric protective colloids and / or emulsifiers can be added before or during the polymerization. Additional addition of polymeric stabilizers and / or emulsifiers is also possible. If appropriate, additives intended for the desired application are then added to this dispersion.

The formulation of the binder according to the invention can be carried out in the devices known to those skilled in the art, for example in stirred kettles or suitable mixers.

After the preparation of the binder, this is usually applied directly to mineral wool fibers for the production of mineral wool fiber mats. This can be done by relevant, known to those skilled application method, for example by spraying, impregnation with the dispersion. The reactive binder cures after the application and thermal treatment of the wet raw nonwoven and thus solidifies and stabilizes the mineral wool fiber mat. The curing reaction will preferably triggered by a temperature increase. The rate of cure can be affected by appropriate choice of formulation. Typical curing temperatures are preferably from 70 ⁰ C - 250 ⁰ C ₁ C ⁰ in particular 130 - 180 ⁰ C.

The invention also relates to a process for the preparation of the above-defined mineral wool fiber mat comprising the steps: i) applying a crosslinkable composition containing carboxyl groups and / or salts thereof containing polymer and a crosslinker selected from the group of compounds having at least divalent metal ions, the bis- or polyoxazolines , the bis- or polyiminooxazolidines, the carbodiimides, the bis- or polyepoxides and the capped isocyanates, onto an unbound mineral wool fiber mat, and j) solidifying the mineral wool fibers into a bonded mineral wool fiber mat, activating the binder

The mineral wool fiber mats according to the invention are distinguished by very low, preferably no formaldehyde emissions, with comparable mechanical strengths and application properties.

The mineral wool fiber mats according to the invention can be used above all as insulating material, in particular for insulation, in particular thermal insulation of buildings and construction objects of all kinds.

The following examples serve to illustrate the invention. The in the

Examples given parts and percentages are by weight unless otherwise stated.

Examples:

Dispersion A: These were ^® Resyn 1601, a commercial product from Celanese, a polyvinyl alcohol-stabilized polyvinyl acetate dispersion containing about 1 weight of acrylic acid units in the polymer.

The pattern used had the following properties:

Solids content: 54%

Viscosity Brookfield RVT (23 ⁰ C), spindle 3, 20 rpm: 4500 mPas pH: 4.5.

Dispersions B and C:

In a glass stirred kettle with stirrer, anchor stirrer, feed options and electronic temperature control were initially 2.25 parts ^® Celvol 840 (partially saponified polyvinyl alcohol Fa. Celanese), 0.1 parts of anhydrous sodium acetate and 1, 11 parts ^® Genapol O-109 (nonionic emulsifier the Fa.

Clariant) in 81, 75 parts of deionized water. At room temperature, 0.1 parts of glacial acetic acid were added. The solution was heated to 65 ° C. Thereafter, a mixture of 3.5 parts Monoisooctylmaleinat (in the case of dispersions B and C), 2.13 parts of dibutyl maleate and 5.75 parts of vinyl acetate was added. Five minutes after completion of the addition, the initiator solution consisting of 0.18 parts of ammonium persulfate and 1.8 parts of water was added, whereby the reaction was started and the internal temperature rose to 70 ⁰ C.

After 15 minutes of prepolymerization with the addition of a monomer mixture consisting of 10 parts of dibutyl maleate and 78.62 parts of vinyl acetate (in

Case of the dispersion B) or from 4 parts of mono-isooctylmaleinat, 10 parts of dibutyl maleate and 74.62 parts of vinyl acetate (in the case of the dispersion C) started. The monomer mixture was added over 4 hours. In parallel, a solution consisting of 0.05 parts of ammonium persulfate and 0.18 parts of sodium acetate (anhydrous) in 4.3 parts of water was added. The polymerization proceeded at a reactor internal temperature between 70 ⁰ C and 72 ° C and a jacket temperature of 66 ° C to 68 ° C under low reflux. Five minutes before the end of monomer metering, the jacket temperature was raised to 72 ° C. After completion of the dosing, a solution of 0.05 part of ammonium persulfate in 1 part of water was added. The internal reactor temperature rose to 90 ⁰ C, the jacket temperature was raised in parallel to 90 ⁰ C. Reached the internal temperature 88 ° C was again a solution

