CA2003899A1 - Adhesive - Google Patents
AdhesiveInfo
- Publication number
- CA2003899A1 CA2003899A1 CA 2003899 CA2003899A CA2003899A1 CA 2003899 A1 CA2003899 A1 CA 2003899A1 CA 2003899 CA2003899 CA 2003899 CA 2003899 A CA2003899 A CA 2003899A CA 2003899 A1 CA2003899 A1 CA 2003899A1
- Authority
- CA
- Canada
- Prior art keywords
- wood
- adhesive composition
- wood adhesive
- phenol
- total weight
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D161/00—Coating compositions based on condensation polymers of aldehydes or ketones; Coating compositions based on derivatives of such polymers
- C09D161/04—Condensation polymers of aldehydes or ketones with phenols only
- C09D161/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
Abstract
ABSTRACT
A wood adhesive composition 1 including an effective amount of a phenol-formaldohydo resin; and a modifying agent which agent randers the composition capable of bonding to a hard wood.
A wood adhesive composition 1 including an effective amount of a phenol-formaldohydo resin; and a modifying agent which agent randers the composition capable of bonding to a hard wood.
Description
ADHES IVE
200:~8~39 The pr-s~nt inventlon relate~ to adhesive co~position~ an~ ~p~ci~lly to ad~sivo composition~ u~d in the manufacture of wood product~ In particular the invention relato~ to improved phenolic-ty~e adhe~lve~ u~eful in the manufacture o plywood, but the invention is al~o applicable to oth r adheQive typ~ and to the manufacture of other reconstituted wood products ~ or- particula~ly ~h adho~ve compositions of the pre~ent invent~on ar usoful a~ adhe~iv~ in the manufacture o~ plywood utilisin~ re~ativ~ly high den~ity wood ma~eri~ls, such as, for ex~mplo, c-rtain eucalypt ~pocles Sinco ~he availability of thc more traditional wood ~pocies, ~uch as those obtained from rain forests i8 becoming increaJingly le~, particularly for u~o in plywood manufacture o~ing to ecological reason~, so~e plywood ~nufacturers must ~u~rn the~ att~ntion to the u~Q of high d n~ity specie~, particularly eucalypt 8pQc~es~ as substitue8 ~i .
fo~ the more traditional rain forest species Reconstituted ~ood ~anufacturer~ h~ve ~ound difficultie- in bonding woad sp cios of relatively high den~ity or cont~ining certain xtractives known to make these ~pec$e~ more difficult to bond with traditional phenolic type adhe~ive~ For Ya~plo, it ha~ been found tha~ traditional phenol~c reQin~ p~o~uce poor adhesive bond~ with ply~ood manufactured from high den~ity eucalypt ~p~cies, such a~ for ex~mple Bl~ckbutt (~ucalyptus pilularis) Extractive~
present in the wood snd bar~ of certain ~peci~s and known to inferfere with the glueability o~ wood include polyphenolic compound~ ~uch a~ giSannin# and certain organic acids, but ~he range of ~ nt-rfer~ng substances i~ not r~stricted to theJe alassos of co~pound We ha~e ~ound th~t the lnferior bonding of th~e ~pecio8 wlth traditional phenolic adhesives i~ cau~ed pr~tomin~ntly ~y interaction between extract~ve~ contaLned withln the wood or b~rk and the phenolic rosin thus a~ecting the ability o~ the phenolic rQsin to produce a fitrOng and du~able gluelino It i~ accordinqly an ob~ect of thQ pre~ont invention to overcomo, or at lea~t alloviate, one or more of the dlfficultie~ related to the prior art . -- 1 --20(~3~9 Accordlngly, in a flr~t aspoct of the pre~ent invention there i~ provid~d a wood adhe~ive co~osltlon including an e~ective ~ount of a phenol-form~ldehyde r~in; and a modlfying agent which ~gent r~ndor~ the compo~ition aapablo of bonding to a hard wood.
The wood adhe~lve composition ~cording to the presen~ invention has been ~ound to be useful in the ~anufacture of wood products, includin~ re~on~tituted wood products of various types. Fo~ example, the wood ~he~ive eomposition according to tho present in~ention may b~
utilised in the manufact~ro of plywoods an~ simil~r lamin~ted wood pro~uat~ as well a~ in prod~ct~ based ~n wood veneer~.
The wood adhe~ive co~positi~n according to the present invention ha~ b~en ~ound to be particularly sultable for the manufacture of ~ypo A ~aterproof plywoods, i.e. plywoods which are fully weather- and ~oil-proof (wsP plywood~.
The wood adhesive composition according to the present inventio~ may b~ applied to wood ~pecies of re~a~ively hi~h d nsity or conta~ning certain e~ractives know~ to make the specie8 ~ore difficult to bond with traditional phenolic adh~sLves. ~8 used herein in the description and claims, the ~erm Nhard wood" is used to d~note ~uch wood speci~s. .
The phenol ~ormaldehyde ~PF) re~in utili~ed in the wood adh~i~e compo~ition according to the present invention may be of any ~uit~bl0 type. A phenol form~ldehyde resin having a low ~ro~ formaldehyde content i~ proferr~d. The free ~ormaldehyde-content may range from 0 to approxLmately 2%, more preferably from 0 to 0.S%. Ph~nol formaldehyde re~in~ having a low free fo~maldehyd~ content are availa~le commercially fro~ ~ariou~ sources including Chemplex Aus~ralia, Bo~den Ch micals and ICI. Prefe~red phenol ~o~ldehyde r~sins are alkaline catalys~d phenol ~orm~ldehyde re~ins. A #uit~blo alkalin~ phenol formaldehyde ro~in is ~he re~in sold under the txa~e designat~on 775.
The phenol fo~aldehyde resin may be pre~ent in the wood adh~sive compo~ition in any effective amountQ. ~he phenol formaldehyde re~in ~ay be present in amounts o~ ~rom appxoximately 50 to 99,9% by weifht, preferably approximately 20~ 8~39 90 to 99.95~ by weight, more preferably approximately 90 to 99~ by weight, ~ased on the total weiqht of the wood adhe~ive compo~ition, exclu~v0 of any fill~r content. ~ore preferably, the phenol for~ld~hyde re~in i~ pre~ent ~n amounts of from approximately 95 to 99.9% by w~ight.
In a pref~red a~p~ct o~ th~ pxesent invention thero i~ pxovided a wood adhesive compo~itlon including an effective amount of a phenal-for~al~ehyd~ resin5 and a ~odi~ying agent which i~ difunc~ional or :- multifunc~ion~l ~nd capable of reacting wit~ eith~r an aldehyde or me~hylol group.
Pre~erably ~aid modifying agent i8 ~elected from the g~oup con~i~tinq of meta-amino-ph~nol, x~sorcinol, phlorogluci~ol, phonolic novolac , cond~n~ed tannins, polymers manufacturcd thara~o~, ox ~ixturee thereo~.
Typical modi~ying a~ents u~eful in this wood adh~ive com~o~ition according to ~hi~ aspect of the pre~ent inv~ntion are phenolio novolac~ ~pecially high orthonovolacs euch as u~ed in ~he production of moulding powders, for example a~ i~ de~crib~d in United Statee Paten~ Nos~
2,475,581 (12/7/49) or No. 3,476,707 (4111/69), meta-a~ino-~henol, re~orcinol, phloroglucinol, ~aXd a~ino phænol, re80~inol and re~orcinol phenol re~ns ~nd othe~
such ~uitable compound~ known to ~e very react~ve to ~ethylol ph~nol known in the ~rt. Theoe modifying ag~nts may be u~ful alone or prefe~ably a combination of phenolic noYol~c together with anothær curing a~ent may be u~ad.
