CA2152108A1 - Resorcinol resin adhesive composition - Google Patents
Resorcinol resin adhesive compositionInfo
- Publication number
- CA2152108A1 CA2152108A1 CA002152108A CA2152108A CA2152108A1 CA 2152108 A1 CA2152108 A1 CA 2152108A1 CA 002152108 A CA002152108 A CA 002152108A CA 2152108 A CA2152108 A CA 2152108A CA 2152108 A1 CA2152108 A1 CA 2152108A1
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- Canada
- Prior art keywords
- resorcinol
- resin
- adhesive composition
- resin adhesive
- resorcinol resin
- 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
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Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B21/00—Layered products comprising a layer of wood, e.g. wood board, veneer, wood particle board
- B32B21/13—Layered products comprising a layer of wood, e.g. wood board, veneer, wood particle board all layers being exclusively wood
-
- 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
-
- 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
- C08G8/16—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ with amino- or nitrophenols
-
- 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
- C08G8/22—Resorcinol
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08H—DERIVATIVES OF NATURAL MACROMOLECULAR COMPOUNDS
- C08H6/00—Macromolecular compounds derived from lignin, e.g. tannins, humic acids
-
- 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
-
- 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
- C08L61/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with 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
- C08L97/005—Lignin
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J161/00—Adhesives based on condensation polymers of aldehydes or ketones; Adhesives based on derivatives of such polymers
- C09J161/04—Condensation polymers of aldehydes or ketones with phenols only
- C09J161/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J161/00—Adhesives based on condensation polymers of aldehydes or ketones; Adhesives based on derivatives of such polymers
- C09J161/04—Condensation polymers of aldehydes or ketones with phenols only
- C09J161/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
- C09J161/12—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols with polyhydric phenols
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J197/00—Adhesives based on lignin-containing materials
- C09J197/005—Lignin
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
- C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
- C08L2666/14—Macromolecular compounds according to C08L59/00 - C08L87/00; Derivatives thereof
- C08L2666/16—Addition or condensation polymers of aldehydes or ketones according to C08L59/00 - C08L61/00; Derivatives thereof
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- Wood Science & Technology (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
Disclosed are a resorcinol resin adhesive composition which comprises a resorcinol resin modified by m-aminophenol, and a process for bonding wood materials by using the same.
Description
TITLE OF THE INVENTION
RESORCINOL RESIN ADHESIVE COMPOSITION
BACKGROUND OF TIIE INVENTION
1. Field of the Invention Thls invention relates to a resorcinol resin adhesive composition and a method of adhering, more specif ically, to a resorcinol resin adhesive composition and the method of adhering using the same, which are excellent in curing rate, and particularly excellent in curability under a low temperature to exhibit excellent adhesion power. Thus, even when it is used in a winter season with a low temperature, it can be cured wit~lin a short time to exhibit excellent adhesive properties, whereby a pressing time can be shortened and releasing the pressure can be effected within a short time. Further, productivities using a resorclnol resin adhesive can be improved. Therefore, it is particularly avallable for the uses of panel bonding such as a plywood and a lumber, or a squarebar, etc. which is required to lmprove productivlty, rub-out of LVLs (Laminated Veneer Lumber) for structure, and wood bonding such as longitudinal seam of woods for structure.
RESORCINOL RESIN ADHESIVE COMPOSITION
BACKGROUND OF TIIE INVENTION
1. Field of the Invention Thls invention relates to a resorcinol resin adhesive composition and a method of adhering, more specif ically, to a resorcinol resin adhesive composition and the method of adhering using the same, which are excellent in curing rate, and particularly excellent in curability under a low temperature to exhibit excellent adhesion power. Thus, even when it is used in a winter season with a low temperature, it can be cured wit~lin a short time to exhibit excellent adhesive properties, whereby a pressing time can be shortened and releasing the pressure can be effected within a short time. Further, productivities using a resorclnol resin adhesive can be improved. Therefore, it is particularly avallable for the uses of panel bonding such as a plywood and a lumber, or a squarebar, etc. which is required to lmprove productivlty, rub-out of LVLs (Laminated Veneer Lumber) for structure, and wood bonding such as longitudinal seam of woods for structure.
2. Related Art Statement A resorcinol resin adhesive has been used for bonding of wood materials, and has been used, for example, in a laminated lumber ln which a lumber or a squarebar, etc. are located substantially parallel to its fiber direction with each other and bound to the thickness, width and length directions. It has an excellent adhesion strength, water resistance, durability, fire resistance, etc. so that it is available for bonding of laminated lumbers for structure, laminated lumbers for structure with a large section, laminated lumbers for exterior, etc. and for bonding of a tire cord and a rubber, etc.
As a resorcinol resin adhesive for wood bonding, there has heretofore been provided, in general, a mixed material (a paste solution) comprising a resorcinol resin, a curing agent such as paraformaldehyde and a filler such as a coconut shell flour.
However, in the said resorcinol resin adhesive, curing of the paste solu~ion becomes slow when an atmospheric temperature and a temperature of a material to be adhered are low during a winter season, and at a temperature lower than a normal temperature, sufficient adhesive property cannot be obtained. Also, at the normal temperature of 20 to 25 C, it is necessary to cure the paste solution for a long time of 8 to 24 hours.
21~2108 Since the resorclnol resin adhesive has such a drawback, it is required to install a temperature maintaining device as a preparation equipment or to effect long time pressing of 8 to 48 hours as adhesion conditions.
