DE202014101620U1 - Container with 2-component polyurea synthetic resins - Google Patents

Abstract

Closed 2-chamber film bag, which has at least one separable separating agent that can be removed from the outside and seals the two chambers from one another, characterized in that it contains an aliphatic polyisocyanate component A) and a polyaspartic acid ester component B) in separate chambers.

Description

The application relates to a new container for 2-component polyurea resins based on aliphatic polyisocyanate and polyaspartic esters

The use of 2-component synthetic resins such as polyurethanes, epoxy resins or acrylate resins has been state of the art for many years, especially in the construction industry, where these products are widely used, for example, as fixing compounds, as coating compounds or as sealing compounds. Basically, such 2-component synthetic resins must be mixed thoroughly before processing in a predetermined mixing ratio. This is always problematic when smaller amounts of 2-component resins are used, or when very reactive, fast-curing resins are used. In these cases, more recently 2 chamber foil pouches are used. In these foil bags, the two components are stored in the predetermined mixing ratio in separate chambers, wherein the chambers are reversibly separated by a relatively weak sealing seam or a clamping web. Immediately prior to use, the components are brought into contact with each other by breaking the seal seam or by removing the clamp ridge, mixing the components by kneading the pouch. This technology enables fast and clean mixing in a precisely predetermined mixing ratio in particularly environmentally friendly packaging. In the meantime, this technology has become common prior art and is described by way of example in US Pat DE 7606374 U , of the DE 20 2008 012 883 U1 or combined with a soakable tissue in the DE 20 2005 000 854 U1 ,

Kneading bag technology has so far been described for 2-component polyurethane-epoxy resin and acrylate systems. For 2-component polyurea systems, including in the context of the present application, reactive systems to understand that consist of an isocyanate group-containing component A) and an amine group-containing component B), the kneading bag technology is not yet known.

More recently, certain 2-component polyurea systems described in more detail below are available on the market, which have advantageous properties, especially for the construction sector. These polyurea systems are highly reactive, allowing you to cure in a relatively short time, which is desirable in terms of rapid construction progress. At the same time, the fast curing reaction reaction largely avoids the competing reaction of isocyanates with moisture, which leads to bubble formation. On the other hand, these systems have the great disadvantage of a very short processing time, so that after mixing the components only little time remains for a professional application. The fundamental disadvantage of such polyurea systems is thus the very unfavorable ratio of processing time on the one hand and curing time on the other.

The object of the present invention was therefore to provide polyurea systems with a prolonged processing time while maintaining the short curing time.

Surprisingly, this object could be achieved by means of a suitable packaging, namely a 2-chamber foil bag according to claim 1. The invention relates to a closed 2-chamber film bag, which has at least one externally removable sealing release agent, characterized in that it contains in separate chambers an aliphatic polyisocyanate component A) and a polyaspartic ester component B).

The invention is based on the surprising observation that mixtures of aliphatic polyisocyanates and amine-functional polyaspartic esters in the closed kneading bag have an extended processing time. After opening the kneading bag and applying the mixture of the synthetic resin of components A) and B), the mixture then hardens very quickly, as known from polyurea systems, to give the polymeric synthetic resin. The 2-component synthetic resin is preferably formed as a fixing compound, as a coating composition or as a sealing compound, in particular for use in the construction sector, with its total composition being selected accordingly. In a transparent setting, the 2-component resin is also well suited as a binder for natural stones such as marble or quartz, e.g. for the production of natural stone floor coverings.

The mixing of components A) and B) in the kneading bag takes place until a - at least essentially - homogeneous mixture is obtained. The application is preferably carried out immediately after mixing, ie at the beginning of the curing or at the latest in the course of incipient hardening. It understands in that the foil bag encloses the two components A) and B) in each case in a manner that is air-tight and moisture-proof and separates them from the outside atmosphere of the bag.

