DK169821B1 - Cold stable adhesive resin solution containing a phenolurea melamine formaldehyde condensate, process for its preparation and use of epsilon-aminocaprolactam or epsilon-aminocaproic acid as a cold stabilizer for the solution - Google Patents
Cold stable adhesive resin solution containing a phenolurea melamine formaldehyde condensate, process for its preparation and use of epsilon-aminocaprolactam or epsilon-aminocaproic acid as a cold stabilizer for the solution Download PDFInfo
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- DK169821B1 DK169821B1 DK103486A DK103486A DK169821B1 DK 169821 B1 DK169821 B1 DK 169821B1 DK 103486 A DK103486 A DK 103486A DK 103486 A DK103486 A DK 103486A DK 169821 B1 DK169821 B1 DK 169821B1
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J161/00—Adhesives based on condensation polymers of aldehydes or ketones; Adhesives based on derivatives of such polymers
- C09J161/34—Condensation polymers of aldehydes or ketones with monomers covered by at least two of the groups C09J161/04, C09J161/18 and C09J161/20
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G14/00—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00
- C08G14/02—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes
- C08G14/04—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes with phenols
- C08G14/06—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes with phenols and monomers containing hydrogen attached to nitrogen
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- Adhesives Or Adhesive Processes (AREA)
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- Preparation Of Clay, And Manufacture Of Mixtures Containing Clay Or Cement (AREA)
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Abstract
Description
i DK 169821 B1in DK 169821 B1
Opfindelsen angår en kuldestabil, vandig limharpiksopløs-ning af kondensationsprodukter af formaldehyd med en kombination af phenol-, urinstof- og melamin-komponenter, en fremgangsmåde til fremstilling deraf samt anvendelsen af 5 6-aminocaprolactam eller e-aminocapronsyre som kuldestabilisator for denne limharpiksopløsning.This invention relates to a cold-stable aqueous adhesive resin solution of condensation products of formaldehyde with a combination of phenolic, urea and melamine components, a process for their preparation, and the use of 5-aminocaprolactam or e-aminocaproic acid as a cold stabilizer for this adhesive resin solution.
Det er kendt, at phenol-melamin-formaldehyd-limharpikser udviser fænomenet kuldeinstabilitet. Dette manifesterer 10 sig på den måde, at viskositeten af limharpiksopløsningen ved sænkning af temperaturen under ca. 12 °C ved længere tids oplagringsrid, f.eks. en uge, stiger meget stærkt og fører til en pastaagtig eller gelatinøs beskaffenhed. Årsagen er ikke f.eks. viskositetens temperaturafhængig-15 hed. Dette fænomen ville ved temperaturforøgelse vise sig at være reversibelt. Viskositetsændringen er af en sådan art, at der ved længere oplagringstid og lav temperatur finder en ændring af makrostrukturen sted på en sådan måde, at systemet bliver højviskost og også thixotropt.It is known that phenol-melamine-formaldehyde glue resins exhibit the phenomenon of cold instability. This manifests itself in the way that the viscosity of the adhesive resin solution, by lowering the temperature below ca. 12 ° C for longer periods of storage, e.g. a week, increases very strongly and leads to a paste-like or gelatinous condition. The reason is not e.g. the temperature dependence of the viscosity. This phenomenon would, by temperature increase, prove to be reversible. The viscosity change is such that at longer storage times and low temperatures, a change in the macrostructure takes place in such a way that the system becomes high viscous and also thixotropic.
20 Viskositetsforøgelsen kan føre til den pastaagtige tilstand. Denne tilstand kan man kun ødelægge igen ved stærk opvarmning til 60 til 70 °C over længere tid. I så tilfælde er opløsningen dog forud belastet og går væsentligt hurtigere over til pastatilstanden igen, når den igen 25 afkøles. Dette fænomen kan kun forklares ved en ændring af væskens intermolekylære struktur.The viscosity increase can lead to the paste-like state. This condition can only be destroyed again by strong heating to 60 to 70 ° C over a longer period of time. In that case, however, the solution is pre-loaded and goes back to the paste state substantially faster when it is cooled again. This phenomenon can only be explained by a change in the intermolecular structure of the liquid.
Fænomenet kuldeinstabilitet er uønsket. Det hæmmer transporten, oplagringen og fremføringen igennem pumper i den 30 kolde årstid, koster meget energi til tilbageføringen til den tyndtflydende tilstand eller kræver manuel nedbrydning af harpiksen, der er blevet tyktflydende, fra beholderen, uanset om denne er en tog tank, en tønde, en tank, en container eller en tankvogn. I den pastaagtige til-35 stand er forarbejdningen af limharpiksen ikke mere mulig.The phenomenon of cold instability is undesirable. It inhibits the transport, storage and feeding through pumps in the 30 cold season, costs a lot of energy to return to the thin-liquid state, or requires manual decomposition of the viscous resin from the container, whether it is a train tank, a barrel, a tank, a container or a tanker. In the paste-like condition, the processing of the glue resin is no longer possible.