~ ho modifying agent may be pre~ent in any effective a~ount. The amount to be added ~ 8 dependent on the formaldehydo to phenol ~a~io an~ the me~hylol cont-nt of th~
ba~e re~in. Re~in~ containing hiqh formaldehyde to phenol ratio~ and l~rgÆ pHrcentage~ of methylol group~ require ~lativoly large amount~ of no~olac or other reactive to ~ethylol compount~ to ~e ad~e~ . ~he amo~nt of modi~y~ng a~ent may r4nge fro~ approx~mately 0.05 ~o 50% by weight, preferably ~.OS to lO~ by weight, more preferably approximately O.l tO S% by weight, ba~ed on the total weight of the wood adhe~ivæ composition, excluding fill~rs when ~resent.
2 0 ~ 3~ 9 ~ phen~lic xe~in having a F/P ratlo of 1:1.5 and con~aining mos~ly methylene linkages and thu~ low methylol cont~nt would roqu~re very low amount~ of, for oxampl~, meta a~ino phenol to be ~dded for complete reaction. This amount 1~ u~ually lo-~ than approYimat-ly 3 part~ o~ m~t~ amino phenol per 100 pA~t~ of re~in.
~ h~ amount of modifying agent to b sdded may b~
dete~m~ned by gela~ion time e~pe~iments in which increasing amount~ of a likel~ compound aro added until the gelation tLm~ of th~ mixtur~ begin~ to rapidly length~n which i~ an $ndication of in~uf~icient ~ethylol remaining. S$ngle or combinat~on~ of ~u~table compounds may be add d.
It ha~ been found that the point at which rapid lengthening of the gelation ti~e is ob~rvQd is r~lated to the total mola~ content of mod~fying agent. Thus ~xovided the total numb~r of mol-- $~ k~pt con~tant, a co~bination of two or more Dodi~ying ~gent~ m~y be us~d to ~chieve a desir~d gelation t~me. Fo~ e~ample, the gelation time of a ~ix~ur~
of phenolic re~$n and meta-am~no-phenol wa~ ~ound to increase rapidly afte~ the addition of more than 0.96 gm p~r 100 pts re~in ~olution. ~h~ ~ame increa~e in gelation ti~e could be ob~erved ~hen equal part~ ~0-48B I 0.~8g) of r~orcinol and meta-~mino-phenol were added in co~bination ~a~ their mol-cular weight~ ~re e8~entially egual at llO and 10~
re~pect~v~ly). Th~ 8~ o~cur~ with other compounds, for ex~mple such a~ novolac~ and for instance phloroglucinol and polymer~ 8uch as re~orc~nol formAldehyde.
-Accord~ngly, in a pr f~rred a~pect the~e is provided - A wood adhe~ive compo~ltlon $ncluding approximately 50 to 99.99%, p~e~rably 90 to 99.95~ by weight ba~ed on the total weight of the wood adhe~ive compo~ition, excluding fillers, of ~ phenol-f~maldehyde resin having a low free for~aldchyde content; nnd a~pro~im4tely 0.01 to S0~, preferdbly approximat-ly O.OS to lO~ by wel~ht ~a8ed o~ the to~al weight of the wood adhesive compos~tion, ~x¢luding filler~, of one or more modifying a9ent~.
A typical wood adhe8ive composition accordlng tO
thi~ aspec~ of the present invention includeR
approx~mately 94 to 97.25~ by weight based on the Z00~8~t9 total weight of th~ woo~ adhe~ive compo~ition, exaluding f~ller~, of a phanol-~or~aldehyd~ xe~in haY~ng d lo~
frae-for~aldehydH content;
approsimately ~.5 to 5% by weight b~ed on the total weight of the wood ~dh~s1ve compo~i~ion, exclud$ng $iller~, of a phenolic novolac ro-$n; ~nd ap~roximat~ly 0~2S to 1% by w~ight ba~ed on th~
total weight of the wood adhesive co~po~it~on, excluding fillors, of ~eta-amino ~henol.
In an ~lternati~ preferred aspect of th~ pre~ent inve~tion thore i~ provided a wood adhe~ive composition including an effectivo Dmoun~ of ~ phenol formald~hyde re~int ~nd an ~xtractive~ neutrali~in~ agent capable, in u~e, of reducing or eliminating th~ advor~ effect~
of eYtract~ves contain~d in a hard ~ood.
This a~pect of the pre~nt invention involve~ tho addition of an extractiveo noutralising agent to the adhosive and/or the tr~atm~nt, with th~s~ compound~, of the ~b~tra~e to be glued. These compounds interact.with the extrac~ives within the wood or bark and sub~tantially negate th~
deleter~ou~ effect o~ the extractives ~o that superior adh~ive perform~nce i~ obtained.
Prefer~bly, the extractives neutral~ing agent i~
ca~a~le o~ forming complexe~ with and/or precLpitating the ex~ract~ve~, thor~by ~ub~ant~ally inac~ivating the extractive~ oo a~ to minimi~e interference w~th the bonding act~on, ~articularly at the glueline.
Acco~din~ly in a pr ~-rred form of ~his ~pec~ of the pre~ent inven~ion there i8 prov~d~d a w40d adhesive composition including approximat~ly 30 to 99.95S by ~ght ba~ed on the total weight o~ the ~ood adhe~ive compo~ition, axcluding f~l}er~, of ~ phenol-ormaldehyde resin; and approximately 0.05~. to 10~ by weight ba~ed on th total weight of the wood adhesive composition, excluding filler~, of an extractives n~utrali~ing agent ~elected from metallic compounds and o~ganic compounds capable of forming precipit~tes and/or complox~ with extractiv~ contained in a hard ~ood.
2003~3~9 Pre~erably th~ extractivos neutr~lising agent i~
~ol~cted from metallie compounds of m~als ~el~cted from th~
g~oup conai~ting of ~opp~r, iron, zinc, lead, mangane~e and nickel and organ~c compound~ ~elected from the group consi~tin~ of hexamethylenetetramine, melamine, ethyl~nedi~mine~etraac~tic acid (ED$A), triethylenetetr~min~, and complex~s thereof.
It will be under~tood that the invention may func~io~ a~ follow~. For exampl~, the wood extractive, the polyphenol$c ~ompound ellngitannin, forMs precipit~te~ and/or comploxe~ with d~rivativo~ of ~etal~ ~uch as copper, i~on, zinc, mangan~se, nickel etc and ~ith organic compound~ such a~ urea, ~el~n~, hexamin and EDTA. Co~plex formation i~
thought to b~ due mainly to th exi~t~nce in th~ extractives of polyphenol~c compound~ containing ortho~diphenol units ~uch a~ catechol and pyrogallol. Monomer~c and oligomeric catechols and pyroqallol~ ~ay also be pre~nt. ~Q have found for ex~mple that the ma~or compound~ in the extractives of Blackbutt ~ood are polyphonolic co~ound~ (ellagitannin~) which are cla~ Lod ~ pyrogallol typo compound~.
The e~tract$vos neutrallsing agent inacti~ating compound ~ay b inorganic or or~anic. Typical inorganic compound~ u~oful in tho pre~ent invention are metall~c compound# ~uch aJ copper, iron, zinc, lead, ~angane~e, n$ckel, and the like, derivativ~ and p~rticularly i~orqanic and organic salt~ of metal~ which can precipitat~ or complsx extractivo~ p~e~ont in wood or bark. Ex~mples of organic compound~ ~uit~ble. $n the pre~ent inv~ntion are hex~methyl~netetr~mino ~hesamin~)~ melamine, ethylenediamine-tetraacetic acid (EDTA), triethylen totramine (Trien), and derivat~vo~ thor~of capabl~ of procipitating and/or complexlng extractiveo ~hlch interfer~ with tho bonding action.
