SI9400325A - Heat-curable adhesives - Google Patents

Heat-curable adhesives Download PDF

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SI9400325A
SI9400325A SI9400325A SI9400325A SI9400325A SI 9400325 A SI9400325 A SI 9400325A SI 9400325 A SI9400325 A SI 9400325A SI 9400325 A SI9400325 A SI 9400325A SI 9400325 A SI9400325 A SI 9400325A
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tannin
binder
binders
weight
heat
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SI9400325A
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Slovenian (sl)
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Antonio Pizzi
Willi Roll
Berthold Dombo
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Ruetgerswerke Ag
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08H—DERIVATIVES OF NATURAL MACROMOLECULAR COMPOUNDS
    • C08H99/00—Subject matter not provided for in other groups of this subclass, e.g. flours, kernels
    • 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
    • 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
    • C08G16/00—Condensation polymers of aldehydes or ketones with monomers not provided for in the groups C08G4/00 - C08G14/00
    • C08G16/02—Condensation polymers of aldehydes or ketones with monomers not provided for in the groups C08G4/00 - C08G14/00 of aldehydes
    • 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
    • C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
    • C08G8/04—Condensation polymers of aldehydes or ketones with phenols only of aldehydes
    • C08G8/08—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ
    • C08G8/20—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ with polyhydric phenols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L97/00—Compositions of lignin-containing materials
    • C08L97/02—Lignocellulosic material, e.g. wood, straw or bagasse
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
    • C08L61/04—Condensation polymers of aldehydes or ketones with phenols only

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Materials Engineering (AREA)
  • Biochemistry (AREA)
  • Wood Science & Technology (AREA)
  • Dry Formation Of Fiberboard And The Like (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Polysaccharides And Polysaccharide Derivatives (AREA)
  • Braking Arrangements (AREA)
  • Mechanical Operated Clutches (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Soft Magnetic Materials (AREA)
  • Laminated Bodies (AREA)
  • Inorganic Insulating Materials (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Compounds Of Unknown Constitution (AREA)
  • Chemical And Physical Treatments For Wood And The Like (AREA)

Abstract

Thermocurable binders for cellulose-containing products contain tannin and a substance which liberates formaldehyde at elevated temperature. Materials produced using these binders exhibit good strength properties and low swelling values after immersion in water.

Description

Rutgerswerke AktiengesellschaftRutgerswerke Aktiengesellschaft

Toplotno utrdljiva vezivaThermal hardening binders

Izum se nanaša na veziva, ki se lahko utrjujejo v toploti, ki so prenesljiva z lesom in drugimi produkti, ki vsebujejo celulozo, in so zlasti primerna za pripravo lesnih gradiv, kot npr. ivernih plošč.The invention relates to binders that can be cured in heat, which are transferable to wood and other cellulose-containing products and are particularly suitable for the preparation of wood materials, such as e.g. particle boards.

V teku iskanja naravnih surovin in zlasti obnovljivih surovin za pripravo veziv za lesna gradiva je postala znana tudi uporaba taninov (J. Macromol. SCI.-Chem. A 16 (7), 1243-250 (1981).The use of tannins (J. Macromol. SCI.-Chem. A 16 (7), 1243-250 (1981)) also became known in the course of the search for natural raw materials, and in particular renewable raw materials for the preparation of binders for wood materials.

Kljub dobri razpoložljivosti pa njihova uporaba ni prodrla, ker natezna trdnost, zlasti po vodnem skladiščenju s taninom vezanih lesnih gradiv ni zadovoljiva. Zato je naloga izuma, da bi zagotovili vezivo na osnovi taninov, s katerim bi se dala pripraviti lesna gradiva z bistveno izboljšanimi mehanskimi lastnostmi. Nalogo rešimo z vezivi, ki vsebujejo tanin, po zahtevkih 1 do 6 oz. z uporabo veziv za pripravo gradiv na osnovi produktov, ki vsebujejo celulozo, po zahtevku 7, kot tudi s postopkom za pripravo gradiv, kot ivernih plošč, po zahtevkih 8 do 10.Despite their good availability, their use did not penetrate because the tensile strength, especially after water storage with tannin-bound timber, is not satisfactory. Therefore, it is an object of the invention to provide a tannin-based binder to prepare wood materials with significantly improved mechanical properties. The task is solved with binders containing tannin according to claims 1 to 6, respectively. using binders for the preparation of materials based on cellulose-containing products according to claim 7, as well as a process for preparing materials such as particle boards according to claims 8 to 10.