Selv når viskositetstilvæksten endnu ikke har ført til den pastaagtige konsistens, er forarbejdningen allerede DK 169821 B1 2 væsentligt dårligere.Even when viscosity growth has not yet led to the paste-like consistency, the processing is already considerably poorer.
Problemet i forbindelse med kuldeinstabilitet kan løses, når man ved lagringen eller transporten holder harpiksen 5 på en temperatur over 12 °C. Dette kan foregå ved en god emballageisolation eller ved en opvarmning, f.eks. oplagring af tønderne i opvarmede lokaler. Undertiden er det muligt at forarbejde harpiksen så hurtigt, at den endnu ikke har antaget den lave temperatur, eller at der endnu 10 ikke er tid nok til den viskositetsforøgelse, der skyldes den lave temperatur.The problem of cold instability can be solved when the resin 5 is kept at a temperature above 12 ° C during storage or transport. This can be done by a good packaging insulation or by heating, e.g. storage of the barrels in heated premises. Sometimes it is possible to process the resin so quickly that it has not yet assumed the low temperature or that there is still not enough time for the viscosity increase due to the low temperature.
Phenol-urinstof-melamin-formaldehyd-limharpikserne finder anvendelse til fremstilling af spånplader, der er resi-15 stente overfor vind og vejr, og til limning af massivt træ, der er resistent overfor vind og vejr, dvs. limning af brædder til bærende bræddekonstruktioner, f.eks. bjæl ker. Kuldestabiliteten er overordentlig vigtig til transport af harpiksen over lange vejstrækninger og ved oplag-20 ringen på forarbejdningsstedet. I den pastaagtige tilstand lader harpiksen sig ikke mere pumpe. Ved forsendelse per skib, der tager længere tid, eller ved oplagring i ydre tanklagre over længere tidsrum er den voksende viskositet på grund af kulden særlig problematisk, fordi 25 store limharpiksmængder, der befinder sig i tanke, ikke mere lader sig opvarme med et teknisk opbud, der er praktisk tilgængeligt.The phenol-urea-melamine-formaldehyde glue resins are used for the production of wind and weather-resistant particle board and for the bonding of wind and weather-resistant solid wood, ie. gluing boards to load-bearing board structures, e.g. beams. The cold stability is extremely important for transporting the resin over long stretches of road and at storage at the processing site. In the paste-like state, the resin no longer pumps. For shipment per ship that takes longer, or for storage in outer tank warehouses over a longer period of time, the increasing viscosity due to the cold is particularly problematic, because 25 large amounts of glue resin contained in tanks can no longer be heated with a technical supply. that is conveniently accessible.
DE-C 15 94 368 beskæftiger sig med et andet teknisk pro-30 biem. Det angår aminoplast-imprægneringsharpiksopløsnin- ger til imprægnering af bærestoffer af papir eller vævet materiale, hvilke er fremkommet ved kondensation af melamin med formaldehyd i vandigt medium, eventuelt med andre modifikationsmidler, der er i stand til at danne 35 aminoplaster. Disse imprægneringsharpiksopløsninger udvi ser en forøget lagerstabilitet. Forøgelsen af lagerstabiliteten opnås ved, at man foretager kondensationen i nær- DK 169821 B1 3 værelse af mellem 3 og 15 vægt-% e-aminocaprolactam.DE-C 15 94 368 deals with another technical problem. It relates to aminoplast impregnation resin solutions for impregnating carriers of paper or woven material obtained by condensing melamine with formaldehyde in aqueous medium, optionally with other modifiers capable of forming 35 aminoplasts. These impregnating resin solutions exhibit increased storage stability. The enhancement of storage stability is achieved by conducting the condensation in the vicinity of between 3 and 15% by weight of e-aminocaprolactam.
Ved forlængelsen af lagerstabiliteten i henhold til DE-C 15 95 368 drejer det sig om et fænomen, der har be-5 tydning ved lime- eller imprægneringsharpikser, og som intet har at gøre med fænomenet kuldestabilitet.In the extension of the storage stability according to DE-C 15 95 368, this is a phenomenon that has significance in adhesive or impregnation resins and which has nothing to do with the phenomenon of cold stability.