It i~ al~o kno~n that ~o~ wood oxtractives form proci~itates wlth a variety o~ organic compounds including aldehyde~ and ketone~ le.g. vanillin, cinnamaldehyde~, si~ple n$trogsn cont~ning compounds ~Q.g. urea, ac~tamide~ and heterocycl~c ring co~pound~ (e.g. quinoline, pyridine).
Other compound~ that are able to react and/or interact wi~h extractive~ and to ~uppre4~ the reaction betw~en the wood 20~3~3~9 extractive~ and the adhe~ive are al~o ~uitable additivos.
A single inactivating compound or combirat~on of such compound- may be u~ed.
We have found that the axtractives from Blackbu~t wood ara procipitated from solution on the addition of motall~c derivativ s such a~ tho ions of copper, iron, zinc, lead etc.
we h~o al80 found that t~e extr~ctives from Blackbu~t wood are ~recipitat~d fro~ their aqu~ous solution over a range of p~ from 0 to 14 by tho addition of or~anic compound4 ~uch as EDTA and Tr~en and/or thoir metallic derivat~ves such a~ thcir copper, z~nc, iron and lead d~rivativ~s. In thi~ way, deleteriou~ ax~ractives in the wood can be effectivoly exclud~d from the gluing sy~tom so that blocking of, or interference with, th~ cur$ng of the phenolic adh ~ive by the ~xtractives i8 pre~entcd and high qu~lity konding i~ obtained.
A particularly useful compound for the practice of the invent$on is cupr~c dlsodium ethylenediaminototraacetate (EDTA.Cu.Na2). Further use~ul compound~ include ferric chloride (FeC13), zinc acetate, EDTA.Cu, Trien-Cu, (Cu-Trien) ~nC14. ~ixture~ of compound~ m~y ~lso ~e used, for e~ampl- acetylacetone and Tri n.
The da~ir~d level of addition is rela~ed tO the amount of xtr~ct~ve~ to bo inacti~at~d but in general a ~uitable concentr~tion o~ the metallic or orq~nic component i~ in the range of 0.OS ~o 10% by weight ba~ed on th~ ~otal ~eight of the wood adheslv~s co~position, excluding fillers, wher- pre~ent, more proferably ~ppro~mately 2 to 5% by woight.
Accordingl~, ~n a preferred aspect there i~ provided a wood adhe~ve compo~ition includinq approx~mately 9$ to 98~ by weight ba~ed on th total welgh~ of th ~ood ~dhe~ive compos$t$on of a phenol-ormaldehyde re~ln~ and approxlm~tely 2 to 5~ by weight based on the ~o~al w~ight of th~ wood adhe~ive compo~ition of an ext~aotiYes mod~fying agent ~el~ct~d fro~ the group consisting of ferric chloride and cupric disodium ethylene diaminetetraacetate.
Th~ co~pooitlon~ of the invention ma~ also con~ain Z0038~39 oth~r additiv~s and 6uitabl- ille~ ~aterial~ such as methyl propyl cellulo~o~ ~ood ~lour, shell flour~ c~lcLte or kaolin. The filler may be pre~ent Ln ~mount~ a~
convention~lly u~ed of fro~ app~oximately 1 to 67% by we$ght based on th~ total weight of the wood ~dh~iv~ compo~ltion, pro~erably 5 to ~OS by weight. Alkali~ and water may be added a~ noce~ary fo~ vl~co~ity ad~ustmont.
In accordance with d further aspect of th~ pre6Qnt inv~ntion thero i8 providod a method for pr~par$ng a plywood articl- which method includes provlding a-fir8t ~ood he~t;
at lea-t one second wood ~heet; and a wood adhe~i~ com~osition including an of~ecti~e amount of a phenol-~ormald~hydo r~ ; and a modifying agent which agent render~ the co~o~ition c~p~ble of bonding ~o a hard woodS
coating a portion of a ~urface of said fir~t wood ~hoet w$~h the wood adhesive co~po~ition; and contacting the ~urface of the socond wood she~t with the coated ~urf~ce ol the fir~t wood ~heet.
Prefe~bly, th~ wood adhe~ive compoaition include~
~pprox~mately 94 to 97.25% by weight based on th~ total ~eight of tha wood adha-ive co~po~ition, oxcludi~g filler~, of a phenol-for~aldohyde res~n having A low fr~o-formaldehyde content~
~ pproxiT~tely 2.5 to 5% by weight ba~ed on the total weight o~ the wood adh ~lve compo~ition, exclud~ng fillers, of ~ phenolic novolac re~in) and , ~pprox~m~toly O.25 t~ 1% by weight ba~ed on the total weight of the ~ood ~dheJiv~ compo~ition, excluding flll-r~, o~ ~eta-~m~no phenol.
Alternati~ely, the wood adhe~ive compo~ition ~nclude~ ~ppro~imately 95 to 98~ by weight b~ad on the total we~ght of the wood ~dhe~iYo co~position, excluding filler~, : of a ~henol-~ormald~hyde re~in~ and approximately 2 to 5% by weight ba~ed on the total weight of the wood adhe~lve compo~ition, e~cluding fillers, of an extrac~ive~ modifyi~g ag~nt Jelected from the group , .~
200.38~19 consi~tlng o~ ~erric chlor~de and ~upric d$~odium ethyleno diaminetetraacet~te .
~ he ~ir~t ~nd ~ubse~ent wood heet~ utilised in tho preparatlon o~ the plywood article according to the rRethod aecording to the pre~nt invention may be of any suit~ble type. The wood ~heets m~y be for~d of wood ~peciQ~ of rel~ti~ely high donsity ~uch a~ high den~lty eucalypt ~pecie~. A p~icularly pre~erred form i~ Blackbutt wood (l~ucalyptus pilulari~
~ he mothod of p~eparing the plywood artlcle may be undertaken util ~ ~ing ~tandard t~chnique~ . ~or example, once the eoatod ~urf~ce of the fir~t wood sheet ha~ been contac:ted with the ~urfac~e of tho ~e~ond llrood ~ho~t, ~tandard bonding ~tep~ includ~ng applying heat ~nd/or pre~ure to the sheet ~o B~ to effect bonding o~ the two ~heet~ may be undertaken.
In an al~ernati~e m~thod, however, the wood sheet~
or other article~ to b~ bonded m~y fir~t be treated with the extractive~ neutrali~ing agen~ ~o a~ to reduce or eliminate the adver~o ~ffocts of extract~ves contalnod in tho haxd wood once thi~ prelim$nary treatment is completed, the ~heeS~ may then be treated w~th a ~t~nd~rd wood adhesive compo~it$on $ncluding a ph~nol form~dehydo rosin.
Accordingly, there i~ provided a method ~or prop~ring a plywood ~rticle which method includes pro~tding a ~irst wood sheet;
at len~t one wocd ~he~t; and a wood adhe~ive kit including a pri~r coating compo~ition including an extract$ves neutr~liz$ng agent capable, in u~e, of roduc$n0 the advsr~e effect~ of extractives conta$ned in a h~rd wood; and treat$ng ~t lea~t a surface of ~aid fir~ and ~econd ~he~t~ to bo sdhered wlth ~aid primer coating compo~ition; and contw ti~g ~aid treated ~ rfaces with the wood adhe~ive compo~$tlon Accordingly, in a ~till further aspect of the pxe~ont $nvention there i~ provided a wood adhesive ki~
including ~ primer coatlng co~po~ition including an Z0().38~9 extractivo~ neutral~ng ~gent cap~blo, in u~e, of roducing the adver~o effect~ of extractlve~ contaln~d in a hard wood~
and a wood adhesive compo~ition includ~nq a phenol formaldehyde re~in.
Pre~erably, the pri~er coatin~ co~p~ition Lnclude4 an ~tract~ve~ n~utralizing agent ~elected from fe~ric chloride and cuprlc disodium Rthyl~ne diamin tetraacetate.