0.02 parts of ammonium persulfate in 0.4 parts of water. At an internal temperature of 90 ⁰ C was stirred for one hour. After lowering the internal temperature to 85 ° C, 0.09 part of sodium pyrosulfite (Na ₂ S ₂ O ₅ ) in 1.67 parts of water was added. After cooling to 70 ⁰ C 0.07 part Trigonox ^® were AW 70 (70% aqueous solution of tert-butyl hydroperoxide of Fa. Akzo) in 1, 67

Divide water over 1 hour. After cooling to 40 ⁰ C 0.14 parts of sodium hydroxide in 1, 26 parts of water were added to adjust the pH. After cooling to room temperature, 0.3 parts Agitan ^® have been incorporated, with stirring, 295 (Fa. Münzing).

Dispersion B:

Solids content: 52.5%

Viscosity Brookfield RVT (23 ⁰ C), spindle 3, 20 rpm: 4800 mPas pH: 4.2.

Dispersion C:

Solids content: 51, 8%

Viscosity Brookfield RVT (23 ⁰ C), spindle 3, 20 rpm: 13,300 mPas pH: 3.6.

Determination of Vernetzunαsdichte in mixtures of dispersions and an oxazoline-based crosslinker

In the production of mineral wool fibers are mainly used in the prior art phenol-formaldehyde resins that form close-knit three-dimensional networks on the curing process. The high density of crosslinking results in a plastic with a strong thermoset character. Mice of the combination of functionalized vinyl ester described in this invention based polymer dispersions and suitable crosslinkers, for example, high molecular weight polymeric compounds with oxazoline, also strong crosslinked polymeric systems with thermosetting properties can arise during the curing process. The crosslinking density is therefore used in the following as a measure of the effectiveness of the binding system.

The crosslink density was determined by the determination of insolubles in thermally treated thin films of mixtures of dispersion and crosslinker. For this purpose, the procedure was analogous to that described in US-A-2008 / 0175,997. The film thickness of the substrates applied to the planographic glass plates was 250 μm in all cases, and N-dimethylformamide (DMF) was used as the solvent. For tempering the films a Mathis oven (type Mathis Labdryer LTE-S) was used. The tempering time and the temperatures are shown in the following tables, in which the investigated examples of the invention are shown.

The samples were prepared prior to knife-coating as follows: 2.5 to 7.5% of the corresponding crosslinkers were added to the dispersions. In the examples given here, the water-soluble polymeric oxazoline ® Epocros WS700 from Nippon Shokubai was used. The oxazoline was incorporated into the dispersion with slow stirring for 10 minutes. Subsequently, the pH of the mixture was determined and adjusted to a value around pH 6 by addition of 10% NH 4 OH solution. The mixture was processed immediately.

In a first study, the dependence of the degree of crosslinking on temperature, duration of tempering and crosslinking concentration was determined for dispersion A. The degree of crosslinking can be positively influenced by higher temperature, higher crosslinker concentration and longer tempering times. As a comparative example, the amount of insoluble constituents from a film of dispersion A without Vernetzerzusatz. Table 1

In another study, dispersions B and C were compared with dispersion A. The influence of different acid concentrations and monomer building blocks on the crosslinking density and on the reactivities of the polymer dispersions with respect to the oxazoline crosslinker was evident. The acid concentration increases from A (1%) to B (3.5%) to 7% for C. Temperature and crosslinker concentration were also varied in this series. Table 2

From Tables 1 and 2 it can be seen that by using the appropriate crosslinker in the inventive examples over the comparative examples V1, V2, V3 and V4 (each without added crosslinker), the proportion of insoluble constituents and thus the crosslinking density as a function of amount of added crosslinker , Temperature and tempering time increases. Determination of substrate-specific properties Tear tensile strengths of impregnated glass filter papers.

The increase in the crosslinking density achieved by means of the system according to the invention and the resulting transition from a thermoplastic binder to a material with a thermoset character is reflected in an increased mechanical stability of the film formers. This effect is demonstrated experimentally in the following examples. For this purpose, the binder system was cured on a suitable substrate. The substrate used was glass filter papers.

The dispersions were diluted with water to a solids content of 5%. Depending on the experiment, the dispersions diluted with additional 5% ^® Epocros (Münzing, basic Ammoniumzirkoniumcarbonatlösung Fa.) Were WS700 (Nippon Shokubai, polymeric oxazoline) or 1, 5% Bacote 20 ^® was added. The pH was adjusted to pH 6 with 10% NaOH or 10% acetic acid.

