HK1168121A - New dispersion adhesives, method for their manufacture and application thereof - Google Patents

Abstract

The present invention relates to a new aqueous dispersion adhesive, a method for producing the same and uses thereof in furniture and automobile industry.

Description

The present invention relates to novel aqueous dispersion adhesives, their manufacturing processes and their use in the furniture and automotive industries.

Err1:Expecting ',' delimiter: line 1 column 254 (char 253)

The present invention was therefore intended to provide cost-effective alternatives to aqueous dispersion adhesives, particularly in the automotive industry.

Surprisingly, it has now been found that aqueous dispersion adhesives containing certain carbodiimides and polyurethane dispersions do not have the disadvantages of the state of the art and are excellent as dispersion adhesives for use in the furniture and automotive industries.

Err1:Expecting ',' delimiter: line 1 column 253 (char 252)

Mixtures of carbodiamides of formula (1) including the corresponding oligomers and/or polymers may also be used.

Preferably, monomeric carbodiimides of formula (I) based on aromatic and/or aliphatic diisocyanates are used.

Err1:Expecting ',' delimiter: line 1 column 205 (char 204)

The abovementioned carbodiimides of formulae (I) to (IV) may also be produced by manufacture in mixtures of monomeric, oligomeric and/or polymer compounds, which are also covered by the subject matter of the invention.

The compounds of formula (I) to (IV) are commercially available, e.g. from Rhein Chemie Rheinau GmbH, or can be produced by the usual processes, e.g. as described in DE-A-11 30 594 or US 2 840 589, or by the condensation of diisocyanates by decomposition of carbon dioxide at elevated temperatures, e.g. 40 to 200 °C, in the presence of catalysts. For example, strong bases or phosphorus compounds have proven to be catalysts. Phospholenoxides, phospholidines or phospholinoxides and the corresponding sulfides are preferred.

All diisocyanates are suitable for the preparation of the compounds and/or polymers used, with the present invention using preferably carbodiimides and/or polycarbodiimides based on aromatic isocyanates substituted by C1- to C4-alkyl bases, such as 2,4-toluyl isocyanate (TDI), 2,6-toluyl isocyanate, a mixture of 2,4-toluyl isocyanate and 2,6-toluyl isocyanate, xylene isocyanate, 2,6-diisocyanate, 2,6-diisocyanate, 2,4-diisocyanate, 2,4-diisocyanate, 2,4-diisocyanate, 2,4-diisocyanate, 2,4-diisocyanate, 2,4-diisocyanate, 2,4-diisocyanate, 2,4-diisocyanate, 2,4-diisocyanate, 2,4-diisocyanate, 2,4-diisocyanate, 2,4-diisocyanate, 2,4-diisocyanate, 2,4-diisocyanate, 2,4-diisocyanate, 2,4-diisocyanate, 2,4-diisocyanate, 2,4-diisocyanate, 2,4-diisocyanate, 2,4-diisocyanate, 2,4-diisocyanate, 2,4-diisocyanate, and 2,4-diisocyanate, and 2,4-diisocyanate, and 2,4-diisocyanate, and 2,4-diisocyanate, and 2,4-diisocyanate, and 2,4-diisocyanate, and 2,4-diisocyanate, and 2,4-diisocyanate, and 2,4-diisocyanate, and 2,4-diisocyanate, and 2,4-diisocyanate, and 2,4-diisocyan.

In another embodiment of the present invention, it is also possible to use a mixture of different carbodiimides.

The solid carbodiimides used are particularly suitable for particles < 50 μm.

In another preferred embodiment of the invention, the compounds of formulae I to IV may be present in the form of an aqueous dispersion, in which case the active substance content is preferably 20 to 80%, and preferably 40 to 60%.

Err1:Expecting ',' delimiter: line 1 column 457 (char 456)

Polar groups within the meaning of the invention are e.g. hydroxy, sulfonate, ether or carboxyl groups.

The aqueous dispersion adhesives of the invention shall preferably have the following composition: 0.2 - 10%, preferably 0.5 - 5% or more of a carbodiimide of formulae (I) - (IV) and 99.8 - 90%, preferably 99.5 - 95% PU dispersion.

