CA2129936C - Thermosetting bonding agents - Google Patents
Thermosetting bonding agents Download PDFInfo
- Publication number
- CA2129936C CA2129936C CA002129936A CA2129936A CA2129936C CA 2129936 C CA2129936 C CA 2129936C CA 002129936 A CA002129936 A CA 002129936A CA 2129936 A CA2129936 A CA 2129936A CA 2129936 C CA2129936 C CA 2129936C
- Authority
- CA
- Canada
- Prior art keywords
- bonding agent
- tannin
- heated
- substance
- hexamethylenetetramine
- 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.)
- Expired - Fee Related
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08H—DERIVATIVES OF NATURAL MACROMOLECULAR COMPOUNDS
- C08H99/00—Subject matter not provided for in other groups of this subclass, e.g. flours, kernels
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G14/00—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G16/00—Condensation polymers of aldehydes or ketones with monomers not provided for in the groups C08G4/00 - C08G14/00
- C08G16/02—Condensation polymers of aldehydes or ketones with monomers not provided for in the groups C08G4/00 - C08G14/00 of aldehydes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
- C08G8/04—Condensation polymers of aldehydes or ketones with phenols only of aldehydes
- C08G8/08—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ
- C08G8/20—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ with polyhydric phenols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L97/00—Compositions of lignin-containing materials
- C08L97/02—Lignocellulosic material, e.g. wood, straw or bagasse
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
- C08L61/04—Condensation polymers of aldehydes or ketones with phenols only
Abstract
Thermosetting bonding agents for products that contain cellulose contain tannin and a substance that releases formaldehyde when heated. The working materials produced with them display good strength and low swell values after storage in water.
Description
21.~~93f The present invention relates to bonding agents that can be hardened when heated, that are compatible with wood and other products that contain cellulose, and which axe suitable, in particular, for manufacturing wood materials, s such as, for example, chipboard.
In the course of the search for natural and, in particular, for renewable resources for manufacturing bonding agents for wood materials, it has also been found that tannins can be io used (J. Macromol. SCI.-Chem. A 16 (7), 1243-1250 (1981).
Despite good availability, they have not been widely used because the tensile strength of wood materials that are bonded with tannin is not satisfactory, particularly after i5 such products have been stored in water.
For this reason, it is an object of the present invention to describe a bonding agent that is based on tannin, with which wood materials having significantly improved mechanical 2o properties can be manufactured.
It has been found that tannins that contain units of the general structure R
- O
O
O-O-21.29936 wherein R represents hydrogen or a hydroxy group and the free bonds at the oxygen radicals are either saturated with hydrogen or are bonds to other molecular groups such as sugar radicals or radicals of other or identical polyvalent compounds with phenolic hydroxyl groups, display a bonding capability that is superior in comparison to other tannins if they are used together with a material that liberates formaldehyde when heated and are used as a bonding agent for products that contain cellulose. Tensile strength increases 1o and achieves values as are found, for example, in the case of corresponding materials that are bonded with phenol resin. The reduction of transverse tensile strength aftex storage in water is clearly reduced, and swelling values in boiling water are similarly reduced.
In this regard, it is an added advantage that these tannins can be used without prior breakdown treatment as is known in the case of other tannins.
2o Suitable tannins are those from the group of procyanidines and prodelphinidines, in particular tannin from pine bark or from the pecan nut. Although mixtures of these tannins with, for example, minosa or quebracho tannin in the ratio of 2:5 to 5:2 have a longer hardening time, they cannot, 2s however, be used. These tannins are commercially available products and up to now have been used mainly as tanning agents. Commercial quality is adequate for use as foreseen in the present invention.
In the course of the search for natural and, in particular, for renewable resources for manufacturing bonding agents for wood materials, it has also been found that tannins can be io used (J. Macromol. SCI.-Chem. A 16 (7), 1243-1250 (1981).
Despite good availability, they have not been widely used because the tensile strength of wood materials that are bonded with tannin is not satisfactory, particularly after i5 such products have been stored in water.