From such a drawback of the resorcinol resin adhesive, an adhesion process o:E a laminated lumber for structure generally employed is a process in which lumbers are laminated after coating an adhesive to the lumbers, pressed by a turnbuckle, etc., placed in a thermostat chamber at 30 to 50 C for 8 to 48 hours to cure the adhesive, and then subjected to releasing pressure and curing. Since such procedures are required, productivity using the resorcinol resln adhesive is extremely bad.
Moreover, in Japanese Patent Publications No. HEI-5-2715/1993 and No. HEI-4-17139/1992, there is disclosed a method for adhering wood materials by coating a resin component comprising a resorcinol resin or a resorcinol phenol resln and a curing agent separately on the respective surfaces of the materials to be bonded and then laminating these materials.
S~MMAR~ ~F 'rll~. INVF N~ION
An object of the present invention is to overcome the problems possessed ~y the prior art techniques as mentioned 2~$2108 above and to provide a resorcinol resin adhesive having rapid curing speed and good adhesive power at a low temperature whereby improving productivity when using the same .
The present invention relates to a resorcinol resin adhesive composition comprising a resorcinol resin modified by m-aminophenol.
The present invention also relates to a method of adhesion using a resorcinol resin adhesive composition comprising a resorcinol resin modified by m-aminophenol, which comprises coating the resorcinol resin adhesive and a curing agent component to the materials to be adhered separately by a two-liquid separately coating method, and adhering these materials.
DESCRTPTION OE TT~. PRF:~ERR~.n EMBODTMF.N~S
The resorcinol resin adhesive composition comprising a resorcinol resin modified by m-aminophenol to be used in the present invention is a resorcinol resin using m-aminophenol as a modifier, and may include, for example, a resorcinol - formaldehyde resin such as a resorcinol m-aminophenol formaldehyde co-condensed resin obtained by the reaction of resorcinol, m-aminophenol and formaldehyde, and a resorcinol-phenol m-aminophenol-formaldehyde co-condensed f 21521~8 resin obtained by the reaction of resorcinol, phenol, m-amlnophenol and formaldehyde; and a resorcinoL-formaldehyde resin part of the above resins is modified by cresol, xylenol, tannin or lignin.
The molar ratio of formaldehyde to reso~cinol and m-aminophenol at the reaction when the above resorcinol-m-aminophenol formaldehyde co-condensed resin is to be obtained, and the molar ratio of formaldehyde to resorcinol, m-aminophenol and phenol at the reaction when the above ~.
resorcinol-phenol-m-aminophenol-formaldehyde co-condensed resin is to be obtained is desirably 0.9 to 0.8 mole of formaldehyde per mole of the latter mixture.
Also, the pH at the synthetic reaction is preferably adjusted to in the range of 6 to 11 by using an alkali catalyst such as NaOH.
The content of the m-aminophenol in the resorcinol resin modified by the m-2minophenol is preferably 1 to 20 parts by weight based on 100 parts of the total resin. If it is less than 1 part by weight, a curing accelerating effect of the resorcinol resin becomes insufficient, during 1 to 20 parts by weight, curing becomes rapid and if it exceeds 20 parts by weight, the curing accelerating effect is saturated and it is not economical.
_ 5 _ 21~
Accordingly, the content of the resorcinol in the resorclnol resin modified by the m-aminophenol is preferably 15 to 30 parts by weight on 100 parts of the total resin by the some reason as above.
The resorcinol resin adhesive composition of the present invention can be obtained by adding a curing agent to the above m-aminophenol-modified resorcinol resin.
In the resorcinol resin adhesive composition of the present invention, by adding a curing agent to a resin composition in which the m-aminophenol formaldehyde resin or the m-aminophenol phenol formaldehyde resin and, the resorcinol - formaldehyde resin or the resorcinol phenol formaldehyde resin are blended, the resorcinol resin adhesive composition comprising the m-aminophenol-modified resorcinol resin can be constituted by the reaction of the curing agent.
The resin component in the resorcinol resin adhesive composition of the p-esent invention is preferably within the range of 50 to 70 9~i by weight, the pH of 6 to 11, the viscosity of 2 to 100 poise/25 C (BH type viscometer, 20 rotations ~ .
As the curing agent, there may be used a powdery curing agent such as powdery paraformaldehyde and powdery 215210~
hexamethylenetetramine; and a liquid curing agent in which powdery paraformaldehyde or a formalin aqueous solution is blended with water, a phenol resin or a dispersion such as a synthetic rubber type emulsion.
By adding the curing agent, the resin composition can be cured within a short time. Incidentally, when 10 parts by weight of paraformaldehyde as a curing agent is added to 100 parts by weight of the above adhesive resin, the composition gelled within 30 second to 10 minutes/25 C.
Accordingly, it is re~ n-'~d to use the method in which the adhesive resin and the curing agent are separately coated in view of the usable time. For example, there may be preferably employed the method in which the adhesive is coated on one surface while the liquid curing agent is coated on the other surface and the both coated surfaces (the surfaces to be adhered) are faced to each other to blend the both components, and the method in which the adhec7ive and the liquid curing agent are individually sprayed to the coating surfaces (the surfaces to be adhered) of materials to be adhered such as a wood board and blended them on the coated surfaces thereof. Particularly when blend is carried out on the surfaces, the two liquid separately coating method in which the resin component and 2l~2lD8 the curing agent component are separately coated as mentioned above is preferably employed. When the curing agent is added to one or both of the resin to be blended without using the two liquid separately coating method, the usable time is markedly limited.