Th~ pre~ent invention will now ~e more fully de~crib~d with r~-renc~ to the accompanying examples. It ~hould be under~tood, however, that ~he de~cription following i~ lllu~trative only ~nd i~ not inte~ded to re~tr~ct the generalLty of ~he invent$on ~B de~crib~d above.
~
A conventional u$table alkal1ne phenol formaldehyde ba~e re~in i~ ~el-ctod ~uch a~ Cho~plex 775, to this is add~d a ~u$table novol~c such a~ supplied by Chemplex Australia Ltd~, for e~ample GC 1499 (3%) and mota-amino phenol (0.4~) and suitable f~ller matorial~ ~ueh ~ ~ethyl propyl cellulo~e, nut shell flour, calcite and k~olin. Al~alis and ~ater may be ~dded a~ nocossary for viwosity adju~tment.
The rosults of t~ utilizing the co~po~ition~ of the pre~ont lnvent~on indic~te that an adhe~ive ~y~tem ha8 b en develop~d th~t will sat~fy the glue bond requirQments for Type A bond~d plywood from high den~ty eucalypt~ u~ing the chl~el te~t ~ de~cribed in Australlan Standard~ 2098.2 ~1977) ~nd 275~.1 (1985). Tho adhe&ive ~y~tem may be ea~ily miY~d on 8ite, ach part hav~ng adequate ~torage life, but upon m$~ing producing adhe~ive~ of fa~ter cuxe time, and controlled penetr~t~on by reduction of ~xtr~ct~ve interforonce re~ultin~ in the roduc~ion of cohosive failure.
Plywood ~mples were prepAred by bonding veneers rom ~lackbutt (~uc~lyptus pilularis) as a repre~entative high den~ty wood ~pecie~. The adhesive formulation con~ted of Ch~plex 775 ~100 part~) as a suitable convontional alkAl~ne phenol-formaldehyde resin, a nut shell flour ~10 par~) A~d calcite ~10 ~arts) as fillers, and cupric d~ 80dlum ethylened~inetetraacot~te ~EDTA.CuNa2) (4 1 ~
.
.
' ~ .
~ 0 0~ 8~9 parts). ~he ~amo ~ormulation with the cupric disodiu~
ethylenediaminetetraaceta~e emitt~d ~a~ u~ed a~ ~ control.
The bond quallty of the re~ulting ply~ood ~pe~imen~
wa~ then a~ses~ed by the chi~ol test ~ccording to au~tralian Standard# 2098.2 ~1977) and 27S4.1 ~1985). The te~t re~ult~
aro ~ummari~ed in ~able 1.
. . . _ Adhe~iv~
formulation Dry Wet ho~r~_bQilin~
EDTA.Cu.Na2 8.0 9.0 Control 3.0 2.0 EX~Mp1E 3 Plywood ~amples were prepar~d in accordan~e with ~he proc-duro de~cribed in Sx~mple 2. ~he adh~lv~ formulation u~ed here cons~#ted of Cheople~ 77S tlO0 parts), ~ nut ghell flour (lS part#)~ kaolin (10 part~) and P~C13 ~2.2 pa~t~).
The te~t procedure~ uoed ~re tho~o des~ribed in Example 2.
Tabl- 2 give~ the test re~ul~.
~A~a 2 Adho~ive Aver~g~L~L~ond quality formulatlon Dry Wet after 72 hQu~ boilina PeC13 8.0 8~0 The r~sults 8how that the adhesive ~y~tem o~ this ~nv-ntion sati~io~ the ~lu ~on0d38r~equiroment~ ~or Type A
bondQd plywood (fully weather and boil proo~), wh~rea~ the con~entional ~y~tom doo~ not meet the roquirem-n~s o~ the ~tand~rd~. .
Flnally, it i~ to be understood that variou~ other modlfication~ ~nd/or alte~ation~ may be m~do wlthout departing from the ~plrit of th~ pre~nt in~ntion as outlined herein.
.
,~
200:~8~39 The pr-s~nt inventlon relate~ to adhesive co~position~ an~ ~p~ci~lly to ad~sivo composition~ u~d in the manufacture of wood product~ In particular the invention relato~ to improved phenolic-ty~e adhe~lve~ u~eful in the manufacture o plywood, but the invention is al~o applicable to oth r adheQive typ~ and to the manufacture of other reconstituted wood products ~ or- particula~ly ~h adho~ve compositions of the pre~ent invent~on ar usoful a~ adhe~iv~ in the manufacture o~ plywood utilisin~ re~ativ~ly high den~ity wood ma~eri~ls, such as, for ex~mplo, c-rtain eucalypt ~pocles Sinco ~he availability of thc more traditional wood ~pocies, ~uch as those obtained from rain forests i8 becoming increaJingly le~, particularly for u~o in plywood manufacture o~ing to ecological reason~, so~e plywood ~nufacturers must ~u~rn the~ att~ntion to the u~Q of high d n~ity specie~, particularly eucalypt 8pQc~es~ as substitue8 ~i .
fo~ the more traditional rain forest species Reconstituted ~ood ~anufacturer~ h~ve ~ound difficultie- in bonding woad sp cios of relatively high den~ity or cont~ining certain xtractives known to make these ~pec$e~ more difficult to bond with traditional phenolic type adhe~ive~ For Ya~plo, it ha~ been found tha~ traditional phenol~c reQin~ p~o~uce poor adhesive bond~ with ply~ood manufactured from high den~ity eucalypt ~p~cies, such a~ for ex~mple Bl~ckbutt (~ucalyptus pilularis) Extractive~
present in the wood snd bar~ of certain ~peci~s and known to inferfere with the glueability o~ wood include polyphenolic compound~ ~uch a~ giSannin# and certain organic acids, but ~he range of ~ nt-rfer~ng substances i~ not r~stricted to theJe alassos of co~pound We ha~e ~ound th~t the lnferior bonding of th~e ~pecio8 wlth traditional phenolic adhesives i~ cau~ed pr~tomin~ntly ~y interaction between extract~ve~ contaLned withln the wood or b~rk and the phenolic rosin thus a~ecting the ability o~ the phenolic rQsin to produce a fitrOng and du~able gluelino It i~ accordinqly an ob~ect of thQ pre~ont invention to overcomo, or at lea~t alloviate, one or more of the dlfficultie~ related to the prior art . -- 1 --20(~3~9 Accordlngly, in a flr~t aspoct of the pre~ent invention there i~ provid~d a wood adhe~ive co~osltlon including an e~ective ~ount of a phenol-form~ldehyde r~in; and a modlfying agent which ~gent r~ndor~ the compo~ition aapablo of bonding to a hard wood.
The wood adhe~lve composition ~cording to the presen~ invention has been ~ound to be useful in the ~anufacture of wood products, includin~ re~on~tituted wood products of various types. Fo~ example, the wood ~he~ive eomposition according to tho present in~ention may b~
utilised in the manufact~ro of plywoods an~ simil~r lamin~ted wood pro~uat~ as well a~ in prod~ct~ based ~n wood veneer~.
The wood adhe~ive co~positi~n according to the present invention ha~ b~en ~ound to be particularly sultable for the manufacture of ~ypo A ~aterproof plywoods, i.e. plywoods which are fully weather- and ~oil-proof (wsP plywood~.
The wood adhesive composition according to the present inventio~ may b~ applied to wood ~pecies of re~a~ively hi~h d nsity or conta~ning certain e~ractives know~ to make the specie8 ~ore difficult to bond with traditional phenolic adh~sLves. ~8 used herein in the description and claims, the ~erm Nhard wood" is used to d~note ~uch wood speci~s. .
