DE102004034303A1 - Functionalized, aqueous resins - Google Patents

Abstract

Aqueous, functionalized resin dispersions by reaction or proportionate reaction of DOLLAR AA) hydroxyl-containing ketone, ketone / aldehyde, urea / aldehyde resins or their hydrogenated derivatives and DOLLAR AB) at least one modified isocyanate and / or polyisocyanate with at least one free NCO Group obtainable by reacting at least one isocyanate and / or polyisocyanate with compounds which have at least one isocyanate-reactive function in addition to hydrophilic or potentially hydrophilic groups and at least one hydrophilic group and / or a potentially hydrophilic group, DOLLAR AC) and at least a compound which has an isocyanate-reactive function and has additional functional groups, DOLLAR A and subsequent mixing of the optionally neutralized resin with water and a process for their preparation.

Description

The The present invention relates to functionalized, aqueous ketone, Ketone / aldehyde or urea / aldehyde resin dispersions and a Process for their preparation.

The Condensation to ketone, ketone / aldehyde and urea / aldehyde resins is known (Ullmann's Encyclopedia of Industrial Chemistry, VCH Verlagsgesellschaft mbH Weinheim 1993, Vol. 23, pp. 99-105). Such resins are generally water-insoluble.

In the DE-OS 25 42 090 describes water-soluble compounds carrying sulfonic acid groups, which are available deviating from the process of the invention in a common condensation reaction of cycloalkanone, formaldehyde and alkali metal bisulfite.

In the DE-OS 31 44 673 Water-soluble condensation products are listed, which are also obtained by co-reaction of ketones, aldehydes and acid group-introducing compounds. Examples of the latter are sulfates, amidosulfonic acid, aminoacetic acid and phosphorous acid salts.

To DE-OS 25 42 090 and DE-OS 31 44 673 For example, products containing electrolyte (eg Na ions) are obtained. Such resins, however, deteriorate inter alia the corrosion protection of coating systems.

The EP 0 617 103 A1 describes the reaction of polyisocyanates (a) and dihydroxy compounds (b) having a molecular weight of 500 to 5000, which does not convert groups into ionic groups (eg carboxylic acid groups), but other functional groups such as ester or ether groups (see S 3, lines 17 - 21). The polyurethane thus obtained is still with a compound (c) which contains not only NCO-reactive groups nor a group convertible into an ionic group, and optionally with diols or polyols (d) having a molecular weight of 60 to 500, which are no further functional Wear groups (see page 4, lines 5 to 15), implemented. Subsequently, this reaction product is reacted with a condensation resin and brought into the water. The resins of the present invention are not mentioned.

The DE-OS 24 08 865 describes melamine-formaldehyde-polyurethane resins which are water-dilutable or water-dispersible. The base of the polyurethane resin is based on alkyd resin based polycondensation products (see page 2, first paragraph). Alkyd resins are made from carboxylic acids, unsaturated fatty acids, diols and polyols.

DE-OS 34 06 473 such as DE-OS 34 06 474 or EP-A-0 154 835 describe processes for the preparation of stable aqueous dispersions of urea / aldehyde resins or ketone / (aldehyde) resins, after which the resin melt or its highly concentrated solution in the presence of organic protective colloids optionally with addition of emulsifiers dispersed in water. A disadvantage of these processes is the fact that the organic protective colloids and emulsifiers interfere with the application of the aqueous ketone / (aldehyde) or urea / aldehyde resins in the coating sector. The hydrophilic protective colloids and optionally emulsifiers remain in the coating and make them sensitive to moisture. The coating swells when exposed to moisture, loses its hardness and loses its anti-corrosion effect.

Water-dispersible condensation products are described in EP 0 838 486 A1 . EP 0 838 485 . EP 0 498 301 . DE 25 42 090 . DE 31 44 673 and EP 0 154 835 , The targeted introduction of tailor-made compounds for further functionalization is not the subject of these applications.

The The object of the invention was functionalized ketone, ketone / aldehyde or urea / aldehyde resin dispersions and a process for their To develop production. The resin dispersions should be saponified or be stable on storage and not the disadvantages described above exhibit.