Lagerstabiliteten af formaldehyd-kondensationsprodukter er altid begrænset, fordi disse oligomere produkter i ti-10 dens løb viderekondenseres. Dette foregår hurtigt ved høj temperatur og langsomt ved lav temperatur. Viderekonden-sationen manifesterer sig i en irreversibel forøgelse af viskositeten. Viskositeten selv er en temperaturafhængig egenskab, og derfor måles den ved en bestemt temperatur, 15 for det meste 20 °C.The storage stability of formaldehyde condensation products is always limited because these oligomeric products are condensed over time. This is done quickly at high temperature and slowly at low temperature. The re-condensation manifests itself in an irreversible increase in viscosity. The viscosity itself is a temperature dependent property and therefore it is measured at a certain temperature, usually 20 ° C.
Harpikser, der - som det teknisk set er sædvanligt - oplagres med en initial viskositet, der i afhængighed af typen ligger mellem 200 og 1200 mPa.s, kan i løbet af 20 længere tids opbevaring ved højere temperatur, f.eks. ca.Resins which - as is technically customary - are stored with an initial viscosity which, depending on the type, are between 200 and 1200 mPa.s, can be stored over a longer period of time at higher temperature, e.g. ca.
30 °C, udvikle viskositeter, der er så høje som 5000 mPa.s og endnu højere. I så fald er harpikserne ikke mere pumpbare med simple pumper. En anden egenskab er den irreversible dannelse af vanduopløselige polymere, der 25 viser sig ved en uklarhed og som eventuelt sedimenterer. Dette fænomen er især uønsket i forbindelse med imprægneringsharpikser, der som bekendt skal forblive vandklare.30 ° C, develop viscosities as high as 5000 mPa.s and even higher. In that case, the resins are no longer pumpable with simple pumps. Another feature is the irreversible formation of water-insoluble polymers, which appear in a cloud and optionally settle. This phenomenon is particularly undesirable in the case of impregnation resins which, as you know, must remain water-clear.
I modsætning dertil er kuldeinstabiliteten et fænomen, 30 der under indflydelse af lave temperaturer giver sig til kende som dannelsen af thixotrope og pastaagtige harpikser. Disse pastaer lader sig dog igen for flydige, når harpiksen i nogen tid er opvarmet til 60 °C eller derover. Den tyndere tilstand bibeholdes i så fald igen i 35 længere tid, men dog ikke så langt tid som ved en ubelastet harpiks. Disse ændrede egenskaber synes at være en følge af makrostrukturændring, hvorfor man ved bestemte DK 169821 B1 4 fænomener i forbindelse med thioxotropi også plejer at tale om strukturviskositet.In contrast, the cold instability is a phenomenon known as the formation of thixotropic and paste-like resins under the influence of low temperatures. However, these pastes become liquid again when the resin is heated to 60 ° C or higher for some time. In this case, the thinner state is retained for a longer period of time, but not as long as with an unloaded resin. These altered properties appear to be a consequence of macrostructure change, which is why, for certain DK 169821 B1 4 phenomena associated with thioxotropy, it is also customary to talk about structural viscosity.
Problemet kuldeinstabilitet optræder ikke ved de fleste 5 typer af kondensationsprodukter, og således heller ikke ved kondensationsprodukterne fra DE-A 15 95 368. I forbindelse med de phenolholdige phenol-urinstof-melamin-formaldehyd-limharpikser er det dog et for den tekniske anvendelse yderst ubehageligt fænomen.The problem of cold instability does not occur in most of the 5 types of condensation products, and thus also in the condensation products of DE-A 15 95 368. However, for the phenol-containing phenol-urea-melamine-formaldehyde glue resins, it is extremely unpleasant for the technical application. phenomena.
10 FR-A-898 175 angår aminoplaster, der med henblik på forøgelse af alkaliopløseligheden og syrefældbarheden blev kondenseret i nærværelse af aminocarboxylsyrer, f.eks. e-aminocapronsyre eller e-aminocaprolactam, Trykskriftet 15 angår ikke problemet omfattende kuldestabilitet af harpiksopløsninger, da dette problem ikke foreligger ved de phenolfrie aminoplaster.FR-A-898 175 relates to aminoplasts which, for the purpose of increasing the alkali solubility and acid precipitability, were condensed in the presence of aminocarboxylic acids, e.g. e-aminocaproic acid or e-aminocaprolactam, The printing press 15 does not address the problem of cold stability of resin solutions as this problem does not exist with the phenol-free aminoplasts.
Det er opfindelsens formål at tilvejebringe en kuldesta-20 bil, vandig limharpiksopløsning af kondensationsprodukter af formaldehyd med en kombination af phenol-, urinstof-og melamin-komponenter, hvorved det allerede diskuteret problem i forbindelse med kuldeinstabiliteten ikke mere optræder.It is an object of the invention to provide a cold-stable, aqueous, glue resin solution of condensation products of formaldehyde with a combination of phenolic, urea and melamine components, thereby eliminating the already discussed problem of cold instability.