The phenol ~ormaldehyde ~PF) re~in utili~ed in the wood adh~i~e compo~ition according to the present invention may be of any ~uit~bl0 type. A phenol form~ldehyde resin having a low ~ro~ formaldehyde content i~ proferr~d. The free ~ormaldehyde-content may range from 0 to approxLmately 2%, more preferably from 0 to 0.S%. Ph~nol formaldehyde re~in~ having a low free fo~maldehyd~ content are availa~le commercially fro~ ~ariou~ sources including Chemplex Aus~ralia, Bo~den Ch micals and ICI. Prefe~red phenol ~o~ldehyde r~sins are alkaline catalys~d phenol ~orm~ldehyde re~ins. A #uit~blo alkalin~ phenol formaldehyde ro~in is ~he re~in sold under the txa~e designat~on 775.
The phenol fo~aldehyde resin may be pre~ent in the wood adh~sive compo~ition in any effective amountQ. ~he phenol formaldehyde re~in ~ay be present in amounts o~ ~rom appxoximately 50 to 99,9% by weifht, preferably approximately 20~ 8~39 90 to 99.95~ by weight, more preferably approximately 90 to 99~ by weight, ~ased on the total weiqht of the wood adhe~ive compo~ition, exclu~v0 of any fill~r content. ~ore preferably, the phenol for~ld~hyde re~in i~ pre~ent ~n amounts of from approximately 95 to 99.9% by w~ight.
In a pref~red a~p~ct o~ th~ pxesent invention thero i~ pxovided a wood adhesive compo~itlon including an effective amount of a phenal-for~al~ehyd~ resin5 and a ~odi~ying agent which i~ difunc~ional or :- multifunc~ion~l ~nd capable of reacting wit~ eith~r an aldehyde or me~hylol group.
Pre~erably ~aid modifying agent i8 ~elected from the g~oup con~i~tinq of meta-amino-ph~nol, x~sorcinol, phlorogluci~ol, phonolic novolac , cond~n~ed tannins, polymers manufacturcd thara~o~, ox ~ixturee thereo~.
Typical modi~ying a~ents u~eful in this wood adh~ive com~o~ition according to ~hi~ aspect of the pre~ent inv~ntion are phenolio novolac~ ~pecially high orthonovolacs euch as u~ed in ~he production of moulding powders, for example a~ i~ de~crib~d in United Statee Paten~ Nos~
2,475,581 (12/7/49) or No. 3,476,707 (4111/69), meta-a~ino-~henol, re~orcinol, phloroglucinol, ~aXd a~ino phænol, re80~inol and re~orcinol phenol re~ns ~nd othe~
such ~uitable compound~ known to ~e very react~ve to ~ethylol ph~nol known in the ~rt. Theoe modifying ag~nts may be u~ful alone or prefe~ably a combination of phenolic noYol~c together with anothær curing a~ent may be u~ad.
~ ho modifying agent may be pre~ent in any effective a~ount. The amount to be added ~ 8 dependent on the formaldehydo to phenol ~a~io an~ the me~hylol cont-nt of th~
ba~e re~in. Re~in~ containing hiqh formaldehyde to phenol ratio~ and l~rgÆ pHrcentage~ of methylol group~ require ~lativoly large amount~ of no~olac or other reactive to ~ethylol compount~ to ~e ad~e~ . ~he amo~nt of modi~y~ng a~ent may r4nge fro~ approx~mately 0.05 ~o 50% by weight, preferably ~.OS to lO~ by weight, more preferably approximately O.l tO S% by weight, ba~ed on the total weight of the wood adhe~ivæ composition, excluding fill~rs when ~resent.
2 0 ~ 3~ 9 ~ phen~lic xe~in having a F/P ratlo of 1:1.5 and con~aining mos~ly methylene linkages and thu~ low methylol cont~nt would roqu~re very low amount~ of, for oxampl~, meta a~ino phenol to be ~dded for complete reaction. This amount 1~ u~ually lo-~ than approYimat-ly 3 part~ o~ m~t~ amino phenol per 100 pA~t~ of re~in.
~ h~ amount of modifying agent to b sdded may b~
dete~m~ned by gela~ion time e~pe~iments in which increasing amount~ of a likel~ compound aro added until the gelation tLm~ of th~ mixtur~ begin~ to rapidly length~n which i~ an $ndication of in~uf~icient ~ethylol remaining. S$ngle or combinat~on~ of ~u~table compounds may be add d.
It ha~ been found that the point at which rapid lengthening of the gelation ti~e is ob~rvQd is r~lated to the total mola~ content of mod~fying agent. Thus ~xovided the total numb~r of mol-- $~ k~pt con~tant, a co~bination of two or more Dodi~ying ~gent~ m~y be us~d to ~chieve a desir~d gelation t~me. Fo~ e~ample, the gelation time of a ~ix~ur~
of phenolic re~$n and meta-am~no-phenol wa~ ~ound to increase rapidly afte~ the addition of more than 0.96 gm p~r 100 pts re~in ~olution. ~h~ ~ame increa~e in gelation ti~e could be ob~erved ~hen equal part~ ~0-48B I 0.~8g) of r~orcinol and meta-~mino-phenol were added in co~bination ~a~ their mol-cular weight~ ~re e8~entially egual at llO and 10~
re~pect~v~ly). Th~ 8~ o~cur~ with other compounds, for ex~mple such a~ novolac~ and for instance phloroglucinol and polymer~ 8uch as re~orc~nol formAldehyde.
-Accord~ngly, in a pr f~rred a~pect the~e is provided - A wood adhe~ive compo~ltlon $ncluding approximately 50 to 99.99%, p~e~rably 90 to 99.95~ by weight ba~ed on the total weight of the wood adhe~ive compo~ition, excluding fillers, of ~ phenol-f~maldehyde resin having a low free for~aldchyde content; nnd a~pro~im4tely 0.01 to S0~, preferdbly approximat-ly O.OS to lO~ by wel~ht ~a8ed o~ the to~al weight of the wood adhesive compos~tion, ~x¢luding filler~, of one or more modifying a9ent~.
A typical wood adhe8ive composition accordlng tO
thi~ aspec~ of the present invention includeR
approx~mately 94 to 97.25~ by weight based on the Z00~8~t9 total weight of th~ woo~ adhe~ive compo~ition, exaluding f~ller~, of a phanol-~or~aldehyd~ xe~in haY~ng d lo~
frae-for~aldehydH content;
approsimately ~.5 to 5% by weight b~ed on the total weight of the wood ~dh~s1ve compo~i~ion, exclud$ng $iller~, of a phenolic novolac ro-$n; ~nd ap~roximat~ly 0~2S to 1% by w~ight ba~ed on th~
total weight of the wood adhesive co~po~it~on, excluding fillors, of ~eta-amino ~henol.
In an ~lternati~ preferred aspect of th~ pre~ent inve~tion thore i~ provided a wood adhe~ive composition including an effectivo Dmoun~ of ~ phenol formald~hyde re~int ~nd an ~xtractive~ neutrali~in~ agent capable, in u~e, of reducing or eliminating th~ advor~ effect~
of eYtract~ves contain~d in a hard ~ood.
This a~pect of the pre~nt invention involve~ tho addition of an extractiveo noutralising agent to the adhosive and/or the tr~atm~nt, with th~s~ compound~, of the ~b~tra~e to be glued. These compounds interact.with the extrac~ives within the wood or bark and sub~tantially negate th~
deleter~ou~ effect o~ the extractives ~o that superior adh~ive perform~nce i~ obtained.
Prefer~bly, the extractives neutral~ing agent i~
ca~a~le o~ forming complexe~ with and/or precLpitating the ex~ract~ve~, thor~by ~ub~ant~ally inac~ivating the extractive~ oo a~ to minimi~e interference w~th the bonding act~on, ~articularly at the glueline.