The The object underlying the invention is surprisingly achieved according to the claims by hydroxyl-containing ketone, ketone / aldehyde, urea / aldehyde resins or their hydrogenated derivatives with hydrophilic modified (poly) isocyanates be implemented and above In addition, functional groups are incorporated into the polymer.

To Neutralization and addition of water result in the thus modified inventive ketone, Ketone / aldehyde, urea / aldehyde resins stable aqueous solutions, dilutions and dispersions.

The aqueous according to the invention Systems are already compared to those of the prior art known systems completely saponification-stable and contain no disturbing Additives z. B. in the form of emulsifiers, protective colloids or electrolytes.

• A) Hydroxygruppen-haltigen Keton-, Keton/Aldehyd-, Harnstoff/Aldehyd-Harzen oder deren hydrierten Folgeprodukten und
• B) mindestens einem modifizierten Isocyanat und/oder Polyisocyanat mit mindestens einer freien NCO-Gruppe, erhältlich durch Umsetzung mindestens eines Isocyanats und/oder Polyisocyanats mit Verbindungen, die zusätzlich zur hydrophilen oder potentiell hydrophilen Gruppe mindestens eine gegenüber Isocyanatgruppen reaktionsfähige Funktion aufweisen sowie mindestens eine hydrophile Gruppe und/oder eine potentiell hydrophile Gruppe besitzen,
• C) sowie mindestens einer Verbindung, die eine gegenüber Isocyanatgruppen reaktionsfähige Funktion aufweist und zusätzliche funktionelle Gruppen besitzt, und anschließender Vermengung des ggf. neutralisierten Harzes mit Wasser.

The present invention relates to aqueous resin dispersions, and a process for their preparation obtainable by reaction or proportionate reaction of

• A) hydroxyl-containing ketone, ketone / aldehyde, urea / aldehyde resins or their hydrogenated derivatives and
• B) at least one modified isocyanate and / or polyisocyanate having at least one free NCO group, obtainable by reacting at least one isocyanate and / or polyisocyanate with compounds which have at least one isocyanate-reactive function in addition to the hydrophilic or potentially hydrophilic group and at least one hydrophilic Have a group and / or a potentially hydrophilic group,
• C) and at least one compound which has an isocyanate-reactive function and has additional functional groups, and subsequent mixing of the optionally neutralized resin with water.

Suitable as component A) are all resins which are available in DE-OS 10 2004 005 208.5 and DE-OS 10 2004 005 204.7 are listed. Hydroxy-containing ketone-aldehyde resins, urea-aldehyde resins, phenol-aldehyde resins and their hydrogenated secondary products are preferably used. The hydrophilic modification of B) is carried out by reacting a (poly) isocyanate and / or mixtures of different (poly) isocyanates with compounds having (in addition to the hydrophilic or potentially hydrophilic group) at least one isocyanate-reactive function, eg. For example, OH, NH, and having at least one hydrophilic group and / or a potentially hydrophilic group, that is hydrophilic after neutralization. Examples of such compounds for the hydrophilic modification of the polyisocyanates are aminocarboxylic acids, hydroxysulfonic acids, aminosulfonic acids and hydroxycarboxylic acids.

The Hydrophilic modification can also be achieved with already neutralized Connections are made.

Hydroxycarboxylic acids such as for example, dimethylolpropionic acid, dimethylolbutyric acid, bis (hydroxyphenyl) valeric acid and / or hydroxypivalic are particularly preferred because they are neutralized with volatile Bases, such as As amines, show strong hydrophilic effect, after Evaporation of the volatile Base this effect, however, decreases greatly, so that z. B. coatings Do not soften or start to whiten when exposed to moisture.

Dimethylolpropionic acid and 2 - [(2-aminoethyl) amino] -ethanesulfonic acid also becomes especially preferred because they are two hydrophobic polyisocyanates (potentially) hydrophilic to modify.