To the above adhesive composition, a filler such as coconut shell flour, walnut shell flour, wood flour, wheat flour, soy bean flour, calc$um carbonate, zeolite and clay may be formulated.
Also, a rubber type emulsion such as SBR
(styrene-butadiene rubber) and NBR (nitrile-butadiene rubber), and an aqueous polymer thickener such as a polyvinyl alcohol, methyl cellulose, polyethylene oxide, carboxymethyl cellulose and alginic acld may be formulated.
Further, an alcohol such as ethanol, methanol and ethylene glycol may be formlllated.
EXA~PT F s Next, the present invention will be explained by referring to Examples.
F.Xi le 1 In a three-necked flask equipped with a reflux condenser and a stirrer were charged 280 g of formalin (37%), 1~0 g of pherlol and 100 g of water, and after -; :
2l~2la8 ad ~usting the pH to 9 . 8 to 10 . 4 with NaOH, the mixture was reacted at 80 C for one hour. Then, to the mixture were added 330 g of resorcinol and 50 g of m-aminophenol, and the mixture was reacted at 90 to 100 C for 3 hours to obtain a resorcinol-phenol m-aminophenol formaldehyde co-condensed res in .
With 100 parts by weight of the resulting resin was mixed 50 parts by weight of a liquld curing agent (D-100, trade name, avallable from Oshika Shinko Co . T td, a curing agent for a resorcinol resin containing 30% formaldehyde) and a gel time thereof was measured to give the result of 40 sec/25 C. The viscosity was 10 poise/25 C.
Then, under the following operation conditions, adhesion of laminated lumbers was carried out and adhesion characteristics of the resulting material were measured according to the following test method.
(1~ Operation conditions Coating method: The above resorcinol phenol m-aminophenol formaldehyde co-condensed resin was coated on one surface of a Western hemlock lumber and the above liquid curing agent was coated on one surface of ==
another Western hemlock lumber, and the both coated surfaces were laminated.
_ g _ 21~21~8 Materials to be adhered: Western hemlock lumber with a thickness of 30 mm, water content of 8 to 10 %/5 C
Constitution: Two sheets of Western hemlock lumbers were laminated.
Coating amount: 200 g/m2 of the resin component and 100 g/m2 of the liquid curing agent.
Pressing: 2 hours, 5 C, 10 kg/cm2.
(2) Test method sased on Japanese Agricultural and Forestry Standard of a laminated lumber for structure, a block shear test, a dipping peel test and a boiling peel test were carried out.
The results are shown in Table 1.
F~tA~rle 2 In a three-necked flask equipped with a reflux condenser and a stirrer were charged 230 g of formalin ~37%), 130 g of m-aminophenol, 200 g of methanol and 130 g of water, and after adjusting the pH to 9 . O with NaOI~, the mixture was reacted at 80 C for one hour. Then, to the mixture was added dropwise 160 g of formalin (37%) over one hour, and the mixture was further reacted at 80 to 85 C for 3 hours to obtain a ~n-aminophenol formaldehyde resin .
20 parts by weight of the resulting resin was blended with 80 parts by weight of a resorcinol-phenol-formaldehyde 21~2108 co-condensed resln. ~Oshika resin D-300, trade name, available from Oshlka Shinko Co. Ltd., ) .
To 100 parts by weight of the blended resin was added 50 parts by weight of the liquid curing agent used in Example 1, and a gel time thereof was measured to give the result of 70 sec/25 C. The viscosity was 60 poise/25 C.
In the same manner as in Example 1, adhesion of lumbers was carried out by coating the blended resin on one surface of a Western hemlock lumber and coating the liquid curing agent on one surface of another Western hemlock lumber, and laminating the both coated surfaces thereof. Adhesion characteristics were measured according to the same test-methods as in Example 1.
The results are shown in ~able 1.
Example 3 In the same manner as in Example 2 except for using 50 parts by weight of the m-aminophenol formaldehyde resin and 50 parts by weight of the resorcinol phenol formaldehyde co-condensed resin, a blend resin was prepared. To 100 parts by weight of the blend resin was blended 50 parts by weight of the liquid curing agent used in Example 1, and a gel time thereof was measured to give the result of 40 sec/25 C. The viscosity was 40 po.se/25 C.
2~S~1~8 In the same manner ~s in Example 1, adhesion of lumbers was carried out by coating the blended resin on one surface of a Western hemlock lumber and coating the liquid curing agent on one surface of another Western hemlock lumber, and laminating the both coated surfaces thereof. Adhesion characteristics were measured according to the same test methods as in Example 1.
The results are shown in Table 1 C .2, rative F'X le 1 As a resorcinol resin, the resorcinol formaldehyde resin (Deernol No 50, trade name, available from Oshika Shinko Co. Ltd., ) having the following characteristics was us ed .
Resin characteristics Viscosity; 5 poise/25 C
l~esin component; 65 ~
Gel time; 120 min/25 C (in the case of the resin/-paraformaldehyde = 100/10 parts by weight) With 100 parts by weight of the above resorcinol formaldehyde resin were blended 10 parts by weight of paraformaldehyde and 5 parts by weight of wood flour to obtain a formulated paste solution having a viscosity of 22 poise/25 C
Then, under the following operation conditions, adhesion of lumbers for lamination was carried out and adheslon characteristics of the resulting laminated lumber were measured according to the same test method as in Example 1.