The polyurea systems to be used according to the invention are known in principle and are described by way of example in the following patent applications: EP403921 . US 6605684 . WO 2001007504 . WO 2001007399 . US 6458293 . EP 1426397 . DE 10 2006 002 153 A1 or the WO 2004033517 A1 , The disclosure of these documents, in particular with regard to the composition of the polyurea systems, in particular with respect to the components A) and B), is hereby fully comprehended.

According to the invention suitable as aliphatic polyisocyanate component A) are polyisocyanates based on the monomeric diisocyanates hexamethylene diisocyanate (HDI) and / or isophorone diisocyanate (IPDI), which by means of suitable modification reactions, such as. As trimerization, biuretization, allophanatization and / or urethanization are prepared, wherein excess monomeric diisocyanate is then removed by distillation from the mixture, whereby the polyisocyanates low residual contents of monomeric diisocyanate of <0.5% bez. to the total mixture of the polyisocyanate mixture (see also: Laas et al. J. Prakt. Chem, 336, 1, 94, 185-200 and News from Chemistry, 55, 380-384, 2007 ). The present patent application therefore uses the term polyisocyanate in particular for the designation of oligomeric polyisocyanate mixtures.

Preference is given to using in particular biuret-containing polyisocyanates, as in, for example, in U.S. Patent 3,124,605 . U.S. Patent 3,201,372 or DE-OS 1 101 394 are described, having isocyanurate polyisocyanates, such as those in the U.S. Patent 3,001,973 , in the DE-PS 1 022 789 . 1 222 067 and 1 027 394 as well as in the DE-OS 1 929 034 and 2 004 048 urethane-containing polyisocyanates, as described for example in the DE-OS 953 012 , of the BE-PS 752 261 or in the U.S. Patent 3,394,164 and 3 644 457 be described and allophanate polyisocyanates, as described for example in the GB-PS 994 890 , in the BE-PS 761 626 and in the NL-OS 7 102 524 to be discribed.

Further preferred polyisocyanate component A) are prepolymers based on HDI and / or IPDI and / or the above-mentioned prepolymers containing isocyanate groups. Polyisocyanates on the one hand and organic polyhydroxyl compounds on the other hand used. These prepolymers are prepared in a conventional manner by reacting said di- or polyisocyanates while maintaining an NCO / OH equivalent ratio of 1.2: 1 to 10: 1, preferably 1.8: 1 to 8: 1, wherein im Following the reaction, if appropriate, a distillative removal of optionally present free volatile diisocyanate follows. Preferably, higher molecular weight polyhydroxyl compounds of the molecular weight range from 300 to 12,000, preferably from 1,000 to 8,000, of the kind known per se from polyurethane chemistry are used to prepare the prepolymers.

Higher molecular weight polyhydroxyl compounds for the preparation of prepolymers or semiprepolymers are in particular the polyester polyols based on low molecular weight simple alcohols and polybasic carboxylic acids such as adipic acid, sebacic acid, phthalic acid, isophthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, maleic acid, the anhydrides of such acids or any mixtures of such acids or acid anhydrides. Hydroxyl-containing polylactones, in particular polycaprolactones corresponding to the above statements, are also suitable for the preparation of the prepolymers or semiprepolymers.

For the preparation of isocyanate group-containing prepolymers are also well suited, the above statements, polyether polyols, as they are accessible in a conventional manner by alkoxylation of suitable starter molecules. Suitable starter molecules are, for example, simple polyols, water, organic polyamines having at least two N-H bonds or any mixtures of such starter molecules. Suitable for the alkoxylation reaction alkylene oxides are in particular ethylene oxide and / or propylene oxide, which can be used in any order or in admixture in the alkoxylation reaction.

Also suitable for the preparation of the prepolymers or semiprepolymers are the hydroxyl-containing polycarbonates corresponding to the above, as can be prepared, for example, by reacting simple diols of the type already mentioned above with dialkyl or diaryl carbonates, for example dimethyl carbonate or diphenyl carbonate.

