DE10253498A1 - Binders for wood glue comprise aqueous polymer dispersions obtained by radical polymerisation in presence of copolymers of unsaturated carboxylic acids and/or esters with hydroxy-amine compounds - Google Patents

Abstract

Aqueous polymer dispersions for use as binders in wood glue contain polymers obtained by radical polymerisation of monomers in presence of copolymers of unsaturated mono- or di-carboxylic acids and esters of unsaturated acids with hydroxy-amines. The use of an aqueous polymer dispersion (D) containing dispersed particles of polymer(s) (A1) obtained by radical polymerisation in presence of a polymer (A2), as a binder in structural glues for wood. Polymer (A2) is derived from 50-99.5 wt% unsaturated mono- and/or di-carboxylic acid, 0.5-50 wt% unsaturated compound(s) selected from esters of unsaturated monocarboxylic acids and half-esters and di-esters of unsaturated dicarboxylic acids with hydroxy-amine(s) and up to 20 wt% other comonomer(s). An Independent claim is also included for the use as a wood glue binder of an aqueous solution (S) containing (A) a polymer obtained by radical polymerisation, comprising 5-100 wt% unsaturated acid anhydride or unsaturated dicarboxylic acid capable of forming an anhydride and (B) an alkanolamine with at least 2 hydroxyl groups.

Description

• - 50 bis 99,5 Gew.-% mindestens einer ethylenisch ungesättigten Mono- und/oder Dicarbonsäure,
• - 0,5 bis 50 Gew.-% wenigstens einer ethylenisch ungesättigten Verbindung, die ausgewählt ist unter den Estern ethylenisch ungesättigter Monocarbonsäuren und den Halbestern und Diestern ethylenisch ungesättigter Dicarbonsäuren mit einem mindestens eine Hydroxylgruppe aufweisenden Amin,
• - bis zu 20 Gew.-% mindestens eines weiteren Monomers

oder einer wäßrigen Lösung, enthaltend

• A) ein durch radikalische Polymerisation erhaltenes Polymerisat, welches zu 5 bis 100 Gew.-% aus einem ethylenisch ungesättigten Säureanhydrid oder einer ethylenisch ungesättigten Dicarbonsäure, deren Carbonsäuregruppen eine Anhydridgruppe bilden können, besteht und
• B) ein Alkanolamin mit mindestens zwei Hydroxylgruppen,

als Bindemittel für die konstruktive Holzverleimung. The present invention relates to the use of an aqueous polymer dispersion containing dispersed polymer particles of at least one polymer A1 which can be obtained by radical emulsion polymerization in the presence of a polymer A2 which is composed of

• 50 to 99.5% by weight of at least one ethylenically unsaturated mono- and / or dicarboxylic acid,
• 0.5 to 50% by weight of at least one ethylenically unsaturated compound which is selected from the esters of ethylenically unsaturated monocarboxylic acids and the half-esters and diesters of ethylenically unsaturated dicarboxylic acids with an amine having at least one hydroxyl group,
• - Up to 20 wt .-% of at least one other monomer

or containing an aqueous solution

• A) a polymer obtained by radical polymerization, which consists of 5 to 100% by weight of an ethylenically unsaturated acid anhydride or an ethylenically unsaturated dicarboxylic acid, the carboxylic acid groups of which can form an anhydride group, and
• B) an alkanolamine with at least two hydroxyl groups,

as a binder for constructive wood gluing.

The solidification of sheet-like binders, for example Nonwoven fabrics, or of moldings, such as fiberboard or Chipboard, is often made chemically using a polymeric binder. The polymeric binders can u. a. in Form of an aqueous solution or an aqueous dispersion be used.

EP-A-445 578 discloses plates made of finely divided materials, such as known glass fibers, in which mixtures of high molecular weight polycarboxylic acids and polyhydric alcohols, Alkanolamines or polyvalent amines act as binders.

For example, EP-A-583 086 describes aqueous binders Production of non-woven fabrics, in particular non-woven glass fabrics, known. The binders also contain a polycarboxylic acid at least two carboxylic acid groups and optionally also Anhydride groups and a polyol. These binders need one phosphorus-containing reaction accelerator to sufficient To achieve strength of the glass fiber fleece. It will be on it noted that the presence of such Reaction accelerator can only be dispensed with if a highly reactive polyol is used. As highly reactive polyols called β-hydroxyalkylamides.

EP-A 882 093 describes binders for moldings described, which consists of a radical polymerization polymer obtained from an unsaturated acid anhydride or an unsaturated dicarboxylic acid and an alkanolamine. Such binders are u. a. along with wood shavings Manufacture of chipboard or fiberboard used.

DE-A 199 49 592 relates to aqueous polymer solutions, containing dissolved polymer particles from at least one polymer from ethylenically unsaturated carboxylic acids and esters of unsaturated carboxylic acids and other monomers. such aqueous polymer solutions are also u. a. as a binder for Wood fibers used.

However, EP-A 882 093 and DE-A 199 49 592 do not known, such aqueous solutions or such aqueous Polymer dispersions as binders for constructive wood glue construction use. In constructive wood glue construction, are compared with the gluing of wood shavings or wood chips, relatively large wooden components are used, which are considerably smaller Show surface / volume ratio as small wood chips or wood chips.

In constructive wood glue construction, the is used to glue the large wooden slats usually used as binders phenolic Formaldehyde resins or urea-formaldehyde resins. adversely on these binders there is both the emission of formaldehyde when gluing the wooden slats to larger wooden components than even when used later.

The present invention was therefore based on the object remedied disadvantages and a formaldehyde-free To provide binders for constructive wood glue construction, which is a good adhesion of the wooden slats to each other allows.

• - 50 bis 99,5 Gew.-% mindestens einer ethylenisch ungesättigten Mono- und/oder Dicarbonsäure,
• - 0,5 bis 50 Gew.-% wenigstens einer ethylenisch ungesättigten Verbindung, die ausgewählt ist unter den Estern ethylenisch ungesättigter Monocarbonsäuren und den Halbestern und Diestern ethylenisch ungesättigter Dicarbonsäuren mit einem mindestens eine Hydroxylgruppe aufweisenden Amin,
• - bis zu 20 Gew.-% mindestens eines weiteren Monomers

als Bindemittel für die konstruktive Holzverleimung gefunden. Accordingly, the use of an aqueous polymer dispersion containing dispersed polymer particles of at least one polymer A1, which can be obtained by radical emulsion polymerization in the presence of a polymer A2, is composed of

• 50 to 99.5% by weight of at least one ethylenically unsaturated mono- and / or dicarboxylic acid,
• 0.5 to 50% by weight of at least one ethylenically unsaturated compound which is selected from the esters of ethylenically unsaturated monocarboxylic acids and the half-esters and diesters of ethylenically unsaturated dicarboxylic acids with an amine having at least one hydroxyl group,
• - Up to 20 wt .-% of at least one other monomer

found as a binder for constructive wood gluing.

In connection with the monomer components of the polymer A1, alkyl in the following preferably represents straight-chain or branched C ₁ -C ₂₂ -alkyl radicals, in particular C ₁ -C ₁₂ - and particularly preferably C ₁ -C ₆ -alkyl radicals, such as methyl, ethyl, n- Propyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, 2-ethylhexyl, n-dodecyl or n-stearyl.

Hydroxyalkyl is preferably hydroxy-C ₁ -C ₆ -alkyl, where the alkyl radicals can be straight-chain or branched, and in particular 2-hydroxyethyl, 2- or 3-hydroxypropyl, 2-methyl-2-hydroxypropyl and 4-hydroxybutyl.

Cycloalkyl is preferably C ₅ -C ₇ cyclohexyl, especially cyclopentyl and cyclohexyl.

Aryl is preferably phenyl or naphthyl.

• - 80 bis 100 Gew.-%, bevorzugt 85 bis 99,9 Gew.-%, bezogen auf das Gesamtgewicht der Monomere für das Polymerisat, wenigstens eines ethylenisch ungesättigten Hauptmonomeren sowie
• - 0 bis 20 Gew.-%, bevorzugt 0,1 bis 15 Gew.-%, bezogen auf das Gesamtgewicht der Monomere für das Polymerisat, wenigstens eines ethylenisch ungesättigten Comonomeren.

The polymer A1 is a free-radical emulsion polymer. All monomers polymerizable by free-radical polymerization can be used to produce it. The polymer is generally composed of

• 80 to 100% by weight, preferably 85 to 99.9% by weight, based on the total weight of the monomers for the polymer, of at least one ethylenically unsaturated main monomer and
• 0 to 20% by weight, preferably 0.1 to 15% by weight, based on the total weight of the monomers for the polymer, of at least one ethylenically unsaturated comonomer.

• - Estern aus vorzugsweise 3 bis 6 C-Atomen aufweisenden α,β-monoethylenisch ungesättigten Mono- oder Dicarbonsäuren, wie Acrylsäure, Methacrylsäure, Maleinsäure, Fumarsäure und Itaconsäure mit C₁-C₁₂-, vorzugsweise C₁-C₈-Alkanolen. Derartige Ester sind insbesondere Methyl-, Ethyl-, n-Butyl-, Isobutyl-, tert-Butyl-, n-Pentyl-, iso-Pentyl- und 2-Ethylhexylacrylat und/oder -methacrylat;
• - vinylaromatischen Verbindungen, bevorzugt Styrol, α-Methylstyrol, o-Chlorstyrol, Vinyltoluolen und Mischungen davon;
• - Vinylestern von C₁-C₁₈-Mono- oder Dicarbonsäuren, wie Vinylacetat, Vinylpropionat, Vinyl-n-butyrat, Vinyllaurat und/oder Vinylstearat;
• - Butadien;
• - linearen 1-Olefinen, verzweigtkettigen 1-Olefinen oder cyclischen Olefinen, wie z. B. Ethen, Propen, Buten, Isobuten, Penten, Cyclopenten, Hexen oder Cyclohexen. Des Weiteren sind auch Metallocen-katalysiert hergestellte Oligoolefine mit endständiger Doppelbindung, wie z. B. Oligopropen oder Oligohexen geeignet;
• - Acrylnitril, Methacrylnitril;
• - Vinyl- und Allylalkylethern mit 1 bis 40 Kohlenstoffatomen im Alkylrest, wobei der Alkylrest noch weitere Substituenten, wie eine oder mehrere Hydroxylgruppen, eine oder mehrere Amino- oder Diaminogruppen oder eine bzw. mehrere Alkoxylatgruppen tragen kann, wie z. B. Methylvinylether, Ethylvinylether, Propylvinylether und 2-Ethylhexylvinylether, Isobutylvinylether, Vinylcyclohexylether, Vinyl-4-hydroxybutylether, Decylvinylether, Dodecylvinylether, Octadecylvinylether, 2-(Diethylamino)ethylvinylether, 2-(Di-nbutyl-amino)ethylvinylether, Methyldiglykolvinylether sowie die entsprechenden Allylether bzw. deren Mischungen.

