Hardening composition for urea-formaldehyde glues, process for its preparation and kit comprising it

Abstract: The hardening composition for glues of the urea-formaldehyde type comprises an aqueous solution of an ammonium salt as polymerization catalyst for the urea-formaldehyde resin and, in emulsion with said aqueous solution, a resin deriving from the polymerization of one or more vinyl alcohol esters either with each other or with other monomers containing the vinyl group, said resin being able to cross-link in acidic surrounding. The composition can further comprise other ingredients, such as an antifoaming agent, a metal salt having acidic reactivity which catalyzes the crosslinking of the vinyl resin, an inorganic filler, and urea which controls the catalytic activity of the ammonium salt.

Description: The present invention relates to a hardening composition for urea-formaldehyde glues, to a process for its preparation and to a kit for its use together with urea-formaldehyde glues. There are known hardening compositions based on aqueous solutions of an ammonium salt, particularly ammonium chloride, which act as a catalyst for polymerization reactions of urea-formaldehyde glues. Thus, US-A-4 506 060 discloses a binder composition which comprises a urea-formaldehyde resin and polyvinylacetate polymers. Ammonium sulfate and/or chloride are stated to be suitable curing catalysts. However, the binder composition according to US-A-4 506 060 suffers from poor curing rate and water resistance. It is an object of the present invention to provide a hardening composition for urea-formaldehyde glues which composition improves the use properties of the polymerized glue, such as the adhesiveness, water resistance etc., while maintaining the hardening capacity substantially unchanged. This object is achieved by a hardening composition of the above indicated type which is characterized in that it also comprises in emulsion with the ammonium salt solution, a resin deriving from the polymerization of one or more vinyl esters or of one or more vinyl esters and other monomers containing the vinyl group with at least one post-crosslinking monomer, said resin being able to cross-link in acidic surrounding. Preferred post-crosslinking monomers are for example N-methylolacrylamide or tri-allylcyanurate. These reactive groups further control the cross-linking of the vinyl resin by attaching to the polymer chains of the urea-formaldehyde glue. Examples of preferred vinyl resins are polyvinyl acetate, ethylene vinylacetate and polyvinyl propionate. The presence of the vinyl resin in the emulsion improves the properties of pore filling, adhesion and water resistance of the polymerized glue after the addition of the hardening composition. The latter further guarantees a rapid hardening of the glue when the glue is brought together with the hardening composition at a temperature of about 100°. In a preferred embodiment of the invention the hardening composition further comprises an antifoaming agent in adequate amount to avoid the formation of air bubbles therein. Thus the composition is suitable for the use in automatic pumping and dosage systems which are currently used in the preparation of glue mixtures. According to a preferred embodiment of the invention the hardening composition comprises a metal salt having acidic reactivity which acts as a catalyst for the cross-linking of the vinyl resin and, together with the ammonium salt, as a co-catalyst for the polymerization of the urea-formaldehyde adhesive. Such salts, which are generally good electrolytes, have the further advantage of rendering the hardening composition suitable to be heated by high frequency radiations. Among the metal salts the preferred compounds are zinc chloride, chromium nitrate, aluminum nitrate and, in particular, aluminum chloride. According to a preferred embodiment of the invention, the hardening composition further comprises an inorganic filler showing stability in acidic surrounding. Examples of such fillers are calcium sulfate, barium sulfate and preferably kaolin. The inorganic filler, particularly kaolin, reinforces the achieved glue joints. Being compatible with the other ingredients, it further allows the compositon to be stored for long periods of time of at least up to six months. In a further preferred embodiment of the invention the hardening composition also comprises urea. The presence of this latter additive allows to control the catalytic activity of the ammonium salt during the polymerization of the glue. Urea, in particular, reduces this activity at room temperature or slightly higher temperatures, so that the mixture of hardener and glue may be applied without hurry to the surfaces to be adhered, while there is no decrease of catalytic activity at temperatures around 100°, at which the polymerization is usually carried out. A further object of the present invention is a kit, comprising, separated from each other, a hardening composition of any one of the above described types and a urea-formaldehyde glue, which are to be mixed at the moment of use, the weight ratio between the hardening