CA1173584A - Process for preparing hardenable binders and the use thereof - Google Patents
Process for preparing hardenable binders and the use thereofInfo
- Publication number
- CA1173584A CA1173584A CA000380569A CA380569A CA1173584A CA 1173584 A CA1173584 A CA 1173584A CA 000380569 A CA000380569 A CA 000380569A CA 380569 A CA380569 A CA 380569A CA 1173584 A CA1173584 A CA 1173584A
- Authority
- CA
- Canada
- Prior art keywords
- resin
- composition
- phenol
- reaction product
- group
- 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
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08H—DERIVATIVES OF NATURAL MACROMOLECULAR COMPOUNDS
- C08H8/00—Macromolecular compounds derived from lignocellulosic materials
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Wood Science & Technology (AREA)
- Biochemistry (AREA)
- Paints Or Removers (AREA)
- Phenolic Resins Or Amino Resins (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Epoxy Resins (AREA)
- Materials For Medical Uses (AREA)
- Measurement And Recording Of Electrical Phenomena And Electrical Characteristics Of The Living Body (AREA)
- Medicines Containing Antibodies Or Antigens For Use As Internal Diagnostic Agents (AREA)
Abstract
Abstract of the Disclosure Process for preparing hardenable binders based on phenolic reaction products, characterised in that a phenol is reacted with comminuted wood, preferably wood dust, in the presence of a minor amount of a mineral acid, and the use of these binders for the preparation of hardened moulded objects or coatings.
Description
This invention relates to a coating composition containing a reaction product of a phenol and comminuted wood in the presence of an acid catalyst and an article with a substrated coated with such reaction product.
It is known to react simple or polymeric sugars with phenols in the presence of acidic or basic catalysts to form synthetic resins. These sugars or polymeric sugars have to have been sub-jected to complex purification processes in order to extract them from their natural sources, i.e. crops or wood. The known processes do not yield high-grade binders and, in particular, do not yield synthetic resins for use in coating compositions, of the kind which are compatible with other crosslinkable or non-cross-linkable but plasticising synthetic resins or with metal alcoholates.
It is also known to react a 24-hour-old mixture of pine sawdust, phenol and sulphuric acid with a phenolic resol.
Another known process describes the treatment of ligno-cellulose with steam, followed by extraction and condensation with phenols, cresols, etc.
However, none of these processes relates to the reaction of phenols on their own, i.e. with no aldehyde present. Moreover, the products prepared according to these two known processes are not compatible with phenolic and melamine resins.
The present invention provides a coating composition com-prising. A) a reaction product of a phenol and comminuted wood, prepared in the presence of a minor amount of a mineral acid, B) a crosslinking agent selected from the group consisting of hexa-methylenetetramine, a resol, a urea resin and a melamine resin and C) a plasticiser selected from the group consisting of an epoxide ~ -1 - ~
1 17358~
resin and a urethane resin.
The present invention further prov~des an article camprising a metal, glass or ceramic substrate coated w~th a composition comprising: A) a reaction product of a phenol and comminuted wood, prepared in the presence of a minor amount of a mineral acid, B~ a crosslinking agent selected from the group consisting of hexamethyl-enetetramine, a resol, a urea resin and a melamine resin, C) a plasticizer selected from the group consisting of an epoxide resin and a urethane res~n and D) a metal alcoholate.
Unlike the known reaction products of phenols wIth purified, possibly polymer~c sugars or wi~th cellulose compounds, the reaction products A~ mentioned above show exceptiGnal compatibilIty with various raw materials for coat~ng compositions.
The react~on of phenol and comminuted wood i~s generally carried out at a temperature of from 120 to 200~C, preferably 130 to 180C, appropriately in the presence of catalytic amounts~ e.g.
0.1 to 5% by weight, preferably 0.3 to 2% by weight, based on the phenol, of an inorganic acid such as phosphoric acid, hydrochloric acid, hydrobromic ac~d, but preferably sulphuric acid.
~henols which may be used Include, for example, cresols and xylenols, but preferably phenol itself.