For this reason, it is an object of the present invention to describe a bonding agent that is based on tannin, with which wood materials having significantly improved mechanical 2o properties can be manufactured.
It has been found that tannins that contain units of the general structure R
- O
O
O-O-21.29936 wherein R represents hydrogen or a hydroxy group and the free bonds at the oxygen radicals are either saturated with hydrogen or are bonds to other molecular groups such as sugar radicals or radicals of other or identical polyvalent compounds with phenolic hydroxyl groups, display a bonding capability that is superior in comparison to other tannins if they are used together with a material that liberates formaldehyde when heated and are used as a bonding agent for products that contain cellulose. Tensile strength increases 1o and achieves values as are found, for example, in the case of corresponding materials that are bonded with phenol resin. The reduction of transverse tensile strength aftex storage in water is clearly reduced, and swelling values in boiling water are similarly reduced.
In this regard, it is an added advantage that these tannins can be used without prior breakdown treatment as is known in the case of other tannins.
2o Suitable tannins are those from the group of procyanidines and prodelphinidines, in particular tannin from pine bark or from the pecan nut. Although mixtures of these tannins with, for example, minosa or quebracho tannin in the ratio of 2:5 to 5:2 have a longer hardening time, they cannot, 2s however, be used. These tannins are commercially available products and up to now have been used mainly as tanning agents. Commercial quality is adequate for use as foreseen in the present invention.
Substances that liberate formaldehyde when heated are, for example, paraformaldehyde, trioxane and, in particular, hexamethylenetetramine (hexa).
In the simplest case, the thermosetting bonding agents according to the present invention are mixtures of tannin that contains structural units of the formula O-- O
O v O -io and a substance that releases formaldehyde when heated, the proportion of material that releases formaldehyde, in particular hexamethylenetetramine, amounting to 3.0 to 9%-wt, relative to the tannin.
i5 However, it is also within the scope of the present invention if, in addition to the special types of tannin and a substance that releases formaldehyde when heated, the bonding agent also contains up to 50%-wt of a novolak or up to 20%-wt of an isocyanate compound that is at least 2o difunctional, such as, for example, diisocyanatonaphthaline, 4,4,°,4 " -triisocyanato-triphenylmethane, isophoron-, toluol- or hexamethylene- diisocyanate or diisocyanato-diphenylmethane (MDI), when, in practical use, the di- or polyisocyanates are applied to the products that contain 2s cellulose in parallel with the dry mixture of the tannin ;.
;:
that is used according to the present invention and the substance that releases formaldehyde when heated, before these are pressed to form the appropriate materials.
Suitable products that contain cellulose are, for example, wood chips, fibres based on cellulose, such as, for example, cotton or flax, or straw, from which chipboards, textile fleeces, or accoustic and thermal insulating panels are produced.
io The materials are manufactured in such a way that the bonding agents according to the present invention are mixed with products that contain cellulose, the mixture is placed in a mould, and then hardened under pressure at a is temperature that is above the decomposition temperature of the substance that releases the formaldehyde and below the decomposition temperature of the tannin, preferably at 150 to 210°C. Depending on the working material that is used and the thickness that is desixed, the pressure will be in 2o the range from 0.1 to 4 MPa/mm2. Because it is possible, for example, to manufacture three layered chipboards, with a pressure of 2 to 3.5 MPa/mm2.
Depending on the desired material and the desired strength, 25 the quantity of bonding agent will in the range of 4 to 20%-wt, relative to the product that contains the cellulose.
The bonding agent can be in the form of a solid mixture or a~ a solution of the components in water, alcohol, or water-alcohol mixtures.