Ugotovili smo, da imajo tanini, ki vsebujejo enote s splošno strukturoWe have found that they have tannins containing units of general structure

RR

0“ pri čemer R predstavlja vodik ali hidroksi skupino in so proste vezi na kisikovih ostankih bodisi nasičene z vodikom ali so vezi z drugimi molekulskimi skupinami, kot so npr. ostanki sladkorjev ali ostanki drugih ali enakih polivalentnih spojin s fenolnimi hidroksilnimi skupinami, v primerjavi z drugimi tanini boljšo vezivnost, če jih uporabimo skupaj s snovjo, ki v toploti sprošča formaldehid, kot vezivo za produkte, ki vsebujejo celulozo. Natezna trdnost se zviša in doseže vrednosti, kot so znane npr. pri ustreznih, s fenolno smolo vezanih gradivih. Padec prečne natezne trdnosti po vodnem skladiščenju je znatno zmanjšan in prav tako so zmanjšane vrednosti nabrekanja v vreli vodi.0 'wherein R represents hydrogen or a hydroxy group and the free bonds on the oxygen moieties are either saturated with hydrogen or bonded to other molecular groups such as e.g. sugars residues or residues of other or the same polyvalent compounds with phenolic hydroxyl groups, as compared to other tannins, have better binding properties when used together with a substance which releases formaldehyde in heat as a binder for products containing cellulose. The tensile strength increases and reaches the values known as e.g. with suitable phenolic resin-bound materials. The drop in transverse tensile strength after water storage is significantly reduced and swelling values in boiling water are also reduced.

Pri tem je nadaljnja prednost, da lahko te tanine uporabimo brez obdelave z razklopom, kot je znana pri drugih taninih.It is a further advantage that these tannins can be used without digestion as is known in other tannins.

Ustrezni tanini so taki iz skupine procianidinov in prodelfinidinov, zlasti tanin borovega lubja ali oreha pekan. Zmesi teh taninov z npr. mimoza taninom ali kebračo taninom v razmerju 2:5 do 5:2 imajo sicer podaljšan utrjevalni čas, vendar se dajo še uporabiti. Ti tanini so tržni produkti in so se doslej uporabljali pretežno kot strojila. Tržna kvaliteta je za uporabo v smislu izuma zadostna.Suitable tannins are those of the group of procyanidins and prodelfinidins, in particular tannins of pine bark or pecan. Mixtures of these tannins with e.g. mimosa tannins or tannins in a ratio of 2: 5 to 5: 2 have an extended curing time, but they can still be used. These tannins are marketed products and have hitherto been used predominantly as tanneries. Market quality is sufficient for use according to the invention.

Snovi, ki v toploti sprooščajo formaldehid, so npr. paraformaldehid, trioksan in zlasti heksametilentetramin (heksa).Substances that release formaldehyde in heat are e.g. paraformaldehyde, trioxane, and in particular hexamethylenetetramine (hexa).

Toplotno utrdljiva veziva v smislu izuma so v najenostavnejšem primeru zmesi iz tanina, ki vsebuje strukturne enote s formuloThe heat-curable binders of the invention are, in the simplest case, a tannin mixture containing structural units of the formula

-o-o

o3 in iz snovi, ki v toploti sprošča formaldehid, pri čemer znaša delež snovi, ki sprošča formaldehid, zlasti heksametilentetramina, 3,0 do 9 mas.% glede na tanin.o3 and from a substance that releases formaldehyde in heat, the proportion of substance which releases formaldehyde, in particular hexamethylenetetramine, is 3.0 to 9% by weight relative to tannin.