Suitable polyisocyanates for the preparation of B) are preferably di- to tetrafunctional polyisocyanates having a molecular weight below 800 g / mol with aliphatically, (cyclo) aliphatically and / or cycloaliphatically bonded isocyanate groups, as are commonly used in the field of polyurethane coatings, as well as mixtures of these: 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane (isophorone diisocyanate; IPDI), trimethylhexamethylene diisocyanate (TMDI), 1,6-diisocyanatohexane (HDI), bis (4-isocyanatohexyl) -methane (H ₁₂ MDI), as well as other polyisocyanates which are used in the DE-OS 24 56 469 , P. 5 and 6 are listed.

Also are suitable obtainable from the monomeric polyisocyanates Oligomers whose extraction corresponds to the prior art and e.g. in the journal for Practical Chemistry 336 (1994), 185-200 and paint and varnish 100, 5 (1994), 330-335 and the literature specified therein are described. It is polyisocyanates with biuret, uretdione or isocyanurate structure, the latter available by cyclotrimerization of the monomers. Also suitable are Polyisocyanates as products of polyhydric alcohols and / or from amines with monomeric isocyanates, such as. B. the product Trimethylolpropane and isophorone diisocyanate.

In addition, can a non-ionic hydrophilization e.g. via polyether, the e.g. reacted with the above polyisocyanates and component A) can be.

Particularly preferred is a hydrophilically modified polyisocyanate (B) of dimethylolpropionic acid and / or 2 - [(2-aminoethyl) amino] ethanesulfonic acid or derivatives thereof and IPDI and / or H ₁₂ MDI and / or HDI in a molar ratio of 1: 2.

The introduction of the functional components (C) can be carried out by reacting a (poly) isocyanate and / or mixtures of different (poly) isocyanates with compounds having at least one isocyanate-reactive function, for. B. OH, NH and with at least one further functional group in the way that at least one NCO function is maintained and subsequent reaction with A) before or after reaction with B). However, the preparation of the component C) can also be carried out in-situ during the pre-adduct preparation. As component C) it is possible in principle to use aliphatic or aromatic alcohols and / or amines or aromatic heteroaromatic ring systems which have a further functionality in addition to the NCO-reactive group. Preferred examples of such compounds are di methylaminopropylamine, diethanolamine, pyrrolidone and / or hydroxypivalic acid. The introduction of unsaturated groups, as in DE-OS 103 38 560 . DE-OS 103 38 562 . DE-OS 10 2004 005 208.5 . DE-OS 10 2004 005 207.7 is not the subject of the present invention.

The Reaction of A) with B) and / or C) may be carried out in bulk or preferably in the presence of a suitable auxiliary solvent. preferred Solid contents are when using an auxiliary solvent 50 to 95% by mass, more preferably 60 to 80% by mass.

suitable Auxiliary solvent are either preferred those having a boiling point below 100 ° C at 1013 hPa and distillative from the final aqueous System again completely up to a residual content of 0.5% by mass and reuse let, such as Acetone, methyl ethyl ketone or tetrahydrofuran, or possibly higher boiling, in the aqueous System remain, such as Butyl glycol, butyl diglycol or N-methylpyrrolidone. The below 100 ° C boiling auxiliary solvents are therefore preferred because they make the production of purely aqueous, solvent-free and thus especially environmentally friendly Allow dispersions. The use of higher boiling Solvents - if necessary also proportionally - or solvent mixtures with boiling point above 100 ° C is technically possible but not preferred and not desired. An advantage of the method according to the invention also lies in the fact that organic solvents in the final aqueous Resin dispersion completely can be dispensed with and yet solids-rich, stable dispersions to be obtained.

In a preferred embodiment 1) is used as component C) e.g. an adduct of 1 mol of diisocyanate and 1 mol of a functional NCO-reactive component optionally under Use of a suitable solvent and a suitable catalyst.

When Component B) may be e.g. an adduct of 2 moles of diisocyanate and 1 mole Dimethylolpropionic acid and / or 2 - [(2-aminoethyl) amino] -ethanesulfonic acid or derivatives thereof, if appropriate using a suitable solvent and suitable Catalyst can be produced.

The separately prepared products become a solution or melt of hydroxy-containing Ketone, ketone-aldehyde, urea-aldehyde or their hydrogenated Subsequent products (A) were added and reacted.

It has proved to be advantageous to react 1 mol of component A, based on M _n , with from 0.1 to 10 mol, in particular from 0.25 to 5 mol, of component C).

