SI22167A - Water-soluble melamine urea formaldehyde binder for mineral fibres - Google Patents

Water-soluble melamine urea formaldehyde binder for mineral fibres Download PDF

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SI22167A
SI22167A SI200500339A SI200500339A SI22167A SI 22167 A SI22167 A SI 22167A SI 200500339 A SI200500339 A SI 200500339A SI 200500339 A SI200500339 A SI 200500339A SI 22167 A SI22167 A SI 22167A
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Slovenia
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binder
mineral
mineral fiber
resin
melamine
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SI200500339A
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Slovenian (sl)
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Gregor KEJŽAR
Aleksander Jovanovic
Anton Platisa
Joze Hafner
Primoz Ogorelec
Mateja ALJAŽ-ROŽIC
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Termo D.D.
Melamin D.D. Kocevje
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Publication of SI22167A publication Critical patent/SI22167A/en

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Abstract

The invention relates to the process of manufacture of a partly etherified water-soluble melamine formaldehyde resin, to the manufacture of a binder for mineral fibres on the basis of this resin, to the method for production of a mineral-fibre product bound by this binder, and to the product made of mineral fibres, which comprises mineral fibres in contact with the cured composition of the above mentioned binder. According to the invention, condensation and etherification are conducted in a single-stage process under atmospheric pressure in such a way that the pH value of the mixture of melamine (0.5 - 1.5 moles), urea (0.5 - 1.5 moles) and formaldehyde (30 - 50 % solution in water, 1.6 - 2.6 moles per mole of combined amines) is adjusted to 8.0 - 11 and the mixture heated during intensive mixing to 80 up to 100 degrees Celsius, after which the reaction is taking place in the reactor under reflux conditions for 100 up to 300 minutes, and this under checking of hydrophobicity, viscosity and/or index of refraction. The process of manufacture of standard thermal or sound insulation materials is characterized in that the binder is applied in amounts of 0.3 - 10 % on the weight of the bound mineral fibre product, between 10 and 30 % in the case of HDT (high density) panels and 20 - 40 % in the case of composite products made of the mineral fibre reinforced binder, that a catalyst is added to the binder directly prior to its entering into dosing pumps which apply the binder by spraying immediately after defibration of a molten mineral material, that the temperature in the settling chamber lies under the temperature at the beginning of the setting of the resin, and that the thus formed layer of mineral fibres is cured in a curing chamber, where hot air at temperatures of 200 - 400 degrees Celsius is blown through the mineral wool layer.

Description

Vodotopno melaminsko sečninsko formaldehidno vezivo za mineralna vlaknaWater-soluble urea formaldehyde binder for mineral fibers

Izum se nanaša na postopek izdelave delno zaetrene vodotopne melaminsko sečninsko formaldehidne smole, izdelavo veziva za mineralna vlakna na osnovi te smole, na metodo za proizvodnjo vezanega izdelka iz mineralnih vlaken s tem vezivom in na izdelek iz mineralnih vlaken, ki vključuje mineralna vlakna v stiku z utijeno sestavo zgoraj omenjenega veziva.The invention relates to a process for the manufacture of a partially etched water-soluble melamine urea formaldehyde resin, the manufacture of a mineral fiber binder based on this resin, to a method for the manufacture of a bonded mineral fiber product with this binder and to a mineral fiber product comprising mineral fibers in contact with the stitched composition of the binder mentioned above.

Izdelki iz mineralnih vlaken običajno vsebujejo mineralna vlakna kot so npr. umetno narejena steklasta vlakna (MMVF), steklena vlakna, keramična vlakna, bazaltna vlakna, žlindrina in kamena volna, vezana skupaj z utrjenim termoplastičnim ali največkrat duroplastičnim polimernim vezivnim materialom. Za uporabo za izdelke za toplotno ali zvočno izolacijo, so vezane plošče iz mineralnih vlaken običajno proizvedene s preoblikovanjem taline iz ustreznih surovin v vlakna po običajnem postopku, kot npr. s procesom hitro vrteče perforirane posode ali kaskadnim rotorskim procesom. Vlakna se odpihnejo v zbiralno komoro in se ob formiranju, ko so še vroča, omočijo z raztopino veziva in naključno naložijo kot plast ali mreža na transportni trak. Plast vlaken je nato prepeljana do utrjevalne komore, kjer se prepihuje z ogretim zrakom, da se utrdi vezivo in togo poveže skupaj mineralna vlakna.Mineral fiber products typically contain mineral fibers such as, for example, mineral fibers. Artificial fiberglass (MMVF), glass fiber, ceramic fiber, basalt fiber, slag and rock wool, bonded together with a cured thermoplastic or most commonly duroplastic polymeric binder material. For use in thermal or acoustic insulation products, mineral fiber plywood is usually produced by converting the melt from the corresponding raw materials into fibers according to a conventional process, such as e.g. by a process of rapidly rotating perforated vessels or by a cascading rotor process. The fibers are blown into the collecting chamber and, when formed while still hot, are wetted with a binder solution and randomly loaded as a layer or net onto a conveyor belt. The fiber layer is then transported to a curing chamber where it is blown with heated air to harden the binder and rigidly bond the mineral fibers together.

Z vezivom oplaščena vlakna so pogosto predraga za uporabnike, kot odločilni cenovni faktor pa se običajno izpostavlja drage vezivne smole. Zaradi njihovega odličnega faktorja cena/lastnosti so bile v preteklosti običajno izbrane fenol formaldehidne smole, ki so lahko ekonomično proizvedene in so lahko modificirane s sečnino, preden jih uporabimo kot vezivo, kar dodatno poceni vezivo.Binder-coated fibers are often too expensive for users, and expensive binder resins are usually the determining price factor. Because of their excellent price / performance factor, phenol formaldehyde resins have typically been selected in the past, which can be economically produced and can be modified with urea before being used as a binder, which is an additional inexpensive binder.

