HK1168121B - 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 248 (char 247)

Mixtures of carbodiamides of formula (I), 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 202 (char 201)

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, the present invention being intended to use 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, xylenediisocyanate, 2,6-benopropyl isocenylenediamine, 2,4-toluyl isopropyl isocyanate, 2,4-toluyl isocyanate, 2,4-toluyl isocyanate, 2,4-toluyl isocyanate, 2,4-toluyl isocyanate, 2,4-toluyl isocyanate, 2,4-toluyl isocyanate, 2,4-toluyl isocyanate, 2,4-toluyl isocyanate, 2,4-toluyl isocyanate, 2,4-toluyl isocyanate, 2,4-toluyl isocyanate, 2,4-toluyl isocyanate, 2,4-toluyl isocyanate, 2,4-toluyl isocyanate, 2,4-toluyl isocyanate, 2,4-toluyl isocyanate, 2,4-toluyl isocyanate, 2,4-toluyl isocyanate, 1,4-toluyl and 2,4-toluyl isocyanate, and 2,4-toluyl isocyanate, and 2,4-toluyl isocyanate, and 1,4-toluyl isocyanate, and 2,4-toluyl isocyanate, and 2,4-toluyl, and 2,4-toluyl, and 1,4-toluyl, and 1,4-toluyl, 2,4-toluyl, 2,4-toluyl, and 1,4-toluyl, 2,4-toluyl, and 1,4-toluyl, 2,4-toluyl, and 1,4-toluyl, and 1,4-toluyl, and 2,5-toluyl, and 1,4-toluyl, and 2,4-toluyl.

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 with a particle size of < 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 458 (char 457)

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 invention: 2-pentamethylene-1,5-diamine and its isomers and homologues such as 1,6-hexamethylenediamine; di-sec-butylamine; ethylene-diamine; 1,3-propylene-diamine; diethylene-triamine; triethylentetramine; 3,3'-dimethyl-4,4'-diaminodicyclohexylmethane; methylnonandiamine; isophorondiamine; 4,4'-diaminodicyclohexylmethane; alkanolamines and diamines such as ethanolamine and dietetamine and/or amidolamines. Among these, the most preferred are the 2-pentamethylene-1,5-diamine and its homologues, such as 1,6-diethylene-diamine and its homologues.

These are particularly preferred to be multifunctional primary and secondary, and particularly 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.

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 achieved by adding 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 deactivation of carbodiimides is carried out in a way that is known in itself, see in particular EP 0 205 970 A and US-A-4 888 124, the contents of which are hereby included in full by reference, e.g. 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 production of the aqueous dispersion nitrogen according to 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 additional additives, where appropriate.

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 as an aqueous dispersion, if necessary, and then surface-deactivated 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. The 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 citations: Chemicals used:

TDI-carbodiamide, a carbodiamide based on 2,4-toluetendiisocyanate with 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	Bsp. 2	Bsp. 3	Bsp. 4	Bsp. 5
	(erf.)	(VV)	(VV)	(VV)	(VV)
TDI-Carbodiimid	40
Addolink TT	40
Stabaxol P 200	40
Carbodilite LA-01	40
Carbodilite HMV 8CA	40
Wasser	52,6	52,6	60	52,6	55,0
Tween 85	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 defoamer (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 prepared 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 wood panel to a PVC board and applying 0,15 g of dispersion adhesives of examples 6, 7, 8, 9, 10 or 11 on the hot 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: Tabelle 3:

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

Tabelle 3:

VV= Vergleichsbeispiel, 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. Aqueous dispersion adhesives comprising at least one polyurethane dispersion and at least one carbodiimide of the formula (I)         R'-(-N=C=N-R-)_m-R"     (I), in which

   m corresponds to an integer from 1 to 500,

   R = arylene and/or C₇-C₁₁ aralkylene,

   R' = R-NCO, R-NHCONHR¹ or R-NHCONR¹R² and

   R" = -NCO, -NHCONHR¹ or -NHCONR¹R²,

   where in R', independently of one another, R¹ and R² are identical or different and represent a C₁-C₆ alkyl, C₆-C₁₀ cycloalkyl or C₇-C₁₈ aralkyl radical.
2. Aqueous dispersion adhesives according to Claim 1, characterized in that said carbodiimide comprises carbodiimides of the formulae (II), (III) and/or (IV) where R'" = C₁-C₁₈ alkylene, C₅-C₁₈ cycloalkylene, arylene and/or C₇-C₁₈ aralkylene and j within the molecule is identical or different and denotes 1 to 5, and p can be = 0 to 500, where x = 1 to 500.
3. Aqueous dispersion adhesives according to Claim 1 or 2, characterized in that the carbodiimides of the formulae (I) to (IV) are surface-deactivated by reaction with at least one amine.
4. Aqueous dispersion adhesives according to one or more of Claims 1 to 3, characterized in that the carbodiimides of the formulae (I) to (IV) are present in the form of an aqueous dispersion.
5. Aqueous dispersion adhesives according to one or more of Claims 1 to 4, characterized in that the polyurethane dispersion is substantially an aqueous dispersion.
6. Aqueous dispersion adhesives according to one or more of Claims 1 to 4, characterized in that the polyurethane dispersion comprises aqueous, ionic or non-ionic polyurethanes or polyester polyurethanes which contain polar groups and/or contain solvent, and which are based on aromatic and/or aliphatic isocyanates.
7. Aqueous dispersion adhesives according to one or more of Claims 1 to 4, further comprising stabilizers, emulsifiers, thickeners and/or defoamers.
8. Process for preparing the aqueous dispersion adhesives according to one or more of Claims 1 to 7, characterized in that at least one carbodiimide of the formulae (I) to (IV), optionally in the form of an aqueous dispersion and/or in surface-deactivated form, is incorporated by stirring into the polyurethane dispersion, which optionally comprises further 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 footwear manufacture.