Acco~din~ly in a pr ~-rred form of ~his ~pec~ of the pre~ent inven~ion there i8 prov~d~d a w40d adhesive composition including approximat~ly 30 to 99.95S by ~ght ba~ed on the total weight o~ the ~ood adhe~ive compo~ition, axcluding f~l}er~, of ~ phenol-ormaldehyde resin; and approximately 0.05~. to 10~ by weight ba~ed on th total weight of the wood adhesive composition, excluding filler~, of an extractives n~utrali~ing agent ~elected from metallic compounds and o~ganic compounds capable of forming precipit~tes and/or complox~ with extractiv~ contained in a hard ~ood.
2003~3~9 Pre~erably th~ extractivos neutr~lising agent i~
~ol~cted from metallie compounds of m~als ~el~cted from th~
g~oup conai~ting of ~opp~r, iron, zinc, lead, mangane~e and nickel and organ~c compound~ ~elected from the group consi~tin~ of hexamethylenetetramine, melamine, ethyl~nedi~mine~etraac~tic acid (ED$A), triethylenetetr~min~, and complex~s thereof.
It will be under~tood that the invention may func~io~ a~ follow~. For exampl~, the wood extractive, the polyphenol$c ~ompound ellngitannin, forMs precipit~te~ and/or comploxe~ with d~rivativo~ of ~etal~ ~uch as copper, i~on, zinc, mangan~se, nickel etc and ~ith organic compound~ such a~ urea, ~el~n~, hexamin and EDTA. Co~plex formation i~
thought to b~ due mainly to th exi~t~nce in th~ extractives of polyphenol~c compound~ containing ortho~diphenol units ~uch a~ catechol and pyrogallol. Monomer~c and oligomeric catechols and pyroqallol~ ~ay also be pre~nt. ~Q have found for ex~mple that the ma~or compound~ in the extractives of Blackbutt ~ood are polyphonolic co~ound~ (ellagitannin~) which are cla~ Lod ~ pyrogallol typo compound~.
The e~tract$vos neutrallsing agent inacti~ating compound ~ay b inorganic or or~anic. Typical inorganic compound~ u~oful in tho pre~ent invention are metall~c compound# ~uch aJ copper, iron, zinc, lead, ~angane~e, n$ckel, and the like, derivativ~ and p~rticularly i~orqanic and organic salt~ of metal~ which can precipitat~ or complsx extractivo~ p~e~ont in wood or bark. Ex~mples of organic compound~ ~uit~ble. $n the pre~ent inv~ntion are hex~methyl~netetr~mino ~hesamin~)~ melamine, ethylenediamine-tetraacetic acid (EDTA), triethylen totramine (Trien), and derivat~vo~ thor~of capabl~ of procipitating and/or complexlng extractiveo ~hlch interfer~ with tho bonding action.
It i~ al~o kno~n that ~o~ wood oxtractives form proci~itates wlth a variety o~ organic compounds including aldehyde~ and ketone~ le.g. vanillin, cinnamaldehyde~, si~ple n$trogsn cont~ning compounds ~Q.g. urea, ac~tamide~ and heterocycl~c ring co~pound~ (e.g. quinoline, pyridine).
Other compound~ that are able to react and/or interact wi~h extractive~ and to ~uppre4~ the reaction betw~en the wood 20~3~3~9 extractive~ and the adhe~ive are al~o ~uitable additivos.
A single inactivating compound or combirat~on of such compound- may be u~ed.
We have found that the axtractives from Blackbu~t wood ara procipitated from solution on the addition of motall~c derivativ s such a~ tho ions of copper, iron, zinc, lead etc.
we h~o al80 found that t~e extr~ctives from Blackbu~t wood are ~recipitat~d fro~ their aqu~ous solution over a range of p~ from 0 to 14 by tho addition of or~anic compound4 ~uch as EDTA and Tr~en and/or thoir metallic derivat~ves such a~ thcir copper, z~nc, iron and lead d~rivativ~s. In thi~ way, deleteriou~ ax~ractives in the wood can be effectivoly exclud~d from the gluing sy~tom so that blocking of, or interference with, th~ cur$ng of the phenolic adh ~ive by the ~xtractives i8 pre~entcd and high qu~lity konding i~ obtained.
A particularly useful compound for the practice of the invent$on is cupr~c dlsodium ethylenediaminototraacetate (EDTA.Cu.Na2). Further use~ul compound~ include ferric chloride (FeC13), zinc acetate, EDTA.Cu, Trien-Cu, (Cu-Trien) ~nC14. ~ixture~ of compound~ m~y ~lso ~e used, for e~ampl- acetylacetone and Tri n.
The da~ir~d level of addition is rela~ed tO the amount of xtr~ct~ve~ to bo inacti~at~d but in general a ~uitable concentr~tion o~ the metallic or orq~nic component i~ in the range of 0.OS ~o 10% by weight ba~ed on th~ ~otal ~eight of the wood adheslv~s co~position, excluding fillers, wher- pre~ent, more proferably ~ppro~mately 2 to 5% by woight.
Accordingl~, ~n a preferred aspect there i~ provided a wood adhe~ve compo~ition includinq approx~mately 9$ to 98~ by weight ba~ed on th total welgh~ of th ~ood ~dhe~ive compos$t$on of a phenol-ormaldehyde re~ln~ and approxlm~tely 2 to 5~ by weight based on the ~o~al w~ight of th~ wood adhe~ive compo~ition of an ext~aotiYes mod~fying agent ~el~ct~d fro~ the group consisting of ferric chloride and cupric disodium ethylene diaminetetraacetate.
Th~ co~pooitlon~ of the invention ma~ also con~ain Z0038~39 oth~r additiv~s and 6uitabl- ille~ ~aterial~ such as methyl propyl cellulo~o~ ~ood ~lour, shell flour~ c~lcLte or kaolin. The filler may be pre~ent Ln ~mount~ a~
convention~lly u~ed of fro~ app~oximately 1 to 67% by we$ght based on th~ total weight of the wood ~dh~iv~ compo~ltion, pro~erably 5 to ~OS by weight. Alkali~ and water may be added a~ noce~ary fo~ vl~co~ity ad~ustmont.
In accordance with d further aspect of th~ pre6Qnt inv~ntion thero i8 providod a method for pr~par$ng a plywood articl- which method includes provlding a-fir8t ~ood he~t;
at lea-t one second wood ~heet; and a wood adhe~i~ com~osition including an of~ecti~e amount of a phenol-~ormald~hydo r~ ; and a modifying agent which agent render~ the co~o~ition c~p~ble of bonding ~o a hard woodS
coating a portion of a ~urface of said fir~t wood ~hoet w$~h the wood adhesive co~po~ition; and contacting the ~urface of the socond wood she~t with the coated ~urf~ce ol the fir~t wood ~heet.
Prefe~bly, th~ wood adhe~ive compoaition include~
~pprox~mately 94 to 97.25% by weight based on th~ total ~eight of tha wood adha-ive co~po~ition, oxcludi~g filler~, of a phenol-for~aldohyde res~n having A low fr~o-formaldehyde content~
~ pproxiT~tely 2.5 to 5% by weight ba~ed on the total weight o~ the wood adh ~lve compo~ition, exclud~ng fillers, of ~ phenolic novolac re~in) and , ~pprox~m~toly O.25 t~ 1% by weight ba~ed on the total weight of the ~ood ~dheJiv~ compo~ition, excluding flll-r~, o~ ~eta-~m~no phenol.
Alternati~ely, the wood adhe~ive compo~ition ~nclude~ ~ppro~imately 95 to 98~ by weight b~ad on the total we~ght of the wood ~dhe~iYo co~position, excluding filler~, : of a ~henol-~ormald~hyde re~in~ and approximately 2 to 5% by weight ba~ed on the total weight of the wood adhe~lve compo~ition, e~cluding fillers, of an extrac~ive~ modifyi~g ag~nt Jelected from the group , .~
200.38~19 consi~tlng o~ ~erric chlor~de and ~upric d$~odium ethyleno diaminetetraacet~te .