Polyisocyanate component A) is particularly preferably polyisocyanate mixtures based on HDI, optionally mixed with minor amounts of IPDI, ie <50% based on IPDI on the total weight of the diisocyanates used, preferably <25% of IPDI, which isocyanurate, allophanate, urethane and / or Iminooxadiazindiongruppen and by a content of free diisocyanate of <0.5% and a content of isocyanate groups of 5% to 24 % bez. are characterized on the total weight of the polyisocyanate component. The component A) is preferably solvent-free, but can lacquer solvents of the known type in small amounts, preferably up to a maximum of 5 wt .-% contain, respectively. on the total weight of component A).

As component B) can be used Polyasparaginsäureester of from EP 403921 A1 known type, which are prepared by reacting cycloaliphatic diamines with at least one cycloaliphatic ring with diethyl maleate and / or Maleinsäuredimethylester. Useful according to the invention are aspartic acid esters based on 1-amino-3,3,5-trimethyl-5-aminomethylcyclohexane (isophoronediamine), 2,4- and / or 2,6-hexahydrotoluylenediamine, 2,4'- and / or 4,4 'Diamino-dicyclohexylmethane and / or 3,3'-dimethyl-4,4'-diaminodicyclohexylmethane. Preferably used according to the invention are aspartic acid esters based on 4,4'-diamino-dicyclohexylmethane and / or 3,3'-dimethyl-4,4'-diaminodicyclohexylmethane and diethyl maleate. The aspartic acid ester based on 4,4'-diamino-dicyclohexylmethane and diethyl maleate is particularly preferably usable as component B). Of course, it is also possible to use mixtures of the aspartic acid esters mentioned as component B).

Component B) may further contain the additives, auxiliaries and additives customary in the plastics and coating industry. These are, in particular, inorganic and / or organic pigments and fillers, plasticizers, leveling agents, deaerating agents, anti-settling agents, moisture-binding agents such as zeolites or orthoformic esters and lacquer solvents of the known type, whereby the co-use of alcoholic or aminic reactive components or alcoholic solvents is possible in minor amounts. Component B) preferably contains less than 10% by weight, based on the total weight of component B), of reactive components or organic solvents, preferably less than 5% by weight, particularly preferably less than 3% by weight. The total content of additives, auxiliaries and additives in component B) is typically less than 60% by weight, preferably less than 50%, particularly preferably less than 35%, based on the total weight of component B).

In a particular embodiment of the present invention, component B) contains no fillers and pigments and is used as a transparent coating agent or as a binder for natural stones such as marble or quartz.

The components A) and B) according to the invention are introduced into separate chambers of a 2-chamber foil bag and sealed there, the chambers being separated from one another by at least one sealing agent which can be removed from the outside. The foil pouches typically consist of a transparent foil material or foil composite material, preferably polyethylene or polyester. As separation means between the individual chambers, in principle any separation is possible, for example by welding or mechanical separation, for example by means of a clamping means. Preferably, the separation is carried out by means of a slotted tube, in which a plug-in part such as a rubber cord is inserted for tight clamping, wherein the bag wall is clamped between the insertion part and slotted tube. On the DE 7606374 U , the DE 20 2008 012 883 U1 and the DE 20 2005 000 854 U1 Reference should be made here by way of example, which are hereby incorporated in full with respect to the formation of the release agent. After pulling out the insertion part, the slotted tube can be removed and the components can be easily mixed together by kneading the bag.

The proportions of components A) and B) in the chambers of the film bag are typically such that per mole of isocyanate of component A) (determined from the percentage content of isocyanate groups) 0.7 to 1.0 moles of amine groups of component B) ( determined from the molecular structure). Preferably 0.8 to 0.98 moles of amine groups of component B) are used per mole of isocyanate of component A), more preferably 0.9 to 0.97 moles of amine groups of component B) are used per mole of isocyanate of component A).