It has proved to be advantageous to react 1 mol of the reaction product of components A and C with respect to M _n with 0.1 to 1.0 mol, preferably 0.3 to 0.75 mol, with component B.

ever after reactivity the components of each other, the temperature of the reaction is selected. It have temperatures between 30 and 245 ° C, preferably between 50 and 140 ° C proven.

If necessary can first be neutralized with a suitable neutralizing agent and then the neutralized reaction product dispersed in water become. Alternatively, directly in a water / neutralizer mixture be dispersed.

The optionally contained solvents if desired are separated after completion of the reaction, in which case usually a solution up Dispersion of the product according to the invention becomes.

In a preferred embodiment 2) can be used as component B) z. B. an adduct of 2 moles of diisocyanate and 1 mole of dimethylolpropionic acid and / or 2 - [(2-aminoethyl) amino] -ethanesulfonic acid or derivatives thereof, if appropriate using a suitable solvent and suitable Catalyst can be produced.

The Product becomes a solution or melt of the hydroxyl-containing ketone, ketone-aldehyde, urea-aldehyde or their hydrogenated secondary products (A) and component C) and others Polyisocyanate given and reacted.

It has proved to be advantageous to react 1 mol of component A, based on M _n , with from 0.1 to 10 mol, in particular from 0.25 to 5 mol, of component C).

It has proved to be advantageous to react 1 mol of the reaction product of components A and C with respect to M _n with 0.1 to 1.0 mol, preferably 0.3 to 0.75 mol, with component B.

ever after reactivity the components of each other, the temperature of the reaction is selected. It have temperatures between 30 and 245 ° C, preferably between 50 and 140 ° C proven.

If necessary, first with a ge suitable neutralizing agents are neutralized and then the neutralized reaction product are dispersed in water. Alternatively, it may be dispersed directly in a water / neutralizer mixture.

The optionally contained solvents if desired are separated after completion of the reaction, in which case usually a solution up Dispersion of the product according to the invention becomes.

Possibly For example, a suitable catalyst may be used to prepare the resins of this invention become. All compounds known in the literature are suitable, the one NH or OH-NCO reaction speed up, such as As diazabicyclooctane (DABCO) or dibutyltin dilaurate (DBTL), titanic acid ester, Bismuth salts.

Becomes by the hydrophilizing agent a potentially hydrophilic group, z. As a carboxyl group or a tertiary amino group, in the polyisocyanate introduced, so this can be done by subsequent Neutralization be converted into an ionic hydrophilic group.

The Neutralization of the invention produced Resins according to the anionic modified embodiments 1) and 2) can be carried out with inorganic and organic bases, such as As ammonia or organic amines. Preferably used one primary, secondary and tertiary Amines, such as Ethylamine, propylamine, dimethylamine, dibutylamine, Cyclohexylamine, benzylamine, morpholine, piperidine and triethanolamine. Particularly preferred are volatile tertiary Amines, in particular dimethylethanolamine, diethylethanolamine, 2-dimethylamino-2-methyl-1-propanol, Triethylamine, tripropylamine and tributylamine.

The Neutralization amount depends on the content of potentially neutralisable Groups in the hydrophilic modified polyisocyanate and is preferably 50 to 130% of the neutralization amount required for stoichiometric neutralization necessary is. In the case of cationically hydrophilized systems neutralized in the same way with suitable acids, such as e.g. Acetic acid, formic acid, benzoic acid or lactic acid.

In front Water addition, the reaction product of A, B and C optionally with other non-hydrophilic resins or other water-soluble or water-dilutable Components are combined and then dispersed together. By This measure let yourself technically advantageous a high solids content of the dispersions of more than 35% by mass, preferably from 35 to 40% by weight, to about 50% by weight.

The Resin dispersions according to the invention have good storage stability and are suitable as resins or additional resins in coating materials, ballpoint pen pastes Printing inks and inks, polishes, glazes, fillers, cosmetic articles and / or Sealing and insulating materials. Also for the use in adhesives, such. B. for the bonding of textiles, Leather, paper and the like Materials, such resin dispersions are suitable.

by virtue of usually very high softening point results coatings with faster Drying and drying and good blocking resistance. The resin dispersions of the invention are at least 6 weeks at 50 ° C sedimentation.