Ker pa zakonodajalci zadnja leta zelo znižujejo dovoljene emisije hlapnih organskih komponent (VOC) in ker se zakonodaja glede uporabe fenol vsebujočih pripravkov v Evropi zaostruje, se je veliko truda vložilo v obširne raziskave alternativnih veziv brez fenola.However, as legislators have been reducing emissions of volatile organic components (VOCs) very much in recent years, and as legislation on the use of phenol-containing preparations in Europe has intensified, much effort has been put into extensive research into alternative phenol-free binders.

Na podlagi teh raziskav seje pojavilo kar nekaj sestav veziv brez fenola, npr. vezivo na osnovi polikarboksi polimerov in poliolov.Based on these studies, quite a few phenolic binder compositions have emerged, e.g. binder based on polycarboxy polymers and polyols.

-2Druga skupina veziv brez fenola za mineralna vlakna so produkti reakcij adicije/eliminacije alifatskih in aromatskih anhidridov z alkanolamini. Ta veziva za mineralna vlakna imajo odlične vezivne lastnosti ampak zahtevajo drage surovine in predvsem visok delež dragega anhidridnega reagenta, da dosežejo želeno vodotopnost, hitrost utrjevanja in utijevalno gostoto.-2 Another group of phenol-free binders for mineral fibers are the products of the addition / elimination reactions of aliphatic and aromatic anhydrides with alkanolamines. These mineral fiber binders have excellent bonding properties, but they require expensive raw materials and, above all, a high proportion of expensive anhydride reagent to achieve the desired water solubility, cure rate and thickening density.

Melaminsko-formaldehidne smole, ki so do sedaj poznane, bi zadostile zahtevam za vezivo za mineralna vlakna kar se tiče negorljivosti in reaktivnosti. Za sintezo vodotopnih melaminskosečninskih smol je do sedaj poznanih mnogo postopkov, ki jih lahko razdelimo v dve skupini.The melamine-formaldehyde resins known so far would meet the requirements for a mineral fiber binder in terms of flammability and reactivity. So far, the synthesis of water-soluble melamine-urea resins is well known in the art and can be divided into two groups.

Tipični postopek prve skupine je tak, da melamin, sečnino in formaldehid v molskem razmeiju 1 : (0 - 2) : (1,3 - 4) med mešanjem segrevamo na 70 - 90°C, reagiramo pri pH 6.5 do 8.5 dokler ne dosežemo želene stopnje polikondenzacije, kar merimo preko viskoznosti in/ali hidrofobnosti, oziroma lomnega količnika. Običajno traja sinteza 3 do 10 ur. Po takem postopku so se sintetizirala predvsem lepila za les in smole za impregnacijo papiijev.A typical method of the first group is that melamine, urea and formaldehyde in a molar ratio of 1: (0 - 2): (1.3 - 4) is heated to 70-90 ° C while stirring, reacting at pH 6.5 to 8.5 until reached the desired degree of polycondensation, as measured by viscosity and / or hydrophobicity, or refractive index. It usually takes 3 to 10 hours to synthesize. Such a process mainly synthesized wood adhesives and papyrus impregnation resins.

Tipični postopek iz druge skupine pa je tak, da najprej reagiramo melamin in formaldehid v razmeiju 1 : (3 - 10) pri pH 8 - 10 in temperaturi 60 - 80 °C. Nato pa dodamo 10 do 50 molskih delov metanola, temperaturo spustimo na 30 do 60 °C, pH pa znižamo na 1 do 6. Reakcijo vodimo do željene stopnje zaetrenja in polikondenzacije, nato pa odvečno topilo oddestiliramo. Po takem postopku so sintetizirane predvsem vodotopne smole za lake.A typical process from the second group is that first react melamine and formaldehyde in a ratio of 1: (3 - 10) at pH 8 - 10 and temperature 60 - 80 ° C. Then 10 to 50 molar parts of methanol are added, the temperature is lowered to 30 to 60 ° C, and the pH is lowered to 1 to 6. The reaction is led to the desired degree of etching and polycondensation, and then the excess solvent is distilled off. Such a process mainly synthesizes water-soluble resins for varnishes.

Smole iz prve skupine imajo dovolj dobre lepilne lastnosti, nimajo velike količine gorljivih komponent in so po lastnostih primerne za vezanje mineralnih vlaken, vendar pa nimajo visoke vodorazredčljivosti in imajo kratko stabilnost, kar onemogoča njihovo uporabo v obstoječih tehnologijah proizvodnje izdelkov iz mineralnih vlaken.The resins in the first group have good enough adhesive properties, do not have a large amount of combustible components and are suitable for bonding mineral fibers, but they do not have high water-solubility and have short stability, which makes it impossible to use them in existing technologies of production of mineral fiber products.

Smole iz druge skupine pa imajo dobro obstojnost in visoko vodorazredčljivost, pa tudi zadovoljive lepilne lastnosti, vendar pa imajo večji delež gorljivih komponent, postopek sinteze pa je drag, tako da ne pridejo v poštev kot vezivo za mineralna vlakna.The resins in the second group have good durability and high water solubility, as well as satisfactory adhesive properties, but they have a higher proportion of combustible components, and the synthesis process is expensive, so they are not suitable as a mineral fiber binder.

Do sedaj se je ta problem veziva mineralnih vlaken reševal tako, da so izdelovali za uporabo pri višjih temperaturah (nad 200° C) izdelke iz mineralnih vlaken z zelo majhno vsebnostjo veziva, cca 1%, kar pa je imelo za posledico zelo slabe mehanske lastnosti izdelkov, težave pri manipulaciji in velik izmet.So far, this problem of mineral fiber binder has been solved by producing mineral fiber products with very low binder content, approximately 1%, for use at higher temperatures (above 200 ° C), which has resulted in very poor mechanical properties. products, manipulation issues, and major ejection.