In the simplest case, the thermosetting bonding agents according to the present invention are mixtures of tannin that contains structural units of the formula O-- O
O v O -io and a substance that releases formaldehyde when heated, the proportion of material that releases formaldehyde, in particular hexamethylenetetramine, amounting to 3.0 to 9%-wt, relative to the tannin.
i5 However, it is also within the scope of the present invention if, in addition to the special types of tannin and a substance that releases formaldehyde when heated, the bonding agent also contains up to 50%-wt of a novolak or up to 20%-wt of an isocyanate compound that is at least 2o difunctional, such as, for example, diisocyanatonaphthaline, 4,4,°,4 " -triisocyanato-triphenylmethane, isophoron-, toluol- or hexamethylene- diisocyanate or diisocyanato-diphenylmethane (MDI), when, in practical use, the di- or polyisocyanates are applied to the products that contain 2s cellulose in parallel with the dry mixture of the tannin ;.
;:
that is used according to the present invention and the substance that releases formaldehyde when heated, before these are pressed to form the appropriate materials.
Suitable products that contain cellulose are, for example, wood chips, fibres based on cellulose, such as, for example, cotton or flax, or straw, from which chipboards, textile fleeces, or accoustic and thermal insulating panels are produced.
io The materials are manufactured in such a way that the bonding agents according to the present invention are mixed with products that contain cellulose, the mixture is placed in a mould, and then hardened under pressure at a is temperature that is above the decomposition temperature of the substance that releases the formaldehyde and below the decomposition temperature of the tannin, preferably at 150 to 210°C. Depending on the working material that is used and the thickness that is desixed, the pressure will be in 2o the range from 0.1 to 4 MPa/mm2. Because it is possible, for example, to manufacture three layered chipboards, with a pressure of 2 to 3.5 MPa/mm2.
Depending on the desired material and the desired strength, 25 the quantity of bonding agent will in the range of 4 to 20%-wt, relative to the product that contains the cellulose.
The bonding agent can be in the form of a solid mixture or a~ a solution of the components in water, alcohol, or water-alcohol mixtures.
'",:>:' . ,-; ,.' 2~.~9~36 Suitable solutions can be stored at room temperature for several weeks without any major increase in viscosity. In the case of aqueous solutions, it is recommended that a fungicide be added in order to prevent the formation of s fungus.
The following examples illustrate the binding agent according to the present invention, as used to manufacture chipboards.
io Example Woodchips are sprayed with a water-alcohol solution that contains bonding agent at the rate of 11%-wt of the wood, is and these are then dried. Subsequently, they are formed in the usual manner (2.5 N/mm2; 195°C) to form panels measuring 400 x 350 x 12 mm, pressed, and hardened.
Density, transverse tensile strength of the panels, a. dry 2o and b. after storage in water (2 hours in boiling water, subsequently dried for 16 hours at 105°C) as well as the swell thickness are determined after 2 hour storage in boiling water, with various mixture proportions of the bonding agent components, the quantity of bonding agent, and 2s the press time.
proportion of pecan nut tannin varies accordingly, from 92.5 to 94.5%.
In Example 2, the proportion of hexamethylenetetramine relative to the tannin, amounts to 6.4%, i.e., the proportion of pecan nut tannin is 93.6%. The press time is varied.
Example 3 shows values for a three-layer chipboard at 6.4%
io hexamethylenetetramine in the bonding agent, and with a bonding agent content of 10% in the inner layers, and 12% in the outer layers.
Examples 4 and 5 show values that axe analogous to Examples is 1 and 2 when mimosa (wattle) tannin is used..