The main monomer is preferably selected from

• Esters of α, β-monoethylenically unsaturated mono- or dicarboxylic acids, preferably having 3 to 6 carbon atoms, such as acrylic acid, methacrylic acid, maleic acid, fumaric acid and itaconic acid with C ₁ -C ₁₂ -, preferably C ₁ -C ₈ -alkanols. Such esters are in particular methyl, ethyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl and 2-ethylhexyl acrylate and / or methacrylate;
• vinyl aromatic compounds, preferably styrene, α-methylstyrene, o-chlorostyrene, vinyltoluenes and mixtures thereof;
• - Vinyl esters of C ₁ -C ₁₈ mono- or dicarboxylic acids, such as vinyl acetate, vinyl propionate, vinyl n-butyrate, vinyl laurate and / or vinyl stearate;
• - butadiene;
• - Linear 1-olefins, branched-chain 1-olefins or cyclic olefins, such as. B. ethene, propene, butene, isobutene, pentene, cyclopentene, hexene or cyclohexene. Furthermore, metallocene-catalyzed oligoolefins with a terminal double bond, such as. B. oligopropene or oligohexene suitable;
• - acrylonitrile, methacrylonitrile;
• - Vinyl and allyl alkyl ethers having 1 to 40 carbon atoms in the alkyl radical, where the alkyl radical can also carry further substituents, such as one or more hydroxyl groups, one or more amino or diamino groups or one or more alkoxylate groups, such as, for. B. methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether and 2-ethylhexyl vinyl ether, isobutyl vinyl ether, vinyl cyclohexyl ether, vinyl 4-hydroxybutyl ether, decyl vinyl ether, dodecyl vinyl ether, octadecyl vinyl ether, 2- (diethylamino) ethyl vinyl ether, 2- (di-n-butylamino) ethyl vinyl ether, and methyl digly Allyl ether or mixtures thereof.

Particularly preferred main monomers are styrene, Methyl methacrylate, n-butyl acrylate, ethyl acrylate, 2-ethylhexyl acrylate, Vinyl acetate, ethene and butadiene.

• - ethylenisch ungesättigten Mono- oder Dicarbonsäuren oder deren Anhydriden, vorzugsweise Acrylsäure, Methacrylsäure, Methacrylsäureanhydrid, Maleinsäure, Maleinsäureanhydrid, Fumarsäure und/oder Itaconsäure;
• - Acrylamiden und alkylsubstituierten Acrylamiden, wie z. B. Acrylamid, Methacrylamid, N,N-Dimethylacrylamid, N-Methylolmethacrylamid, N-tert.-Butylacrylamid, N-Methylmethacrylamid und Mischungen davon;
• - sulfogruppenhaltigen Monomeren, wie z. B. Allylsulfonsäure, Methallylsulfonsäure, Styrolsulfonsäure, Vinylsulfonsäure, 2-Acrylamido-2-methylpropansulfonsäure, Allyloxybenzolsulfonsäure, deren entsprechenden Alkali- oder Anznoniumsalzen bzw. deren Mischungen sowie Sulfopropylacrylat und/oder Sulfopropylmethacrylat;
• - C₁-C₄-Hydroxyalkylestern von C₃-C₆-Mono- oder Dicarbonsäuren, insbesondere der Acrylsäure, Methacrylsäure oder Maleinsäure, oder deren mit 2 bis 50 Mol Ethylenoxid, Propylenoxid, Butylenoxid oder Mischungen davon alkoxylierten Derivate oder Estern von mit 2 bis 50 Mol Ethylenoxid, Propylenoxid, Butylenoxid oder Mischungen davon alkoxylierten C₁-C₁₈-Alkoholen mit den erwähnten Säuren, wie z. B. Hydroxyethylacrylat, Hydroxyethylmethacrylat, Hydroxypropylacrylat, Hydroxypropylmethacrylat, Butandiol-1,4-monoacrylat, Ethyldiglykolacrylat, Methylpolyglykolacrylat (11 EO), (Meth)acrylsäureester von mit 3,5,7,10 oder 30 Mol Ethylenoxid umgesetztem C₁₃/C₁₅ -Oxoalkohol bzw. deren Mischungen;
• - Vinylphosphonsäuren und deren Salzen, Vinylphosphonsäuredimethylester und anderen phosphorhaltigen Monomeren;
• - Alkylaminoalkyl(meth)acrylaten oder Alkylaminoalkyl(meth)acrylamiden oder deren Quarternisierungsprodukten, wie z. B. 2-(N,N-Dimethylamino)-ethyl(meth)acrylat oder 2-(N,N,N-Trimethylammonium)-ethylmethacrylat-chlorid, 3-(N,N- Dimethylamino)-propyl(meth)acrylat, 2-Dimethylaminoethyl(meth)acrylamid, 3-Dimethylaminopropyl(meth)acrylamid, 3-Trimethylammoniumpropyl(meth)acrylamid-chlorid und Mischungen davon;
• - Allylestern von C₁-C₃₀-Monocarbonsäuren;
• - N-Vinylverbindungen, wie N-Vinylformamid, N-Vinyl-N-methylformamid, N-Vinylpyrrolidon, N-Vinylimidazol, 1-Vinyl-2-methyl-imidazol, 1-Vinyl-2-methylimidazolin, 2-Vinylpyridin, 4-Vinylpyridin, N-Vinylcarbazol und/oder N-Vinylcaprolactam;
• - Diallyldimethylammoniumchlorid, Vinylidenchlorid, Vinylchlorid, Acrolein, Methacrolein;
• - 1,3-Diketogruppen enthaltenden Monomeren, wie z. B. Acetoacetoxyethyl(meth)acrylat oder Diacetonacrylamid, harnstoffgruppenhaltigen Monomeren, wie Ureidoethyl(meth)acrylat, Acrylamidoglykolsäure, Methacrylamidoglykolatmethylether;
• - Silylgruppen enthaltenden Monomeren, wie z. B. Trimethoxysilylpropylmethacrylat;
• - Glycidylgruppen enthaltenden Monomeren, wie z. B. Glycidylmethacrylat.

The comonomer is preferably selected from

• - Ethylenically unsaturated mono- or dicarboxylic acids or their anhydrides, preferably acrylic acid, methacrylic acid, methacrylic anhydride, maleic acid, maleic anhydride, fumaric acid and / or itaconic acid;
• - Acrylamides and alkyl-substituted acrylamides, such as. B. acrylamide, methacrylamide, N, N-dimethylacrylamide, N-methylol methacrylamide, N-tert-butylacrylamide, N-methyl methacrylamide and mixtures thereof;
• - Monomers containing sulfo groups, such as. B. allylsulfonic acid, methallylsulfonic acid, styrenesulfonic acid, vinylsulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, allyloxybenzenesulfonic acid, their corresponding alkali or anznonium salts or their mixtures, and sulfopropyl acrylate and / or sulfopropyl methacrylate;
• - C ₁ -C ₄ hydroxyalkyl esters of C ₃ -C ₆ mono- or dicarboxylic acids, in particular acrylic acid, methacrylic acid or maleic acid, or their derivatives or alkoxylated derivatives or esters of with 2 to 50 mol ethylene oxide, propylene oxide, butylene oxide or mixtures thereof up to 50 moles of ethylene oxide, propylene oxide, butylene oxide or mixtures thereof alkoxylated C ₁ -C ₁₈ alcohols with the acids mentioned, such as. B. hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, butanediol-1,4-monoacrylate, ethyl diglycol acrylate, methyl polyglycol acrylate (11 EO), (meth) acrylic acid ester of C ₁₃ / C ₁₅ - reacted with 3,5,7,10 or 30 mol ethylene oxide - Oxo alcohol or mixtures thereof;
• - Vinylphosphonic acids and their salts, dimethyl vinylphosphonate and other phosphorus-containing monomers;
• - Alkylaminoalkyl (meth) acrylates or alkylaminoalkyl (meth) acrylamides or their quaternization products, such as. B. 2- (N, N-dimethylamino) ethyl (meth) acrylate or 2- (N, N, N-trimethylammonium) ethyl methacrylate chloride, 3- (N, N-dimethylamino) propyl (meth) acrylate, 2-dimethylaminoethyl (meth) acrylamide, 3-dimethylaminopropyl (meth) acrylamide, 3-trimethylammonium propyl (meth) acrylamide chloride and mixtures thereof;
• - Allyl esters of C ₁ -C ₃₀ monocarboxylic acids;
• - N-vinyl compounds, such as N-vinylformamide, N-vinyl-N-methylformamide, N-vinylpyrrolidone, N-vinylimidazole, 1-vinyl-2-methylimidazole, 1-vinyl-2-methylimidazoline, 2-vinylpyridine, 4- Vinyl pyridine, N-vinyl carbazole and / or N-vinyl caprolactam;
• - diallyldimethylammonium chloride, vinylidene chloride, vinyl chloride, acrolein, methacrolein;
• - Monomers containing 1,3-diketo groups, such as. B. acetoacetoxyethyl (meth) acrylate or diacetone acrylamide, monomers containing urea groups, such as ureidoethyl (meth) acrylate, acrylamidoglycolic acid, methacrylamidoglycolate methyl ether;
• - Monomers containing silyl groups, such as. B. trimethoxysilylpropyl methacrylate;
• - Monomers containing glycidyl groups, such as. B. Glycidyl methacrylate.

Particularly preferred comonomers are hydroxyethyl acrylate, Hydroxypropyl acrylate, hydroxybutyl acrylate, hydroxyethyl methacrylate and Mixtures of these. Are very particularly preferred Hydroxyethyl acrylate and hydroxyethyl methacrylate, especially in amounts of 2 to 20 wt .-%, based on the total monomer A1.