-3Naloga predstavljenega izuma je pripraviti vezivo brez fenola, kije posebej primemo za vezavo mineralnih vlaken, ki bo imelo odlične vezivne karakteristike, še posebej ustrezno hitrost in moč utrjevanja, da bo dobro topno v vodi in bo imelo dobro redčljivost ter bo lahko ekonomično proizvedeno iz manj dragih surovin.The object of the present invention is to provide a phenol-free binder, which is particularly suitable for mineral fiber bonding, which will have excellent bonding properties, especially adequate speed and curing power, to be well soluble in water and have good dilution and can be economically produced from less expensive raw materials.

Nadaljnja naloga predstavljenega izuma je pripraviti izdelek iz mineralnih vlaken, v katerem so mineralna vlakna povezana z utijenim vezivom brez fenola po izumu.It is a further object of the present invention to provide a mineral fiber product in which the mineral fibers are bonded to a woven phenol-free binder of the invention.

Po izumu je naloga rešena po neodvisnih patentnih zahtevkih.According to the invention, the problem is solved according to independent claims.

Izdelava delno zaetrenega vodotopnega melaminsko sečninsko formaldehidnega veziva za mineralna vlakna je značilna po tem, da vodimo kondenzacijo in zaetrevanje v enostopenjskem procesu pri pH 8 do 11, pod atmosferskim tlakom in v temperaturnem območju 80 do 100 °C ob kontroli hidrofobnosti, viskoznosti in/ ali lomnega količnika.The production of a partially etched water-soluble melamine urea formaldehyde binder for mineral fibers is characterized by the condensation and etching in a one-step process at pH 8 to 11, under atmospheric pressure and in the temperature range 80 to 100 ° C with control of hydrophobicity, viscosity and / or the refractive index.

V skladu s prvo nalogo predstavljenega izuma je pripravljena osnova za vodno vezivo brez fenola: melaminsko sečninsko formaldehidna smola, ki ustreza tehnološkim zahtevam za vezivo mineralnih vlaken, je vodorazredčljiva, ima dobro vezivnost za mineralna vlakna in je kot vezivo v utgeni obliki negorljiva .According to the first object of the present invention, a base for a phenol-free aqueous binder is prepared: a melamine urea formaldehyde resin that meets the technological requirements for a mineral fiber binder, is water-soluble, has good mineral-fiber binder and is flame retardant as a binder.

Postopek izdelave melaminsko formaldehidne smole in po tem postopku izdelano vezivo po izumu v primerjavi z znanimi melaminsko formaldehidnimi smolami s svojimi lastnostimi dodatno zadovolji vse druge zahteve, to je, daje vodotopna, kot utrjeno vezivo pa vodoodpoma, obenem dovolj reaktivna, z dobrim oprijemom na mineralna vlakna, ter ne bistveno dražja od fenolne smole za ta namen.The process of making melamine formaldehyde resin and the binder according to the invention according to the invention, in comparison with the known melamine formaldehyde resins, additionally satisfies all other requirements, that is, it is water-soluble and, as a hardened binder, water-repellent, at the same time sufficiently reactive, with good adhesion to mineral fibers, and not significantly more expensive than phenolic resin for this purpose.

V skladu z nadaljnim aspektom predstavljenega izuma je pripravljena metoda za proizvodnjo produktov iz vezanih mineralnih vlaken, ki zajema koraka stika mineralnih vlaken ali izdelka iz mineralnih vlaken z vodnim vezivom brez fenola po izumu, kot je opisano zgoraj, in utrjevanja sestave veziva.According to a further aspect of the present invention, there is provided a method for the production of bonded mineral fiber products, comprising the steps of contacting a mineral fiber or mineral fiber product with an aqueous binder without phenol of the invention as described above, and curing the composition of the binder.

V skladu nadaljnim aspektom predstavljenega izuma je pripravljen izdelek iz mineralnih vlaken, ki vključuje mineralna vlakna v stiku z utrjeno sestavo veziva po izumu.According to a further aspect of the present invention, a mineral fiber product is prepared which includes mineral fibers in contact with the cured binder composition of the invention.

-4Opis izuma-4Description of the invention

Bistvo izuma je originalna sinteza melaminsko sečninske delno zaetrene formaldehidne smole, ki vključuje postopek zaetrevanja v alkalnem pH območju od 8 do 11, ter v temperaturnem območju 80 -120°C.An inventive synthesis of the melamine urea partially ethereal formaldehyde resin, comprising the etching process in an alkaline pH range of 8 to 11 and a temperature range of 80-120 ° C.

Dobljena smola ima naslednje lastnosti: je popolnoma vodotopna, vsebuje visok odstotek dušika, med utrjevanjem in sušenjem pa ne izloča škodljivih komponent v ekološko in tehnološko neugodnih količinah.The resin obtained has the following properties: it is completely water-soluble, contains a high percentage of nitrogen, and does not eliminate harmful components in ecologically and technologically unfavorable quantities during curing and drying.

Utrjena smola dobro veže mineralna vlakna, je negorljiva in vodoodpoma. Termičen razpad utrjene smole je počasen in enakomeren v temperaturnem območju 240 do 580°C kar omogoča izdelavo plošč iz mineralnih vlaken, ki vsebujejo to smolo kot osnovo za vezivo na tak način, da imajo te plošče posebne lastnosti glede termične odpornosti in negorljivosti.The hardened resin binds mineral fibers well, is non-combustible and water repellent. The thermal decomposition of the cured resin is slow and uniform over a temperature range of 240 to 580 ° C, enabling the production of mineral fiber panels containing this resin as a binder base in such a way that these panels have special thermal resistance and non-combustibility properties.

Izum bo opisan na izvedbenih primerih.The invention will be described in embodiments.