~1) Operation conditions Coating method: The above formulated paste solution was coated on one surface of a Western hemlock lumber and another Western hemlock lumber was laminated thereon .
Materials to be adhered: Western hemlock lumber with a thickness of 30 mm, water content of 8 to 10 %/5 C
Constitution: Two sheets of Western hemlock lumbers were laminated.
Coating amount: 300 g/m2, one surface coating.
Pressing: 2 hours, 5 C, 10 kg/cm2.
C~ rat i ve ~ le 2 As a resorcinol resin, the resorcinol-phenol-formaldehyde resin (Deernol No. 35, trade name, available from Oshika Shinko Co. Ltd., ) having the following characteristics was used.
~esin characteristics Viscosity; 4 poise/25 C
21~210~
Resin component; 60 %
Gel time; 100 min/25 C (in the case of the resin/-paraformaldehyde = 100/10 parts by weight) With 100 parts by weight of the above resorcinol-phenol-formaldehyde resin were blended 10 parts by weight of para~ormaldehyde and 5 parts by weight of wood flour to obtain a formulated paste solution having a viscosity of 2C poise~25 C.
Then, in the same manner as in Comparative example 1, adhesion of lumbers for lamination was carried out and adhesion characteristics of the resulting laminated lumber were measured according to the same test method as in Example l.
The results are shown in Table 1.
C, ~ rat ive ~ le 3 As a resorcinol resin, the resorcinol-phenol-formaldehyde resin (Deernol No. 300, trade name, available from Oshika Shinko Co. [Jtd., ) having the following characteristics was used.
Res in characteristics ViscosLty; 70 poise/25 C
Resin compon~nt; 65 %
Gel time; 70 min/25 C (in the case of the resin/-21~2108 paraformaldehyde = 100/10 parts by weight) With 100 parts by weight of the aboveresorcinol phenol formaldehyde resin was blended lO parts by weight of paraformaldehyde to obtain a formulated paste solution having a viscosity of 80 poise/2S ' C .
Then, in the same manner as in Comparative example 1, adhesion of lumbers for lamination was carried out and adhesion characteristics of the resulting laminated lumber were measured according to the same test method as in Example 1.
~ he results are shown in Table 1.
~able 1 ~o. Example Comparative example Adhesion Pressing l 2 3 1 2 3 strength time and 2 hr 2 hr 2 hr 2 hr 2 hr 2 hr test t~ , ' e 5 C 5 ' C 5 C 5 ' C 5 C 5 C
Average adhesion lOl 95 103 0 0 0 Block strength shear ( kgf /cm2 ) test Average wcod ~normal) portion 86 83 92 0 0 0 breakage rate (%) I~ipping peel test Pass Pass Pass Failure Failure Failure 21~2108 .
¦Boiling peel test ¦¦ Pass ¦ Pass ¦ Pass ¦Failure¦Failure¦Failure¦
r le ~
By using 100 parts by weight of the resorcinol phenol m-aminophenol- formaldehyde co-condensed resln obtained ln Example l and 50 parts by welght of the llquid curing agent (D-100, trade name, available from Oshika Shinko Co. Ltd., ) used in Example l, to obtain compounded paste, finger bonding of longitudinally seamed woods was carried out under the following operation condltions. Adhesion characteristics of the bonded portion were measured according to the following test method.
~l) Operation conditions Coating method: The resin was coated on one surface of a finger portion and the liquid curing agent was coated on one surface of another finger portion (separately coating system), and coating was carried out by using a brush .
Materials to be adhered: Japanese larch flnger processed material with a water content of 8 to 10 %/5 C and a speciflc gravity of 0.53 to 0.57 (thickness: 20 mm, width: 150 mm, length: 500 mm) Shape of finger: Vertical flnger processed material with a length of 18 mm and a pitch of 5 . 5 mm Coating amount: ~00 g/m2 (resin: 267 g/m2, liquid 21~21~8 curing agent: 133 g/m2) Assembly: 5 C, 5 min.
Pressing: 80 kg/cm2.
Cure: S C, 1 hour, 3 hours, 24 hours.
~2 ) Test method Based on 2apanese Agricultural and Forestry Standard of a lamlnated lumber for structure wlth a large section, a bendlng test of a longltudlnal seam wood was carrled out.
The results are shown ln Table 2.
C~ aratlve ~- le 4 By uslng the formulated paste solutlon obtained ln Comparatlve example 2, flnger bonding of longitudlnally seamed woods was carrled out under the following operatlon conditions, and adhesion characterlstlcs of the bonded portlon were measured accordlng to the followlng test method .
(1) Operation condltlons Coating method: The above formulated paste solutlon was coated- by using a brush .
Materlals to be adhered: ~Japanese larch finger processed materlal wlth a water content of 8 to 10 %/5 C and a speclflc gravity of 0.53 to 0.57 (thlckness: 20 mm, width: 150 mm, length: 500 mm) 21~108 Shape of finger: Vertlcal finger processed material with a length of 18 mm and a pitch of 5 . 5 mm Coating amount: 400 g/m2 Assembly: 5 C, 5 min.
Pressing: 80 kg/cm2.