The polymer A2 contains 50 to 99.5% by weight, preferably 70 to 99% by weight of such structural elements built in, which differ from at least one ethylenically unsaturated mono- or dicarboxylic acid derived. If desired, these acids can be present in the polymer also partially or completely in the form of a salt. The acid form is preferred.

Polymer A2 is preferably more than 10 g / l (at 25 ° C.) soluble in water.

Useful ethylenically unsaturated carboxylic acids have already been mentioned above in connection with the polymer A1. Preferred carboxylic acids are C ₃ - to C ₁₀ -monocarboxylic acids and C ₄ - to C ₈ -dicarboxylic acids, in particular acrylic acid, methacrylic acid, crotonic acid, fumaric acid, maleic acid, 2-methylmaleic acid and / or itaconic acid. Acrylic acid, methacrylic acid, maleic acid and mixtures thereof are particularly preferred. In the preparation of polymer A2, it is of course also possible to use anhydrides such as maleic anhydride, acrylic or methacrylic anhydride instead of or together with the acids.

Polymer A2 also contains 0.5 to 50% by weight, preferably 1 up to 30 wt .-%, at least one ethylenically unsaturated Compound which is selected from the ethylenic esters unsaturated monocarboxylic acids and the half-esters and diesters ethylenically unsaturated dicarboxylic acids with at least one hydroxyl-containing amine, in copolymerized form.

The polymer A2 is preferably covalent as a comb polymer bound amine side chains.

Monocarboxylic acids suitable as components of the esters are the aforementioned C ₃ to C ₁₀ monocarboxylic acids, in particular acrylic acid, methacrylic acid, crotonic acid, and mixtures thereof.

Dicarboxylic acids suitable as components of the half esters and diesters are the aforementioned C ₄ to C ₈ dicarboxylic acids, in particular fumaric acid, maleic acid, 2-methyl maleic acid, itaconic acid, and mixtures thereof.

The amine having at least one hydroxyl group is preferably selected from secondary and tertiary amines which have at least one C ₆ -C ₂₂ -alkyl, C ₆ -C ₂₂ -alkenyl, aryl-C ₆ -C ₂₂ -alkyl or Aryl-C ₆ - to C ₂₂ -alkenyl radical, where the alkenyl group 1, 2 or 3 may not have adjacent double bonds.

The amine is preferably hydroxyalkylated and / or alkoxylated. Alkoxylated amines preferably have one or two Alkylene oxide residues with terminal hydroxyl groups. Preferably point the alkylene oxide residues are 1 to 100, preferably 1 to 50, the same or different alkylene oxide units, randomly distributed or in the form of blocks. Preferred alkylene oxides are Ethylene oxide, propylene oxide and / or butylene oxide. Is particularly preferred Ethylene oxide.

The polymer A2 preferably contains an unsaturated compound based on an amine component, which contains at least one amine of the general formula (I)

R ^c NR ^a R ^b (I)

contains, where
R ^c is C ₆ - to C ₂₂ -alkyl, C ₆ - to C ₂₂ alkenyl, aryl-C ₆ -C ₂₂ alkyl or aryl-C ₆ -C ₂₂ alkenyl, wherein the alkenyl group 1, 2 or 3 may not have adjacent double bonds,
R ^a for hydroxy-C ₁ -C ₆ alkyl or a radical of formula II

- (CH ₂ CH ₂ O) _x (CH ₂ CH (CH ₃ ) O) _y -H (II)

stands where
in the formula II the order of the alkylene oxide units is arbitrary and x and y independently of one another represent an integer from 0 to 100, preferably 0 to 50, the sum of x and y being> 1,
R ^{b is} hydrogen, C ₁ - to C ₂₂ -alkyl, hydroxy-C ₁ -C ₆ -alkyl, C ₆ - to C ₂₂ -alkenyl, aryl-C ₆ -C ₂₂ -alkyl, aryl-C ₆ -C ₂₂ -alkenyl or C ₅ - to C ₈ -cycloalkyl, where the alkenyl radical 1, 2 or 3 may not have adjacent double bonds, or R ^{b represents} a radical of the formula III

- (CH ₂ CH ₂ O) _v (CH ₂ CH (CH ₃ ) O) _w -H (III)

stands where
in the formula III the order of the alkylene oxide units is arbitrary and v and w independently of one another represent an integer from 0 to 100, preferably 0 to 50.

R ^c is preferably C ₅ -C ₂₀ -alkyl or C ₅ -C ₂₀ -alkenyl, where the alkenyl radical may have 1, 2 or 3 non-adjacent double bonds. R ^c is preferably the hydrocarbon radical of a saturated or mono- or polyunsaturated fatty acid. Preferred radicals R ^c are e.g. B. n-octyl, ethylhexyl, undecyl, lauryl, tridecyl, myristyl, pentadecyl, palmityl, margarinyl, stearyl, palmitoleinyl, oleyl and linolyl.

The amine component is particularly preferably an alkoxylated fatty amine or an alkoxylated fatty amine mixture. The ethoxylates are particularly preferred. In particular, alkoxylates of amines based on naturally occurring fatty acids are used, such as. B. tallow fatty amines which contain predominantly saturated and unsaturated C ₁₄ -, C ₁₆ - and C ₁₈ -alkylamines or coconut amines which contain saturated, mono- and di-unsaturated C ₆ -C ₂₂ -, preferably C ₁₂ -C ₁₄ -alkylamines. Suitable amine mixtures for alkoxylation are e.g. B. various armies® -Mar-. brands from Akzo or Noram® brands from Ceca.

Suitable, commercially available alkoxylated amines are e.g. B. the Noramox® brands from Ceca, preferably ethoxylated Oleylamines, such as Noramox® 05 (5 EO units), and those under Lutensol® FA brand products from BASF AG.

The polymerization of the aforementioned esters, half esters and Diester generally causes pronounced stabilization the polymer dispersions to be used according to the invention. This maintain their colloidal stability of the latex particles Dilution with water or dilute electrolytes or surfactant solutions reliable at.

The esterification for the preparation of the esters, half esters and diesters described above is carried out by customary processes known to the person skilled in the art. To prepare esters of unsaturated monocarboxylic acids, the free acids or suitable derivatives such as anhydrides, halides, e.g. As chlorides, and (C ₁ - to C ₄ ) alkyl esters are used. Half-esters of unsaturated dicarboxylic acids are preferably prepared starting from the corresponding dicarboxylic acid anhydrides. The reaction is preferably carried out in the presence of a catalyst, such as. B. a dialkyl titanate or an acid such as sulfuric acid, toluenesulfonic acid or methanesulfonic acid. The reaction is generally carried out at reaction temperatures of 60 to 200 ° C. According to a suitable embodiment, the reaction takes place in the presence of an inert gas, such as nitrogen. Water formed in the reaction can be removed from the reaction mixture by suitable measures, such as distillation. If desired, the reaction can be carried out in the presence of customary polymerization inhibitors. The esterification reaction can be carried out essentially completely or only up to a partial conversion. If desired, one of the ester components, preferably the amine containing hydroxyl groups, can be used in excess. The proportion of ester formation can be determined using infrared spectroscopy.

According to a preferred embodiment, the production takes place the unsaturated esters, half esters or diesters and their others Conversion to the polymers A2 used according to the invention without intermediate isolation of the esters and preferably in succession in the same reaction vessel.

A is preferred for the preparation of the polymers A2 Reaction product from a dicarboxylic anhydride, preferably Maleic anhydride, and one of those previously described hydroxyl-containing amines used.

In addition to the components carboxylic acid and ester, half-ester and / or diesters, polymer A2 can still contain 0 to 20% by weight, preferably 0.1 to 10 wt .-%, other monomers copolymerized contain. Useful monomers are those related to the Monomers named polymer A1, vinyl aromatics, such as styrene, Olefins, for example ethylene, or (meth) acrylic acid esters such as Methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate and mixtures thereof in particular are preferred.

The polymers A2 are preferably prepared by radical polymerization in bulk or in solution. suitable Solvents for solvent polymerization are e.g. B. Water, water-miscible organic solvents such as alcohols and ketones, for example methanol, ethanol, n-propanol, Isopropanol, n-butanol, acetone, methyl ethyl ketone etc., and mixtures from that. Suitable polymerization initiators are, for example Peroxides, hydroperoxides, peroxodisulfates, percarbonates, Peroxoesters, hydrogen peroxide and azo compounds, as in Described in more detail below for the preparation of the polymer dispersions become. If desired, the polymers A2 can be separated manufactured and isolated and / or cleaned by conventional methods become. The polymers A2 are preferred immediately before Preparation of those to be used according to the invention Polymer dispersions made and without intermediate insulation for the Dispersion polymerization used.

The preparation of the polymers A2 can advantageously also by polymer-analogous implementation take place. For this purpose, a polymer that 80 to 100 wt .-% of at least one ethylenically unsaturated Mono- and / or dicarboxylic acid and 0 to 20 wt .-% of the previous contains other polymers mentioned, with at least one hydroxyl-containing amine are implemented.

Suitable ethylenically unsaturated mono- and dicarboxylic acids are those mentioned above as components of the polymers A1 and A2. Suitable amines which have at least one hydroxyl group are also those mentioned above. If desired, some or all of the acids in the polymer used for the polymer-analogous reaction can be present in the form of a derivative, preferably a C ₁ -C ₆ -alkyl ester.

The preparation of polymers A2 by polymer-analog The reaction is preferably carried out in a suitable non-aqueous Solvent or in bulk. When implemented in substance the amine enthalpy can optionally be used in excess to serve as a solvent. Are preferred Solvents that form an azeotrope with water and thus a easy removal of the water formed in the reaction enable. The reaction is preferably carried out in the presence of a Esterification catalyst as previously described. The The reaction temperature is preferably in a range from 100 to 200 ° C. In the Reaction water can be taken by appropriate measures, such as z. B. distilling, are removed.

The weight ratio of polymer A1 to polymer A2 Solids basis, is preferably in the range from 7: 1 to 1: 7, especially 3: 1 to 1: 3.