According to one embodiment of the invent~on, a vxnyl-aromatic hydrocarbon such as vinyltoluene, divinylbenzene, ~-methylstyrene, but preferably styrene, may also be added to the reaction m~xture before, during or after the reaction, Although the products obtained according to the invention demonstrate good compat~bility with other res~ns, this compatibi~lity is improved still further by the addition of vinyl~aromatic compounds.
R
1 1735~
The synthetic resins obtained as above are not self-cross-linking. In this respect, they correspond to phenolic resins of the novolak type prepared from phenols and aldehydes. They may, however, be cross-linked jointly with cross-linking agents selected from phenolic resols optionally substituted at the nucleus, for example, with alkyl groups, such as methyl, ethyl, propyl, butyl or the like, urea resins, melamine resins or hexamethylenetetramine.
For use in this way, it is essential that the products should be satisfactorily compatible with these other synthetic resins.
The resins may be cured at a temperature of from 130 to 280C, preferably 170 to 210C. The curing conditions generally depend on the curing temperature of the hardenable synthetic resin added.
The combination of the reaction product A) with the above-mentioned cross-linking agents and plasticising synthetic resins such as epoxy resins or urethane resins produces binders which may be used for preparing coatings, such as stoving enamels having high elasticity and high chemical resistance, e.g. to organic acids such as lactic acid and acetic ac~d or to basic substances such as amines and ammonia, such as may be found in foodstuffs, e.g. canned fish.
According to one embodi~ent of the invention, it is also poss;~ble to incorporate ~n the coating composition of the invent~on metal alcoholates, e.g aluminium propylate or butylate, titanium propylate, and preferably titanium butylate, In this way, hardening coatings having a paxticularly attxactive golden colour can be produced. These are therefore suitable for coating metals, e.g.
ixon, steel, tin-plated steel, tin, zinc and aluminium, but 1 1735~
particularly as compositions for coating the interior of food packaging containers. However, they are also suitable for coating other substrates, e.g. for glass, ceramics and the like.
The invention will now be illustrated in the following non-limiting Examples in which, T indicates parts by weight and % indicates percent by weight.
Examples 1. Preparation of a synthetic resin for cross-link~ng with hexamethylene tetramine.
~ j - 3a -940 T of phenol are melted in a reaction vessel fitted with a stirrer, a thermometer, a metering device for wood dust and a reflux condenser, then 9.4 T
of concentrated sulphuric acid are added and the mixture is heated to 150C. At this temperature, 400 T of beech-wood dust are stirred in over one hour. When everything has dissolved, after a further hour, the mixture is heated to 180C. The mixture is refluxed at this temperature for 3 hours. Then 4.7 T of magnesium oxide are added, the pressure reduced and the unreacted phenol is distilled off at a bottom temperature of not more than 220C.
590 T of a solid, brittle synthetic resin are obtained, melting point 142C, viscosity 2180 mPa.s/20C (50 %
ethylene glycol monoethyl ether).
100 T of the resin are dissolved in 100 T of ethylene glycol monoethyl ether, 10 T of hexamethylene tetramine are added and the mixture is stirred at 40C for 1 hour.
Under these conditions, the hexamethylene tetramine is dissolved. The solution thus obtained is tested for its hardening characteristics by the so-called B-time method (cf. Ullmann, Volume 18, 4th Edition (1979), page 252).
The B-time at 120C is 10 minutes 55 seconds and the B-time at 150C i5 3 minutes 25 seconds.
The resin obtained may be used, for example, as a reinforcing resin for rubber or plastics mixtures or for moulding compositions.
2a) Preparatior. of a synthetic resin for stoving enamels.
1175 T of phenol are mixed with 13.3 T of concen-trated sulphuric acid in the same apparatus as in Example 1 and 500 T of a distillate are separated off from the condenser. The mixture is then refluxed and 1300 T of styrene are introduced over 1 hour. After the mixture has been reacted for a further 2 hours at 11735~
160C, the reaction mixture is dissolved in a mixture of 300 T of xylene and 300 T of ethylene glycol mono-ethyl ether, and 3253 T of a resin solution are ob-tained, residue (1 hour at 135C) 75.5%, correspon-ding to a solid resin content of 2460 T.