Cure: 5 C, 1 hour, 3 hours, 24 hours.
(2) Test method Based on Japanese Agricultural and Forestry Standard of a laminated lumber for structure with a large section, a bending test of a longitudinal seam wood was carried out.
The results are shoNn in Table 2.
Tab le 2 No. Example 4 Comparative example Bending Cure time and 1 hr 3 hrs 24 hrs 1 hr 3 hrs 24 hrs test t~ 5 C 5 C 5 C 5 C 5 C 5 C
Average bending 261 430 530 151 186 313 strength (ks/cm2~
According to the present invention, the adhesive has rapid curing rate, and shows particularly excellent curability under a low temperature and exhibits excellent adhesion power. Thus, even when it is used in a winter season with a low temperature, it can be cured within a -- 19 -- ~
2~10~
short time to exhibit excellent adhesive properties, whereby a pressing time can be shortened and releasing the pressure can be effected within a short time. Further, productivities using a resorclnol resin adhesive can be improved. Therefore, it can be provided an adhesive particularly avallable for the uses of panel bonding such as a plywood and a ~ umber, or a squarebar, etc . which is required to improve productivity, rub-out of LVLs for structure, and wood bonding such as lohgitudinal seam of woods for structure.
As a resorcinol resin adhesive for wood bonding, there has heretofore been provided, in general, a mixed material (a paste solution) comprising a resorcinol resin, a curing agent such as paraformaldehyde and a filler such as a coconut shell flour.
However, in the said resorcinol resin adhesive, curing of the paste solu~ion becomes slow when an atmospheric temperature and a temperature of a material to be adhered are low during a winter season, and at a temperature lower than a normal temperature, sufficient adhesive property cannot be obtained. Also, at the normal temperature of 20 to 25 C, it is necessary to cure the paste solution for a long time of 8 to 24 hours.
21~2108 Since the resorclnol resin adhesive has such a drawback, it is required to install a temperature maintaining device as a preparation equipment or to effect long time pressing of 8 to 48 hours as adhesion conditions.
From such a drawback of the resorcinol resin adhesive, an adhesion process o:E a laminated lumber for structure generally employed is a process in which lumbers are laminated after coating an adhesive to the lumbers, pressed by a turnbuckle, etc., placed in a thermostat chamber at 30 to 50 C for 8 to 48 hours to cure the adhesive, and then subjected to releasing pressure and curing. Since such procedures are required, productivity using the resorcinol resln adhesive is extremely bad.
Moreover, in Japanese Patent Publications No. HEI-5-2715/1993 and No. HEI-4-17139/1992, there is disclosed a method for adhering wood materials by coating a resin component comprising a resorcinol resin or a resorcinol phenol resln and a curing agent separately on the respective surfaces of the materials to be bonded and then laminating these materials.
S~MMAR~ ~F 'rll~. INVF N~ION
An object of the present invention is to overcome the problems possessed ~y the prior art techniques as mentioned 2~$2108 above and to provide a resorcinol resin adhesive having rapid curing speed and good adhesive power at a low temperature whereby improving productivity when using the same .
The present invention relates to a resorcinol resin adhesive composition comprising a resorcinol resin modified by m-aminophenol.
The present invention also relates to a method of adhesion using a resorcinol resin adhesive composition comprising a resorcinol resin modified by m-aminophenol, which comprises coating the resorcinol resin adhesive and a curing agent component to the materials to be adhered separately by a two-liquid separately coating method, and adhering these materials.
DESCRTPTION OE TT~. PRF:~ERR~.n EMBODTMF.N~S
The resorcinol resin adhesive composition comprising a resorcinol resin modified by m-aminophenol to be used in the present invention is a resorcinol resin using m-aminophenol as a modifier, and may include, for example, a resorcinol - formaldehyde resin such as a resorcinol m-aminophenol formaldehyde co-condensed resin obtained by the reaction of resorcinol, m-aminophenol and formaldehyde, and a resorcinol-phenol m-aminophenol-formaldehyde co-condensed f 21521~8 resin obtained by the reaction of resorcinol, phenol, m-amlnophenol and formaldehyde; and a resorcinoL-formaldehyde resin part of the above resins is modified by cresol, xylenol, tannin or lignin.
The molar ratio of formaldehyde to reso~cinol and m-aminophenol at the reaction when the above resorcinol-m-aminophenol formaldehyde co-condensed resin is to be obtained, and the molar ratio of formaldehyde to resorcinol, m-aminophenol and phenol at the reaction when the above ~.
resorcinol-phenol-m-aminophenol-formaldehyde co-condensed resin is to be obtained is desirably 0.9 to 0.8 mole of formaldehyde per mole of the latter mixture.
Also, the pH at the synthetic reaction is preferably adjusted to in the range of 6 to 11 by using an alkali catalyst such as NaOH.
The content of the m-aminophenol in the resorcinol resin modified by the m-2minophenol is preferably 1 to 20 parts by weight based on 100 parts of the total resin. If it is less than 1 part by weight, a curing accelerating effect of the resorcinol resin becomes insufficient, during 1 to 20 parts by weight, curing becomes rapid and if it exceeds 20 parts by weight, the curing accelerating effect is saturated and it is not economical.
_ 5 _ 21~
Accordingly, the content of the resorcinol in the resorclnol resin modified by the m-aminophenol is preferably 15 to 30 parts by weight on 100 parts of the total resin by the some reason as above.