In both cases, the active substance content is preferably between 20% and 80%.

The carbodiimides of formulae (I) to (IV) used are preferably solid or liquid at room temperature.

In another preferred embodiment of the invention, the solid carbodiimides according to the formulae (I) to (IV) are deactivated by implementation with at least one surface amine.

For surface deactivation (microencapsulation), all amino functional compounds can be used as amines. Preferably, these are multifunctional primary and secondary, especially multifunctional aliphatic amines. The appropriate amines according to the invention are selected in particular from the group of cyclic and aliphatic, straight-chain or branched (C2-C14) alkylamines, diamines and polyamines, in particular (C2-C10) alkylamines, diamines and polyamines, preferably (C2-C6) alkylamines, diamines and polyamines, where the alkylate may contain at least partially but not entirely salicylic acid atoms, in particular heteroxyl or sulfur, and may be further sub-groups, such as carboxyl or halogen, and may contain alkyl groups or substituents, such as carboxyl hydroxyl.

The following compounds are examples of amines suitable for the purpose of the present invention: 2-pentamethylene-1,5-diamine and its isomers and homologs such as 1,6-hexamethylenediamine; di-sec-butylamine; ethylene-diamine; 1,3-propylene-diamine; diethylene-triamine; triethylentetramine; 3,3'-dimethyl-4,4'-diaminodicylohexylmethane; methylnonandiamine; isophorondiamine; 4,4'-diaminodicylohexymethane; alkanolamines and diamines such as ethanolamine and dietetamine and/or amidolamine.

Particularly preferred are multifunctional primary and secondary, and particularly preferred are multifunctional aliphatic amines such as Jeffamine® T 403 from Huntsmann, diisopropanolamine from BASF AG or amidoamines such as Versamid® 140 from Cognis or Euretek 505 from Witco. These are in particular compounds with hydrophilic groups, such as especially amines or hydroxyl groups, which can react with the free isocyanate groups of the solid diisocyanate, thus forming a surface hyal on the isocyanate which initially deactivates the isocyanate, such as amines, diamines and polynides.

In a preferred embodiment of the invention, a low molecular weight mono-, di- or polyamine with one or more primary and/or secondary amino groups (n) is used as a surface activator, at a rate such that the degree of inactivation (DG), calculated as the equivalent ratio of the amino groups of the surface activator to the isocyanate and/or carbodiimide groups of the carbodiimide to be inactivated (n NH2/n NCO), is between 0,2 and 8 equivalent%.

In particular, the surfactant may have a molecular weight of up to MG 600 g/mol.

The concentration of surface activators (amines) in relation to the amount of binding agents is preferred at 1 to 10% by weight, in particular 2 to 5% by weight.

The surface activation is preferably by addition of the amine to an aqueous dispersion of the carbodiimide, possibly containing dispersants and anti-caking agents, by stirring and/or grinding.

The stirring/grinding process may be carried out using commercial machines such as bead mills, solvents or leaf stirring machines.

The inactivation of carbodiimides is carried out in a known way, see in particular EP 0 205 970 A and US-A-4 888 124, the contents of which are hereby incorporated in full by reference, e.g. B, by: (b) Addition of the amine or a solution of the amine to disperse the solid fine carbodiimides.

Surface deactivation can be carried out in water and/or in organic solvents.

In another embodiment of the present invention, the aqueous dispersion adhesives of the invention additionally contain net and dispersion agents such as Tamol® NN 9104 by BASF AG or Aerosol® OT45 by Cytec Surface Specialities GmbH, Dispersogen® HR by Clariant International Ltd. and/or stabilizers, emulsifiers, thickeners such as anti-fouling agents such as Borchi® ALA (OMG Borchers GmbH) or Kelzan® S, available from Monsanto, or Tragacanth, available from R.T. Vanderbilt, and/or defoamers.

The proportions of stabilisers, emulsifiers, thickeners and/or defoamers should preferably be between 0.1 and 10%.