Prav tako pa je v območju izuma, če vezivo poleg specialne vrste tanina in snovi, ki v toploti sprošča formaldehid, vsebuje do 50 mas.% novolaka ali do 20 mas.% vsaj difunkcionalne izocianatne spojine, kot npr. diizocianatonaftalina, 4,4’,4”triizocianato-trifenilmetana, izoforon-, toluen- ali heksametilendiizocianata ali diizocianato-difenilmetana (MDI), pri čemer pri praktični uporabi nanesemo di- ali poliizocianate vzporedno k suhi zmesi iz tanina, ki ga je treba uporabiti v smislu izuma, in snovi, ki sprošča v toploti formaldehid, na produkte, ki vsebujejo celulozo, preden le-te stisnemo v ustrezna gradiva.It is also within the scope of the invention that, in addition to a special type of tannin and a substance which releases formaldehyde in heat, the binder contains up to 50% by weight of novolac or up to 20% by weight of at least a functional isocyanate compound, such as e.g. diisocyanatonaphthalene, 4,4 ', 4' triisocyanato-triphenylmethane, isophorone, toluene or hexamethylenediisocyanate or diisocyanato-diphenylmethane (MDI), where practical use is applied di- or polyisocyanates in parallel to the dry tannin mixture to be used of the invention, and the heat-releasing substance formaldehyde, on the products containing the pulp before squeezing them into suitable materials.

Ustrezni produkti, ki vsebujejo celulozo, so npr. lesne iveri, vlakna na celulozni osnovi, kot npr. bombaž ali lan ali tudi slama, iz katerih pripravimo iverne plošče, tekstilno runo ali plošče za zvočno in toplotno izoliranje.Suitable products containing cellulose are e.g. wood chipboard, cellulose based fibers, such as cotton or linen or straw, from which chipboards, textile fleece or sound and thermal insulation boards are prepared.

Gradiva pripravimo tako, da veziva v smislu izuma pomešamo s produkti, ki vsebujejo celulozo, zmes spravimo v kalup in utrjujemo pri temperaturi nad temperaturo razpada snovi, ki sprošča formaldehid, in pod temperaturo razpada tanina, prednostno pri 150-210°C, pod tlakom. Tlak je pri tem glede na uporabljeni material in želeno gostoto v območju od ,0,1 do 4 MPa/mm2.The materials are prepared by mixing the binders of the invention with products containing cellulose, molding the mixture and curing at a temperature above the decomposition temperature of the formaldehyde releasing substance and under the decaying temperature of tannin, preferably at 150-210 ° C, under pressure. . Depending on the material used and the desired density, the pressure is in the range of 0.1 to 4 MPa / mm 2 .

Tako je npr. mogoča tudi priprava troslojnih ivernih plošč s tlakom 2 do 3,5 MPa/mm2.Thus, e.g. it is also possible to prepare three-layer particle boards with a pressure of 2 to 3.5 MPa / mm 2 .

Količina veziva je glede na želeno gradivo in želeno trdnost v območju od 4 do 20 mas.% glede na produkt, ki vsebuje celulozo. Vezivo se lahko nahaja kot zmes trdnih snovi ali kot raztopina komponent v vodi, alkoholu ali zmeseh vode-alkohola.The amount of binder is in the range of 4 to 20% by weight, depending on the desired material and the desired strength, relative to the cellulose-containing product. The binder may be present as a mixture of solids or as a solution of components in water, alcohol or water-alcohol mixtures.

Ustrezne raztopine so pri sobni temperaturi sposobne skladiščenja več tednov brez velikega povečanja viskoznosti. Pri vodnih raztopinah se priporoča le dodatek fungicida, da bi preprečili morebitno glivično okužbo.Suitable solutions at room temperature are capable of storage for several weeks without a significant increase in viscosity. In aqueous solutions, only the addition of fungicide is recommended to prevent any fungal infection.