This resin solution is mixed with 260 T of butyl titanate and, as the diluent, with 174 T of xylene and 174 T of ethylene glycol monoethyl ether. At the end, a synthetic resin coating solution is ob-tained in a yield of 3820 T, residue 66% (1 hour at 135C), viscosity 3280 mPa.s/20. This synthetic resin solution is stable and its viscosity changes only slightly even on long storage. To evaluate the shelf life, a sample of this synthetic resin solution was stored at 50C for 7 days. There was an increase in viscosity to 3420 mPa.s/20C. Thus the synthetic resin solution is satisfactorily stable on storage.
2b) Preparation of the stovinq enamel From this resin, a resin for coating food cans is prepared by mixing or dissolving 50 T of a standard commercial epoxy resin based on diphenylol propane and epichlorohydrin (melting point 125 to 132C (Durrans), epoxy equivalent weight 1700 to 2000), 30 T of a resol based on tert.-butylphenol and formaldehyde (viscosity 80 to 150 mPa.s/20C, 40% in ethylene glycol monoethyl ether) and 10 T of the resin solution obtained above in 100 T of ethylene glycol monoethyl ether. This coating composition is adjusted to an immersion viscosity of 14 DIN seconds with additional ethylene glycol monoethyl ether.
Sheets of tinned tin-plate are coated with this composition by the dip method and, after the solvents have been dried, the product is stoved at 190C for 30 minutes. The coating films obtained are distinguished by an attractive golden colour, they are resistant to 2 acetic acid in the sterilisation test and are resistant - ~617358~
to 2% sodium sulphide solution and readily formable.
If the resin according to the invention is omitted from the coating composition described above, coatings are obtained having otherwise comparable properties but with a bright yellowish colour which is not desirable in coatings for the interior of food cans.
_mparison tests C1) 500 T of phenol, 5 T of concentrated sulphuric acid and 150 T of cellulose are solubilised at 160C
in the same apparatus as in Example 1 and worked up as in Example 2. A 50% solution of this resin in ethylene glycol monoethyl ether is not compatible with titanium butylate. The resin obtained is alkylated with 692 T of styrene as in Example 2 and the resultant product is dissolved to give a 50~ solution in ethylene glycol monoethyl ether. This solution is not compatible with titanium butylate either.
C2) 500 T of phenol, 5 T of concentrated sulphuric acid and 150 T of powdered cane sugar are reacted together as in comparison test 1 and the compatibility of the reaction product with titanium butylate is tested.
The product is not compatible therewith. The remaining resin is alkylated with styrene as in comparison test 1.
The solution of this resin is not compatible with titanium butylate.
It is known to react simple or polymeric sugars with phenols in the presence of acidic or basic catalysts to form synthetic resins. These sugars or polymeric sugars have to have been sub-jected to complex purification processes in order to extract them from their natural sources, i.e. crops or wood. The known processes do not yield high-grade binders and, in particular, do not yield synthetic resins for use in coating compositions, of the kind which are compatible with other crosslinkable or non-cross-linkable but plasticising synthetic resins or with metal alcoholates.
It is also known to react a 24-hour-old mixture of pine sawdust, phenol and sulphuric acid with a phenolic resol.
Another known process describes the treatment of ligno-cellulose with steam, followed by extraction and condensation with phenols, cresols, etc.
However, none of these processes relates to the reaction of phenols on their own, i.e. with no aldehyde present. Moreover, the products prepared according to these two known processes are not compatible with phenolic and melamine resins.
The present invention provides a coating composition com-prising. A) a reaction product of a phenol and comminuted wood, prepared in the presence of a minor amount of a mineral acid, B) a crosslinking agent selected from the group consisting of hexa-methylenetetramine, a resol, a urea resin and a melamine resin and C) a plasticiser selected from the group consisting of an epoxide ~ -1 - ~
1 17358~
resin and a urethane resin.