composition and the glue being between 0.15 and 0.30 and preferably 0.20. A further object of the present invention is a process for the preparation of a hardening composition of the above described type, characterized in that it comprises the successive additions into a stirred vessel of the following ingredients: an aqueous emulsion of a cross-linking vinyl resin, an antifoaming agent, optionally an aqueous solution of a metal salt having acidic reactivity, an ammonium salt and water for its dissolution, and optionally urea, that optionally an inorganic filler is added to the other ingredients in two distinct steps after the addition of the aqueous solution of the aluminum chloride and of the urea, and that stirring is continued for 15 to 20 minutes after the addition of all ingredients has been completed. In a preferred embodiment of the above indicated process, an aqueous solution of an ammonium salt is prepared in advance by dissolving the ammonium salt in water which had been preheated to a temperature between 40 and 55°, whereupon said solution is added to the other ingredients. In particular, it was found to be advantageous to prepare hardening compositions of the following type by adding the ingredients in the indicated order: As indicated above, it is preferred to first dissolve the ammonium chloride in water (ingredients 5 and 6) and to then add the so prepared solution to the other ingredients in the indicated order. Kaolin is added in two distinct steps in order to enhance mixing with the other ingredients. The essential properties of the obtained compositions are indicated in the following table: Epprecht viscosity 700 to 3000 mPa.s Brookfield viscosity 1500 to 7000 mPa.s pH 3 to 3.5 solids content 55 to 65 % specific weight 1.15 ± 0.1 It is important that the final pH-value of the composition stabilizes around at the above indicated values, because lower values may cause the hydrolysis of the vinyl resin, while higher values impair the subsequent polymerization reactions. Further advantages and characteristics of the present invention will become apparent from the examples given below which examples are considered to be non-limiting. Example 1 The following ingredients were added with stirring in the indicated sequence and quantities into a vessel: The emulsion of the cross-linking polyvinyl acetate used was VINNAPAS DPN 15 (ex Wacker Germany) and had a solids content of 50 %. As indicated above it is preferred to separately mix the ammonium chloride and water and to then add the so prepared solution to the other ingredients. When all ingredients have been added stirring in the vessel is continued for 15 to 20 minutes. Example 2 The employed process is analogous to that of the preceding example. The following ingredients are used: emulsion of slightly cross-linking polyvinyl acetate 25.48 parts emulsion of highly cross-linking polyvinyl acetate 38.22 parts Nopco (antifoaming agent) 0,3 parts aqueous solution of AlCl 3 (water content 55 %) 1.3 parts kaolin 7.7 parts ammonium chloride 5 parts water 8.00 parts urea 7.00 parts kaolin 7.00 parts The emulsion of slightly cross-linking polyvinyl acetate was represented by a 50/50 combination of VINNAPAS DPN 15 and conventional not cross-linking polyvinylacetate. The emulsion of highly cross-linking polyvinyl acetate was represented by VINNAPAS DPN 15. Both polyvinyl acetate emulsions used have a solids content of 50 %. The following table indicates the essential physical properties of the two compositions obtained: Example 1 Example 2 Epprecht viscosity t=0 1900 mPa.s 800 mPa.s Epprecht viscosity t=5 days 1650 mPa.s 720 mPa.s Epprecht viscosity t=16 days 1700 mPa.s 750 mPa.s stratification after 36 days absent absent Brookfield viscosity, 20 rpm, 20°C, t=0 5480 mPa.s 1900 mPa.s pH 3.28 3.4 solids content 60.5 % 58 % specific weight 1.16 1.14 Then the hardening compositions of the above described examples and a comparative hardening composition, prepared according to the prior art on the basis of ammonium chloride and without addition of an emulsion of a cross-linking vinyl resin, were separately mixed in a ratio of 20 to 100 with two resins of the liquid urea-formaldehyde type in order to evaluate the polymerization. Of the two urea-formaldehyde resins used one had a mean reactivity and a content of free formaldehyde between 0.4 and 0.5 %, and the other had a high reactivity and a content of free formaldehyde between 1 and 1.2 %. The dry content of both urea-formaldehyde resins used was 65 ± 1 %. The following table 3 summarizes the essential properties of the glue mixtures thus obtained. liquid u.f resin with mean reactivity (dry content about 65 %) liquid u.f. resin with high reactivity (dry content about 65 ) comp. examp. examp 1 examp. 2 comp. examp. examp. 1 examp. 