In addition to the polymers A1 and A2, the latices according to the invention can also contain 0 to 50% by weight, preferably 0.1 to 40% by weight, based on the polymer A2, of at least one surface-active, alkoxylated, preferably ethoxylated or propoxylated, alkylamine contain. Preferred alkyl amines are the alkyl amines of the formula R ^c NR ^a R ^b , as previously defined, which are also contained in the polymer A2, alkyl alkyl of the formula


in which R represents an alkyl, alkenyl or alkylvinyl radical having at least 6 carbon atoms and m and n independently of one another are ≥ 1, are particularly preferred. Preferred radicals R have 8 to 22 carbon atoms.

The alkoxylated alkylamines contained in polymer A2 and the additional alkylamine crosslinkers can be the same or be different connections.

If desired, the one to be used according to the invention Polymer dispersion contain other crosslinkers, for example one Amine or amide crosslinker with at least two hydroxyl groups. Suitable crosslinkers are in particular those in DE-A 197 29 161 disclosed alkanolamines, which are hereby incorporated by reference Disclosure content of the present invention can be made.

Further suitable crosslinkers are preferably β-hydroxyalkylamines of the formula


wherein R ^{1 represents} an H atom, a C ₁ to C ₁₀ alkyl group, a C _{1 to} C ₁₀ hydroxyalkyl group or a radical of the formula IV

- (CH ₂ CH ₂ O) _x (CH ₂ CH (CH ₃ ) O) _y -H (IV)

stands, in the formula IV the order of the alkylene oxide units is arbitrary and x and y independently of one another represent an integer from 0 to 100, the sum of x and y> 1 and R ² and R ³ independently of one another for a C. ₁ - to C ₁₀ hydroxyalkyl group.

R ² and R ³ are particularly preferably independently of one another a C ₂ - to C ₅ -hydroxyalkyl group and R ¹ for an H atom, a C ₁ - to C ₅ -alkyl group or a C ₂ - to C ₅ -hydroxyalkyl group.

Diethanolamine, triethanolamine, Diisopropanolamine, triisopropanolamine, methyldiethanolamine, Butyldiethanolamine and methyldiisopropanolamine, especially triethanolamine.

Further preferred β-hydroxyalkylamines are the amines disclosed as component A in DE-A 196 21 573, which are hereby incorporated by reference into the disclosure content of the present invention. These preferably include linear or branched aliphatic compounds which have at least two functional amino groups of type (a) or (b) per molecule


wherein R is hydroxyalkyl and R 'is alkyl, is preferably a compound of formula I.


wherein
A represents C ₂ -C ₁₈ alkylene, which is optionally substituted by one or more groups which are selected independently of one another from alkyl, hydroxyalkyl, cycloalkyl, OH and NR ⁶ R ⁷ , where R ⁶ and R ⁷ independently of one another are H. , Hydroxyalkyl or alkyl,
and which is optionally interrupted by one or more oxygen atoms and / or NR ⁵ groups, where R ^{5 is} H, hydroxyalkyl, (CH ₂ ) _n NR ⁶ R ⁷ , where n is 2 to 5 and R ⁶ and R ⁷ are have meanings given above, or alkyl, which in turn can be interrupted by one or more NR ⁵ groups, where R ^{5 has} the meanings given above and / or substituted by one or more NR ⁶ R ⁷ groups, where R ⁶ and R ^{7 has} the meanings given above;
or A represents a radical of the formula:


wherein
o, q and s independently of one another represent 0 or an integer from 1 to 6,
p and r independently of one another represent 1 or 2 and
t represents 0.1 or 2,
the cycloaliphatic radicals can also be substituted by 1, 2 or 3 alkyl radicals and
R ¹ , R ² and R ³ and R ^{4 are} independently H, hydroxyalkyl, alkyl or cycloalkyl.

Preferred higher-functional β-hydroxyalkylamines are in particular at least double ethoxylated amines with a molecular weight of below 1000 g / mol, e.g. B. diethanolamine, triethanolamine and ethoxylated diethylenetriamine, preferably stoichiometric ethoxylated diethylene triamine, d. H. Diethylenetriamine, in which all NH- Hydrogen atoms are simply ethoxylated on average.

Additional suitable crosslinkers are also β-hydroxyalkylamides, preferably the β-hydroxyalkylamides of the formula mentioned in US Pat. No. 5,143,582

Particularly preferred are the β-hydroxyalkylamides of the above formula, in which R ^{1 is} hydrogen, a short-chain alkyl group or HO (R ³ ) ₂ C (R ² ) ₂ C-, n and n 'each 1, -A- a - (CH ₂ ) _m group, m 0 to 8, preferably 2 to 8, R ^{2 are} each hydrogen, and one of the R ³ groups is each hydrogen and the other is hydrogen or C ₁ -C ₅ alkyl. Bis [N, N-di (2-hydroxyethyl)] adipic acid amide is particularly preferred.

The addition of the crosslinker generally produces a better one Hardening of the compositions to be used according to the invention given curing temperature or curing at a lower Temperature at a given curing time. The weight fraction of the Crosslinker relative to the sum of polymer A1 and A2 is 0 to 50% by weight, preferably 0.1 to 30% by weight.

Furthermore can be used in the invention Polymer dispersions are added to a reaction accelerator. Prefers are phosphorus-containing compounds, in particular hypophosphorous acid and its alkali and alkaline earth metal salts or alkali Tetrafluoroborates. Salts of Mn (II), Ca (II), Zn (II), Al (III), Sb (III) or Ti (IV) or strong acids, such as para-toluenesulfonic acid, trichloroacetic acid and chlorosulfonic acid can be used as Reaction accelerators are added. The weight fraction of the Reaction accelerator relative to the sum of polymer A1 and A2 is 0.1 to 5% by weight, preferably 0.1 to 2% by weight.

Particularly preferred compositions of the polymer dispersions to be used according to the invention are
70 to 45% by weight of polymer A1,
25 to 45% by weight of polymer A2 and, if appropriate
0 to 10% by weight of surface-active alkoxylated alkylamine,
0 to 30% by weight of crosslinker containing hydroxyl groups,
0 to 5 wt .-% reaction accelerator.

The preparation of those to be used according to the invention Polymer dispersion is preferably carried out by aqueous Emulsion polymerization, a batch, a semi-continuous or a continuous driving style is possible. It turned out to be advantageous to polymer A2 together with the monomers of Polymer A1 in the form of an emulsion feed into the reaction vessel to meter. If desired, the polymer A1 forming monomers and the polymer A2 partially or completely via two or more separate inlets to the reaction vessel be fed. The monomers can be pre-emulsified as well also supplied to the reaction vessel in non-pre-emulsified form become. According to a preferred embodiment, at least part of the polymer A2 together with at least one Monomer component of A1 fed to the reaction vessel. In general, aqueous polymer dispersions are advantageous obtained that have a lower viscosity than conventional dispersions. The polymer A2 can be partially or can be used completely as a reactor template. The use of a defined amount of a seed latex as a reactor template is for the Polymer dispersions to be used according to the invention are advantageous for the targeted setting of a particle size distribution. there can be 0 to 25% by weight, preferably 0.1 to 10% by weight, based on the polymer A1, a suitable seed latex use Find.

The polymer dispersion is usually prepared in Water as a dispersing medium. However, it can also be done with water miscible organic solvents, such as alcohols and ketones, for example methanol, ethanol, n-propanol, isopropanol, n-butanol, acetone or methyl ethyl ketone, up to a proportion of about 30 vol .-% be included.

The polymer A1 is thus by aqueous Emulsion polymerization in the presence of polymer A2 and, if present, preferably in the presence of a surface active amine, as before described, manufactured.

Those to be used according to the invention are preferred No additional emulsifiers added to dispersions.

The polymerization is preferably carried out in the presence of radicals forming compounds (initiators) carried out. You need of these compounds, preferably 0.05 to 10, especially preferably 0.2 to 5 wt .-%, based on the at Polymerization used monomers.

Suitable polymerization initiators are, for example, peroxides, hydroperoxides, peroxodisulfates, percarbonates, peroxoesters, hydrogen peroxide and azo compounds. Examples of initiators which can be water-soluble or water-insoluble are hydrogen peroxide, dibenzoyl peroxide, dicyclohexyl peroxidicarbonate, dilauroyl peroxide, methyl ethyl ketone peroxide, di-tert.-butyl peroxide, acetylacetone peroxide, tert.-butyl hydroperoxide, cumene hydroperoxide, tert.-butyl peroxide, tert.-butyl peryl .-Butyl perpivalate, tert.-butyl perneohexanoate, tert.-butyl per-2-ethylhexanoate, tert.-butyl perbenzoate, lithium, sodium, potassium and ammonium peroxydisulfate, azodiisobutyronitrile, 2,2'-azobis (2-amidinopropane) dihydrochloride , 2- (carbamoylazo) isobutyronitrile and 4,4-azobis (4-cyanovaleric acid). The known redox initiator systems such. B. H ₂ O ₂ / ascorbic acid or t-butyl hydroperoxide / sodium hydroxymethanesulfinate can be used as polymerization initiators.

The initiators can be used alone or as a mixture with one another be applied, e.g. B. mixtures of hydrogen peroxide and Sodium peroxodisulfate. For polymerization in an aqueous medium water-soluble initiators are preferably used.

To low average molecular weight polymers it is often advantageous to prepare the copolymerization in the presence by regulators. Common controllers can do this are used, such as organic SH groups containing compounds, such as 2-mercaptoethanol, 2-mercaptopropanol, Mercaptoacetic acid, tert-butyl mercaptan, n-octyl mercaptan, n- Dodecyl mercaptan and tert-dodecyl mercaptan, Hydroxylammonium salts such as hydroxylammonium sulfate, formic acid, sodium bisulfite or isopropanol. The polymerization regulators are generally in amounts of 0.05 to 5% by weight, based on the monomers, used.

It is often necessary to produce higher molecular weight copolymers useful to in the polymerization in the presence of crosslinkers work. Such crosslinkers are compounds with two or more ethylenically unsaturated groups, such as diacrylates or dimethacrylates of at least divalent saturated Alcohols such as B. ethylene glycol diacrylate, Ethylene glycol dimethacrylate, 1,2-propylene glycol diacrylate, 1,2-propylene glycol dimethacrylate, butanediol 1,4-diacrylate, butanediol 1,4-dimethacrylate, Hexanediol diacrylate, hexanediol dimethacrylate, Neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, 3-methylpentanediol diacrylate and 3-methylpentanediol dimethacrylate. The acrylic acid and methacrylic acid esters of alcohols with more than 2 OH groups can be used as crosslinkers, e.g. B. Trimethylolpropane triacrylate or trimethylolpropane trimethacrylate. Another Class of crosslinkers are diacrylates or dimethacrylates from Polyethylene glycols or polypropylene glycols with Molecular weights of 200 to 9,000 each.