2525
Limharpiksopløsningen ifølge opfindelsen, der er af den i indledningen til krav 1 angivne art, er ejendommelig ved det i den kendetegnende del af krav 1 angivne. Herved opfyldes opfindelsens formål.The adhesive resin solution according to the invention, which is of the kind specified in the preamble of claim 1, is characterized by the characterizing part of claim 1. The object of the invention is thus fulfilled.
3030
Ved en foretrukken udførelsesform for opfindelsen kan limharpiksopløsningen fremstilles ved kondensation i nærværelse af 0,5 til 2 vægt-%, fortrinsvis 0,8 til 1,3 vægt-%, af e-aminocaprolactam eller e-aminocapronsyre, 35 beregnet i forhold til limharpiksopløsningens totalvægt.In a preferred embodiment of the invention, the adhesive resin solution may be prepared by condensation in the presence of 0.5 to 2% by weight, preferably 0.8 to 1.3% by weight, of e-aminocaprolactam or e-aminocaproic acid, calculated relative to that of the glue resin solution. total weight.
DK 169821 B1 5DK 169821 B1 5
Limharpiksopløsningen ifølge opfindelsen kan indeholde modifikationsmidler for phenolplast. Som eksempler på modifikationsmidler kan man anføre natriumsulfit, natri-umhydrogensulfit, methanol ethylenglycol og andre sædvan-5 lige modifikationsmidler, f.eks. sådanne, der er aktive mod termit- og svampeangreb eller som tjener til at forlænge holdbarheden af det træmateriale, der er behandlet med limharpiksopløsningen.The adhesive resin solution of the invention may contain phenolic resin modifiers. As examples of modifiers may be cited sodium sulphite, sodium hydrogen sulphite, methanol ethylene glycol and other conventional modifiers, e.g. those which are active against termite and fungal infestations or which serve to extend the shelf life of the wood material treated with the adhesive resin solution.
10 Opfindelsen angår også en fremgangsmåde, der er af den i indledningen til krav 5 angivne art og som er ejendommelig ved det i den kendetegnende del af krav 5 angivne.The invention also relates to a method which is of the kind specified in the preamble of claim 5 and which is characterized by the characterizing part of claim 5.
Opfindelsen angår også en anvendelse, der er af den i 15 indledningen til krav 6 angivne og som er ejendommelig ved det i den kendetegnende del af krav 6 angivne.The invention also relates to an application which is one of the features of the preamble of claim 6 and which is characterized by the characterizing part of claim 6.
Det har overraskende vist sig, at limharpiksopløsningerne ved tilsætning af e-aminocaprolactam eller e-aminocapron-20 syre bliver kuldestabile, og de også ved -3 °C forbliver stabile dvs. flydedygtige, i mindst 4 uger, mens ubehandlede harpikser i mange tilfælde allerede efter 1 uges forløb bliver pastaagtige. Ved tilsætninger på under 0,5 vægt-% e-aminocaprolactam eller e-aminocapronsyre er den 25 kuldeinstabiliserende effekt meget ringe. Hvis man anvender mere end 2 vægt-% e-aminocaprolactam eller e-aminocapronsyre, opnår man ikke nogen yderligere nyttevirkning. Dette større forbrug skader dog ikke, men fører til en unødvendig fordyrelse af harpiksen.Surprisingly, it has been found that, by the addition of e-aminocaprolactam or e-aminocaproic acid, the glue resin solutions become cold stable and they also remain stable at -3 ° C. liquid, for at least 4 weeks, while in many cases untreated resins already become paste-like after 1 week. For additions below 0.5% by weight of e-aminocaprolactam or e-aminocaproic acid, the cold-stabilizing effect is very low. If more than 2% by weight of e-aminocaprolactam or e-aminocaproic acid is used, no further benefit is obtained. This higher consumption, however, does not harm, but leads to unnecessary costing of the resin.
30 Årsagen til aktiviteten af e-aminocaprolactamen eller e-aminocapronsyren som kuldestabilisator i de her omhandlede limharpikser er endnu ikke kendt.The cause of the activity of the e-aminocaprolactam or e-aminocaproic acid as a cold stabilizer in the present adhesive resins is not yet known.