Afterwards, glass filter papers (type Whatman GF / A 20 No: 1820-866) were soaked in the solution for 60 seconds, clamped in a horizontal position in a frame and hung to drip off. This resulted in a uniform binder application of 25% (+/- 1%). The impregnated glass filter papers (type Mathis Labdryer LTE-S) were dried for 4 minutes at 200 ⁰ C in a forced air oven and furnace into strips of 5x30 cm (BreitexLänge) cut.

After storage for 24 h at 50% relative humidity ("RH") and 23 ° C., the test specimens were tested for tensile strength on a tensile stress gauge (Lloyd Negygen type, pulling speed 100 mm / min, clamping length 20 cm, maximum load capacity of the load cell 1 kN) The following table shows the force examinations when the specimen ruptures, averaging the tensile strengths of four specimens in each case The force absorbed by the unbound substrate is 15 N / 20 cm, as indicated in the following

Table shown force absorption was taken into account.

Table 3

From this table it can be seen that, compared with the comparative examples V5 and V6, which do not use any added crosslinker, the force absorption during the tensile test of the bonded glass filters increases significantly.

Claims

claims

1. mineral wool fiber mat bound with a binder containing a carboxyl groups and / or salts thereof containing polymer and a crosslinker selected from the group of compounds having at least bivalent

Metal ions, bis- or polyoxazolines, bis- or polyiminooxazolidines, carbodiimides, bis- or polyepoxides and capped isocyanates.

2. mineral wool fiber mat according to claim 1, characterized in that the carboxyl-containing polymer is selected from the group of

Vinyl esters derived copolymers, of esters of α, ß-ethylenically unsaturated C ₃ -C ₈ mono- or dicarboxylic acids derived copolymers and / or derived from alkenyl aromatic copolymers, said copolymers each having at least 1% by weight of copolymerized mono- or Have dicarboxylic acid units.

3. mineral wool fiber mat according to at least one of claims 1 or 2, characterized in that the carboxyl-containing polymer has at least 1 to 10 wt.% Of polymerized mono- or dicarboxylic acid units.

4. mineral wool fiber mat according to at least one of claims 1 to 3, characterized in that the polymer is selected from the group of copolymers derived from one or more vinyl esters and monomers containing carboxyl groups, the copolymers derived from vinyl esters,

Esters of α, ß-ethylenically unsaturated C ₃ -Cs-MOnO- or dicarboxylic acids with CrC ₈ - alkanols and monomers containing carboxyl groups, the copolymers derived from vinyl esters of olefins and monomers containing carboxyl groups, the copolymers derived from vinyl esters, ethylene , Esters of α, β-ethylenically unsaturated C ₃ -C ₈ -mono- or dicarboxylic acids with CrC ₈ -

Alkanols and monomers containing carboxyl groups, the copolymers of esters of acrylic acid and / or methacrylic acid and monomers containing carboxyl groups, the copolymers derived from Styrene, butadiene and / or esters of α, ß-ethylenically unsaturated C ₃ -C ₈ mono- or dicarboxylic acids with Ci-C ₈ -alkanols and carboxyl-containing monomers.

5. mineral wool fiber mat according to claim 4, characterized in that the

Polymer is selected from the group derived from vinyl acetate with carboxyl-containing monomers copolymers, the copolymers derived from vinyl esters, esters of acrylic acid and / or methacrylic acid and / or fumaric acid and / or maleic acid with d-Cβ-alkanols and with carboxyl groups Monomers derived from copolymers

Vinyl acetate with ethylene and with carboxyl group-containing monomers, the copolymers derived from vinyl esters, ethylene, esters of acrylic acid and / or methacrylic acid and / or fumaric acid and / or maleic acid with Cr Cβ-alkanols and carboxyl-containing monomers, the copolymers derived from esters of acrylic acid and / or methacrylic acid and with

Carboxyl-containing monomers, the copolymers derived from styrene with butadiene and / or with esters of acrylic acid and / or methacrylic acid with CrCs-alkanols and with carboxyl-containing monomers.

6. mineral wool fiber mat according to claim 5, characterized marked records that the

Polymer is a polyvinyl ester functionalized with carboxyl group-containing monomers containing at least 50% by weight of vinyl acetate monomer units.