Except for the homopolymers of ethylene oxide or propylene oxide can also block copolymers of ethylene oxide and propylene oxide or copolymers of ethylene oxide and propylene oxide be the ethylene oxide and propylene oxide units included statistically distributed. Also the oligomers of ethylene oxide or propylene oxide are for the production of the crosslinkers suitable, e.g. B. diethylene glycol diacrylate, diethylene glycol dimethacrylate, Triethylene glycol diacrylate, triethylene glycol dimethacrylate, Tetraethylene glycol diacrylate and / or tetraethylene glycol dimethacrylate.

Also suitable as crosslinkers are vinyl acrylate, Vinyl methacrylate, vinyl itaconate, adipic acid divinyl ester, Butanediol divinyl ether, trimethylolpropane trivinyl ether, allyl acrylate, Allyl methacrylate, pentaerythritol triallyl ether, triallyl sucrose, Pentaallyl sucrose, pentaallyl sucrose, Methylenebis (meth) acrylamide, divinylethylene urea, divinyl propylene urea, Divinylbenzene, divinyldioxane, triallyl cyanurate, tetraallylsilane, Tetravinylsilane and bis- or polyacrylic siloxanes (e.g. Tegomere® der Goldschmidt AG). The crosslinkers are preferably used in quantities from 10 ppm to 5% by weight, based on those to be polymerized monomers; used.

In addition to the ingredients mentioned, the aqueous Polymer dispersions are common additives depending on the application be included.

If necessary, additionally in the aqueous polymer dispersion contained components are after the end of Emulsion polymerization added.

Furthermore, the aqueous polymer dispersions can be conventional additives included according to application. For example, they can Contain bactericides or fungicides. In addition, they can Hydrophobing agent to increase the water resistance of the treated substrates included. Suitable water repellents are usual aqueous paraffin dispersions or silicones. Further The compositions can include wetting agents, thickeners, Plasticizers, retention aids, pigments and fillers contain. The mixing of these fillers can also be done by Induction heating takes place, which facilitates curing.

In addition, it can be recommended for faster Cross-linking at lower temperatures still certain Add epoxy compounds, for example, di- or trifunctional Glycidyl ethers such as bisphenol A diglycidyl ether or Butanediol diglycidyl ether, especially aromatic and aliphatic glycidyl ether. Other suitable epoxy compounds are cycloaliphatic Glycidyl compounds, heterocyclic glycidyl compounds and cycloaliphatic epoxy resins.

Finally, the aqueous polymer dispersions can be conventional Fire retardants such as B. aluminum silicates, Contain aluminum hydroxides, borates and / or phosphates.

The aqueous polymer dispersions often also contain Coupling reagents such as alkoxysilanes, for example 3-aminopropyltriethoxysilane, soluble or emulsifiable oils as lubricants and Dust binders and wetting aids.

The aqueous polymer dispersions can also be mixed with other binders, such as urea-formaldehyde Resins, melamine-formaldehyde resins or Phenol-formaldehyde resins, as well as be used with epoxy resins.

The aqueous polymer dispersions are free of formaldehyde. Formaldehyde-free means that the compositions according to the invention do not contain any significant amounts of formaldehyde and also at Drying and / or curing no significant amounts Formaldehyde are released. Generally they contain Compositions <100 ppm formaldehyde.

The formaldehyde-free, aqueous polymer dispersions are before Application essentially uncrosslinked and therefore thermoplastic. If necessary, however, a low level of pre-crosslinking can be used the polymer A1 can be set, for. B. by use of monomers with two or more polymerizable groups.

The aqueous dispersions to be used according to the invention consist essentially of finely divided emulsion polymer particles of A1 and an aqueous phase containing the polymer A2 and optionally added separately or during the esterification unreacted amine, and optionally other water-soluble additives, e.g. B. crosslinker.

It can form in the aqueous phase Superstructures come, such as B. by lamellar or spherical Aggregates formed lyotropic phases.

The monomer composition is generally chosen such that a glass transition temperature Tg in the range from -60 ° C. to + 150 ° C. results for the polymer A1. The glass transition temperature Tg of the polymers can in a known manner, for. B. can be determined by means of differential scanning calorimetry (DSC). The Tg can also be calculated approximately using the Fox equation. According to Fox TG, Bull. Am. Physics Soc. 1.3, page 123 (1956) applies: 1 / Tg = x ₁ / Tg ₁ + x ₂ / Tg ₂ +. , , + x _n / Tg _n , where x _{n stands} for the mass fraction (% by weight / 100) of the monomer n, and Tg _{n is} the glass transition temperature in Kelvin of the homopolymer of the monomer n. Tg values for homopolymers are listed in Polymer Handbook 3rd Edition, J. Wiley & Sons, New York (1989). For further processing into fiber insulation panels, polymers A1 with a glass transition temperature in the range from 60 to 120 ° C. are preferably used. For further processing into cork products, the glass transition temperature is preferably in a range from -50 to 90 ° C.

The aqueous polymer dispersions to be used according to the invention represent finely divided, stable latices. The weight-average Particle size of the latex particles is about 10 to 1500 nm, preferably 20 to 1000 nm, particularly preferably 30 to 500 nm, measured with the help of the analytical ultracentrifuge (AUZ).

The aqueous polymer dispersions to be used according to the invention can be diluted indefinitely with water or dilute salt or surfactant solutions without the latex particles coagulating. They have a nonvolatile content (solids content) in the range from about 20 to 75% by weight, preferably 25 to 65% by weight. The viscosity (with a solids content of 40% by weight) is generally in a range from about 10 to 4000 mPas, measured with a rotary viscometer in accordance with DIN 53019 at 23 ° C. and a shear rate of 250 s ^-1 .

The aqueous dispersions described are used according to the invention for constructive wood gluing. The aqueous polymer dispersion is first applied to the wooden lamellae to be glued on one or both sides and then hardened. Thermal curing at temperatures of 25 to 200 ° C. is preferred. The curing can also take place under a pressure of more than 0.02 N / mm ² , in particular more than 0.025 N / mm ^2, for a period of 1 to 120 minutes, in particular 2 to 60 minutes.

When heated, this evaporates in the aqueous dispersions contained water and the binder hardens. This Processes can run sequentially or simultaneously. Under In this context, hardening also becomes the chemical change understood the binder, e.g. B. networking through knotting of covalent bonds between the different components of compositions, formations of ionic interactions and clusters, hydrogen bond formation. Can continue during hardening also physical changes in the binder expire such. B. phase changes or phase inversions. An advantage of the aqueous dispersion is that it hardens comparatively low temperatures can take place. The duration and the temperature of the heating affect the Of cure.

Curing can also take place in two or more stages. So can e.g. B. in a first step the curing temperature and -Time should be chosen so that only a low degree of hardening is achieved and largely complete curing in one second step is done. This second step can be spatial and take place separately from the first step.

The aqueous dispersions described are well suited for the constructive wood glue construction, for example wooden slats a thickness of 2 to 5 cm, a width of 10 to approx. 25 cm and a length of 0.5 to approx. 6 m in layers to form slabs, beams or other wooden components can be glued. The Production of the wooden components takes place in constructive wood glue construction in general in automatic production lines, all preparatory steps like planing, width, thickness and Moisture measurement with sorting out, visual quality class sorting, Binder assembly and the actual gluing (Becker / Braun, Kunststoff-Handbuch, 10, Thermosets, Chapter 7.11 DM. Dunky "constructive wood glue construction").

• A) ein durch radikalische Polymerisation erhaltenes Polymerisat, welches zu 5 bis 100 Gew.-% aus einem ethylenisch ungesättigten Säureanhydrid oder einer ethylenisch ungesättigten Dicarbonsäure, deren Carbonsäuregruppen eine Anhydridgruppe bilden können, besteht und
• B) ein Alkanolamin mit mindestens zwei Hydroxylgruppen,

als Bindemittel für die konstruktive Holzverleimung. Furthermore, the present invention also relates to the use of an aqueous solution containing

• A) a polymer obtained by free-radical polymerization, which consists of 5 to 100% by weight of an ethylenically unsaturated acid anhydride or an ethylenically unsaturated dicarboxylic acid, the carboxylic acid groups of which can form an anhydride group, and
• B) an alkanolamine with at least two hydroxyl groups,

as a binder for constructive wood gluing.

The aqueous binder contains a polymer A) which 5 up to 100% by weight, preferably 5 to 50% by weight, particularly preferably 10 up to 40 wt .-% of an ethylenically unsaturated acid anhydride or an ethylenically unsaturated dicarboxylic acid, the Carboxylic acid groups can form an anhydride group, is built (im called the following monomers a)).

Dicarboxylic acid anhydrides are preferred as acid anhydrides. Suitable ethylenically unsaturated dicarboxylic acids are generally those with carboxylic acid groups on adjacent carbon atoms. The carboxylic acid groups can also be in the form of their salts.

Preferred monomers a) are maleic acid, Maleic anhydride, itaconic acid, norbornenedicarboxylic acid, 1,2,3,6-tetrahydrophthalic acid, 1,2,3,6-tetrahydrophthalic anhydride, the Alkali and ammonium salts or mixtures thereof are used. Maleic acid and maleic anhydride are particularly preferred.

In addition to monomers a), the polymer can also monomers b) contain.

Examples of monomers b) which can be used are:
Monoethylenically unsaturated C ₃ - to C ₁₀ -monocarboxylic acids (monomers b ₁ ), such as. As acrylic acid, methacrylic acid, ethyl acrylic acid, allylacetic acid, crotonic acid, vinyl acetic acid, maleic acid semiesters such as monomethyl maleate, their mixtures or their alkali and ammonium salts.