35 Da lagerinstabilitet og kuldeinstabilitet beror på helt af hinanden uafhængigt fænomener og desuden også optræder i forbindelse med forskellige harpiksarter, kunne man på DK 169821 B1 6 basis af den problemløsning hvad angår lagerstabiliteten, som i henhold til DE-C 15 95 368 tilbydes for phenolfrie melaminharpikser, ikke udlede nogen tilskyndelse til løsning af det tekniske problem omfattende kuldestabilite-5 ten, der ligger til grund for opfindelsen. Det er interessant at notere sig, at forholdsvis høje koncentrationer af e-aminocaprolactam er nødvendig til forbedring af lagerstabiliteten i henhold til DE-C 15 95 368, nemlig 3-15 vægt-%, beregnet i forhold til blandingen af melamin 10 og formaldehyd, mens forbedringen af kuldestabiliteten i forbindelse med de foreliggende limharpiksopløsninger allerede sætter ind ved en tilsætning af kun 0,5 vægt-%, beregnet i forhold til limharpiksopløsningens totale vægt.35 Since storage instability and cold instability depend on completely independent phenomena and also occur in connection with different resin species, the problem solving regarding the storage stability offered by phenol-free according to DE-C 15 95 368 could be based on DK 169821 B1 6 melamine resins, do not derive any incentive to solve the technical problem comprising the cold stability underlying the invention. It is interesting to note that relatively high concentrations of e-aminocaprolactam are required to improve the storage stability according to DE-C 15 95 368, namely 3-15% by weight, calculated in relation to the mixture of melamine 10 and formaldehyde, while the improvement of the cold stability associated with the present adhesive resin solutions already adds in by the addition of only 0.5% by weight, calculated in relation to the total weight of the adhesive resin solution.
1515
Som phenolkomponenter kan man ifølge opfindelsen fortrinsvis anvende usubstitueret phenol eller substituerede phenoler. Som substituerede phenoler kommer cresoler og xylenoler i betragtning. Disse skulle mindst være usub-20 stitueret på to carbonatomer, der foreligger i o- eller p-stilling til OH-gruppen.As phenol components, the invention may preferably use unsubstituted phenol or substituted phenols. As substituted phenols, cresols and xylenols are considered. These should be at least unsubstituted on two carbon atoms present in the o- or β-position of the OH group.
Som phenol-urinstof-melamin-formaldehyd-kondensationspro dukter kan man udvælge sådanne med den sædvanlige sammen-25 sætning, såsom som de f.eks. er beskrevet i DE-C 29 51 957 og i EP-B 31 533. Med henblik på fremstilling af en typisk limharpiksopløsning ifølge opfindelsen går man ud fra 1-10 vægt-% phenol, 15-25 vægt-% urinstof, 10-20 vægt-% melamin, 20-45 vægt-% formaldehyd, 0,1-0,2 vægt-% 30 natriumhydroxid og 0,5-2 vægt-% e-aminocaprolactam eller e-aminocapronsyre. Forskellen op til 100% er vand.As phenol-urea-melamine-formaldehyde condensation products, one can select such with the usual composition such as those e.g. are disclosed in DE-C 29 51 957 and in EP-B 31 533. For the preparation of a typical glue resin solution according to the invention, starting from 1-10 wt% phenol, 15-25 wt% urea, 10-20 wt% melamine, 20-45 wt% formaldehyde, 0.1-0.2 wt% sodium hydroxide and 0.5-2 wt% e-aminocaprolactam or e-aminocaproic acid. The difference up to 100% is water.
Til fremstilling af en typisk limharpiksopløsning ifølge opfindelsen anvendes 5 vægt-% phenol, 21 vægt-% urinstof, 35 13 vægt-% melamin, 32 vægt-% formaldehyd, 0,12 vægt-% natriumhydroxid og 1 vægt-% e-aminocaprolactam eller e-aminocapronsyre. Resten er vand.To prepare a typical glue resin solution of the invention, 5 wt% phenol, 21 wt% urea, 35 wt% melamine, 32 wt% formaldehyde, 0.12 wt% sodium hydroxide and 1 wt% e-aminocaprolactam or e-aminocaproic acid. The rest is water.
DK 169821 B1 7DK 169821 B1 7
Limharpiksopløsningerne ifølge opfindelsen fremstilles under anvendelse af i og for sig kendte fremgangsmåder, herunder de i de før angivne patentskrifter angivne fremgangsmåder, under medkondensation af e-aminocaprolactam 5 eller e-aminocapronsyre fra begyndelsen af kondensationen. Men man kan også arbejde i henhold til andre metoder, der er beskrevet i litteraturen.The adhesive resin solutions of the invention are prepared using methods known per se, including the methods set forth in the aforementioned patents, under the condensation of e-aminocaprolactam 5 or e-aminocaproic acid from the beginning of the condensation. But one can also work according to other methods described in the literature.
Hvis man tilsætter e-aminocaprolactam efter kondensatio-10 nen af komponenterne, opnår man praktisk talt ingen kuldestabiliserende effekt.Adding e-aminocaprolactam after condensation of the components gives virtually no cold-stabilizing effect.
Opfindelsen skal forklares nøjere under henvisning til de følgende eksempler.The invention will be explained in more detail with reference to the following examples.