Primer 1:Example 1:

Kondenzacijo in zaetrevanje vodimo v enostopenjskem procesu pri atmosferskem tlaku pod pogoji refluksa. Zmesi melamina (0.5-1,5 mola), sečnine (0.5-1.5 mola) ter formaldehida (40% vodna raztopina, 1.6-2.6 mola na mol združenih aminov), ter metanola (2-3 mole na mol aminov) nastavimo pH na 8.5 - 10 in med intenzivnim mešanjem ogrevamo na 80 do 100 °C. V reaktorju pod pogoji refluksa reakcija poteka 100 do 300 minut. Med reakcijo jemljemo vzorce in merimo pH, viskoznost, lomni količnik in hidrofobnost smole. pH vrednost reguliramo navzgor najbolje z dodatki NaOH, KOH, ali sode, navzdol pa najbolje z dodatki dušikove, fosforne, ali mravljične kisline.Condensation and etching are conducted in a one-step process at atmospheric pressure under reflux conditions. Mixtures of melamine (0.5-1.5 moles), urea (0.5-1.5 moles) and formaldehyde (40% aqueous solution, 1.6-2.6 moles per mole of combined amines) and methanol (2-3 moles per mole of amines) were adjusted to pH 8.5 - 10 and heated to 80-100 ° C during vigorous stirring. In a reactor under reflux conditions, the reaction takes 100 to 300 minutes. Samples are taken during the reaction and the pH, viscosity, refractive index and hydrophobicity of the resin are measured. The pH is best regulated upwards with the addition of NaOH, KOH, or soda, and the downstream is best adjusted with the addition of nitric, phosphoric or formic acid.

Hidrofobnost smole določamo tako, da merimo število delov 20% vodne raztopine natrijevega acetata, s katero lahko razredčimo 1 del smole pri 20 °C, brez da bi se pri temu pojavila motnost. Ko hidrofobnost smole merjena po zgornjem postopku doseže vrednost 2.2 do 2.8, nastavimo pH na 9,5 do 10,5 in vakuumsko oddestiliramo presežek topila, tako da smola vsebuje 50 - 60 % suhe snovi.The hydrophobicity of the resin is determined by measuring the number of parts of 20% aqueous sodium acetate solution by which it is possible to dilute 1 part of the resin at 20 ° C without causing turbidity. When the hydrophobicity of the resin measured in the above procedure reaches a value of 2.2 to 2.8, the pH is set to 9.5 to 10.5 and the excess solvent is vacuum-distilled so that the resin contains 50-60% of the dry matter.

-5Dobljena smola je popolnoma vodotopna, pH ima 9.5 do 10 suho snov 50 do 60 %, viskoznost pri 52 % suhe snovi pa od 27 - 40 cPas.-5The resin obtained is completely water-soluble, with a pH of 9.5 to 10 dry matter of 50 to 60% and a viscosity of 52% of dry matter of 27-40 cPas.

Smola je bistra, prozorna, obarvanost pod 100 Apha. Svoje osnovne lastnosti zadrži pri 20 °C vsaj 14 dni. B čas smole pri 180 °C je 60-100 s.The resin is clear, transparent, under 100 Apha. It retains its basic properties at 20 ° C for at least 14 days. B resin time at 180 ° C is 60-100 s.

Primer 2:Example 2:

V kemijski reaktor iz nerjavečega jekla, opremljenim za delo pod pritiskom do 10 bar doziramo surovine kot pri primeru 1. Med intenzivnim mešanjem vodimo reakcijo pri pH 8.5 do 10 in temperaturi 90 do 110 C . Pritisk v zaprtem reaktoiju naraste na 1 do 5 bar. Med reakcijo merimo pH , viskoznost, lomni količnik in hidrofobnost smole, kot v primeru 1. Ko dosežemo prvo netopnost reakcijske zmesi v raztopini natrijevega acetata (20 %), reakcijsko zmes ohladimo na temperaturo refluksa pri atmosferskem pritisku in nadaljujemo kot v primeru 1.Raw materials are dosed into a stainless steel chemical reactor equipped to work under pressure of up to 10 bar as in Example 1. During intense stirring, the reaction is conducted at pH 8.5 to 10 and temperature 90 to 110 C. The pressure in the closed reactor increases to 1 to 5 bar. During the reaction, the pH, viscosity, refractive index and hydrophobicity of the resin were measured as in Example 1. When the first insolubility of the reaction mixture in sodium acetate solution (20%) was achieved, the reaction mixture was cooled to reflux at atmospheric pressure and continued as in Example 1.

Dobljena smola je popolnoma vodotopna, pH ima 9.5 do 10 suho snov 50 do 60 %, viskoznost pri 52 % suhe snovi pa od 27-40 cPas. Smola je bistra, prozorna, obarvanost pod 100 Apha. Svoje osnovne lastnosti zadrži pri 20 C vsaj 30 dni. B čas smole pri 180 C je 60-100 s.The resulting resin is completely water-soluble, with a pH of 9.5 to 10 dry matter of 50 to 60% and a viscosity of 52% of dry matter of 27-40 cPas. The resin is clear, transparent, under 100 Apha. It retains its basic properties at 20 C for at least 30 days. B resin time at 180 C is 60-100 s.