The following tables show the values that were obtained:
t:v ~1~~~~~
TABLES
Example 1 Example 4 s Hexamethylenetetramine (comparison) 7.50 6.40 5.5% 7.50 6.50 Press time io [sec/mm] 17.5 17.5 17.5 17.5 17.5 Density [kg/m3] 729 730 736 731 711 15 Transverse tensile strength, dry [MPa] 0.82 0.81 0.79 0.45 0.43 2o Transverse tensile strength after storage in water [MPa] 0.25 0.27 0.26 0.09 0.07 Swelling [%] 25.0 23.9 22.1 32.1 31.5 HCHO emission 30 [mg/100 g; WKI] 1.71 1.45 0.84 2.01 1.87 23.2~~~6 Example 2 Example 5 (6.4o (comparison) hexa) (6.5% hexa) Press time [sec/mm] 17.5 12.5 8.5 30.0 17.5 12.5 Density io[kg/m3] 730 738 733 714 731 Transverse tensile strength, i dry s [MPa] 0.81 0.75 0.67 0.5 0.45 0.41 Transverse 2otensile strength after storage in water [MPa] 0.27 0.19 0.17 0.13 0.09 0.03 Swelling [%] 23.9 22.4 20.9 29.7 32.1 36.7 3oHCHQ emission [mg/100 g; WKI] 1.45 1.32 1.1 1.64 2.01 1.28 _ g _ y 21 :;336 Example 3 Press time [sec/mm] 12 . 5 Bonding agent [o]
middle-/cover layers 10/I2 ioMoisture - chips after coating [%]
middle-/cover layer 28/26 i5Density [kg/m3] 723 Transverse tensile strength, 2odry [MPa] 0 . 03 Transverse tensile strength 25after storage in water [MPa] 0 . 2 7 Swelling 30[%] 22.1 HCHO emission [mg/100 g; WKI] 1.4 - 21.~9~36 Examx>le 6 Single layer chipboards were produced and tested according to the general description for the examples (press time 15 s/mm at 190°C, 2.5 N/mm2) .
Bonding agent:
Tannin from pine bark io (37% aqueous solution) 337 parts by weight .
Hexamethylenetetramine (40% aqueous solution) 19.3 parts by weight Zinc acetate (25% aqueous solution) 19.3 parts by weight 1s Water 10 parts by weight Results:
Density (kg/m3) : 708 2o Transverse tensile strength, dry (MPa): 0.23 Transverse tensile strength after storage in water (MPa) : 0.1 HCHO emission (mg/100 g): 0.1 25 Examt~le 7 Three-layer chipboards were produced and tested according to the general description of the examples (press time 15 s/mm at 190°C; 2.5 N/mm2).
,. : . : . . , , ; ~ .. , .. : :; ;.
-. v , ; . . , . ::
, ~ ' ~, ~
~ .
. .,', v , !'; . ,,. ~
- ' . ; ; . ' '. i,~:
, . ~,,,.:.,~ . f ~~..i~~'~~~
Bonding agent: Core layers Outer layers Tannin from pine bark s (37% aqueous solution) 327 327 parts by weight Hexamethylenetetramine (40% aqueous solution) 19.5 19.5 parts by weight Zinc acetate (25% aqueous solution) 24.0 19.5 parts by weight ao Water 12 -- parts by weight Results:
Density (kg/m3) : 723 15 Transverse tensile strength, dry (MPa): 0.80 Transverse tensile strength after storage in water (MPa): 0.29 HCHO emission (mg/100 g): 0.16
The following examples illustrate the binding agent according to the present invention, as used to manufacture chipboards.
io Example Woodchips are sprayed with a water-alcohol solution that contains bonding agent at the rate of 11%-wt of the wood, is and these are then dried. Subsequently, they are formed in the usual manner (2.5 N/mm2; 195°C) to form panels measuring 400 x 350 x 12 mm, pressed, and hardened.
Density, transverse tensile strength of the panels, a. dry 2o and b. after storage in water (2 hours in boiling water, subsequently dried for 16 hours at 105°C) as well as the swell thickness are determined after 2 hour storage in boiling water, with various mixture proportions of the bonding agent components, the quantity of bonding agent, and 2s the press time.
proportion of pecan nut tannin varies accordingly, from 92.5 to 94.5%.
In Example 2, the proportion of hexamethylenetetramine relative to the tannin, amounts to 6.4%, i.e., the proportion of pecan nut tannin is 93.6%. The press time is varied.
Example 3 shows values for a three-layer chipboard at 6.4%
io hexamethylenetetramine in the bonding agent, and with a bonding agent content of 10% in the inner layers, and 12% in the outer layers.