The present invention further prov~des an article camprising a metal, glass or ceramic substrate coated w~th a composition comprising: A) a reaction product of a phenol and comminuted wood, prepared in the presence of a minor amount of a mineral acid, B~ a crosslinking agent selected from the group consisting of hexamethyl-enetetramine, a resol, a urea resin and a melamine resin, C) a plasticizer selected from the group consisting of an epoxide resin and a urethane res~n and D) a metal alcoholate.
Unlike the known reaction products of phenols wIth purified, possibly polymer~c sugars or wi~th cellulose compounds, the reaction products A~ mentioned above show exceptiGnal compatibilIty with various raw materials for coat~ng compositions.
The react~on of phenol and comminuted wood i~s generally carried out at a temperature of from 120 to 200~C, preferably 130 to 180C, appropriately in the presence of catalytic amounts~ e.g.
0.1 to 5% by weight, preferably 0.3 to 2% by weight, based on the phenol, of an inorganic acid such as phosphoric acid, hydrochloric acid, hydrobromic ac~d, but preferably sulphuric acid.
~henols which may be used Include, for example, cresols and xylenols, but preferably phenol itself.
According to one embodiment of the invent~on, a vxnyl-aromatic hydrocarbon such as vinyltoluene, divinylbenzene, ~-methylstyrene, but preferably styrene, may also be added to the reaction m~xture before, during or after the reaction, Although the products obtained according to the invention demonstrate good compat~bility with other res~ns, this compatibi~lity is improved still further by the addition of vinyl~aromatic compounds.
R
1 1735~
The synthetic resins obtained as above are not self-cross-linking. In this respect, they correspond to phenolic resins of the novolak type prepared from phenols and aldehydes. They may, however, be cross-linked jointly with cross-linking agents selected from phenolic resols optionally substituted at the nucleus, for example, with alkyl groups, such as methyl, ethyl, propyl, butyl or the like, urea resins, melamine resins or hexamethylenetetramine.
For use in this way, it is essential that the products should be satisfactorily compatible with these other synthetic resins.
The resins may be cured at a temperature of from 130 to 280C, preferably 170 to 210C. The curing conditions generally depend on the curing temperature of the hardenable synthetic resin added.
The combination of the reaction product A) with the above-mentioned cross-linking agents and plasticising synthetic resins such as epoxy resins or urethane resins produces binders which may be used for preparing coatings, such as stoving enamels having high elasticity and high chemical resistance, e.g. to organic acids such as lactic acid and acetic ac~d or to basic substances such as amines and ammonia, such as may be found in foodstuffs, e.g. canned fish.
According to one embodi~ent of the invention, it is also poss;~ble to incorporate ~n the coating composition of the invent~on metal alcoholates, e.g aluminium propylate or butylate, titanium propylate, and preferably titanium butylate, In this way, hardening coatings having a paxticularly attxactive golden colour can be produced. These are therefore suitable for coating metals, e.g.
ixon, steel, tin-plated steel, tin, zinc and aluminium, but 1 1735~
particularly as compositions for coating the interior of food packaging containers. However, they are also suitable for coating other substrates, e.g. for glass, ceramics and the like.
The invention will now be illustrated in the following non-limiting Examples in which, T indicates parts by weight and % indicates percent by weight.
Examples 1. Preparation of a synthetic resin for cross-link~ng with hexamethylene tetramine.
~ j - 3a -940 T of phenol are melted in a reaction vessel fitted with a stirrer, a thermometer, a metering device for wood dust and a reflux condenser, then 9.4 T
of concentrated sulphuric acid are added and the mixture is heated to 150C. At this temperature, 400 T of beech-wood dust are stirred in over one hour. When everything has dissolved, after a further hour, the mixture is heated to 180C. The mixture is refluxed at this temperature for 3 hours. Then 4.7 T of magnesium oxide are added, the pressure reduced and the unreacted phenol is distilled off at a bottom temperature of not more than 220C.