15 EKSEMPEL 1 3230 dele vandig 40% formaldehydopløsning, 4887 dele af en kommerciel, vandig urinstof-formaldehyd-limharpiks, 20 som udviser et molforhold mellem formaldehyd og urinstof på 1,8:1 og et tørstofindhold på ca. 65%, bringes til at foreligge i en reaktionskedel, og der blandes under omrøring med 1300 dele melamin, 466 dele phenol, 99 dele e-aminocaprolactam og 23 dele af 50% natronlud.EXAMPLE 1 3230 parts of aqueous 40% formaldehyde solution, 4887 parts of a commercial aqueous urea-formaldehyde glue resin, 20 exhibiting a mole ratio of formaldehyde to urea of 1.8: 1 and a solids content of about 65%, are made in a reaction kettle and are mixed with stirring with 1300 parts of melamine, 466 parts of phenol, 99 parts of e-aminocaprolactam and 23 parts of 50% sodium hydroxide solution.
2525
Blandingen opvarmes til 90 °C og kondenseres ved 90 til 95 °C indenfor 2 timer til en viskositet af 700 mPa.s (20 °C), hvorved der ved tilsætning af 4 dele af en 50% natronlud opretholdes en konstant pH-værdi af 8,9. Den 30 således opnåede limharpiks afkøles derpå til 20 °C og har følgende egenskaber:The mixture is heated to 90 ° C and condensed at 90 to 95 ° C within 2 hours to a viscosity of 700 mPa.s (20 ° C), thereby maintaining a constant pH value of 4 parts of a 50% sodium hydroxide solution. 8.9. The glue resin thus obtained is then cooled to 20 ° C and has the following properties:
Viskositet: 750 mPa.s (20 °C) 35 pH-værdi ved 20 0C: 9,1 DK 169821 B1 8Viscosity: 750 mPa.s (20 ° C) pH at 20 ° C: 9.1 DK 169821 B1 8
Massefylde ved 20 °C: 1,262 g/cm* Tørstofindhold: 61% 5 Geleringstid ved 40 0C: 32 minutter (efter tilsæt ning af 3% hærdemiddel * 34% myresyre)Density at 20 ° C: 1,262 g / cm * Solids content: 61% 5 Gelling time at 40 ° C: 32 minutes (after addition of 3% curing agent * 34% formic acid)
Lagerstabilitet ved 25 °C: 6 uger (viskositetsstigning 10 indtil 2500 mPa.s)Storage stability at 25 ° C: 6 weeks (viscosity increase 10 to 2500 mPa.s)
Kuldestabilitet ved 0 °C: mere end 3 måneder.Cold stability at 0 ° C: more than 3 months.
Ved anvendelse af en tilsvarende mængde e-aminocapronsyre 15 i stedet for e-aminocaprolactam opnår man i det væsentlige de samme resultater.By using a similar amount of e-aminocaproic acid 15 instead of e-aminocaprolactam, substantially the same results are obtained.
Sammenligningsforsøg 1 20 3230 dele vandig 40% formaldehydopløsning og 4887 dele af en kommerciel, vandig urinstof-formaldehyd-limharpiks, som beskrevet i eksempel 1, bringes til at foreligge i en reaktionsbeholder og blandes under omrøring med 1300 dele melamin, 466 dele phenol og 23 dele 50% natronlud.Comparative Experiment 1 20 3230 parts of aqueous 40% formaldehyde solution and 4887 parts of a commercial aqueous urea-formaldehyde glue resin, as described in Example 1, are made in a reaction vessel and mixed with 1300 parts of melamine, 466 parts of phenol and 23 divide 50% baking soda.
2525
Blandingen opvarmes til 90 °C og kondenseres ved denne temperatur indenfor 2 timer indtil en viskositet på 700 mPa.s (20 °C), ved en konstant pH-værdi af 8,9.The mixture is heated to 90 ° C and condensed at this temperature within 2 hours to a viscosity of 700 mPa.s (20 ° C), at a constant pH of 8.9.
30 Den således opnåede limharpiks afkøles derpå til 20 °C og viser følgende egenskaber:The glue resin thus obtained is then cooled to 20 ° C and shows the following properties:
Viskositet: 720 mPa.s (20 °C) 35 pH-værdi ved 20 °C: 9,0 DK 169821 B1 9Viscosity: 720 mPa.s (20 ° C) pH at 20 ° C: 9.0 DK 169821 B1 9
Massefylde ved 20 °C: 1,26 g/cm3 Tørstofindhold: 59% 5 Geleringstid ved 40 °C: 32 minutter (efter tilsæt ning af 3% hærdemiddel = 3% myresyre)Density at 20 ° C: 1.26 g / cm3 Solids content: 59% 5 Gelling time at 40 ° C: 32 minutes (after addition of 3% curing agent = 3% formic acid)
Lagerstabilitet ved 25 °C: 5 uger (viskositetsstigning 10 indtil 2500 mPa.s)Storage stability at 25 ° C: 5 weeks (viscosity increase 10 to 2500 mPa.s)
Kuldestabilitet ved 0 °C: efter 3 uger pastaagtig.Cold stability at 0 ° C: after 3 weeks pasty.