The present invention also relates to a process for the manufacture of the aqueous dispersion adhesives of the invention, in which at least one compound of the formulae (I) to (IV), where appropriate in the form of an aqueous dispersion and/or where appropriate in microencapsulated form, is introduced into the polyurethane dispersion containing, where appropriate, additional additives.

In cases where the microencapsulated carbodiimides of formulae (I) to (IV) are to be used, the aqueous dispersion adhesives of the invention may also be prepared as follows:

The carbodiimide (s) of formulae (I) to (IV) is (are) first introduced into the polyurethane dispersion, where appropriate in the form of an aqueous dispersion, and then surface-activated by the above implementation with amines.

All commercially available mixing units, such as solvents, can be used for stirring.

The production of an aqueous dispersion with carbodiamides/compounds of formulae (I) to (IV) is carried out by the techniques of the skilled, where appropriate in the presence of additional additives, such as net and dispersion agents, anti-foaming agents, defoamers, etc., in commercial aggregates, such as solvents.

The temperature during manufacture is preferably in the range of 5 to 50 °C.

The carbodiimides are mixed with commercial mixing units such as stir-boilers and dispersers.

The present invention also relates to the use of the aqueous dispersion adhesives of the invention, which may contain additional additives, in the furniture and automotive industries, in the footwear industry or in the textile industry, e.g. for the production of fabric/film composites.

The following applications are preferred: kitchen countertops and front panels and dashboards in the automotive industry.

The invention also covers processes for the manufacture of kitchen countertops and front panels and the dashboard in the automotive industry in which at least one of the water dispersions of the invention is applied to the surface of the material to be glued. This application is preferably by application or spraying. The material to be coated may be, for example, wood or laminate, which is glued with other materials, such as further laminate.

Err1:Expecting ',' delimiter: line 1 column 116 (char 115)

The following examples are intended to illustrate the invention without being limiting.

Examples of implementations: Chemicals used:

TDI-carbodiamide, a carbodiamide based on 2,4-toluyl isocyanate of formula (II),

Addolink® TT, a TDI urethonium, which is available from Fa. Rhein Chemie Rheinau GmbH,

Stabaxol® P 200, a carbodiimide based on 1,3-tetramethylxylylendiisocyanate (TMXDI) which is available from Fa. Rhein Chemie Rheinau GmbH,

Carbodilite LA-01, a carbodiimide based on dicyclohexylmethane-4,4'-diisocyanate (H12MDI) which still contains isocyanate groups, available from Fa. Nisshinbo Chemical Inc.,

Carbodilite HMV8 CA, a carbodiimide based on dicyclohexylmethane-4,4'-diisocyanate (H12MDI) which is available from Fa. Nisshinbo Chemical Inc.,

Tween 85 , net/dispersant, available from the company Münzing Chemie GmbH,

Kelzan® S, an anti-swelling agent, available from Monsanto,

Jeffamin® T 403, surface activation polyetheramine, available from Huntsman International LLC,

Agitan 281, a defoamer, available from Fluka,

Dispercoll U53, a 40% dispersion of an anionic high molecular weight polyurethane dispersion, available from BayerMaterialScience AG and

Borchi Gel ® L 75, an anti-aging agent, is available from OMG Borchers GmbH.

Table 1 summarises the amounts used to produce an aqueous Addolink ® TT or TDI carbodiamide dispersion: Other Tabelle 1:

Material	Bsp. 1 (erf.)	Bsp. 2 (VV)	Bsp. 3 (VV)	Bsp. 4 (VV)	Bsp. 5 (VV)
TDI-Carbodiimid	40
Addolink TT	40
Stabaxol P 200	40
CarbodititeLA-01	40
Carbodilite HMV 8CA	40
Wasser	52,6	52,6	60	52,6	55,0
Tween85	0,5	0,5	0,5	0,5
Agitan 281	0,45	0,45	0,45	0,45
Jeffamin® T 403	2,5	2,5	2,5
Kelzan® S, 3% in Wasser	4	4	4	4

Tabelle 1:

VV= Vergleichsbeispiel, erf= erfindungsgemäß, die Einsatzmengen sind in Gew. Teilen angegeben.