Naslednji primeri prikazujejo vezivo v smislu izuma pri njegovi uporabi za pripravo ivernih plošč.The following examples show a binder of the invention in its use for the preparation of particle boards.

PrimeriExamples

Lesne iveri napršimo z vodno-alkoholno raztopino, ki vsebuje vezivo v količini 11 mas.% lesa, in posušimo. Zatem jih na znan način (2,5 N/mm2; 195°C) oblikujemo v plošče z dimenzijo 400 x 350 x 12 mm, stisnemo in utrdimo.Wood chips are sprayed with an aqueous-alcoholic solution containing a binder in an amount of 11% by weight of wood and dried. Then, in a known manner (2.5 N / mm 2 ; 195 ° C), they are molded into 400 x 350 x 12 mm plates, compacted and cured.

Določimo gostoto, prečno natezno trdnost plošč a. suho in b. po vodnem skladiščenju (2 uri v vreli vodi, nato sušeno 16 ur pri 105°C) kot tudi debelinsko nabrekanje po 2-urnem skladiščenju v vreli vodi ob spreminjanju mešalnih razmerij komponent veziva, količine veziva in stiskalnega časa.Determine the density, the transverse tensile strength of the plates a. dry and b. after water storage (2 hours in boiling water, then dried for 16 hours at 105 ° C) as well as thickness swelling after 2 hours storage in boiling water, changing the mixing ratios of binder components, binder quantity and compression time.

Primeri 1 - 5Examples 1 - 5

Pri primeru 1 variira delež heksametilentetramina od 7,5 do 5,5 % veziva. Ustrezno variira tudi delež tanina oreha pekan od 92,5 do 94,5 %.In Example 1, the proportion of hexamethylenetetramine varies from 7.5 to 5.5% of the binder. The proportion of pecan tannin varies accordingly from 92.5 to 94.5%.

V primeru 2 znaša delež heksametilentetramina glede na tanin 6,4 %, t.j. delež tanina oreha pekan 93,6 %. Variiramo stiskalne čase.In Example 2, the proportion of hexamethylenetetramine relative to tannin was 6.4%, i.e. pecan tannin content 93.6%. We vary compression times.

Primer 3 kaže vrednosti troslojne iverne plošče pri 6,4 % heksametilentetramina v vezivu, vsebnosti veziva 10 % v notranjih in 12 % v zunanjih slojih.Example 3 shows the values of the three-layer particle board at 6.4% hexamethylenetetramine in the binder, the binder content 10% in the inner and 12% in the outer layers.

Primera 4 in 5 kažeta analogne vrednosti glede na primera 1 in 2 pri uporabi mimoza (Wattle) tanina.Cases 4 and 5 show analogous values to Cases 1 and 2 when using mimosas (Wattle) tannin.

Naslednje tabele kažejo dobljene vrednosti:The following tables show the values obtained:

TABELETABLES

Stiskalni čas (sek/mm) gostota (kg/m3) prečna natezna trdnost, suha (MPa) prečna natezna trdnost po vodnem skladiščenju (MPa) nabrekanje (%)Compression time (sec / mm) density (kg / m 3 ) transverse tensile strength, dry (MPa) transverse tensile strength after water storage (MPa) swelling (%)

HCHO-emisija (mg/100 g; WKI)HCHO emission (mg / 100 g; WKI)

Primer 1Example 1

Keksameti1entetrami nKeksameti1entetrams n

7,5 % 6,4 % 5,5 %7.5% 6.4% 5.5%

17,5 % 17,5 % 17,5 %17.5% 17.5% 17.5%

729 730 736729 730 736

0,82 0,81 0,790.82 0.81 0.79

0,25 0,27 0,260.25 0.27 0.26

25.,0 23,9 22,125, 0 23.9 22.1

1,71 1,45 0,841.71 1.45 0.84

Primer 4 (primerjava)Example 4 (comparison)