2 Epprecht visc. 20°C 280 450 400 260 440 420 pH 5,4 4,8 4,7 5,3 4,6 4,5 gelling time at 30°C 240' 205' 198' 88' 81' 82' gelling time at 100°C 38" 35" 36" 31" 24" 25" homogenity good good good good good good prevention of exudation with a 6/10 veneering and a pressing temperature of 90°C poor good good good good good Furthermore the water resistance of joints made with mixtures of adhesvies and hardining compositions of the above identified types was tested according to DIN 68705-IW67. The tests were carried out with glue mixtures consisting of the type having mean reactivity and hardening compositions according to examples 1 and 2 and the comparative example respectively. The weight ratio of the hardening compositon and the glue was 20 to 100. Several plywood samples for testing were prepared in the laboratoy by adhering together 5 layers of beech-wood having a thickness of 1 mm. After conditioning, the samples were immersed in water at 67° for 3 hours and then subjected to a further immersion in cold water for 2 hours. The following table 4 shows the results of this test. liquid u.f. resin with mean reactivity admixed with a hardening composition according to water resistance according to DIN 68705-IW67 comparative example failure (the adhered layers separated after 15 to 20 min in warm water) example 1 fully successful example 2 satisfying (bonding force between the layers after immersion is acceptable but not as good as with the composition according to example 1)

Claims: Hardening composition for glues of the urea-formaldehyde type, comprising as polymerisation catalyst for the urea-formaldehyde resin an aqueous solution of an ammonium salt, characterized in that said composition furthermore comprises, in emulsion with said aqueous solution, a resin deriving from the polymerization of one or more vinyl esters or of one or more vinyl esters and other monomers containing the vinyl group with at least one post-crosslinking monomer. Hardening composition according to claim 1, characterized in that said vinyl resin is polyvinyl acetate, ethylene vinylacetate or polyvinyl propionate. Hardening composition according to claim 1, characterized in that said post-crosslinking monomer is N-methylolacrylamide or triallyl cyanurate. Hardening composition according to any one of the previous claims, characterized in that the emulsion further comprises an antifoaming agent in an effective amount to avoid the formation of air bubbles. Hardening composition according to any one of the previous claims, characterized in that the emulsion further comprises a metal salt having acidic reactivcity in an effective amount to catalyze the cross-linking of the vinyl resin. Hardening composition according to claim 5, characterized in that the metal salt is zinc chloride, chromium or aluminum nitrate or preferably aluminum chloride. Hardening composition according to any one of the previous claims, characterized in that the emulsion further comprises an inorganic filler which is stable in acidic surrounding in an effective amcunt to reinforce the glue joint. Hardening composition according to claim 7, characterized in that the inorganic filler is calcium sulfate, barium sulfate or preferably kaolin. Hardening composition according to any one of the previous claims, characterized in that the emulsion further comprises urea in an effective amount to control the catalytic activity of the ammonium salt. Hardening composition according to any one of the previous claims, characterized in that it is obtainable by mixing the following ingredients in the indicated quantities: aqueous emulsion of cross-linking vinyl resin from 50 to 70 parts antifoaming agent from 0.1 to 0.5 parts aqueous solution of AlCl 3 from 0.5 to 3 parts kaolin from 10 to 20 parts aqueous solution of ammonium salt from 9 to 16 parts urea from 5 to 10 parts. Kit, comprising, separated from each other, a composition according to any one of the previous claims and a glue of the urea-formaldehyde type, intended to be mixed at the moment of use, the weight ratio between the hardening composition and the glue being between 0.15 and 0.30. Kit according to claim 11, characterized in that the weight ratio between the hardening composition and the glue is 0.2. Process for the preparation of a hardening composition according to claims 1 to 10, characterized in that it comprises the successive additions into a stirred vessel of the following ingredients: an emulsion of a cross-linking vinyl resin, an antifoaming agent, optionally an aqueous solution of an aluminum salt, an aqueous solution of a metal salt having acidic reactivity, and optionally urea, that optionally an inorganic filler, which is stable in acidic surrounding, is added in two distinct steps after the addition of the aqueous solution of the aluminum chloride and the urea and that stirring is continued for 15 to 20 minutes after the addition of all ingredients has been completed. Process according to claim 13, characterized in that the aqueous solution of the ammonium salt is prepared in advance by dissolving the ammonium salt in water, which had been previously heated to a temperature between 40 and 55°C, whereupon said solution of the ammonium salt is added to the other ingredients in the indicated order.

Inventors: PINCIROLI ALBERTO, PINCIROLI, ALBERTO
Applicants: NAT STARCH CHEM INVEST, NATIONAL STARCH AND CHEMICAL INVESTMENT HOLDING CORPORATION
Application year: 1992
Main classification: C09J61
IPC codes: C09J161, C08L61