Linear 1-olefins, branched-chain 1-olefins or cyclic olefins (monomers b ₂ ), such as, for. B. ethene, propene, butene, isobutene, pentene, cyclopentene, hexene, cyclohexene, octene, 2,4,4-trimethyl-1-pentene, optionally in a mixture with 2,4,4-trimethyl-2-pentene, C ₈ - C ₁₀ olefin, 1-dodecene, C ₁₂ -C ₁₄ olefin, octadecene, 1-eicosen (C ₂₀ ), C ₂₀ -C ₂₄ olefin; Metallocene-catalyzed oligo-olefins with a terminal double bond, such as. B. oligopropene, oligohexene and oligooctadecene; olefins produced by cationic polymerization with a high α-olefin content, such as. B. polyisobutene.

Vinyl and allyl alkyl ethers having 1 to 40 carbon atoms in the alkyl radical, where the alkyl radical can also carry further substituents such as a hydroxyl group, an amino or dialkylamino group or one or more alkoxylate groups (monomers b ₃ ), such as, for. B. methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, isobutyl vinyl ether, 2-ethylhexyl vinyl ether, vinyl cyclohexyl ether, vinyl 4-hydroxybutyl ether, decyl vinyl ether, dodecyl vinyl ether, octadecyl vinyl ether, 2- (diethylamino) ethyl vinyl ether, 2- (di-nbutylamino) ethyl vinyl ether, and methyl digly Allyl ether or mixtures thereof.

Acrylamides and alkyl-substituted acrylamides (monomers b ₄ ), such as. B. acrylamide, methacrylamide, N-tert-butylacrylamide, N-methyl (meth) acrylamide.

Monomers containing sulfo groups (monomers b ₅ ), such as, for. B. allylsulfonic acid, methallylsulfonic acid, styrene sulfonate, vinyl sulfonic acid, allyloxybenzenesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, their corresponding alkali metal or ammonium salts or mixtures thereof.

C ₁ to C ₈ alkyl esters or C ₁ to C ₄ hydroxyalkyl esters of acrylic acid, methacrylic acid or maleic acid or esters of C ₁ to C ₁₈ alcohols alkoxylated with 2 to 50 moles of ethylene oxide, propylene oxide, butylene oxide or mixtures thereof with acrylic acid , Methacrylic acid or maleic acid (monomers b ₆ ), such as. B. methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, butanediol-1,4-monoacrylate, maleic acid dibutyl ester, ethyl diglycol acrylate, methyl polyglycol acrylate (11 EO), (meth) acrylic acid ester of C ₁₃ / C ₁₅ - reacted with 3,5,7,10 or 30 mol ethylene oxide Oxo alcohol or mixtures thereof.

Alkylaminoalkyl (meth) acrylates or alkylaminoalkyl (meth) acrylamides or their quaternization products (monomers b ₇ ), such as. B. 2- (N, N-Dimethylamino) ethyl (meth) acrylate, 3- (N, N-Dimethylamino) propyl (meth) acrylate, 2- (N, N, N-Trimethylammonium) ethyl (meth) acrylate chloride , 2-dimethylaminoethyl (meth) acrylamide, 3-dimethylaminopropyl (meth) acrylamide, 3-trimethylammonium propyl (meth) acrylamide chloride.

Vinyl and allyl esters of C ₁ - to C ₃₀ -monocarboxylic acids (monomers b ₈ ), such as. B. vinyl formate, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl valerate, vinyl 2-ethylhexanoate, vinyl nonoate, vinyl decanoate, vinyl pivalate, vinyl palmitate, vinyl stearate, vinyl laurate.

The following may also be mentioned as further monomers b ₉ ):
N-vinylformamide, N-vinyl-N-methylformamide, styrene, α-methylstyrene, 3-methylstyrene, butadiene, N-vinylpyrrolidone, N-vinylimidazole, 1-vinyl-2-methylimidazole, 1-vinyl-2-methylimidazoline, N- Vinylcaprolactam, acrylonitrile, methacrylonitrile, allyl alcohol, 2-vinylpyridine, 4-vinylpyridine, diallyldimethylammonium chloride, vinylidene chloride, vinyl chloride, acrolein, methacrolein and vinylcarbazole or mixtures thereof.

In addition to monomers a), the polymer can also contain 0 to 95% by weight Monomers b) contain. The polymer preferably contains Monomers a) or monomers b) in amounts of 50 to 95, especially preferably from 60 to 90% by weight.

Preferred monomers are acrylic acid, methacrylic acid, ethene, Propene, butene, isobutene, cyclopentene, methyl vinyl ether, Ethyl vinyl ether, acrylamide, 2-acrylamido-2-methylpropanesulfonic acid, Vinyl acetate, styrene, butadiene, acrylonitrile or mixtures thereof.

Acrylic acid, methacrylic acid, ethene, Acrylamide, styrene and acrylonitrile or mixtures thereof.

Acrylic acid, methacrylic acid and Acrylamide or mixtures thereof.

The polymers can be prepared by customary polymerization processes are produced, e.g. B. by substance, emulsion, Suspension, dispersion, precipitation and solution polymerization. at the polymerization process mentioned is preferred under Exclusion of oxygen worked, preferably in one Nitrogen stream. For all polymerization methods, the usual Apparatus used, e.g. B. stirred tanks, stirred tank cascades, Autoclaves, tubular reactors and kneaders. Preference is given to the method the solution, emulsion, precipitation or Suspension polymerization worked. The methods of Solution and emulsion polymerization. The polymerization can take place in Solvents or diluents, such as. B. toluene, o-xylene, p-xylene, cumene, chlorobenzene, ethylbenzene, technical mixtures of Alkyl aromatics, cyclohexane, technical aliphatic mixtures, Acetone, cyclohexanone, tetrahydrofuran, dioxane, glycols and Glycol derivatives, polyalkylene glycols and their derivatives, diethyl ether, tert-butyl methyl ether, methyl acetate, isopropanol, Ethanol, water or mixtures such as B. Isopropanol / water mixtures can be run. Preferably as a solution or Diluent water, if necessary, in proportions up to 60 wt .-% of alcohols or glycols used. Especially water is preferably used.

The polymerization can be carried out at temperatures from 20 to 300, preferably from 60 to 200 W. Depending on the choice of the polymerization conditions, weight-average molecular weights, for. B. from 800 to 5,000,000, in particular from 1000 to 1,000,000. The weight average molecular weights M _w are preferably in the range from 2000 to 400 000. M _w is determined by gel permeation chromatography.

The polymerization is preferably carried out in the presence of radicals forming compounds carried out. You need of these Compounds up to 30, preferably 0.05 to 15, particularly preferably 0.2 to 8 wt .-%, based on that during the polymerization monomers used. With multi-component initiator systems (e.g. redox initiator systems) refer to the above Weight information on the sum of the components.

Suitable polymerization initiators are, for example Peroxides, hydroperoxides, peroxydisulfates, percarbonates, peroxiesters, Hydrogen peroxide and azo compounds. examples for Initiators, which can be water-soluble or water-insoluble, are hydrogen peroxide, dibenzoyl peroxide, Dicyclohexyl peroxidicarbonate, dilauroyl peroxide, methyl ethyl ketone peroxide, di-tert.- Butyl peroxide, acetylacetone peroxide, tert-butyl hydroperoxide, Cumene hydroperoxide, tert-butyl perneodecanoate, tert-amyl perpivalate, tert-butyl perpivalate, tert-butyl perneohexanoate, tert.- Butyl per-2-ethylhexanoate, tert-butyl perbenzoate, lithium, Sodium, potassium and ammonium peroxydisulfate, Azodiisobutyronitrile, 2,2'-azobis (2-amidinopropane) dihydrochloride, 2- (carbamoylazo) isobutyronitrile and 4,4-azobis (4-cyanovaleric acid).

The initiators can be used alone or as a mixture with one another be applied, e.g. B. mixtures of hydrogen peroxide and Sodium peroxodisulfate. For polymerization in an aqueous medium water-soluble initiators are preferably used.

The known redox initiator systems can also be used as Polymerization initiators are used. Such redox initiator systems contain at least one peroxide-containing compound in Combination with a redox coinitiator e.g. B. reducing effect Sulfur compounds, for example bisulfites, sulfites, Thiosulfates, dithionites and tetrathionates of alkali metals and Ammonium compounds. So you can make combinations of Use peroxodisulfates with alkali metal or ammonium hydrogen sulfites, z. B. ammonium peroxydisulfate and ammonium disulfite. The amount of peroxide-containing compound to the redox coinitiator is 30: 1 to 0.05: 1.

In combination with the initiators or Redox initiator systems can also use transition metal catalysts are used, e.g. B. salts of iron, cobalt, nickel, copper, Vanadium and manganese. Suitable salts are e.g. B. iron (II) sulfate, Cobalt-II-chloride, nickel-II-sulfate, copper-I-chloride. Related to the monomers become the reducing metal salt used in a concentration of 0.1 ppm to 1000 ppm. So you can combine hydrogen peroxide with iron (II) salts use, such as 0.5 to 30% hydrogen peroxide and 0.1 to 500 ppm of Mohr's salt.

Can also be used for polymerization in organic solvents in combination with the above initiators Redox coinitiators and / or transition metal catalysts are also used, z. As benzoin, dimethylaniline, ascorbic acid and organic soluble complexes of heavy metals, such as copper, cobalt, iron, Manganese, nickel and chrome. The amounts usually used Redox coinitiators or transition metal catalysts here usually about 0.1 to 1000 ppm, based on the Amounts of monomers used.

If the reaction mixture is at the lower limit of that for the Polymerization of the temperature range in question polymerized and then at a higher temperature polymerized out, it is appropriate to at least two different Initiators to use at different temperatures disintegrate, so that a sufficient in each temperature interval Concentration of radicals is available.

In order to produce polymers with a low average molecular weight, it is often expedient to carry out the copolymerization in the presence of regulators. Conventional regulators can be used for this, such as, for example, compounds containing organic SH groups, such as 2-mercaptoethanol, 2-mercaptopropanol, mercaptoacetic acid, tert-butyl mercaptan, n-octyl mercaptan, n-dodecyl mercaptan and tert-dodecyl mercaptan, C ₁ -C ₄ aldehydes, such as formaldehyde, acetaldehyde, propionaldehyde, hydroxylammonium salts such as hydroxylammonium sulfate, formic acid, sodium bisulfite or isopropanol. The polymerization regulators are generally used in amounts of 0.1 to 10% by weight, based on the monomers. The average molecular weight can also be influenced by the choice of a suitable solvent. Thus, the polymerization in the presence of diluents with benzylic H atoms leads to a reduction in the average molecular weight by chain transfer.