En limharpiks, der er blevet pastaagtig på denne måde, 15 kan igen tilbageføres til den flydende tilstand ved efterfølgende temperaturbehandling ved 60 til 70 °C, men derved blev kuldestabiliteten yderligere forringet, og den andrager herefter kun ca. 3 dage.An adhesive resin which has become paste-like in this way can again be returned to the liquid state by subsequent temperature treatment at 60 to 70 ° C, but thereby the cold stability was further deteriorated, and thereafter amounts to only approx. 3 days.
20 EKSEMPEL 2 5343 dele vandig 40% formaldehydopløsning blandes med 912 dele phenol og 54 dele 50% natronlud, opvarmes under omrøring til 90 °C og kondenseres ved denne temperatur i 25 30 minutter. Den fremkomne opløsning afkøles til 25 °C og under omrøring tilsættes 3200 dele melamin og 174 dele e-aminocaprolactam. Reaktionsblandingen opvarmes til 90 °C og omsættes ved 90-95 °C i ca. 70 minutter indtil en viskositet af 400 mPa.s (20 °C).EXAMPLE 2 5343 parts of aqueous 40% formaldehyde solution are mixed with 912 parts of phenol and 54 parts of 50% sodium hydroxide solution, heated with stirring to 90 ° C and condensed at this temperature for 25 minutes. The resulting solution is cooled to 25 ° C and with stirring 3200 parts of melamine and 174 parts of e-aminocaprolactam are added. The reaction mixture is heated to 90 ° C and reacted at 90-95 ° C for approx. 70 minutes until a viscosity of 400 mPa.s (20 ° C).
3030
Den således fremkomne harpiksopløsning afkøles til 25 °C og den blandes med 7940 dele af en kommerciel vandig urinstof-formaldehyd-limharpiks, som beskrevet i eksempel 1.The resin solution thus obtained is cooled to 25 ° C and mixed with 7940 parts of a commercial aqueous urea-formaldehyde glue resin, as described in Example 1.
Limharpiksblandingen har følgende egenskaber: 35 DK 169821 B1 10The adhesive resin composition has the following properties: 35 DK 169821 B1 10
Viskositet: 606 mPa.s (20 °C) pH-værdi ved 20 °C: 9,1 5 Massefylde ved 20 °C: 1,276 g/cm® Tørstofindhold: 62,8%Viscosity: 606 mPa.s (20 ° C) pH at 20 ° C: 9.1 Density at 20 ° C: 1.276 g / cm® Solids content: 62.8%
Geleringstid ved 50 °C: 32 minutter (efter tilsæt- 10 ning af 10% af en 15% NH4C1- opløsning)Gelling time at 50 ° C: 32 minutes (after addition of 10% of a 15% NH 4 Cl solution)
Lagerstabilitet ved 25 °C: 6 uger (viskositetsstigning indtil 2500 mPa.s) 15Storage stability at 25 ° C: 6 weeks (viscosity increase up to 2500 mPa.s) 15
Kuldestabilitet ved 0 °C: 4 uger.Cold stability at 0 ° C: 4 weeks.
Ved anvendelse af en tilsvarende mængde af e-aminocapron-syre i stedet for e-aminocaprolactam opnår man i det 20 væsentlige de samme egenskaber.By using a similar amount of e-aminocaproic acid instead of e-aminocaprolactam, substantially the same properties are obtained.
Sammenligningseksempel 2 5343 dele 40% formaldehydopløsning blandes med 912 dele 25 phenol og 54 dele 50% natronlud, opvarmes under omrøring til 90 °C og kondenseres ved denne temperatur i 30 minutter. Den fremkomne opløsning afkøles til 25 °C, og under omrøring tilsættes 3200 dele melamin. Reaktionsblandingen opvarmes til 90 °C og omsættes ved 90-95 °C i ca. 70 30 minutter indtil en viskositet på 380 mPa.s (20 °C).Comparative Example 2 5343 parts of 40% formaldehyde solution are mixed with 912 parts of 25 phenol and 54 parts of 50% sodium hydroxide solution, heated with stirring to 90 ° C and condensed at this temperature for 30 minutes. The resulting solution is cooled to 25 ° C and with stirring 3200 parts of melamine are added. The reaction mixture is heated to 90 ° C and reacted at 90-95 ° C for approx. 70 30 minutes until a viscosity of 380 mPa.s (20 ° C).