Vezivo iz tako dobljenih smol smo uporabili v postopku industrijske izdelave izolacijskih plošč kot zamenjavo za fenolno vezivo. Dobljene plošče so imele mehanske in izolacijske lastnosti enake ali podobne ploščam izdelanim s fenolnim vezivom. Termična odpornost plošč pa je bila bistveno boljša, tako daje bilo na podlagi preiskav razvidno, da izolacijski material pridobljen po takem postopku lahko smatramo za negorljiv. Pri opisanem postopku izdelave izolacijskih plošč se sprostijo samo manjše količine formaldehida in sledovi metanola, medtem ko se pri klasične postopku z uporabo fenolnega veziva sprostijo v ozračje znatne količine formaldehida in fenola ter sledovi metanola, tako da je opisani postopek ekološko ugodnejši od klasičnega postopka z uporabo fenolne smole. Dobljena smola je popolnoma vodotopna, vsebuje visok odstotek dušika, je kot utrjena negorljiva, med utrjevanjem in sušenjem pa ne izloča nevarnih komponent v ekološko in tehnološko neugodnih količinah. Utrjena smola dobro veže mineralna vlakna, je negorljiva in vodoodpoma. Termičen razpad utrjene Smoleje počasen in enakomeren v temperaturnem območju 240°C do 580°C, kar omogoča izdelavo plošč iz mineralnih vlaken, ki vsebujejo to smolo kot glavno sestavino veziva. Te plošče imajo posebne lastnosti glede termične odpornosti in negorljivosti.The resin binder thus obtained was used in the process of industrial production of insulating boards as a substitute for the phenolic binder. The resulting plates had mechanical and insulating properties identical or similar to those made with a phenolic binder. However, the thermal resistance of the panels was significantly better, so that it was evident from the investigations that the insulating material obtained by such a process could be considered non-combustible. In the described method of manufacturing insulating panels, only small amounts of formaldehyde and traces of methanol are released, while in the classical process using a phenolic binder significant quantities of formaldehyde and phenol and traces of methanol are released into the atmosphere so that the described process is more environmentally friendly than the classical process using phenolic resins. The resulting resin is completely water-soluble, contains a high percentage of nitrogen, is cured, non-combustible, and does not exclude hazardous components in ecologically and technologically unfavorable quantities during curing and drying. The hardened resin binds mineral fibers well, is non-combustible and water repellent. The thermal decomposition of the cured Resin is slow and steady in the temperature range 240 ° C to 580 ° C, which allows the production of mineral fiber panels containing this resin as the main constituent of the binder. These panels have special properties in terms of thermal resistance and non-combustibility.

-6Kot katalizator utrjevanja za melaminsko sečninsko formaldehidno vezivo lahko uporabimo snovi, ki ob segrevanju sprostijo kislo komponento. To so lahko kisline, kisle soli anorganskih kislin, ali adukti organskih kislin in aminov.-6 As a curing catalyst for melamine urea formaldehyde binders can be used which release the acidic component when heated. These may be acids, acid salts of inorganic acids, or adducts of organic acids and amines.

Tipični predstavniki prve skupine so mravljična kislina, klorovodikova kislina, dušikova kislina, druge skupine amonijev sulfat, amonijev nitrat, amonijev klorid, tretje pa monoetanolamid paratoluensulfonske kisline, morfolinijeva sol paratoluensulfonske kisline, itd. Funkcija katalizatorja je nastaviti reaktivnost veziva tako, da ta utrdi na vlaknih med formiranjem plasti v trdilni komori, in da polimerizacija pod pogoji izdelave izdelka iz vlaken poteče do utq enega in premreženenega melaminsko sečninsko formaldehidnega polimera.Typical representatives of the first group are formic acid, hydrochloric acid, nitric acid, the second groups are ammonium sulfate, ammonium nitrate, ammonium chloride, and the third is the monoethanolamide of paratoluenesulfonic acid, the morpholinium salt of paratoluenesulfonic acid, etc. The function of the catalyst is to adjust the reactivity of the binder so that it binds on the fibers during the formation of the layer in the curing chamber, and that the polymerization under the conditions of fabrication of the fiber product proceeds to a utq of one and crosslinked melamine urea formaldehyde polymer.

Drugi primerni dodatki vezivu so povezovalna sredstva na osnovi silanov, prednostno aminopropilsiloksani, toplotni stabilizatorji, UV stabilizatorji, površinsko aktivne snovi, polnila kot so glina, silikati in magnezijev sulfat, pigmenti, hidrofobna sredstva kot so mineralna in silikonska olja, zaviralci gorenja, zaviralci korozije, sečnina in drugi.Other suitable additives to the binder are silane-based binders, preferably aminopropylsiloxanes, thermal stabilizers, UV stabilizers, surfactants, fillers such as clay, silicates and magnesium sulfate, pigments, hydrophobic agents such as mineral and silicone oils, flame retardants, corrosion inhibitors , urea and others.

Ti dodatki vezivu in druga dodana sredstva se običajno dodajajo v količinah, ki ne presegajo 20 % teže trdne snovi veziva. Dodatek katalizatorja utrjevanja v sestavi veziva je običajno med 0,02 in 2 %, glede na trdno snov.These binder additives and other added agents are usually added in amounts not exceeding 20% by weight of the binder solid. The addition of a hardening catalyst in the binder composition is generally between 0.02 and 2%, based on the solid.

Končna sestava vezivaThe final composition of the binder

Zgoraj opisana sestava veziva ima ponavadi 50 - 70 masnih % suhe snovi. To je predvsem običajno, če se mora vezivo transportirati. Vezivo nižje koncentracije ima prevelike transportne stroške, višje pa visoko viskoznost, kije neugodna za manipulacijo.The binder composition described above usually has 50-70% by weight of dry matter. This is especially common if the binder is to be transported. A lower concentration binder has high transport costs and a higher viscosity, which is unfavorable for manipulation.

To je tudi običajno območje koncentracije veziva v skladiščnih cisternah pred uporabo.This is also the normal binder concentration range in storage tanks before use.

V obliki pripravljeni za uporabo ima vezivo skupaj z dodatki po možnosti koncentracijo med 5 in 25 %.In the ready-to-use form, the binder, together with additives, preferably has a concentration of between 5 and 25%.

Z namenom doseganja ustreznih lastnosti za uporabo in predvsem razprševalnih lastnosti, se lahko uravnava viskoznost opisanega veziva. To se doseže npr. z uravnavanjem sestave veziva, količino dodanega katalizatorja in količino dodane vode kot topila.The viscosity of the binder described above can be adjusted in order to achieve suitable application properties and, in particular, spray properties. This is achieved e.g. by regulating the composition of the binder, the amount of catalyst added, and the amount of water added as solvent.