Examples 4 and 5 show values that axe analogous to Examples is 1 and 2 when mimosa (wattle) tannin is used..
The following tables show the values that were obtained:
t:v ~1~~~~~
TABLES
Example 1 Example 4 s Hexamethylenetetramine (comparison) 7.50 6.40 5.5% 7.50 6.50 Press time io [sec/mm] 17.5 17.5 17.5 17.5 17.5 Density [kg/m3] 729 730 736 731 711 15 Transverse tensile strength, dry [MPa] 0.82 0.81 0.79 0.45 0.43 2o Transverse tensile strength after storage in water [MPa] 0.25 0.27 0.26 0.09 0.07 Swelling [%] 25.0 23.9 22.1 32.1 31.5 HCHO emission 30 [mg/100 g; WKI] 1.71 1.45 0.84 2.01 1.87 23.2~~~6 Example 2 Example 5 (6.4o (comparison) hexa) (6.5% hexa) Press time [sec/mm] 17.5 12.5 8.5 30.0 17.5 12.5 Density io[kg/m3] 730 738 733 714 731 Transverse tensile strength, i dry s [MPa] 0.81 0.75 0.67 0.5 0.45 0.41 Transverse 2otensile strength after storage in water [MPa] 0.27 0.19 0.17 0.13 0.09 0.03 Swelling [%] 23.9 22.4 20.9 29.7 32.1 36.7 3oHCHQ emission [mg/100 g; WKI] 1.45 1.32 1.1 1.64 2.01 1.28 _ g _ y 21 :;336 Example 3 Press time [sec/mm] 12 . 5 Bonding agent [o]
middle-/cover layers 10/I2 ioMoisture - chips after coating [%]
middle-/cover layer 28/26 i5Density [kg/m3] 723 Transverse tensile strength, 2odry [MPa] 0 . 03 Transverse tensile strength 25after storage in water [MPa] 0 . 2 7 Swelling 30[%] 22.1 HCHO emission [mg/100 g; WKI] 1.4 - 21.~9~36 Examx>le 6 Single layer chipboards were produced and tested according to the general description for the examples (press time 15 s/mm at 190°C, 2.5 N/mm2) .
Bonding agent:
Tannin from pine bark io (37% aqueous solution) 337 parts by weight .
Hexamethylenetetramine (40% aqueous solution) 19.3 parts by weight Zinc acetate (25% aqueous solution) 19.3 parts by weight 1s Water 10 parts by weight Results:
Density (kg/m3) : 708 2o Transverse tensile strength, dry (MPa): 0.23 Transverse tensile strength after storage in water (MPa) : 0.1 HCHO emission (mg/100 g): 0.1 25 Examt~le 7 Three-layer chipboards were produced and tested according to the general description of the examples (press time 15 s/mm at 190°C; 2.5 N/mm2).
,. : . : . . , , ; ~ .. , .. : :; ;.
-. v , ; . . , . ::
, ~ ' ~, ~
~ .
. .,', v , !'; . ,,. ~
- ' . ; ; . ' '. i,~:
, . ~,,,.:.,~ . f ~~..i~~'~~~
Bonding agent: Core layers Outer layers Tannin from pine bark s (37% aqueous solution) 327 327 parts by weight Hexamethylenetetramine (40% aqueous solution) 19.5 19.5 parts by weight Zinc acetate (25% aqueous solution) 24.0 19.5 parts by weight ao Water 12 -- parts by weight Results:
Density (kg/m3) : 723 15 Transverse tensile strength, dry (MPa): 0.80 Transverse tensile strength after storage in water (MPa): 0.29 HCHO emission (mg/100 g): 0.16
Claims (10)
1. A thermosetting bonding agent for products containing cellulose based on tannin, said bonding agent containing tannin and a substance that releases formaldehyde when heated, the tanning containing units being of the general structure wherein R stands for hydrogen or a hydroxyl group and the free bonds at the oxygen radicals are saturated with hydrogen.