The Invention is illustrated by the following examples.

Example 1.)

1) Preparation of the hydrophilic modified polyisocyanate B), an adduct C) and its reaction with A)

To a mixture of 60 g of dimethylolpropionic acid (DMPS), 217 g of acetone and 0.3 g of a 10% by mass solution of dibutyltin dilaurate (DBTL) in acetone are added with stirring 201 Isophorone diisocyanate added so quickly that, the exothermic reaction remains well manageable. Then it is stirred at 60 ° C for so long Continue until the DMPS completes solved and the NCO number of the solution 8.4% NCO (determination according to DIN 53185) has fallen below.

To 45.6 g of IPDI are added to 17.4 g of pyrrolidone in nitrogen atmosphere and at 80 ° C stirred to an NCO content of 13.6%.

To cooling down at room temperature, the two precursors are combined in a nitrogen atmosphere, with 544 g of a hydroxyl-containing ketone / aldehyde resin (OHZ 310 mg KOH / g, synthetic resin SK, Degussa AG) dissolved in 508 g of acetone, and 1.24 g of a 10% DBTL solution in acetone. It is kept at reflux temperature touched, until an NCO content of less than 0.15% is reached.

2) dispersing the modified Resin 1)

250 g of the solution prepared under 1) are neutralized at room temperature with stirring by the addition of 6.8 g of triethylamine and dispersed by introducing 457 g of deionized water with vigorous stirring. The auxiliary solvent acetone as well proportional water are removed in vacuo, and there is a storage-stable, finely divided, slightly opalescent resin dispersion having a solids content of about 24.8% by mass, a pH of 8.0 and a viscosity of about 90 mPas.

Example 2.)

1) Preparation of the hydrophilic modified polyisocyanate B), an adduct C) and its reaction with A)

To a mixture of 51 g of dimethylolpropionic acid (DMPS), 253 g of acetone and 0.3 g of a 10% by mass solution of dibutyltin dilaurate (DBTL) in acetone is added with stirring 253 Isophorone diisocyanate added so quickly that the exothermic reaction remains well manageable. Then it is stirred at 60 ° C for so long Continue until the DMPS completes solved and the NCO number of the solution 11.8% NCO (determination according to DIN 53185) has fallen below.

To cooling down to room temperature in nitrogen atmosphere, the precursor with 480 g of a hydroxyl-containing ketone / aldehyde resin (OHZ 310 mg KOH / g, synthetic resin SK, Degussa AG), which is dissolved in 400 g of acetone, and with 0.5 g of a 10% DBTL solution in acetone. It is stirred at reflux temperature until an NCO content below 1.3% is reached. Then 38.3 g of diethanolamine, solved in 31.2 g of acetone, and it is added to an NCO content stirred below 0.15%.

2) dispersing the modified Resin 1)

250 g of the solution prepared under 1) are added at room temperature with stirring by addition of 6.3 g Triethylamine neutralized and by entering 335 g of deionized Water with vigorous stirring dispersed. The auxiliary solvent Acetone as well as proportionate water are removed in vacuo, and it will a storage-stable, finely divided, slightly opalescent resin dispersion with a solids content of about 29.5 mass%, a pH of 8.6 and a viscosity received from about 520 mPas.

Claims (22)