Usually, the manual mixing of components A) and B) takes 2 to 3 minutes, after which the bag can be opened and the reacting 2-component mixture removed and fed to the planned application. Optionally, the 2-chamber foil bag can be provided with a resealable spout, whereby the portion-wise removal of the material is facilitated.

The mixing preferably homogeneous mixing of the components A) and B) takes place by kneading, in particular manual kneading, without being limited thereto. In terms of shelf life and the transportability of the filled film bags, the film bags are preferably additionally wrapped in a bag made of aluminum foil or aluminum composite film and sealed.

In the context of the present invention, the surprising observation was made that mixtures of components A) and B) to be used according to the invention produce a significantly lower heat of reaction in the closed film bag and consequently have a significantly longer processing time compared to mixing in an open container. Thus, a significantly extended processing time is made possible by the inventive packaging in the film bag, which is in view of the generally quite short processing times of such systems of great advantage. The advantages resulting according to the invention are explained in more detail by the following examples.

EXAMPLES

Example 1 (according to the invention)

270 g of the aspartic acid ester based on 4,4'-diamino-dicyclohexylmethane and diethyl maleate (Desmophen NH1420, commercial product of Bayer MaterialScience AG, D-51368 Leverkusen) and 330 g of a polyisocyanate mixture having allophanate and isocyanurate structures based on hexamethylene diisocyanate (Basonat HA3000, commercial product from BASF SE, D-67056 Ludwigshafen), are separately filled into the chambers of a transparent foil bag with separating web (slotted plastic tube with inserted rubber cord), the bag is sealed airtight by welding the two chambers. After removal of the separating web, the two components are intimately mixed at a temperature of 20 ° C by kneading the bag for three minutes. The kneading bag can be kneaded even after a period of 120 minutes, the viscous material can still be easily expressed from the bag after this time.

Example 2 (noninventive comparative example)

The experiment of Example 1 is repeated, but components A) and B) are mixed in an open 1000 ml polyethylene mixing cup using a stir bar by stirring for three minutes. The contents of the mixing cup solidified after a time of 90 minutes. Table 1 compares temperatures and viscosities of Examples 1 and 2: Time including mixing Temperature [° C] * (Viscosity [mPas]) ** foil pouch mixing cup 3 minutes 22 ° C 23.5 ° C 5 minutes 23.6 ° C 24.3 ° C 10 mins 25 ° C 27.9 ° C 15 minutes 26.2 ° C 32.1 ° C 25 minutes 27.2 ° C 36.0 ° C 30 minutes 26.5 ° C (8300 mPas) 40.9 ° C (3400 mPas)
* Temperatures were measured on the outside of the bag or mixing cup using a commercially available electronic infrared thermometer
** The viscosities were determined by rotational viscometry, the foil bag was emptied into the measuring cup immediately before the measurement.

Example 3 (according to the invention)

As described in Example 1, 295 g of aspartic acid ester based on 4,4'-diamino-dicyclohexylmethane and diethyl maleate (Desmophen NH1420, commercial product of Bayer MaterialScience AG, D-51368 Leverkusen) and 305g of a polyisocyanate containing isocyanurate structures based on of hexamethylene diisocyanate (Desmodur N3600, commercial product of Bayer MaterialScience AG, D-51368 Leverkusen) packed in a foil bag. After removal of the separating web, the two components are intimately mixed at a temperature of 20 ° C by kneading the bag for three minutes. The kneading bag can still be kneaded on the surface even after a time of 90 minutes The bag is measured after this time, a temperature of 25.4 ° C, the viscous material can be easily expressed after this time from the bag.

Example 4 (noninventive comparative example)

The experiment of Example 3 is repeated, but components A) and B) are mixed in a 1000 ml polyethylene mixing cup using a stir bar by stirring for three minutes. The contents of the mixing cup solidified after a time of 90 minutes. On the surface of the cured material, a temperature of 38.7 ° C is measured.