The resorcinol resin adhesive composition of the present invention can be obtained by adding a curing agent to the above m-aminophenol-modified resorcinol resin.
In the resorcinol resin adhesive composition of the present invention, by adding a curing agent to a resin composition in which the m-aminophenol formaldehyde resin or the m-aminophenol phenol formaldehyde resin and, the resorcinol - formaldehyde resin or the resorcinol phenol formaldehyde resin are blended, the resorcinol resin adhesive composition comprising the m-aminophenol-modified resorcinol resin can be constituted by the reaction of the curing agent.
The resin component in the resorcinol resin adhesive composition of the p-esent invention is preferably within the range of 50 to 70 9~i by weight, the pH of 6 to 11, the viscosity of 2 to 100 poise/25 C (BH type viscometer, 20 rotations ~ .
As the curing agent, there may be used a powdery curing agent such as powdery paraformaldehyde and powdery 215210~
hexamethylenetetramine; and a liquid curing agent in which powdery paraformaldehyde or a formalin aqueous solution is blended with water, a phenol resin or a dispersion such as a synthetic rubber type emulsion.
By adding the curing agent, the resin composition can be cured within a short time. Incidentally, when 10 parts by weight of paraformaldehyde as a curing agent is added to 100 parts by weight of the above adhesive resin, the composition gelled within 30 second to 10 minutes/25 C.
Accordingly, it is re~ n-'~d to use the method in which the adhesive resin and the curing agent are separately coated in view of the usable time. For example, there may be preferably employed the method in which the adhesive is coated on one surface while the liquid curing agent is coated on the other surface and the both coated surfaces (the surfaces to be adhered) are faced to each other to blend the both components, and the method in which the adhec7ive and the liquid curing agent are individually sprayed to the coating surfaces (the surfaces to be adhered) of materials to be adhered such as a wood board and blended them on the coated surfaces thereof. Particularly when blend is carried out on the surfaces, the two liquid separately coating method in which the resin component and 2l~2lD8 the curing agent component are separately coated as mentioned above is preferably employed. When the curing agent is added to one or both of the resin to be blended without using the two liquid separately coating method, the usable time is markedly limited.
To the above adhesive composition, a filler such as coconut shell flour, walnut shell flour, wood flour, wheat flour, soy bean flour, calc$um carbonate, zeolite and clay may be formulated.
Also, a rubber type emulsion such as SBR
(styrene-butadiene rubber) and NBR (nitrile-butadiene rubber), and an aqueous polymer thickener such as a polyvinyl alcohol, methyl cellulose, polyethylene oxide, carboxymethyl cellulose and alginic acld may be formulated.
Further, an alcohol such as ethanol, methanol and ethylene glycol may be formlllated.
EXA~PT F s Next, the present invention will be explained by referring to Examples.
F.Xi le 1 In a three-necked flask equipped with a reflux condenser and a stirrer were charged 280 g of formalin (37%), 1~0 g of pherlol and 100 g of water, and after -; :
2l~2la8 ad ~usting the pH to 9 . 8 to 10 . 4 with NaOH, the mixture was reacted at 80 C for one hour. Then, to the mixture were added 330 g of resorcinol and 50 g of m-aminophenol, and the mixture was reacted at 90 to 100 C for 3 hours to obtain a resorcinol-phenol m-aminophenol formaldehyde co-condensed res in .
With 100 parts by weight of the resulting resin was mixed 50 parts by weight of a liquld curing agent (D-100, trade name, avallable from Oshika Shinko Co . T td, a curing agent for a resorcinol resin containing 30% formaldehyde) and a gel time thereof was measured to give the result of 40 sec/25 C. The viscosity was 10 poise/25 C.
Then, under the following operation conditions, adhesion of laminated lumbers was carried out and adhesion characteristics of the resulting material were measured according to the following test method.
(1~ Operation conditions Coating method: The above resorcinol phenol m-aminophenol formaldehyde co-condensed resin was coated on one surface of a Western hemlock lumber and the above liquid curing agent was coated on one surface of ==
another Western hemlock lumber, and the both coated surfaces were laminated.
_ g _ 21~21~8 Materials to be adhered: Western hemlock lumber with a thickness of 30 mm, water content of 8 to 10 %/5 C
Constitution: Two sheets of Western hemlock lumbers were laminated.
Coating amount: 200 g/m2 of the resin component and 100 g/m2 of the liquid curing agent.
Pressing: 2 hours, 5 C, 10 kg/cm2.
(2) Test method sased on Japanese Agricultural and Forestry Standard of a laminated lumber for structure, a block shear test, a dipping peel test and a boiling peel test were carried out.
The results are shown in Table 1.
F~tA~rle 2 In a three-necked flask equipped with a reflux condenser and a stirrer were charged 230 g of formalin ~37%), 130 g of m-aminophenol, 200 g of methanol and 130 g of water, and after adjusting the pH to 9 . O with NaOI~, the mixture was reacted at 80 C for one hour. Then, to the mixture was added dropwise 160 g of formalin (37%) over one hour, and the mixture was further reacted at 80 to 85 C for 3 hours to obtain a ~n-aminophenol formaldehyde resin .
20 parts by weight of the resulting resin was blended with 80 parts by weight of a resorcinol-phenol-formaldehyde 21~2108 co-condensed resln. ~Oshika resin D-300, trade name, available from Oshlka Shinko Co. Ltd., ) .