Den således fremkomne harpiksopløsning afkøles til 25 °C og blandes med 7940 dele af den kommerciel vandig urinstof-formaldehyd-limharpiks, som beskrevet i eksempel 1.The resin solution thus obtained is cooled to 25 ° C and mixed with 7940 parts of the commercial aqueous urea-formaldehyde glue resin, as described in Example 1.
Limharpiksblandingen har følgende egenskaber: 35 11 DK 169821 B1The adhesive resin mixture has the following properties: 35 11 DK 169821 B1
Viskositet: 560 mPa.s (20 °C) pH-værdi ved 20 °C: 9,0 5 Massefylde ved 20 °C: 1,275 g/cm3 Tørstofindhold: 63,0%Viscosity: 560 mPa.s (20 ° C) pH at 20 ° C: 9.0 Density at 20 ° C: 1,275 g / cm3 Solids content: 63.0%
Geleringstid ved 50 °C: 32 minutter (efter tilsæt- 10 ning af en 15% NH4Cl-opløs- ning)Gelling time at 50 ° C: 32 minutes (after addition of a 15% NH 4 Cl solution)
Lagerstabilitet ved 25 °C: 4 uger (viskositetsstigning indtil 2500 mPa.s) 15Storage stability at 25 ° C: 4 weeks (viscosity increase up to 2500 mPa.s) 15
Kuldestabilitet ved 0 °C: 2 uger.Cold stability at 0 ° C: 2 weeks.
20 25 30 3520 25 30 35
Claims (6)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19853508205 DE3508205A1 (en) | 1985-03-08 | 1985-03-08 | REFRIGERABLE GLUE RESIN SOLUTION |
| DE3508205 | 1985-03-08 |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| DK103486D0 DK103486D0 (en) | 1986-03-07 |
| DK103486A DK103486A (en) | 1986-09-09 |
| DK169821B1 true DK169821B1 (en) | 1995-03-06 |
Family
ID=6264546
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DK103486A DK169821B1 (en) | 1985-03-08 | 1986-03-07 | Cold stable adhesive resin solution containing a phenolurea melamine formaldehyde condensate, process for its preparation and use of epsilon-aminocaprolactam or epsilon-aminocaproic acid as a cold stabilizer for the solution |
Country Status (6)
| Country | Link |
|---|---|
| EP (1) | EP0193960B1 (en) |
| AT (1) | ATE78268T1 (en) |
| DE (2) | DE3508205A1 (en) |
| DK (1) | DK169821B1 (en) |
| FI (1) | FI86073C (en) |
| NO (1) | NO164777C (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| HU216325B (en) * | 1993-03-26 | 1999-06-28 | W.L. Gore And Associates Inc. | Microemulsion polymerization systems and coated materials made therefrom coated articles coated of microemulsion and process for producing them |
| DE4426002A1 (en) * | 1994-07-22 | 1996-01-25 | Basf Ag | Process for the preparation of aqueous aminoplast resins |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1595368B2 (en) * | 1966-12-08 | 1971-07-22 | Badische Anilin & Soda Fabrik AG, 6700 Ludwigshafen | METHOD FOR MANUFACTURING TRAENK RESIN SOLUTIONS |
| DE2212963C3 (en) * | 1972-03-17 | 1979-01-04 | Basf Ag, 6700 Ludwigshafen | Process for the production of melamine impregnating resins |
-
1985
- 1985-03-08 DE DE19853508205 patent/DE3508205A1/en not_active Withdrawn
-
1986
- 1986-03-03 FI FI860887A patent/FI86073C/en not_active IP Right Cessation
- 1986-03-06 DE DE8686102998T patent/DE3685972D1/en not_active Expired - Lifetime
- 1986-03-06 AT AT86102998T patent/ATE78268T1/en not_active IP Right Cessation
- 1986-03-06 EP EP86102998A patent/EP0193960B1/en not_active Expired - Lifetime
- 1986-03-07 NO NO860866A patent/NO164777C/en unknown
- 1986-03-07 DK DK103486A patent/DK169821B1/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| EP0193960A3 (en) | 1989-07-26 |
| NO860866L (en) | 1986-09-09 |
| DE3508205A1 (en) | 1986-09-11 |
| DK103486A (en) | 1986-09-09 |
| FI860887A0 (en) | 1986-03-03 |
| FI860887A (en) | 1986-09-09 |
| DK103486D0 (en) | 1986-03-07 |
| NO164777C (en) | 1990-11-14 |
| FI86073B (en) | 1992-03-31 |
| FI86073C (en) | 1992-07-10 |
| EP0193960B1 (en) | 1992-07-15 |
| NO164777B (en) | 1990-08-06 |
| DE3685972D1 (en) | 1992-08-20 |
| ATE78268T1 (en) | 1992-08-15 |
| EP0193960A2 (en) | 1986-09-10 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| B1 | Patent granted (law 1993) | ||
| PUP | Patent expired |