2. A thermosetting bonding agent for products containing cellulose based on tannin, said bonding agent containing tannin and a substance that releases formaldehyde when heated, the tanning containing units being of the general structure wherein R stands for hydrogen or a hydroxyl group and the free bonds at the oxygen radicals are bonds to other molecular groups.
3. The bonding agent as claimed in claim 1 or 2, wherein the tannin is from the pecan nut or from pine bark.
4. The bonding agent as claimed in claim 1, 2 or 3, wherein the substance that releases formaldehyde when heated is hexamethylenetetramine.
5. The bonding agent as claimed in claim 4, wherein the proportion of hexamethylenetetramine amounts to 3.0 to 9%-wt, relative to the tannin.
6. The bonding agent as claimed in any one of claims 1 through 5, containing up to 50%-wt of a novolak.
7. The bonding agent as claimed in any one of claims 1 through 6, containing up to 20%-wt of an isocyanate compound that is at least difunctional.
8. A method of manufacturing working materials, comprising mixing a bonding agent as defined in any one of claims 1 through 7 with product containing cellulose, placing the mixture in a mould, and processing the mixture in the mould at a temperature in the range from 150°C to 210°C and at a pressure in the range of 0.1 to 4 MPa/mm2.
9. The method as claimed in claim 8, wherein the bonding agent is mixed in the form of powder with the wood chips.
10. The method as claimed in claim 8, wherein the bonding agent is sprayed onto the wood chips in the form of a solution.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4328220 | 1993-08-21 | ||
| DEP4328220.2 | 1993-08-21 | ||
| DE4402159A DE4402159A1 (en) | 1993-08-21 | 1994-01-26 | Thermosetting binders |
| DEP4402159.3 | 1994-01-26 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2129936A1 CA2129936A1 (en) | 1995-02-22 |
| CA2129936C true CA2129936C (en) | 2000-08-15 |
Family
ID=25928829
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002129936A Expired - Fee Related CA2129936C (en) | 1993-08-21 | 1994-08-11 | Thermosetting bonding agents |
Country Status (15)
| Country | Link |
|---|---|
| EP (1) | EP0639608B1 (en) |
| AT (1) | ATE170892T1 (en) |
| AU (1) | AU670702B2 (en) |
| BR (1) | BR9403283A (en) |
| CA (1) | CA2129936C (en) |
| CZ (1) | CZ9402006A3 (en) |
| DE (2) | DE4402159A1 (en) |
| ES (1) | ES2068171T3 (en) |
| FI (1) | FI943836A (en) |
| GR (1) | GR950300015T1 (en) |
| HU (1) | HUT71636A (en) |
| NO (1) | NO943068L (en) |
| NZ (1) | NZ264187A (en) |
| SI (1) | SI9400325A (en) |
| SK (1) | SK99094A3 (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4402341C2 (en) * | 1994-01-27 | 2000-11-02 | Bakelite Ag | Binder solutions for cellulosic products |
| DE4447711C2 (en) * | 1994-01-27 | 2000-08-03 | Bakelite Ag | Heat-curable binders for cellulose-based prods., e.g. chipboard |
| DE59700001D1 (en) * | 1996-02-09 | 1998-06-25 | Schlingmann Gmbh & Co | Process for the production of low-formaldehyde tannin-bound chipboard and fiberboard |
| US5858553A (en) * | 1997-04-02 | 1999-01-12 | Angus Chemical Company | Oxazolidine-based hardeners for the room temperature cure of resorcinol resins in the bonding of wood articles |