7,5 % 6,5 %7.5% 6.5%

17,5 % 17,5 %17.5% 17.5%

731 711731 711

0,45 0,430.45 0.43

0,09 0,070.09 0.07

32,1 31,532,1 31,5

2,01 1,872.01 1.87

Primer 2 Example 2 Primer 5 (primerjava) (6,5 % heksa) Example 5 (comparison) (6.5% hex) (6,4 % (6.4% heksa) hexa) Stiskalni čas (sek/mm) Press time (sec / mm) 17,5 17.5 12,5 12.5 8,5 8.5 30,0 17,5 12,5 30.0 17.5 12.5 gostota (kg/m3)density (kg / m 3 ) 730 730 738 738 733 733 714 731 722 714 731 722

prečna natezna trdnost, suhatransverse tensile strength, dry

(MPa) (MPa) 0,81 0.81 0,75 0.75 0,67 0.67 0,5 0.5 0,45 0.45 0,41 0.41 prečna natezna trdnost po vodnem skladiščenju (MPa) transverse tensile strength after water storage (MPa) 0,27 0.27 0,19 0.19 0,17 0.17 0,13 0.13 0,09 0.09 0,03 0.03 nabrekanje (%) swelling (%) 23,9 23.9 22,4 22,4 20,9 20.9 29,7 29.7 32,1 32.1 36,7 36,7 HCHO-emisija (mg/100 g; WKI) HCHO emission (mg / 100 g; WKI) 1,45 1.45 1,32 1.32 1,1 1.1 1,64 1.64 2,01 2.01 1,28 1,28

Primer 3Example 3

Stiskalni čas (sek/mm) 12,5 vezivo (%) srednji/pokrivni sloj 10/12 vlažnost iveri po lepljenju (%) srednji/pokrivni sloj 28/26 gostota (kg/m3) 723 prečna natezna trdnost, suha (MPa) 0,83 prečna natezna trdnost po vodnem skladiščenju (MPa) 0,27 nabrekanje (%) 22,1Compression time (sec / mm) 12.5 binder (%) medium / cover 10/12 humidity after bonding (%) middle / cover 28/26 density (kg / m 3 ) 723 transverse tensile strength, dry (MPa ) 0.83 transverse tensile strength after water storage (MPa) 0.27 swelling (%) 22.1

HCHO-emisija (mg/100 g; WKI) 1,4HCHO emission (mg / 100 g; WKI) 1.4

Primer 6Example 6

Po splošnem opisu primerov (stiskalni čas 15 s/mm pri 190°C, 2,5 N/mm2) pripravimo in testiramo enoslojne iverne plošče.Following a general description of the examples (compression time of 15 s / mm at 190 ° C, 2.5 N / mm 2 ), single-layer particle boards are prepared and tested.

Vezivo:Binder:

tanin iz borovega lubja (37 %-na vodna raztopina) heksametilentetramin (40 %-na vodna raztopina) cinkov acetat (25 %-na vodna raztopina) vodapine tannin (37% aqueous solution) hexamethylenetetramine (40% aqueous solution) zinc acetate (25% aqueous solution) water

337 mas.delov337 parts by weight

19,3 mas.deli19.3 parts by weight

19,3 mas.deli mas.delov19.3 parts by weight of parts

Rezultati:Results:

gostota (kg/m3): 708 prečna natezna trdnost, suha (MPa): 0,80 prečna natezna trdnost po vodnem skladiščenju (MPa): 0,23 HCHO-emisija (mg/100 g): 0,1density (kg / m 3 ): 708 transverse tensile strength, dry (MPa): 0.80 transverse tensile strength after water storage (MPa): 0.23 HCHO emission (mg / 100 g): 0.1

Primer 7Example 7

Po splošnem opisu primerov (stiskalni čas 15 s/mm pri 190°C; 2,5 N/mm2) pripravimo in testiramo troslojne iverne plošče.According to the general description of the examples (compression time of 15 s / mm at 190 ° C; 2.5 N / mm 2 ), three-layer particle boards are prepared and tested.