QUOTES INCLUDE IN THE DESCRIPTION

This list of the documents listed by the applicant has been generated automatically and is included solely for the better information of the reader. The list is not part of the German patent or utility model application. The DPMA assumes no liability for any errors or omissions.

Cited patent literature

• DE 7606374 U [0002, 0020]
• DE 202008012883 U1 [0002, 0020]
• DE 202005000854 U1 [0002, 0020]
• EP 403921 [0009]
• US 6605684 [0009]
• WO 2001007504 [0009]
• WO 2001007399 [0009]
• US 6458293 [0009]
• EP 1426397 [0009]
• DE 102006002153 A1 [0009]
• WO 2004033517 A1 [0009]
• US 3,124,605 [0011]
• US 3201372 [0011]
• DE 1101394 A [0011]
• US 3001973 [0011]
• DE 1022789 [0011]
• DE 1222067 [0011]
• DE 1027394 [0011]
• DE1929034A [0011]
• DE 2004048A [0011]
• DE 953012 A [0011]
• BE 752261 [0011]
• US 3394164 [0011]
• US 3644457 [0011]
• GB 994890 [0011]
• BE 761626 [0011]
• NL 7102524 A [0011]
• EP 403921 A1 [0017]

Cited non-patent literature

• Laas et al. J. Prakt. Chem, 336, 1, 94, 185-200 and News from Chemistry, 55, 380-384, 2007 [0010]

Claims (11)

Closed 2-chamber film bag, which has at least one externally removable, the two chambers from each other sealing release agent, characterized in that it contains in separate chambers an aliphatic polyisocyanate component A) and a polyaspartic ester component B). Closed two-chamber film bag according to claim 1, characterized in that it as aliphatic polyisocyanate component A) modified polyisocyanates based on hexamethylene diisocyanate and / or isophorone diisocyanate having an isocyanate content of 5 wt.% - To 24 wt .-% and a content of free Diisocyanate of less than 0.5 wt .-% contains. Closed two-chamber film bag according to claim 1 or 2, characterized in that it contains as aliphatic polyisocyanate component A) modified polyisocyanates based on hexamethylene diisocyanate having an organic solvent content of less than 5%. Closed two-chamber foil pouch according to one of claims 1 to 3, characterized in that it contains as aliphatic polyisocyanate component A) isocyanurate, allophanate, urethane and / or iminooxadiazinedione polyisocyanates based on hexamethylene diisocyanate having an organic solvent content of less than 5 contains%. Closed two-chamber foil pouch according to one or more of claims 1 to 4, characterized in that as polyaspartic acid ester component B) reaction products of 4,4'-diamino-dicyclohexylmethane and / or 3,3'-dimethyl-4,4'-diaminodicyclohexylmethane with diethyl maleate. Closed two-chamber film bag according to one or more of claims 1 to 5, characterized in that it contains as polyaspartic acid ester component B) the reaction product of 4,4'-diamino-dicyclohexylmethane and diethyl maleate. Closed 2-chamber foil bag according to one or more of claims 1 to 6, characterized in that component B) additionally pigments and / or fillers and / or plasticizers and / or flow control agents and / or deaerating agents and / or anti-settling agents and / or moisture-binding agents and / or paint solvent. Closed 2-chamber foil bag according to one or more of claims 1 to 7, characterized in that the separation takes place by means of a slotted tube, in which a plug-in part such as a rubber cord is inserted for tight clamping, wherein the bag wall between insertion part or rubber cord and slotted tube is clamped. Film bag according to one or more of claims 1 to 8, characterized in that the synthetic resin resulting from the mixed components A) and B) constitutes a fixing compound, coating compound, sealing compound. Film bag according to one or more of claims 1 to 8, characterized in that the resulting from the mixed components A) and B) resin is a binder for natural stones. Film bag according to one or more of claims 1 to 8, characterized in that the resulting from the mixed components A) and B) resin is a transparent coating agent.