To 100 parts by weight of the blended resin was added 50 parts by weight of the liquid curing agent used in Example 1, and a gel time thereof was measured to give the result of 70 sec/25 C. The viscosity was 60 poise/25 C.
In the same manner as in Example 1, adhesion of lumbers was carried out by coating the blended resin on one surface of a Western hemlock lumber and coating the liquid curing agent on one surface of another Western hemlock lumber, and laminating the both coated surfaces thereof. Adhesion characteristics were measured according to the same test-methods as in Example 1.
The results are shown in ~able 1.
Example 3 In the same manner as in Example 2 except for using 50 parts by weight of the m-aminophenol formaldehyde resin and 50 parts by weight of the resorcinol phenol formaldehyde co-condensed resin, a blend resin was prepared. To 100 parts by weight of the blend resin was blended 50 parts by weight of the liquid curing agent used in Example 1, and a gel time thereof was measured to give the result of 40 sec/25 C. The viscosity was 40 po.se/25 C.
2~S~1~8 In the same manner ~s in Example 1, adhesion of lumbers was carried out by coating the blended resin on one surface of a Western hemlock lumber and coating the liquid curing agent on one surface of another Western hemlock lumber, and laminating the both coated surfaces thereof. Adhesion characteristics were measured according to the same test methods as in Example 1.
The results are shown in Table 1 C .2, rative F'X le 1 As a resorcinol resin, the resorcinol formaldehyde resin (Deernol No 50, trade name, available from Oshika Shinko Co. Ltd., ) having the following characteristics was us ed .
Resin characteristics Viscosity; 5 poise/25 C
l~esin component; 65 ~
Gel time; 120 min/25 C (in the case of the resin/-paraformaldehyde = 100/10 parts by weight) With 100 parts by weight of the above resorcinol formaldehyde resin were blended 10 parts by weight of paraformaldehyde and 5 parts by weight of wood flour to obtain a formulated paste solution having a viscosity of 22 poise/25 C
Then, under the following operation conditions, adhesion of lumbers for lamination was carried out and adheslon characteristics of the resulting laminated lumber were measured according to the same test method as in Example 1.
~1) Operation conditions Coating method: The above formulated paste solution was coated on one surface of a Western hemlock lumber and another Western hemlock lumber was laminated thereon .
Materials to be adhered: Western hemlock lumber with a thickness of 30 mm, water content of 8 to 10 %/5 C
Constitution: Two sheets of Western hemlock lumbers were laminated.
Coating amount: 300 g/m2, one surface coating.
Pressing: 2 hours, 5 C, 10 kg/cm2.
C~ rat i ve ~ le 2 As a resorcinol resin, the resorcinol-phenol-formaldehyde resin (Deernol No. 35, trade name, available from Oshika Shinko Co. Ltd., ) having the following characteristics was used.
~esin characteristics Viscosity; 4 poise/25 C
21~210~
Resin component; 60 %
Gel time; 100 min/25 C (in the case of the resin/-paraformaldehyde = 100/10 parts by weight) With 100 parts by weight of the above resorcinol-phenol-formaldehyde resin were blended 10 parts by weight of para~ormaldehyde and 5 parts by weight of wood flour to obtain a formulated paste solution having a viscosity of 2C poise~25 C.
Then, in the same manner as in Comparative example 1, adhesion of lumbers for lamination was carried out and adhesion characteristics of the resulting laminated lumber were measured according to the same test method as in Example l.
The results are shown in Table 1.
C, ~ rat ive ~ le 3 As a resorcinol resin, the resorcinol-phenol-formaldehyde resin (Deernol No. 300, trade name, available from Oshika Shinko Co. [Jtd., ) having the following characteristics was used.
Res in characteristics ViscosLty; 70 poise/25 C
Resin compon~nt; 65 %
Gel time; 70 min/25 C (in the case of the resin/-21~2108 paraformaldehyde = 100/10 parts by weight) With 100 parts by weight of the aboveresorcinol phenol formaldehyde resin was blended lO parts by weight of paraformaldehyde to obtain a formulated paste solution having a viscosity of 80 poise/2S ' C .
Then, in the same manner as in Comparative example 1, adhesion of lumbers for lamination was carried out and adhesion characteristics of the resulting laminated lumber were measured according to the same test method as in Example 1.
~ he results are shown in Table 1.
~able 1 ~o. Example Comparative example Adhesion Pressing l 2 3 1 2 3 strength time and 2 hr 2 hr 2 hr 2 hr 2 hr 2 hr test t~ , ' e 5 C 5 ' C 5 C 5 ' C 5 C 5 C
Average adhesion lOl 95 103 0 0 0 Block strength shear ( kgf /cm2 ) test Average wcod ~normal) portion 86 83 92 0 0 0 breakage rate (%) I~ipping peel test Pass Pass Pass Failure Failure Failure 21~2108 .
¦Boiling peel test ¦¦ Pass ¦ Pass ¦ Pass ¦Failure¦Failure¦Failure¦
r le ~
By using 100 parts by weight of the resorcinol phenol m-aminophenol- formaldehyde co-condensed resln obtained ln Example l and 50 parts by welght of the llquid curing agent (D-100, trade name, available from Oshika Shinko Co. Ltd., ) used in Example l, to obtain compounded paste, finger bonding of longitudinally seamed woods was carried out under the following operation condltions. Adhesion characteristics of the bonded portion were measured according to the following test method.