In examples 1, 2, 4 and 5, water and net/dispersant and defoamings (Agitan 281 and Tween 85) were added and dissolved/mixed. The net was then added and homogenised in the solvent. Jeffamin® T 403 was added and mixed without shear forces, except in example 5, and the freshly produced Kelzan® S preparation was mixed and homogenised. In example 3, the net was dissolved in water.

Example 6: According to the invention

In 96.5 parts Dispercoll U53, 2.5 parts of the dispersion from Example 1 were mixed together with one (1) part Borchi Gel® L 75.

Example 7: Comparison

In 96.5 parts Dispercoll U53, 2.5 parts of the dispersion from Example 2 were mixed together with one (1) part Borchi Gel® L 75.

Example 8: Comparison

In 96.5 parts Dispercoll U53, 2.5 parts of the solution from Example 3 were stirred together with one (1) part Borchi Gel® L 75.

Example 9: Comparison

In 96.5 parts Dispercoll U53, 2.5 parts of the dispersion from Example 4 were mixed together with one (1) part Borchi Gel® L 75.

Example 10: Comparison

In 96.5 parts Dispercoll U53, 2.5 parts of the dispersion from Example 5 were mixed together with one (1) part Borchi Gel® L 75.

Example 11: Comparison

99.0 parts Dispercoll U53 are mixed with one (1) part Borchi Gel® L 75.

A heat resistance test was carried out on these dispersions by gluing a PVC board to a wood surface and applying 0,15 g of dispersion adhesives of examples 6, 7, 8, 9, 10 or 11 on the wood side and 0,08 g of dispersion adhesives of examples 6, 7, 8, 9, 10 or 11 on the PVC side to an adhesive surface of 20 mm by 20 mm, and then pressing the sheets at 80 °C for 60 minutes with a weight of 5 kg.

Ballast bodies weighing 5 kg each are attached to the test bodies so made in the dry cabinet and heated at a heating rate of 10 K/h starting at 40°C.

The temperature at which the adhesion fails and the weights fall is measured and the test results are given in Table 3: Tabelle3:

Material	Bsp. 6 (erf)	Bsp.7 (VV)	Bs. 8 (VV)	Bsp. 9 (VV)	Bsp. 10 (VV)	Bp. 11 (VV)
Wärmestandfestigkeitstest Temperatur in °C	82,5	64,6	57,2	53,6,	52,7	50,8

Tabelle3:

VV= Vergieichsbeispiet, erf= erfindungsgemäß

The results of the tests clearly show that, in the same quantity, the aqueous dispersion adhesives of the invention have a higher thermal resistance.

Claims (9)

1. Err1:Expecting ',' delimiter: line 1 column 204 (char 203)
2. Err1:Expecting ',' delimiter: line 1 column 202 (char 201)
3. Aqueous dispersion adhesives according to claim 1 or 2, characterised by the surface deactivation of the carbodiimides of formulae (I) to (IV) by translocation with at least one amine.
4. Aqueous dispersion adhesives according to one or more of the claims 1 to 3, characterised by the presence of the carbodiimides of formulae (I) to (IV) in the form of an aqueous dispersion.
5. Aqueous dispersion adhesives according to one or more of claims 1 to 4, characterised by the polyurethane dispersion being essentially an aqueous dispersion.
6. Aqueous dispersion adhesives according to one or more of the claims 1 to 4, characterised by the polyurethane dispersion being aqueous, ionic or non-ionic, polar group and/or solvent-containing polyurethanes or polyester polyurethanes based on aromatic and/or aliphatic isocyanates.
7. Aqueous dispersion adhesives according to one or more of the claims 1 to 4, additionally containing stabilizers, emulsifiers, thickeners and/or defoamers.
8. A process for the preparation of aqueous dispersion adhesives according to one or more of the claims 1 to 7, characterised by the addition of at least one carbodiamide of formulae (I) to (IV), where appropriate in the form of an aqueous dispersion and/or in o6surface7deactivated form, to the polyurethane dispersion containing, where appropriate, additional additives.
9. Use of the aqueous dispersion adhesives according to one or more of claims 1 to 7 in the furniture, textile and automotive industries and/or in the footwear industry.