It is often necessary to produce higher molecular weight copolymers useful to in the polymerization in the presence of crosslinkers work. Such crosslinkers are compounds with two or more ethylenically unsaturated groups, such as diacrylates or dimethacrylates of at least divalent saturated Alcohols such as B. ethylene glycol diacrylate, Ethylene glycol dimethacrylate, 1,2-propylene glycol diacrylate, 1,2-propylene glycol dimethacrylate, butanediol 1,4-diacrylate, butanediol 1,4-dimethacrylate, Hexanediol diacrylate, hexanediol dimethacrylate, Neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, 3-methylpentanediol diacrylate and 3-methylpentanediol dimethacrylate. The acrylic acid and methacrylic acid esters of alcohols with more than 2 OH groups can be used as crosslinkers, e.g. B. Trimethylolpropane triacrylate or trimethylolpropane trimethacrylate. Another Class of crosslinkers are diacrylates or dimethacrylates from Polyethylene glycols or polypropylene glycols with Molecular weights of 200 to 9000 each. Polyethylene glycols or Polypropylene glycols used in the manufacture of diacrylates or Dimethacrylates used preferably have one Molecular weight from 400 to 2000 each. Except for the homopolymers of ethylene oxide or propylene oxide can also Block copolymers of ethylene oxide and propylene oxide or Copolymers of ethylene oxide and propylene oxide are used, which Statistically distributed ethylene oxide and propylene oxide units contain. Also the oligomers of ethylene oxide or propylene oxide are suitable for the production of crosslinkers, e.g. B. Diethylene glycol diacrylate, diethylene glycol dimethacrylate, Triethylene glycol diacrylate, triethylene glycol dimethacrylate, Tetraethylene glycol diacrylate and / or tetraethylene glycol dimethacrylate.

Also suitable as crosslinkers are vinyl acrylate, Vinyl methacrylate, vinyl itaconate, adipic acid divinyl ester, Butanediol divinyl ether, trimethylolpropane trivinyl ether, allyl acrylate, Allyl methacrylate, pentaerythritol triallyl ether, triallyl sucrose, Pentaallyl sucrose, pentaallyl sucrose, Methylenebis (meth) acrylamide, divinylethylene urea, divinyl propylene urea, Divinylbenzene, divinyldioxane, triallyl cyanurate, tetraallylsilane, Tetravinylsilane and bis- or polyacrylic siloxanes (e.g. Tegomere® der Goldschmidt AG). The crosslinkers are preferably used in quantities from 10 ppm to 5% by weight, based on those to be polymerized Monomers.

Is used according to the method of emulsion, precipitation, suspension or dispersion polymerization, it can be advantageous be, the polymer droplets or polymer particles through stabilize surface-active auxiliaries. typically, emulsifiers or protective colloids are used for this. Coming anionic, nonionic, cationic and amphoteric emulsifiers into consideration. Anionic emulsifiers are for example Alkylbenzenesulfonic acids, sulfonated fatty acids, sulfosuccinates, Fatty alcohol sulfates, alkylphenol sulfates and fatty alcohol ether sulfates. Examples of nonionic emulsifiers Alkylphenol ethoxylates, primary alcohol ethoxylates, fatty acid ethoxylates, Alkanolamide ethoxylates, fatty amine ethoxylates, EO / PO block copolymers and Alkyl polyglucosides can be used. As a cationic or Amphoteric emulsifiers are used for example: Quaternized Amine alkoxylates, alkyl betaines, alkyl amido betaines and sulfobetaines.

Typical protective colloids are, for example, cellulose derivatives, Polyethylene glycol, polypropylene glycol, copolymers from Ethylene glycol and propylene glycol, polyvinyl acetate, Polyvinyl alcohol, polyvinyl ether, starch and starch derivatives, dextran, Polyvinyl pyrrolidone, polyvinyl pyridine, polyethylene imine, Polyvinylimidazole, polyvinylsuccinimide, polyvinyl-2-methylsuccinimide, Polyvinyl-1,3-oxazolidone-2, polyvinyl-2-methylimidazoline and Copolymers containing maleic acid or maleic anhydride, as they e.g. B. are described in DE-A 25 01 123.

The emulsifiers or protective colloids are usually in Concentrations of 0.05 to 20% by weight, based on the monomers, used.

If polymerization is carried out in aqueous solution or dilution, then the monomers completely or before or during the polymerization partially neutralized by bases. Come as bases for example alkali or alkaline earth compounds such as Sodium hydroxide, potassium hydroxide, calcium hydroxide, magnesium oxide, Sodium; Ammonia; primary, secondary and tertiary amines, such as ethylamine, propylamine, monoisopropylamine, monobutylamine, Hexylamine, ethanolamine, dimethylamine, diethylamine, Di-n-propylamine. Tributylamine, triethanolamine, dimethoxyethylamine, 2-ethoxyethylamine, 3-ethoxypropylamine, dimethylethanolamine, Diisopropanolamine or morpholine in question.

Polybasic amines can also be used for neutralization are used, such as. B. ethylenediamine, 2-diethylaminethylamine, 2,3-diaminopropane, 1,2-propylenediamine, dimethylaminopropylamine, Neopentanediamine, hexamethylenediamine, 4,9-dioxadodecane-1,12-diamine, polyethyleneimine or polyvinylamine.

Preferably be partial or complete Neutralization of the ethylenically unsaturated carboxylic acids before or during the polymerization of ammonia, triethanolamine and diethanolamine used.

The ethylenically unsaturated are particularly preferred Carboxylic acids not neutralized before and during the polymerization. None is preferred even after the polymerization Neutralizing agent, apart from alkanolamine B), added. The The polymerization can be carried out in a variety of ways be carried out continuously or discontinuously. Usually, some of the monomers are optionally placed in a suitable diluent or solvent and optionally in the presence of an emulsifier, a protective colloid or other auxiliaries before, inerted, and increases the Temperature until the desired one is reached Polymerization temperature. However, it can only be a suitable one Diluent must be submitted. Within a defined Period, the radical initiator, other monomers and others Auxiliaries such as B. controller or crosslinker each optionally metered in a diluent. The approach times can be selected for different lengths. For example, one can choose a longer inflow time for the initiator inflow than for the monomer feed.

If the polymer is a Solution polymerization in water is usually no separation of the solvent necessary. However, there is a wish that Isolating polymer can, for. B. spray drying be performed.

If the polymer is processed using the solution, precipitation or or suspension polymerization in a steam volatile Solvent or solvent mixture prepared, so it can Solvents are separated by introducing steam, so as to arrive at an aqueous solution or dispersion. The Polymer can also from the organic diluent a drying process can be separated.

The polymers A) are preferably in the form of an aqueous Solution with solids contents of preferably 10 to 80% by weight, in particular 40 to 65% by weight.

Polymer A) can also be obtained by grafting maleic acid or Maleic anhydride or a maleic acid or Monomer mixture containing maleic anhydride on a graft base be preserved. Suitable graft bases are, for example Monosaccharides, oligosaccharides, modified polysaccharides and Alkyl polyglycol. Such graft polymers are described for example in DE-A 40 03 172 and EP-A 116 930.

Alkanolamines with at least two OH groups are used as component B). Alkanolamines of the formula (I ') are preferred


in which R ^{1 represents} an H atom, a C ₁ -C ₁₀ alkyl group or a C ₁ -C ₁₀ hydroxyalkyl group and R ² and R ^{3 represent} a C ₁ -C ₁₀ hydroxyalkyl group.

R ² and R ³ are particularly preferably, independently of one another, a C ₂ -C ₅ -hydroxyalkyl group and R ¹ for an H atom, a C ₁ -C ₅ -alkyl group or a C ₂ -C ₅ -hydroxyalkyl group.

As compounds of formula I 'z. B. diethanolamine, Triethanolamine, diisopropanolamine, triisopropanolamine, Methyldiethanolamine, butyldiethanolamine and methyldiisopropanolamine called. Triethanolamine is particularly preferred.

To prepare the aqueous solution, polymer A) and the alkanolamine B) preferably in such a ratio used to each other that the molar ratio of carboxyl groups Component A) and the hydroxyl groups of component B) 20: 1 to 1: 1, preferably 8: 1 to 5: 1 and particularly preferably 5: 1 to 1.7: 1 is (the anhydride groups are here as 2 carboxyl groups calculated).

The aqueous solution is prepared, for. B. just by Addition of the alkanolamine to the aqueous solution of the polymers A).

The aqueous solution preferably contains less than 1.5% by weight, in particular less than 1.0% by weight, particularly preferably less than 0.5% by weight and very particularly preferably less than 0.3% by weight, in particular less than 0.1% by weight, based on the Sum of A) + B) of a phosphorus containing Reaction accelerator. For the reaction accelerators containing phosphorus these are in particular alkali metal hypophosphites, -phosphites, -polyphosphates, -dihydrogenphosphates, Polyphosphoric acid, hypophosphoric acid, phosphoric acid, alkylphosphinic acid or Oligomers or polymers of these salts and acids.

The aqueous solution preferably contains no phosphorus containing reaction accelerator or none to accelerate the reaction effective amounts of a compound containing phosphorus. The aqueous solution may contain an esterification catalyst, such as z. B. sulfuric acid or p-toluenesulfonic acid of the titanates or Zirconates.

The aqueous solution described is used according to the invention for constructive wood gluing. The aqueous solution is first applied on one or two sides to the wooden slats to be glued and then hardened. Thermal curing at temperatures from 25 to 220 ° C., in particular at temperatures from 50 to 200 ° C., is preferred. The curing can also take place under a pressure of more than 0.02 N / mm ² , in particular more than 0.025 N / mm ^2, for a period of 1 to 120 minutes, in particular 2 to 60 minutes.

When heated, the water contained in the aqueous solution evaporates Water and the binder hardens. These processes can run sequentially or simultaneously. Under hardening the chemical change of the Binder understood, e.g. B. networking by knotting covalent bonds between the various components of the Composition, formation of ionic interactions and Clustering, formation of hydrogen bonds. Furthermore, at the hardening also physical changes in the binder expire such. B. phase changes or phase inversions. On The advantage of the aqueous solution is that it hardens comparatively low temperatures can take place. The duration and the temperature of the heating influence the degree of curing.