Vezivo Binder sloj jedra the core layer zunanja sloja the outer layers tanin iz borovega lubja (37 %-na vodna raztopina) pine tannin (37% aqueous solution) 327 327 327 mas.delov 327 parts by weight heksametilentetramin (40 %-na vodna raztopina) hexamethylenetetramine (40% aqueous solution) 19,5 19.5 19,5 mas.delov 19.5 parts by weight cinkov acetat (25 %-na vodna raztopina) zinc acetate (25% aqueous solution) 24,0 24,0 19,5 mas.delov 19.5 parts by weight voda water 12 12 — mas.delov - parts by weight

Rezultati:Results:

gostota (kg/m3): 723 prečna natezna trdnost, suha (MPa): 0,80 prečna natezna trdnost po vodnem skladiščenju (MPa): 0,29 HCHO-emisija (mg/100 g): 0,16density (kg / m 3 ): 723 transverse tensile strength, dry (MPa): 0.80 transverse tensile strength after water storage (MPa): 0.29 HCHO emission (mg / 100 g): 0.16

ZaFor

Rutgerswerke Aktiengesellschaft:Rutgerswerke Aktiengesellschaft:

Claims (10)

1. Toplotno utrdljiva veziva za produkte, ki vsebujejo celulozo, na osnovi tanina, označena s tem, da vsebujejo tanin in snov, ki v toploti sprošča formaldehid, pri čemer vsebuje tanin enote s splošno strukturo1. Tannin-based binders for cellulose-containing products, characterized in that they contain tannin and a substance that releases formaldehyde in heat, containing tannin units of general structure R okjer R predstavlja vodik ali hidroksi skupino in so proste vezi na kisikovih ostankih bodisi nasičene z vodikom in/ali so vezi z drugimi molekulskimi skupinami.R represents R represents a hydrogen or hydroxy group and the free bonds on the oxygen moieties are either saturated with hydrogen and / or bond with other molecular groups. 2. Veziva po zahtevku 1, označena s tem, da je uporabljeni tanin tanin oreha pekan ali borovega lubja.Binder according to claim 1, characterized in that the tannin tannin used is pecan or pine bark. ** 3. Veziva po zahtevkih 1 in 2, označena s tem, da je snov, ki v toploti sprošča formaldehid, heksametilentetramin.Binder according to claims 1 and 2, characterized in that the substance which releases formaldehyde in heat is hexamethylenetetramine. 4. Veziva po zahtevku 3, označena s tem, da znaša delež heksametilentetramina 3,0 do 9 mas.% glede na tanin.Binder according to claim 3, characterized in that the proportion of hexamethylenetetramine is 3.0 to 9% by weight relative to tannin. 5. Veziva po zahtevkih 1 in 2, označena s tem, da vsebujejo do 50 mas.% novolaka.Binders according to claims 1 and 2, characterized in that they contain up to 50% by weight of the novolak. 6. Veziva po zahtevkih 1 in 2, označena s tem, da vsebujejo do 20 mas.% vsaj difunkcionalne izocianatne spojine.Binders according to claims 1 and 2, characterized in that they contain up to 20% by weight of at least a functional isocyanate compound. 7. Uporaba veziv po zahtevkih 1 do 6 za pripravo gradiv na osnovi produktov, ki vsebujejo celulozo.Use of binders according to claims 1 to 6 for the preparation of materials based on products containing cellulose. 8.8. Postopek za pripravo gradiv, označen s tem, da vezivo po zahtevkih 1 do 6 pomešamo s produktom, ki vsebuje celulozo, zmes spravimo v kalup in tam obdelujemo pri temperaturnem območju od 150 do 210 °C in tlaku v območju 0,1 do 4 MPa/mm2.Process for the preparation of materials, characterized in that the binder according to claims 1 to 6 is mixed with a product containing cellulose, the mixture is molded and treated there at a temperature range of 150 to 210 ° C and a pressure in the range of 0.1 to 4 MPa / mm 2 . 9. Postopek po zahtevku 8, označen s tem, da vezivo pomešamo kot prašek z lesnimi ivermi.Method according to claim 8, characterized in that the binder is mixed as a powder with wood chips. 10. Postopek po zahtevku 8, označen s tem, da vezivo napršimo kot raztopino na lesne iveri.10. The method of claim 8, wherein the binder is sprayed as a solution on wood chips.
SI9400325A 1993-08-21 1994-08-19 Heat-curable adhesives SI9400325A (en)