~ he ~ir~t ~nd ~ubse~ent wood heet~ utilised in tho preparatlon o~ the plywood article according to the rRethod aecording to the pre~nt invention may be of any suit~ble type. The wood ~heets m~y be for~d of wood ~peciQ~ of rel~ti~ely high donsity ~uch a~ high den~lty eucalypt ~pecie~. A p~icularly pre~erred form i~ Blackbutt wood (l~ucalyptus pilulari~
~ he mothod of p~eparing the plywood artlcle may be undertaken util ~ ~ing ~tandard t~chnique~ . ~or example, once the eoatod ~urf~ce of the fir~t wood sheet ha~ been contac:ted with the ~urfac~e of tho ~e~ond llrood ~ho~t, ~tandard bonding ~tep~ includ~ng applying heat ~nd/or pre~ure to the sheet ~o B~ to effect bonding o~ the two ~heet~ may be undertaken.
In an al~ernati~e m~thod, however, the wood sheet~
or other article~ to b~ bonded m~y fir~t be treated with the extractive~ neutrali~ing agen~ ~o a~ to reduce or eliminate the adver~o ~ffocts of extract~ves contalnod in tho haxd wood once thi~ prelim$nary treatment is completed, the ~heeS~ may then be treated w~th a ~t~nd~rd wood adhesive compo~it$on $ncluding a ph~nol form~dehydo rosin.
Accordingly, there i~ provided a method ~or prop~ring a plywood ~rticle which method includes pro~tding a ~irst wood sheet;
at len~t one wocd ~he~t; and a wood adhe~ive kit including a pri~r coating compo~ition including an extract$ves neutr~liz$ng agent capable, in u~e, of roduc$n0 the advsr~e effect~ of extractives conta$ned in a h~rd wood; and treat$ng ~t lea~t a surface of ~aid fir~ and ~econd ~he~t~ to bo sdhered wlth ~aid primer coating compo~ition; and contw ti~g ~aid treated ~ rfaces with the wood adhe~ive compo~$tlon Accordingly, in a ~till further aspect of the pxe~ont $nvention there i~ provided a wood adhesive ki~
including ~ primer coatlng co~po~ition including an Z0().38~9 extractivo~ neutral~ng ~gent cap~blo, in u~e, of roducing the adver~o effect~ of extractlve~ contaln~d in a hard wood~
and a wood adhesive compo~ition includ~nq a phenol formaldehyde re~in.
Pre~erably, the pri~er coatin~ co~p~ition Lnclude4 an ~tract~ve~ n~utralizing agent ~elected from fe~ric chloride and cuprlc disodium Rthyl~ne diamin tetraacetate.
Th~ pre~ent invention will now ~e more fully de~crib~d with r~-renc~ to the accompanying examples. It ~hould be under~tood, however, that ~he de~cription following i~ lllu~trative only ~nd i~ not inte~ded to re~tr~ct the generalLty of ~he invent$on ~B de~crib~d above.
~
A conventional u$table alkal1ne phenol formaldehyde ba~e re~in i~ ~el-ctod ~uch a~ Cho~plex 775, to this is add~d a ~u$table novol~c such a~ supplied by Chemplex Australia Ltd~, for e~ample GC 1499 (3%) and mota-amino phenol (0.4~) and suitable f~ller matorial~ ~ueh ~ ~ethyl propyl cellulo~e, nut shell flour, calcite and k~olin. Al~alis and ~ater may be ~dded a~ nocossary for viwosity adju~tment.
The rosults of t~ utilizing the co~po~ition~ of the pre~ont lnvent~on indic~te that an adhe~ive ~y~tem ha8 b en develop~d th~t will sat~fy the glue bond requirQments for Type A bond~d plywood from high den~ty eucalypt~ u~ing the chl~el te~t ~ de~cribed in Australlan Standard~ 2098.2 ~1977) ~nd 275~.1 (1985). Tho adhe&ive ~y~tem may be ea~ily miY~d on 8ite, ach part hav~ng adequate ~torage life, but upon m$~ing producing adhe~ive~ of fa~ter cuxe time, and controlled penetr~t~on by reduction of ~xtr~ct~ve interforonce re~ultin~ in the roduc~ion of cohosive failure.
Plywood ~mples were prepAred by bonding veneers rom ~lackbutt (~uc~lyptus pilularis) as a repre~entative high den~ty wood ~pecie~. The adhesive formulation con~ted of Ch~plex 775 ~100 part~) as a suitable convontional alkAl~ne phenol-formaldehyde resin, a nut shell flour ~10 par~) A~d calcite ~10 ~arts) as fillers, and cupric d~ 80dlum ethylened~inetetraacot~te ~EDTA.CuNa2) (4 1 ~
.
.
' ~ .
~ 0 0~ 8~9 parts). ~he ~amo ~ormulation with the cupric disodiu~
ethylenediaminetetraaceta~e emitt~d ~a~ u~ed a~ ~ control.
The bond quallty of the re~ulting ply~ood ~pe~imen~
wa~ then a~ses~ed by the chi~ol test ~ccording to au~tralian Standard# 2098.2 ~1977) and 27S4.1 ~1985). The te~t re~ult~
aro ~ummari~ed in ~able 1.
. . . _ Adhe~iv~
formulation Dry Wet ho~r~_bQilin~
EDTA.Cu.Na2 8.0 9.0 Control 3.0 2.0 EX~Mp1E 3 Plywood ~amples were prepar~d in accordan~e with ~he proc-duro de~cribed in Sx~mple 2. ~he adh~lv~ formulation u~ed here cons~#ted of Cheople~ 77S tlO0 parts), ~ nut ghell flour (lS part#)~ kaolin (10 part~) and P~C13 ~2.2 pa~t~).
The te~t procedure~ uoed ~re tho~o des~ribed in Example 2.
Tabl- 2 give~ the test re~ul~.
~A~a 2 Adho~ive Aver~g~L~L~ond quality formulatlon Dry Wet after 72 hQu~ boilina PeC13 8.0 8~0 The r~sults 8how that the adhesive ~y~tem o~ this ~nv-ntion sati~io~ the ~lu ~on0d38r~equiroment~ ~or Type A
bondQd plywood (fully weather and boil proo~), wh~rea~ the con~entional ~y~tom doo~ not meet the roquirem-n~s o~ the ~tand~rd~. .
Flnally, it i~ to be understood that variou~ other modlfication~ ~nd/or alte~ation~ may be m~do wlthout departing from the ~plrit of th~ pre~nt in~ntion as outlined herein.
.
,~
Claims (18)
1. A wood adhesive composition including an effective amount of a phenol-formaldohyde rein; and a modifying agent which agent renders the composition capable of bonding to a hard wood.
2. A wood adhesive composition including an effective amount of a phenol-formaldehyde resin; and a modifying agent which is difunctional or multifunctional and capable of reacting with either an aldehyde or methyl group.
3. A wood adhesive composition according to claim 2 wherein the modifying agent. is selected from the group consisting of meta-amino-phenol, resorcinol, phloroglucinol, phenolic novolacs, condensed tannins, polymers manufactured therefrom, or mixtures thereof.
4. A wood adhesive composition according to claim 3 including approximately 50 to 99.99% by weight based on the total weight of the wood adhesive composition, excluding fillers, of a phenol-formaldehyde resin having a low free formaldehyde content; and approximately 0.01 to 50% by weight based on the total weight of the wood adhesive composition, excluding fillers, of a modifying agent.
5. A wood adhesive composition according to claim 2 including approximately 90 to 99.95% by weight based on the total weight of the wood adhesive composition, excluding fillers, of a phenol-formaldehyde resin having a low free formaldehyde content; and approximately 0.05 to 10% by weight based on the total weight of the wood adhesive composition, excluding filers, of a modifying agent.