~l) Operation conditions Coating method: The resin was coated on one surface of a finger portion and the liquid curing agent was coated on one surface of another finger portion (separately coating system), and coating was carried out by using a brush .
Materials to be adhered: Japanese larch flnger processed material with a water content of 8 to 10 %/5 C and a speciflc gravity of 0.53 to 0.57 (thickness: 20 mm, width: 150 mm, length: 500 mm) Shape of finger: Vertical flnger processed material with a length of 18 mm and a pitch of 5 . 5 mm Coating amount: ~00 g/m2 (resin: 267 g/m2, liquid 21~21~8 curing agent: 133 g/m2) Assembly: 5 C, 5 min.
Pressing: 80 kg/cm2.
Cure: S C, 1 hour, 3 hours, 24 hours.
~2 ) Test method Based on 2apanese Agricultural and Forestry Standard of a lamlnated lumber for structure wlth a large section, a bendlng test of a longltudlnal seam wood was carrled out.
The results are shown ln Table 2.
C~ aratlve ~- le 4 By uslng the formulated paste solutlon obtained ln Comparatlve example 2, flnger bonding of longitudlnally seamed woods was carrled out under the following operatlon conditions, and adhesion characterlstlcs of the bonded portlon were measured accordlng to the followlng test method .
(1) Operation condltlons Coating method: The above formulated paste solutlon was coated- by using a brush .
Materlals to be adhered: ~Japanese larch finger processed materlal wlth a water content of 8 to 10 %/5 C and a speclflc gravity of 0.53 to 0.57 (thlckness: 20 mm, width: 150 mm, length: 500 mm) 21~108 Shape of finger: Vertlcal finger processed material with a length of 18 mm and a pitch of 5 . 5 mm Coating amount: 400 g/m2 Assembly: 5 C, 5 min.
Pressing: 80 kg/cm2.
Cure: 5 C, 1 hour, 3 hours, 24 hours.
(2) Test method Based on Japanese Agricultural and Forestry Standard of a laminated lumber for structure with a large section, a bending test of a longitudinal seam wood was carried out.
The results are shoNn in Table 2.
Tab le 2 No. Example 4 Comparative example Bending Cure time and 1 hr 3 hrs 24 hrs 1 hr 3 hrs 24 hrs test t~ 5 C 5 C 5 C 5 C 5 C 5 C
Average bending 261 430 530 151 186 313 strength (ks/cm2~
According to the present invention, the adhesive has rapid curing rate, and shows particularly excellent curability under a low temperature and exhibits excellent adhesion power. Thus, even when it is used in a winter season with a low temperature, it can be cured within a -- 19 -- ~
2~10~
short time to exhibit excellent adhesive properties, whereby a pressing time can be shortened and releasing the pressure can be effected within a short time. Further, productivities using a resorclnol resin adhesive can be improved. Therefore, it can be provided an adhesive particularly avallable for the uses of panel bonding such as a plywood and a ~ umber, or a squarebar, etc . which is required to improve productivity, rub-out of LVLs for structure, and wood bonding such as lohgitudinal seam of woods for structure.
Claims (10)
1. A resorcinol resin adhesive composition comprising a resorcinolm-aminophenolformaldehyde co-condensed resin obtained by the reaction of resorcinol,m-aminophenol and formaldehyde.
2. A resorcinol resin adhesive composition comprising a resorcinolphenolm-aminophenolformaldehyde co-condensed resin obtained by the reaction of resorcinol,phenol,m-aminophenol and formaldehyde.
3. A resorcinol resin adhesive composition according to claim 1 wherein a resorcinolm-aminophenolformaldehyde co -condensed resin portion is modified by a member selected from a group consisting of cresol,xylenol,tannin and lignin.
4. A resorcinol resin adhesive composition according to claim 2 wherein a resorcinolphenolm-aminophenolformaldehyde co-condensed resin portion is modified by a member selected from a group consisting of cresol, xylenol, tannin and lignin.
5. A resorcinol resin adhesive composition according to claim 1 further including a curing agent.
6. A resorcinol resin adhesive composition according to claim 2 further including a curing agent.
7. A method of using the resorcinol resin adhesive composition according to claim 1 comprising bonding only wood material with said resorcinol resin adhesive composition.
8. A method of using the resorcinol resin adhesive composition according to claim 2 comprising bonding only wood material with said resorcinol resin adhesive composition.
9. A method of using the resorcinol resin adhesive composition according to claim 7 wherein said bonding comprises finger bonding of longitudinally seemed wood.
10. A method of using the resorcinol resin adhesive composition according to claim 8 wherein said bonding comprises finger bonding of longitudinally seemed wood.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA002152108A CA2152108A1 (en) | 1995-06-19 | 1995-06-19 | Resorcinol resin adhesive composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA002152108A CA2152108A1 (en) | 1995-06-19 | 1995-06-19 | Resorcinol resin adhesive composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2152108A1 true CA2152108A1 (en) | 1996-12-20 |
Family
ID=4156073
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002152108A Abandoned CA2152108A1 (en) | 1995-06-19 | 1995-06-19 | Resorcinol resin adhesive composition |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA2152108A1 (en) |
-
1995
- 1995-06-19 CA CA002152108A patent/CA2152108A1/en not_active Abandoned
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