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DE4328220 1993-08-21
DE4402159A DE4402159A1 (en) 1993-08-21 1994-01-26 Thermosetting binders

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GR (1) GR950300015T1 (en)
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DE4447711C2 (en) * 1994-01-27 2000-08-03 Bakelite Ag Heat-curable binders for cellulose-based prods., e.g. chipboard
DE4402341C2 (en) * 1994-01-27 2000-11-02 Bakelite Ag Binder solutions for cellulosic products
ATE166279T1 (en) * 1996-02-09 1998-06-15 Schlingmann Gmbh & Co METHOD FOR PRODUCING LOW-FORMALDEHYDE TANNINE BONDED WOOD CHIPBOARD AND FIBERBOARD
US5858553A (en) * 1997-04-02 1999-01-12 Angus Chemical Company Oxazolidine-based hardeners for the room temperature cure of resorcinol resins in the bonding of wood articles
US5912317A (en) * 1997-04-02 1999-06-15 Angus Chemical Company Oxazolidine-based hardeners for the room temperature cure of resorcinol resins in the bonding of wood articles--II
DE19733925A1 (en) * 1997-08-06 1999-02-11 Bakelite Ag Binder composition, its use and a process for the production of particle board
FR2952937B1 (en) 2009-11-20 2013-02-08 Chaire Europeenne De Chimie Now Pour Un Developpement Durable NOVEL PHENOPLAST RESINS OBTAINED FROM PHENOLIC COMPOUNDS AND MACROMOLECULAR HARDENERS WITH ALDEHYDE FUNCTIONS

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GB1225571A (en) * 1968-02-27 1971-03-17
US4098765A (en) * 1977-05-02 1978-07-04 Kays Stanley J Pecan nut by-products and processes
US4201699A (en) * 1977-07-12 1980-05-06 Chen Chia Ming Phenol-aldehyde resin composition containing pecan pith extract and an aldehyde
DK0544927T3 (en) * 1990-12-14 1996-02-12 Diteco Ltda Adhesive composition comprising isocyanate, phenol-formaldehyde and tannin, for the manufacture of plywood for outdoor use
DE9209289U1 (en) * 1992-07-10 1992-08-20 Fraunhofer-Gesellschaft Zur Foerderung Der Angewandten Forschung Ev, 8000 Muenchen, De

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DE4402159A1 (en) 1995-02-23
MX9405910A (en) 1997-10-31
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AU7036694A (en) 1995-03-02
EP0639608B1 (en) 1998-09-09
ATE170892T1 (en) 1998-09-15
CZ9402006A3 (en) 1995-03-15
HU9402410D0 (en) 1994-11-28
NZ264187A (en) 1995-05-26
GR950300015T1 (en) 1995-04-30
FI943836A0 (en) 1994-08-19
EP0639608A1 (en) 1995-02-22
NO943068D0 (en) 1994-08-19
DE59406873D1 (en) 1998-10-15
CA2129936A1 (en) 1995-02-22
HUT71636A (en) 1996-01-29
AU670702B2 (en) 1996-07-25
ES2068171T1 (en) 1995-04-16
CA2129936C (en) 2000-08-15
NO943068L (en) 1995-02-22
ES2068171T3 (en) 1998-11-16
BR9403283A (en) 1995-04-11
SK99094A3 (en) 1995-04-12

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