7. Mineral wool fiber mat according to at least one of claims 1 to 6, characterized in that the binder is introduced in the form of an aqueous dispersion of the polymer.

8. mineral wool fiber mat according to at least one of claims 1 to 7, characterized in that the content of binder 0.5 to 10 wt.%, Preferably

0.1 to 5 wt.%, Is.

9. mineral wool fiber mat according to one of claims 1 to 8, characterized in that it contains at least one compound with at least divalent metal ions as crosslinking agents, which can enter into complexes or coordinative bonds with the carboxyl groups of the binder polymer, in particular salts of Al ³⁺ , Zn ²⁺ , Sn ²⁺ , Sn ⁴⁺ , Ti ⁴⁺ , TiO ²⁺ , Hf ⁴⁺ , HfO ²⁺ Zr ⁴⁺ , ZrO ²⁺ .

10. mineral wool fiber mat according to one of claims 1 to 8, characterized in that it contains at least one bis- or polyoxazoline and / or a bis or polyiminooxazolidine as crosslinking agent.

11. mineral wool fiber mat according to claim 10, characterized in that the bisoxazoline is a compound of formula I and the polyoxazoline is a polymer containing the structural units of the formula II

in which R ^{1 is} alkylene, cycloalkylene, arylene or aralkylene, in particular C ₂ -C ₆ -

Alkylene or phenylene,

R ^{2 is} hydrogen or alkyl, preferably hydrogen or d-Ce-alkyl, and n is an integer from 1 to 50.

12. mineral wool fiber mat according to claim 10, characterized in that the bisiminooxazolidine is a compound of formula IM and the polyiminooxazolidine is a polymer containing the structural units of the formula IV

wherein R ³ and R ⁴ independently of one another are hydrogen, alkyl, cycloalkyl or aryl, preferably hydrogen or C ¹ -C 6 -alkyl, R ¹ , R ² and n have the meanings defined in claim 11, and

R ^{5 is} alkyl, cycloalkyl, aryl or aralkyl, preferably C 1 -C 6 -alkyl or phenyl.

13. Mineral wool fiber mat according to one of claims 1 to 8, characterized in that it contains at least one carbodiimide crosslinker.

14 mineral wool fiber mat according to claim 13, characterized in that the carbodiimide is a compound of formula V.

R ⁶ N c ^~ NR ⁷ (V) ₁

wherein R ⁶ and R ⁷ independently of one another are alkyl, N, N-dialkylaminoalkyl, cycloalkyl, aryl or aralkyl, preferably or C ₁ -C 6 -alkyl, N ₁ N-dialkylaminopropyl, phenyl or cyclohexyl.

15. Mineral wool fiber mat according to one of claims 1 to 8, characterized in that it contains at least one bis- or polyepoxide as crosslinker.

16. mineral wool fiber mat according to claim 15, characterized in that the bisepoxide is a compound of formula VI or VII

wherein R ^{8 is} alkylene, cycloalkylene, arylene or aralkylene, in particular C ₂ -C ₆ -alkylene, phenylene, biphenylene, -C ₆ H ₄ -C (CHa) ₂ -C ₆ H ₄ -, -C ₆ H ₄ -CH ₂ -C ₆ H ₄ -,

-C ₆ H ₄ -OC ₆ H ₄ - or -C ₆ H ₄ -SC ₆ H ₄ -.

17. Mineral wool fiber mat according to one of claims 1 to 8, characterized in that it contains at least one capped isocyanate crosslinker.

18. A process for producing the mineral wool fiber mat according to claim 1 comprising the steps: i) applying a crosslinkable composition containing carboxyl groups and / or salts thereof containing polymer and a crosslinker selected from the group of compounds having at least divalent metal ions, the bis- or polyoxazolines, the Bis- or polyiminooxazolidines, the carbodiimides, the bis- or polyepoxides and the capped isocyanates, on mineral wool fibers, and j) solidifying the mineral wool fibers into a bonded mineral wool fiber mat, activating the binder.

19. The method according to claim 18, characterized in that the crosslinkable composition is applied in the form of an aqueous dispersion.

20. Use of the mineral wool fiber mat according to one of claims 1 to 17 as

Insulating material, in particular in particular for insulation, in particular Thermal insulation of buildings and construction objects of all kinds, preferably for insulating roofs.