-7Postopek za proizvodnjo vezanega izdelka iz mineralnih vlaken z vezivom po izumu Vodno vezivo brez fenola po predstavljenem izumu je lahko naneseno na mineralna vlakna ali produkt iz mineralnih vlaken s konvencionalnimi tehnikami kot so npr. razprševanje skozi šobe z zrakom ali brez, razprševanje z rotirajočimi diski, prepojevanje, nanos z valjem, nanos z zaveso, nanos v pasovih ipd.-7Procedure for the Production of a Mineral Fiber Binder Product of the Invention The aqueous phenolic binder of the present invention may be applied to mineral fibers or mineral fiber products by conventional techniques such as e.g. spray through nozzles, with or without air, spray with rotating discs, soaking, roller application, curtain application, belt application, etc.

Mineralna vlakna sc( lahko katerakoli umetno proizvedena steklasta vlakna (MMVF), steklena vlakna, keramična vlakna, bazaltna vlakna, žlindrina volna, kamena volna in drugo.Mineral fibers sc (may be any man-made glass fiber (MMVF), glass fiber, ceramic fiber, basalt fiber, slag wool, rock wool and more.

Za proizvodnjo običajnih toplotno ali zvočno izolativnih materialov je vezivo naneseno v količinah med 0,3-10 % teže vezanega izdelka iz mineralnih vlaken, med 10 in 30 % pri HDT (high density) ploščah in 20 - 40 % za kompozitne izdelke iz veziva, ojačanega z mineralnimi vlakni.For the production of conventional thermal or acoustic insulation materials, the binder is applied in quantities of between 0.3-10% by weight of the mineral fiber bonded product, between 10 and 30% for HDT (high density) panels and 20-40% for composite binder products, reinforced with mineral fibers.

Katalizator se najbolje dodaja vezivu neposredno pred vstopom v dozirne črpalke s specialnim dozirnim sistemom, ki omogoča doziranje in homogenizacijo neposredno v cevovodu in s tem prepreči prezgodnje utrjevanje smole in eventualne zamašitve cevovodov in črpalk. Črpalke morajo biti iz posebnega materiala, ki je ustrezen za fizikalno - kemijske lastnosti veziva.The catalyst is best added to the binder immediately before entering the metering pumps with a special metering system that allows dosing and homogenization directly in the pipeline, thus preventing the resin from premature hardening and possibly clogging of the pipelines and pumps. The pumps must be made of special material suitable for the physico-chemical properties of the binder.

V glavnem se vezivo nanese, običajno z razprševanjem, takoj po razvlaknjenju mineralne taline, nakar se oplaščena mineralna formira v plast v usedalni komori. Ker je kemizem utajevanja melaminsko sečninsko formaldehidne smole bistveno drugačen od kemizma fenol formaldehidne smole, so pravilni tehnološki parametri tega segmenta bistvenega pomena za nemoteno proizvodnjo. Temperatura v usedalni komori, vključno s transporterjem mora biti namreč pod temperaturo pričetka utajevanja smole, kar lahko dosežemo npr. s hlajenjem s hladnim zrakom, utekočinjenimi plini (CO2), mrzlo vodo itd.In general, the binder is applied, usually by spraying, immediately after the mineral melt is bifurcated, and then the coated mineral is formed into a layer in the settling chamber. As the melting mechanism of melamine urea formaldehyde resin is significantly different from that of phenol formaldehyde resin, the correct technological parameters of this segment are essential for smooth production. The temperature in the settling chamber, including the conveyor, must be below the resin initiation temperature, which can be achieved e.g. by cooling with cold air, liquefied gases (CO2), cold water, etc.

Tako formirana plast mineralnih vlaken se utrdi v utrjevalni komori, kjer se plast mineralne volne prepihuje z vročim zrakom, da utrdi vezivo. Običajno obratuje utajevalna komora pri temperaturah od 200 - 400 °C. Po možnosti se utajevalne temperature gibljejo med 225 in 300 °C. V glavnem je zadrževalni čas utajevalnih komor od 3 min. do 20 min., odvisno npr. od gostote izdelka. Ker je popolno zamreženje smole bistvenega pomena za kvaliteten končni izdelek, je potrebno posebno paziti npr. na vsebnost vode v plasti pred trdilno komoro, količino dodanega katalizatorja in ostale zgoraj naštete parametre temu prilagoditi.The mineral fiber layer thus formed is solidified in a curing chamber where the mineral wool layer is blown with hot air to solidify the binder. Typically, the evasion chamber operates at temperatures of 200 - 400 ° C. Preferably, the escape temperatures range between 225 and 300 ° C. Generally, the dwell time of the escape chambers is 3 min. up to 20 min., depending on e.g. of product density. Since complete crosslinking of the resin is essential for a quality finished product, special care must be taken, for example. adjust the amount of water in the layer in front of the curing chamber, the amount of catalyst added and the other parameters listed above.

-8Poleg običajnega utrjevanja z vročim zrakom se lahko uporabljajo tudi druge metode utrjevanja, npr. utrjevanje z mikrovalovnim ali infrardečim sevanjem. Po želji je lahko plast mineralne volne podvržena tudi oblikovanju pred utrjevanjem.-8In addition to conventional hot air curing, other curing methods may be used, e.g. hardening by microwave or infrared radiation. If desired, a layer of mineral wool may also be subjected to pre-curing.

Izdelek iz mineralne volneMineral wool product

Vezan izdelek iz mineralnih vlaken, ki pride iz utrjevalne komore v obliki npr. plošče, je lahko razrezan v želen format in po želji ustrezno pakiran za transport. Lahko je tudi uporabljen kot polizdelek za proizvodnjo oblikovanih izdelkov in kompozitnih materialov.Mineral fiber bonding product coming from a curing chamber in the form of e.g. panels, can be cut into the desired format and optionally packaged for transportation. It can also be used as a semi-finished product for the production of molded products and composite materials.