6. A wood adhesive composition according to claim 3 further including approximately 1 to 67% by weight based on the total weight of the composition, including filler , of a filler selected from the group consisting of methyl propylcellulose, wood flour, nut shell flour, calcite, kaolin and mixtures thereof.
7, A wood adhesive composition including approximately 94 to 97.25% by weight based on the total weight of the wood adhesive composition, excluding fillers, of a phenol-formaldehyde resin having a low free-formaldehyde content, approximately 2.5 to 5% by weight based on the total weight of the wood adhesive composition, excluding fillers, of a phenolic novolac wood resin; and approximately 0.25 to 1% by weight based on the total weight of the wood adhesive composition, excluding fillers, of meta-amino phenol.
8. A wood adhesive composition including an effective amount of a phenol formaldehyde resin; and an extractives neutralising agent capable, in use, of reducing or eliminating the adverse effects of extractives contained in a hard wood.
9. A wood adhesive composition according to claim 8 including approximately 90 to 99.95% by weight based on the total weight of the wood adhesive composition, excluding fillers, of a phenol-formaldehyde resin; and approximately 0.05% to 10% by weight based on the total weight of the wood adhesive composition, excluding fillers, of an extractives neutralising agent selected from metallic compounds and organic compounds capable of forming precipitates and/or complexes with extractives contained in a hard wood.
10. A wood adhesive composition according to claim 9 wherein the extractives neutralising agent is selected from metallic compounds of metals selected from the group consisting of copper, iron, zinc, lead, manganese and nickel and organic compounds selected from the group consisting of hexamethylenetetramino, melamine, ethylenediaminetetraacetic acid, and complexes thereof.
11. A wood adhesive composition according to claim 10 further including approximately 1 to 67% based on the total weight of the composition, including fillers, of a filler selected from the group consisting of methylpropylcellulose, wood flour, nut shell flour, calcite, kaolin and mixtures thereof.
12. A wood adhesive composition including approximately 95 to 98% by weight based on the total weight of the wood adhesive composition, excluding fillers, of a phenol-formaldehyde resin; and approximately 2 to 5% by weight based on the total weight of the wood adhesive composition, excluding fillers, of an extractives modifying agent selected from the group consisting of ferric chloride and cupric disodium ethylene diaminetetraacetate.
13. A method for preparing a plywood article which method includes providing a first wood sheet;
at least one second wood sheet; and a wood adhesive composition including an effective amount of a phenol-formaldehyde resin; and a modifying agent which agent renders the composition capable of bonding to hard wood;
coating a portion of a surface of said first wood sheet with the wood adhesive composition; and contacting the surface of the second wood sheet with the coated surface of the first wood sheet.
at least one second wood sheet; and a wood adhesive composition including an effective amount of a phenol-formaldehyde resin; and a modifying agent which agent renders the composition capable of bonding to hard wood;
coating a portion of a surface of said first wood sheet with the wood adhesive composition; and contacting the surface of the second wood sheet with the coated surface of the first wood sheet.
14. A method according to claim 13 wherein the wood adhesive composition includes approximately 94 to 97.25%
weight based on the total weight of the wood adhesive composition, excluding fillers, of a phenol-formaldehyde resin having a low free-formaldehyde content;
approximately 2.5 to 5% by weight based on the total weight of the wood adhesive composition, excluding fillers, of a phenolic novolac resin; and approximately o.25 to 1% by weight based on the total weight of the wood adhesive composition, excluding fillers, of meta-amino phenol.
weight based on the total weight of the wood adhesive composition, excluding fillers, of a phenol-formaldehyde resin having a low free-formaldehyde content;
approximately 2.5 to 5% by weight based on the total weight of the wood adhesive composition, excluding fillers, of a phenolic novolac resin; and approximately o.25 to 1% by weight based on the total weight of the wood adhesive composition, excluding fillers, of meta-amino phenol.
15. A method according to claim 13 wherein the wood adhesive composition including approximately 95 to 98% by weight based on the total weight of the wood adhesive composition, excluding fillers, of a phenol-formaldehyde resin; and approximately 2 to 5% by weight based on the total weight of the wood adhesive composition, excluding fillers, of an extractives modifying agent selectod from the group consisting of ferric chloride and cupric disodium ethylene d1aminetetraacetate.
16. A wood adhesive kit includlng a primer coating compositlon including an extractives neutralizing agent capable, in use, of reduclng or elLminating the adverse efects of extractives containod in a hard wood; and a wood adhesive composition including a phenol formaldehydo resin.
17. A wood adhesive kit according to claim 16 wherein the primer coating composition includes an extractives noutralizing agent selected from ferric chloride and cupric disodium ethylene diaminetretraacotate.
18. A method for preparing a plywood article which method includes providing a first wood sheet;
at least one wood sheet; and a wood adhesive kit including a primer coating composition including an extractives neutralizing agent capable, in use, of reducing tho adverse effects of extractives contained in a hard woods; and treating the surfces of said first and second sheets to be adhered with said primer coating composition; and contacting said troated surfaces with the wood adhesive composition.
at least one wood sheet; and a wood adhesive kit including a primer coating composition including an extractives neutralizing agent capable, in use, of reducing tho adverse effects of extractives contained in a hard woods; and treating the surfces of said first and second sheets to be adhered with said primer coating composition; and contacting said troated surfaces with the wood adhesive composition.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AUPJ164488 | 1988-11-25 | ||
| AUPJ1644/88 | 1988-11-25 | ||
| AUPJ551889 | 1989-07-28 | ||
| AUPJ5518/89 | 1989-07-28 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2003899A1 true CA2003899A1 (en) | 1990-05-25 |
Family
ID=25643586
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA 2003899 Abandoned CA2003899A1 (en) | 1988-11-25 | 1989-11-22 | Adhesive |
Country Status (2)
| Country | Link |
|---|---|
| CA (1) | CA2003899A1 (en) |
| WO (1) | WO1990006347A1 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1991017224A1 (en) * | 1990-05-03 | 1991-11-14 | Commonwealth Scientific And Industrial Research Organisation | Adhesive composition |
| FI105788B (en) * | 1995-12-29 | 2000-10-13 | Upm Kymmene Oyj | A method for protecting plywood and chipboard from rot and mold |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB723884A (en) * | 1951-09-12 | 1955-02-16 | Bakelite Ltd | Improvements in or relating to synthetic resin adhesives |
| GB819044A (en) * | 1955-10-24 | 1959-08-26 | Monsanto Chemicals | Methylol melamine phenol-formaldehyde adhesives |
| US3254038A (en) * | 1962-07-20 | 1966-05-31 | Borden Co | Adhesive composition comprising phenolic resin, a tannin and an alkali metal hydroxide |
| US3215653A (en) * | 1962-07-27 | 1965-11-02 | Koppers Co Inc | Resorcinol-modified phenolic resin adhesive mix |
| DE3316352A1 (en) * | 1983-05-05 | 1984-11-08 | Basf Ag, 6700 Ludwigshafen | METHOD FOR GLUING SOLID WOOD |
| AU587406B2 (en) * | 1984-12-11 | 1989-08-17 | Commonwealth Scientific And Industrial Research Organisation | Adhesive compositions based on phenolic resins |
| ES2032337T3 (en) * | 1987-01-26 | 1993-02-01 | Dynobel A/S | AMINIC RESIN AND METHOD FOR ITS PRODUCTION. |
-
1989
- 1989-11-22 CA CA 2003899 patent/CA2003899A1/en not_active Abandoned
- 1989-11-24 WO PCT/AU1989/000514 patent/WO1990006347A1/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| WO1990006347A1 (en) | 1990-06-14 |
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| Date | Code | Title | Description |
|---|---|---|---|
| EEER | Examination request | ||
| FZDE | Dead |