The aqueous solutions described have after drying (at 50 ° C, duration 72 hours) to a film with a thickness of 0.3 to 1 mm and then curing in air at 130 ° C for 15 minutes preferably a gel content above 50% by weight, particularly preferably above 60% by weight and very particularly preferably over 70% by weight. You are suitable is good for constructive wood glue construction, in which e.g. B. Wooden slats are glued.

The inventive use of the aqueous Polymer dispersion or the aqueous solution as a binder for the constructive wood glue construction it is possible to have good adhesion between the to achieve sticking wooden slats. Still stand out the resulting wooden components with a high Waterproof and are free from disturbing emissions of formaldehyde.

Examples

• A) Various aqueous polymer dispersions and aqueous polymer solutions to be used according to the invention were tested with white glue, which is customary as a wood glue, when gluing test specimens made of beech wood (gluing area: 500 mm ² : gluing fixed with clamps).

Acrodur® 950 L:
aqueous polymer solution from BASF Aktiengesellschaft consisting of 70 parts by weight of acrylic acid, 30 parts by weight of maleic acid and 30 parts by weight of triethanolamine
Acrodur® Dispersion (A502 / 121):
aqueous polymer dispersion from BASF Aktiengesellschaft made from 100 parts by weight of acid copolymer (from 56% by weight of acrylic acid, 24% by weight of maleic anhydride, 20% by weight of Uniperol® AC, amine emulsifier from BASF AG), 70 parts by weight of styrene , 25 parts by weight of methyl methacrylate, 5 parts by weight of hydroxyethyl acrylate, 9 parts by weight of TEA (triethanolamine)
Epikote® 828:
Bisphenol A diglycidyl ether, commercial product from Shell AG
substrate:
Buchholz / Buchholz
bond area:
25 × 20 mm
Job Type:
with 1 mm notched trowel on both sides
Coating weight:
100 g / m ² dry
drying:
5 minutes at 60 ° C
Crosslinking: 20 minutes at 100, 130 and 180 ° C with 1 N / mm ² load
Storage conditions:
A = 6 days standard climate
based on
B = 7 days standard climate + 4 days cold water
DIN EN 204
C = 6 days standard climate + 6 hours of cooking water + 2 hours of cold water
Exam:
Compression shear strength in N / mm ² in a standard climate

The results of the tests carried out are shown in Table I below.

It can be seen from the results that the use an aqueous polymer solution (Acrodur 950 L) or an aqueous one Polymer dispersion (Acrodur dispersion) as a binder the previously used white glue to a significantly improved Compressive shear strength leads.

B) Determination of the compressive shear strength Sense and purpose

This test specification describes the preparations and the Testing the dynamic pressure shear strength of technical Laminations.

application frame

This test specification is applicable when testing the Adhesive properties of products for the production of Wood adhesives.

terms

Dynamic compression shear strength - is the force that one Adhesive in a lamination separating under dynamic Opposed to pressure shear stress.

Substrate is the material to which the adhesive is applied Determining its adhesive properties is applied.

Required devices

Tooth spatula, toothing 1 × 1 millimeter
Bonding aid (manufacturer: BASF, 67056 Ludwigshafen)
Screw pinch valve with hexagon screw
Torque wrench to achieve a pressure of 1 N / mm ²
Warming cabinet up to 200 ° C
Pressure shear device (manufacturer: BASF, 67056 Ludwigshafen)
tensile testing machine

substrates

Beech wood, dimensions 35 × 25 × 5 millimeters, angle between the annual ring layers and the surfaces to be glued: 30-90 ° (Supplier: Rocholl GmbH, Alter Gartenweg 6-8, 69436 Schönbrunn-Moosbrunn)

bond area

25 × 20 mm

adhesive application

The adhesive is applied on one or both sides a notched trowel, toothing 1 × 1 millimeter directly on the Buchholz.

desiccation

Coated test specimens 15 minutes at 60 ° C

Networking

Fixed test specimen
20 minutes at 80-160 ° C with a load of 1 N / mm

preparations

The adhesive to be tested is applied to the beechwood test specimens with a notched trowel, serration 1 × 1 millimeter. After drying at 60 ° C, the beechwood bodies are glued overlapping to a surface of 25 × 20 millimeters. For this purpose, it is advantageous to use an adhesive aid in order to exactly adhere to the bonding surface for each test specimen. The glued test specimen is fixed in the adhesive aid with a screw pinch valve, removed and a pressure of 1 N / mm ^{2 is} exerted on the screw pinch valve with a torque wrench. Then the fixed, pressurized test specimen is cross-linked in the heating cabinet for 20 minutes. The screw pinch is then removed and the test specimen is subjected to various storage cycles depending on the desired adhesive properties.

exam

After the storage cycles, the test specimen is placed in the Device of the pressure shaving head inserted and with a Feed speed of 10 millimeters / minute compressed.

evaluation of results

In N / mm ² . Assessment of the fracture pattern A = detachment of the adhesive layer from an active ingredient (adhesion break)
K = separation in the adhesive layer without detachment from a material (cohesive break)
MB = partial or complete breakage of a material C) comparison of the compressive shear strength of the aqueous solutions or dispersions according to the invention with that of conventional white glue at different temperatures substrate: beech wood / beech wood
Glue application with 1 mm notched trowel
Application weight: 100 g / m ²
Drying: 15 min. at 60 ° C

It is also clear from the results in Table II that the aqueous compositions according to the invention are Solutions and dispersions even at different temperatures due to increased pressure shear strength compared to white glue.

Claims (13)

1. Use of an aqueous polymer dispersion containing dispersed polymer particles of at least one polymer A1 which can be obtained by radical emulsion polymerization in the presence of a polymer A2 which is composed of 50 to 99.5% by weight of at least one ethylenically unsaturated mono- and / or dicarboxylic acid, 0.5 to 50% by weight of at least one ethylenically unsaturated compound which is selected from the esters of ethylenically unsaturated monocarboxylic acids and the half-esters and diesters of ethylenically unsaturated dicarboxylic acids with an amine having at least one hydroxyl group, - Up to 20 wt .-% of at least one other monomer as a binder for structural wood gluing. 2. Use of an aqueous polymer dispersion according to claim 1, wherein the polymer A2 contains as ethylenically unsaturated mono- and / or dicarboxylic acid at least one compound which is selected from C ₃ -C ₁₀ monocarboxylic acids and C ₄ -C ₈ dicarboxylic acids. 3. Use of an aqueous polymer dispersion according to one of claims 1 or 2, wherein the amine having at least one hydroxyl group is selected from amines of the general formula (I)

R ^c NR ^a R ^b (I)

in which
R ^c is C ₆ - to C ₂₂ -alkyl, C ₆ - to C ₂₂ alkenyl, aryl-C ₆ -C ₂₂ alkyl or aryl-C ₆ -C ₂₂ alkenyl, wherein the alkenyl group 1, 2 or 3 may not have adjacent double bonds,
R ^a for hydroxy-C ₁ -C ₆ alkyl or a radical of formula II

- (CH ₂ CH ₂ O) _x (CH ₂ CH (CH ₃ ) O) _y -H (II)

stands where
in the formula II the order of the alkylene oxide units is arbitrary and x and y independently of one another represent an integer from 0 to 100, the sum of x and y> 1,
R ^{b is} hydrogen, C ₁ - to C ₂₂ -alkyl, hydroxy-C ₁ -C ₆ -alkyl, C ₆ - to C ₂₂ -alkenyl, aryl-C ₆ -C ₂₂ -alkyl, aryl-C ₆ -C ₂₂ -alkenyl or C ₅ -C ₈ -cycloalkyl, where the alkenyl radical may have 1, 2 or 3 non-adjacent double bonds,
or R ^b for a radical of the formula III

- (CH ₂ CH ₂ O) _v (CH ₂ CH (CH ₃ ) O) _w -H (III)

stands where
in the formula III the order of the alkylene oxide units is arbitrary and v and w independently of one another represent an integer from 0 to 100, and mixtures thereof. 4. Use of an aqueous polymer dispersion according to one of the Claims 1 to 3, wherein the weight ratio Solid basis from polymer A1 to polymer A2 in the range from 7: 1 to 1: 7, preferably 3: 1 to 1: 3. 5. Use of an aqueous polymer dispersion according to one of the Claims 1 to 4, wherein another alkanolamine with at least two hydroxyl groups are added as crosslinkers. 6. Use of an aqueous polymer dispersion as a binder for constructive wood gluing according to one of the claims 1 to 5, wherein the aqueous polymer dispersion initially on the wood slats to be glued is applied and is then cured at temperatures of 25 to 200 ° C. 7. Use of an aqueous polymer dispersion as a binder for constructive wood gluing according to claim 6, wherein the curing takes place under a pressure of more than 0.02 N / mm ² . 8. Use of an aqueous solution containing A) a polymer obtained by free-radical polymerization, which consists of 5 to 100% by weight of an ethylenically unsaturated acid anhydride or an ethylenically unsaturated dicarboxylic acid, the carboxylic acid groups of which can form an anhydride group, and B) an alkanolamine with at least two hydroxyl groups, as a binder for constructive wood gluing. 9. Use of the aqueous solution according to claim 8, wherein the Polymer A from 5 to 100 wt .-% of maleic acid or Maleic anhydride is built up. 10. Use of the aqueous solution according to one of claims 8 or 9, wherein the alkanolamine is a compound of the formula


is in which R ^{1 represents} an H atom, a C ₁ -C ₁₀ alkyl group or a C ₁ -C ₁₀ hydroxyalkyl group and R ² and R ^{3 represent} a C ₁ -C ₁₀ hydroxyalkyl group. 11. Use of the aqueous solution according to one of the claims 8 to 10, the molar ratio of carboxyl groups and Acid anhydride groups (1 acid anhydride group calculated as 2 carboxyl groups) from A) to the hydroxyl groups from B) 20: 1 is up to 1: 1. 12. Use of an aqueous solution as a binder for the constructive wood gluing according to one of claims 8 to 11, whereby the aqueous solution is first to be glued Wood slats is applied and then at Temperatures of 25 to 200 ° C is cured. 13. Use of an aqueous solution as a binder for constructive wood gluing according to claim 12, wherein the curing takes place under a pressure of more than 0.02 N / m ² .