Izdelki iz mineralne volne so npr., tkani in netkani, filci, plošče, bloki, orientirani, neorientirani, in ostali oblikovani izdelki, ki se uporabljajo npr., kot toplotni ali zvočni izolacijski materiali, blažilci tresljajev, gradbeni materiali, ojačitveni materiali za strehe ali talne aplikacije, kompozitni izdelki za tehnične namene, kot filtrimi material, kot vrtnarski rastni medij, in druge aplikacije.Mineral wool products are, for example, woven and non-woven, felt, panels, blocks, oriented, non-oriented, and other shaped products for use, for example, as thermal or acoustic insulation materials, vibration dampers, building materials, roof reinforcement materials or floor applications, composite articles for technical purposes, as filter material, as a horticultural growth medium, and other applications.

Čeprav je vodno vezivo brez fenola glede na predstavljen izum predvsem uporabno za vezavo mineralnih vlaken, je prav tako lahko uporabljeno kot vezivo za npr. lesonitne plošče, celulozna vlakna, netkane papirne izdelke, kompozite, premaze in podobno.Although the phenol-free aqueous binder according to the present invention is particularly useful for mineral fiber binding, it can also be used as a binder for e.g. hardboard, cellulose fibers, nonwovens, composites, coatings and the like.

-9Rezultati industrijskih preizkusov-9Results of industrial tests

Primerjava lastnosti izdelka vezanega s fenol formaldehidno smolo in izdelka vezanega z melaminsko sečninsko formaldehidno smoloComparison of product properties of phenol formaldehyde resin bonded product and melamine urea formaldehyde bonded product

Primerjali smo dva izdelka in sicer DDP (dachdammplatten , strešne plošče) gostote 165 kg/m3 in debeline 60 mm ter BS (Brandschutz, protipožarne plošče) gostote 130 kg/m3 in debeline 50 mm.We compared two products, namely DDP (dachdammplatten, roof panels) with a density of 165 kg / m3 and a thickness of 60 mm, and BS (Brandschutz, fire panels) with a density of 130 kg / m3 and a thickness of 50 mm.

DDP 165/60 DDP 165/60 Fenol-formaldehidna smola Phenol-formaldehyde resin Melaminsko sečninsko formaldehidna smola (0,05% kat.) Melamine urea formaldehyde resin (0.05%) cat.) vezivo binder 3,5% 3.5% 3,5 % 3.5% emulzija emulsion 0,3 % 0.3% 0,3% 0.3% vodoodbojnost water repellency 0,08 kg/m2 0.08 kg / m 2 0,15 kg/m2 0.15 kg / m 2 razplastna trdnost shear strength 38kPa 38kPa 42 kPa 42 kPa E-modul E-module 1400 kPa 1400 kPa 2200 kPa 2200 kPa razpl. trdnost (klimakomora) decomposition strength (air-conditioning) 9kPa 9kPa 8,8 kPa 8,8 kPa delež začetne trdnosti proportion of initial strength 0,24 0.24 0,21 0.21 dvig temp. (negorljivost) raising the temp. (flammability) 17°C (pri 3,8% žaroizgubi) 16 ° C (at 3.8% heat loss) 7°C (pri 4,3% žaroizgubi) 7 ° C (at 4.3% heat loss)

BS 130/50 BS 130/50 fenol-formaldehidna smola phenol-formaldehyde resin Melaminsko-formaldehidna smola (0,05% kat.) Melamine-formaldehyde resin (0.05% Cat.) vezivo binder 1,3% 1.3% 1,3 % 1.3% emulzija emulsion 0,2 % 0.2% 0,2% 0.2% KBV (dT=140 °C) KBV (dT = 140 ° C) 32 min 32 min 43 min 43 min

Rezultati meritev kažejo, da so izdelki vezani z melaminsko sečninsko formaldehidno smolo po izumu, bolj negorljivi in imajo večjo odpornost na preboj toplote ter so kot taki zelo primerni za protipožarne izdelke.The results of the measurements show that the products bound to the melamine urea formaldehyde resin according to the invention are more non-combustible and have greater resistance to heat breakdown and as such are very suitable for fire-fighting products.

Claims (11)