aqueous, functionalized resin dispersions obtainable by reaction or proportionate implementation of A) hydroxyl-containing ketone, Ketone / aldehyde, urea / aldehyde resins or their hydrogenated derivatives and B) at least one modified isocyanate and / or polyisocyanate with at least one free NCO group, obtainable by reaction at least an isocyanate and / or polyisocyanate with compounds in addition to hydrophilic or potentially hydrophilic group at least one towards isocyanate groups reactive Have function and at least one hydrophilic group and / or have a potentially hydrophilic group, C) and at least a connection that faces one Isocyanate reactive groups Has feature and additional has functional groups, and then mixing the resin or of the neutralized resin with water. Resin dispersions according to Claim 1, characterized that as component C) compounds having at least one opposite isocyanate groups reactive Function as well as with at least one further functional group be used. Resin dispersions according to Claim 1, characterized that as component C) alcohols and / or amines, in addition to NCO-reactive group have a further functionality can be used. Resin dispersions according to Claim 1, characterized that as component C) dimethylaminopropylamine, diethanolamine, pyrrolidone and / or hydroxypivalic be used. Resin dispersions according to Claim 1, characterized component C) in such a way with a (poly) isocyanate and / or mixtures various (poly) isocyanates is reacted, that at least one NCO function is retained and then with A) before, during or after reaction with B) is reacted. Resin dispersions according to one of the preceding claims, characterized characterized in that component B) using tert. amino alcohols, amino carboxylic acids, hydroxy sulfonic acids, aminosulfonic or / and hydroxycarboxylic acids will be produced. Resin dispersions according to one of the preceding claims, characterized characterized in that component B) using dimethylolpropionic acid and / or 2 - [(2-aminoethyl) amino] -ethanesulfonic acid becomes. Resin dispersions according to one of the preceding claims, characterized characterized in that for the preparation of B) di- to tetrafunctional Polyisocyanates used with a molecular weight below 800 g / mol become. Resin dispersions according to one of the preceding claims, characterized in that for the preparation of B) polyisocyanates with aromatic, aliphatic and / or cycloaliphatic bound Iso cyanate groups or mixtures of these are used. Resin dispersions according to one of the preceding claims, characterized in that 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane (isophorone diisocyanate; IPDI), trimethylhexamethylene diisocyanate (TMDI), 1,6-diisocyanatohexane (HDI), bis (4-isocyanatohexyl ) -methane (H ₁₂ MDI). Resin dispersions according to one of the preceding claims, characterized characterized in that for the preparation of B polyisocyanates with biuret, Uretdione or isocyanurate structure can be used. Resin dispersions according to one of the preceding claims, characterized characterized in that for the preparation of B) polyisocyanates from the Reaction of polyhydric alcohols and / or amines with monomers Isocyanates are used. Resin dispersions according to one of the preceding claims, characterized characterized in that for the preparation of B) dimethylolpropionic acid and Isophorone diisocyanate (IPDI) in a molar ratio 1: 2 are used. Resin dispersions according to one of the preceding claims, characterized characterized in that the reaction of A) with B) and C) and the Dispersion takes place in substance. Resin dispersions according to one of the preceding claims, characterized characterized in that the reaction of A) with B) and C) and the Dispersion takes place in the presence of an auxiliary solvent. Resin dispersions according to one of the preceding claims, characterized characterized in that the auxiliary solvent used has a boiling point below 100 ° C at 1013 hPa possesses. Resin dispersions according to one of the preceding claims, characterized in that the auxiliary solvent used is N-methylpyrrolidone, Acetone and / or methyl ethyl ketone and / or tetrahydrofuran. Resin dispersions according to one of the preceding claims, characterized characterized in that the neutralization with inorganic or organic Bases takes place. Resin dispersions according to one of the preceding claims, characterized characterized in that for neutralization dimethylethanolamine or / and Diethylethanolamine or / and 2-dimethylamino-2-methyl-1-propanol and / or triethylamine and / or ammonia. Resin dispersions according to one of the preceding claims, characterized characterized in that for neutralization 50 to 130% of the neutralization amount, the for one stoichiometric Neutralization is necessary is used. Resin dispersions according to one of the preceding claims, characterized in that one or more water-insoluble or dilutable Components are added. Process for the preparation of aqueous, functionalized Resin dispersions by reaction or proportionate reaction of A) Hydroxy-containing ketone, ketone / aldehyde, urea / aldehyde resins or their hydrogenated derivatives and B) at least one modified isocyanate and / or polyisocyanate with at least one free NCO group, available by reacting at least one isocyanate and / or polyisocyanate with compounds in addition at least one hydrophilic or potentially hydrophilic group across from Isocyanate reactive groups Have function and at least one hydrophilic group and / or have a potentially hydrophilic group, C) and at least a connection that faces one Isocyanate reactive groups Feature and additional possess functional groups, and subsequent mixing of the possibly neutralized resin with water.