| US5912317A (en) * | 1997-04-02 | 1999-06-15 | Angus Chemical Company | Oxazolidine-based hardeners for the room temperature cure of resorcinol resins in the bonding of wood articles--II |
| DE19733925A1 (en) * | 1997-08-06 | 1999-02-11 | Bakelite Ag | Binder composition, its use and a process for the production of particle board |
| FR2952937B1 (en) | 2009-11-20 | 2013-02-08 | Chaire Europeenne De Chimie Now Pour Un Developpement Durable | NOVEL PHENOPLAST RESINS OBTAINED FROM PHENOLIC COMPOUNDS AND MACROMOLECULAR HARDENERS WITH ALDEHYDE FUNCTIONS |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1225571A (en) * | 1968-02-27 | 1971-03-17 | ||
| US4098765A (en) * | 1977-05-02 | 1978-07-04 | Kays Stanley J | Pecan nut by-products and processes |
| US4201699A (en) * | 1977-07-12 | 1980-05-06 | Chen Chia Ming | Phenol-aldehyde resin composition containing pecan pith extract and an aldehyde |
| DE69113808T2 (en) * | 1990-12-14 | 1996-04-18 | Diteco Ltda | Adhesive composition consisting of isocyanate, phenol formaldehyde and tannin for the production of plywood panels for outdoor use. |
| DE9209289U1 (en) * | 1992-07-10 | 1992-08-20 | Fraunhofer-Gesellschaft Zur Foerderung Der Angewandten Forschung Ev, 8000 Muenchen, De |
-
1994
- 1994-01-26 DE DE4402159A patent/DE4402159A1/en not_active Withdrawn
- 1994-06-16 ES ES94109251T patent/ES2068171T3/en not_active Expired - Lifetime
- 1994-06-16 AT AT94109251T patent/ATE170892T1/en not_active IP Right Cessation
- 1994-06-16 EP EP94109251A patent/EP0639608B1/en not_active Expired - Lifetime
- 1994-06-16 DE DE59406873T patent/DE59406873D1/en not_active Expired - Fee Related
- 1994-08-05 NZ NZ264187A patent/NZ264187A/en unknown
- 1994-08-11 CA CA002129936A patent/CA2129936C/en not_active Expired - Fee Related
- 1994-08-19 FI FI943836A patent/FI943836A/en unknown
- 1994-08-19 BR BR9403283A patent/BR9403283A/en not_active Application Discontinuation
- 1994-08-19 NO NO943068A patent/NO943068L/en unknown
- 1994-08-19 CZ CZ942006A patent/CZ9402006A3/en unknown
- 1994-08-19 AU AU70366/94A patent/AU670702B2/en not_active Ceased
- 1994-08-19 HU HU9402410A patent/HUT71636A/en unknown
- 1994-08-19 SI SI9400325A patent/SI9400325A/en unknown
- 1994-08-19 SK SK990-94A patent/SK99094A3/en unknown
-
1995
- 1995-04-30 GR GR950300015T patent/GR950300015T1/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| BR9403283A (en) | 1995-04-11 |
| HUT71636A (en) | 1996-01-29 |
| EP0639608B1 (en) | 1998-09-09 |
| NO943068D0 (en) | 1994-08-19 |
| FI943836A0 (en) | 1994-08-19 |
| NO943068L (en) | 1995-02-22 |
| AU7036694A (en) | 1995-03-02 |
| SI9400325A (en) | 1995-02-28 |
| ATE170892T1 (en) | 1998-09-15 |
| ES2068171T1 (en) | 1995-04-16 |
| MX9405910A (en) | 1997-10-31 |
| NZ264187A (en) | 1995-05-26 |
| DE4402159A1 (en) | 1995-02-23 |
| CZ9402006A3 (en) | 1995-03-15 |
| ES2068171T3 (en) | 1998-11-16 |
| DE59406873D1 (en) | 1998-10-15 |
| SK99094A3 (en) | 1995-04-12 |
| CA2129936A1 (en) | 1995-02-22 |
| FI943836A (en) | 1995-02-22 |
| GR950300015T1 (en) | 1995-04-30 |
| HU9402410D0 (en) | 1994-11-28 |
| AU670702B2 (en) | 1996-07-25 |
| EP0639608A1 (en) | 1995-02-22 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EEER | Examination request | ||
| MKLA | Lapsed |