PATENTNI ZAHTEVKIPATENT APPLICATIONS 1. Postopek izdelave delno zaetrene vodotopne melaminsko sečninsko formaldehidne smole kot osnove veziva za mineralna vlakna, označen s tem, da sta kondenzacija in zaetrevanje vodena v enostopenjskem procesu pod atmosferskim tlakom tako, da se zmesi melamina (0.5-1,5 mola), sečnine (0.5-1.5 mola) ter formaldehida (30 -50% vodna raztopina, 1.6-2.6 mola na mol združenih aminov), ter metanola( 2-3 mole na mol aminov) nastavi pH na 8.0 -11 in da se zmes med intenzivnim mešanjem ogreva na 80 do 100 °C, pri čemer v reaktoiju pod pogoji refluksa reakcija poteka 100 do 300 minut in to ob kontroli hidrofobnosti, viskoznosti in/ ali lomnega količnika.A process for the manufacture of a partially etched water-soluble melamine urea formaldehyde resin as the basis of a mineral fiber binder, characterized in that the condensation and etching are conducted in a one-step process under atmospheric pressure by mixing the melamine (0.5-1.5 mol), urea (0.5-1.5 moles) and formaldehyde (30 -50% aqueous solution, 1.6-2.6 moles per mole of combined amines), and methanol (2-3 moles per mole of amines) set the pH to 8.0 -11 and stir the mixture with vigorous stirring. it is heated to 80 to 100 ° C, with the reaction taking place in the reactor under reflux conditions for 100 to 300 minutes, controlling the hydrophobicity, viscosity and / or refractive index. 2. Postopek izdelave delno zaetrene vodotopne melaminsko sečninsko formaldehidneg smole kot osnove veziva za mineralna vlakna, označen s tem, da sta kondenzacija in zaetrevanje vodena v enostopenjskem procesu pod tlakom 1-5 bar tako, da se zmesi melamina (0.5-1,5 mola), sečnine (0.5-1.5 mola) ter formaldehida (30 - 50% vodna raztopina, 1.6-2.6 mola na mol združenih aminov), ter metanola( 2-3 mole na mol aminov) nastavi pH na 8.5-10 in reakcija vodi v temperaturnem območju 80 do 120 °C, in to ob kontroli hidrofobnosti, viskoznosti in /ali lomnega količnika.2. A process for making a partially etched water-soluble melamine urea formaldehyde resin as a base of mineral fiber binder, characterized in that the condensation and etching are conducted in a one-step process at a pressure of 1-5 bar by mixing the melamine (0.5-1.5 mol) ), urea (0.5-1.5 moles) and formaldehyde (30 - 50% aqueous solution, 1.6-2.6 moles per mole of combined amines), and methanol (2-3 moles per mole of amines) set the pH to 8.5-10 and the reaction leads to temperature range 80 to 120 ° C, in the control of hydrophobicity, viscosity and / or refractive index. 3. Postopek izdelave veziva za mineralna vlakna, ki vključuje smolo pridobljeno po kateremkoli od zahtevkov 1-2, ki nadalje vključuje katalizator utijevanja in opcijsko, druge primerne dodatke vezivu.A method of manufacturing a mineral fiber binder comprising a resin obtained according to any one of claims 1-2, further comprising a fumigation catalyst and optionally other suitable additives to the binder. 4. Postopek po zahtevku 3, označen s tem, da so kot katalizator utijevanja za melaminsko sečninsko formaldehidno vezivo uporabljene snovi, ki ob segrevanju sprostijo kislo komponento, prednostno kisline, kisle soli anorganskih kislin, ali adukti organskih kislin in aminov, prednostno mravljična kislina, klorovodikova kislina, dušikova kislina, amonijev sulfat, amonijev nitrat, amonijev klorid, monoetanolamid paratoluensulfonske kisline, morfolinijeva sol paratoluensulfonske kisline.Process according to Claim 3, characterized in that substances which release the acidic component, preferably acids, acidic salts of inorganic acids, or adducts of organic acids and amines, preferably formic acid, are used as the catalyst for incubation for the melamine urea formaldehyde binder. hydrochloric acid, nitric acid, ammonium sulfate, ammonium nitrate, ammonium chloride, monoethanolamide of paratoluenesulfonic acid, morpholinium salt of paratoluenesulfonic acid. 5. Postopek po zahtevku 4, označen s tem, da je količina katalizatorja v sestavi veziva prednostno med 0,02 in 2 %, glede na trdno snov.Process according to claim 4, characterized in that the amount of catalyst in the binder composition is preferably between 0.02 and 2%, based on the solid. 6. Postopek po zahtevku 3, označen s tem, da so primerni dodatki vezivu povezovalna sredstva na osnovi silanov, prednostno aminopropilsiloksani, toplotni stabilizatoiji, tJV stabilizatorji, površinsko aktivne snovi, polnila kot so glina, silikati in magnezijev sulfat, pigmenti,Process according to claim 3, characterized in that suitable additives to the binder are silane-based binders, preferably aminopropylsiloxanes, thermal stabilizers, tJV stabilizers, surfactants, fillers such as clay, silicates and magnesium sulfate, pigments, -11hidrofobna sredstva kot so mineralna in silikonska olja, zaviralci gorenja, zaviralci korozije, sečnina in drugi.-11 Hydrophobic agents such as mineral and silicone oils, flame retardants, corrosion inhibitors, urea and others. 7. Postopek po zahtevku 6, označen s tem, da se dodatki vezivu dodajajo v količinah, ki ne presegajo 20 % teže trdne snovi veziva.Method according to claim 6, characterized in that the additives to the binder are added in quantities not exceeding 20% by weight of the binder solid. 8. Vodno vezivo za mineralna vlakna, označeno s tem, daje izdelano po postopku po zahtevkih od 1 do 7.An aqueous mineral fiber binder, characterized in that it is made by the process of claims 1 to 7. 9. Postopek za proizvodnjo vezanega izdelka iz mineralnih vlaken z vezivom po zahtevku 8, označen s tem, daje za proizvodnjo običajnih toplotno ali zvočno izolativnih materialov vezivo nanešeno v količinah med 0,3-10 % teže vezanega izdelka iz mineralnih vlaken, med 10 in 30 % pri HDT (high density) ploščah in 20 - 40 % za kompozitne izdelke iz veziva, ojačanega z mineralnimi vlakni, pri čemer se katalizator se dodaja vezivu neposredno pred vstopom v dozirne črpalke s katerimi se vezivo nanese z razprševanjem takoj po razvlaknjenju mineralne taline in je temperatura v usedalni komori pod temperaturo pričetka utajevanja smole, nakar se tako formirana plast mineralnih vlaken utrdi v utajevalni komori, kjer se plast mineralne volne prepihuje z vročim zrakom pri temperaturah od 200 - 400 °C.9. A process for the production of a mineral fiber binder product according to claim 8, characterized in that for the production of conventional thermal or acoustic materials the binder is applied in quantities of between 0.3-10% by weight of the mineral fiber bonded product, between 10 and 30% for HDT and 20-40% for mineral fiber-reinforced composite products, the catalyst being added to the binder immediately before entering the dosing pumps by which the binder is sprayed immediately after mineral melt and the temperature in the settling chamber is below the resin initiation temperature, after which the mineral fiber layer thus formed is solidified in the evacuation chamber, where the mineral wool layer is blown with hot air at temperatures of 200-400 ° C. 10. Izdelki iz mineralnih vlaken, ki vključujejo mineralna vlakna v stiku z utrjenim vezivom po zahtevku 8.10. Mineral fiber articles, including mineral fibers in contact with a hardened binder according to claim 8. 11. Izdelki iz mineralnih vlaken, označeni s tem, da so izdelani po postopku po zahtevku 9.Mineral fiber articles, characterized in that they are made according to the method of claim 9.
SI200500339A 2005-12-15 2005-12-15 Water-soluble melamine urea formaldehyde binder for mineral fibres SI22167A (en)

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