590 T of a solid, brittle synthetic resin are obtained, melting point 142C, viscosity 2180 mPa.s/20C (50 %
ethylene glycol monoethyl ether).
100 T of the resin are dissolved in 100 T of ethylene glycol monoethyl ether, 10 T of hexamethylene tetramine are added and the mixture is stirred at 40C for 1 hour.
Under these conditions, the hexamethylene tetramine is dissolved. The solution thus obtained is tested for its hardening characteristics by the so-called B-time method (cf. Ullmann, Volume 18, 4th Edition (1979), page 252).
The B-time at 120C is 10 minutes 55 seconds and the B-time at 150C i5 3 minutes 25 seconds.
The resin obtained may be used, for example, as a reinforcing resin for rubber or plastics mixtures or for moulding compositions.
2a) Preparatior. of a synthetic resin for stoving enamels.
1175 T of phenol are mixed with 13.3 T of concen-trated sulphuric acid in the same apparatus as in Example 1 and 500 T of a distillate are separated off from the condenser. The mixture is then refluxed and 1300 T of styrene are introduced over 1 hour. After the mixture has been reacted for a further 2 hours at 11735~
160C, the reaction mixture is dissolved in a mixture of 300 T of xylene and 300 T of ethylene glycol mono-ethyl ether, and 3253 T of a resin solution are ob-tained, residue (1 hour at 135C) 75.5%, correspon-ding to a solid resin content of 2460 T.
This resin solution is mixed with 260 T of butyl titanate and, as the diluent, with 174 T of xylene and 174 T of ethylene glycol monoethyl ether. At the end, a synthetic resin coating solution is ob-tained in a yield of 3820 T, residue 66% (1 hour at 135C), viscosity 3280 mPa.s/20. This synthetic resin solution is stable and its viscosity changes only slightly even on long storage. To evaluate the shelf life, a sample of this synthetic resin solution was stored at 50C for 7 days. There was an increase in viscosity to 3420 mPa.s/20C. Thus the synthetic resin solution is satisfactorily stable on storage.
2b) Preparation of the stovinq enamel From this resin, a resin for coating food cans is prepared by mixing or dissolving 50 T of a standard commercial epoxy resin based on diphenylol propane and epichlorohydrin (melting point 125 to 132C (Durrans), epoxy equivalent weight 1700 to 2000), 30 T of a resol based on tert.-butylphenol and formaldehyde (viscosity 80 to 150 mPa.s/20C, 40% in ethylene glycol monoethyl ether) and 10 T of the resin solution obtained above in 100 T of ethylene glycol monoethyl ether. This coating composition is adjusted to an immersion viscosity of 14 DIN seconds with additional ethylene glycol monoethyl ether.
Sheets of tinned tin-plate are coated with this composition by the dip method and, after the solvents have been dried, the product is stoved at 190C for 30 minutes. The coating films obtained are distinguished by an attractive golden colour, they are resistant to 2 acetic acid in the sterilisation test and are resistant - ~617358~
to 2% sodium sulphide solution and readily formable.
If the resin according to the invention is omitted from the coating composition described above, coatings are obtained having otherwise comparable properties but with a bright yellowish colour which is not desirable in coatings for the interior of food cans.
_mparison tests C1) 500 T of phenol, 5 T of concentrated sulphuric acid and 150 T of cellulose are solubilised at 160C
in the same apparatus as in Example 1 and worked up as in Example 2. A 50% solution of this resin in ethylene glycol monoethyl ether is not compatible with titanium butylate. The resin obtained is alkylated with 692 T of styrene as in Example 2 and the resultant product is dissolved to give a 50~ solution in ethylene glycol monoethyl ether. This solution is not compatible with titanium butylate either.
C2) 500 T of phenol, 5 T of concentrated sulphuric acid and 150 T of powdered cane sugar are reacted together as in comparison test 1 and the compatibility of the reaction product with titanium butylate is tested.
The product is not compatible therewith. The remaining resin is alkylated with styrene as in comparison test 1.
The solution of this resin is not compatible with titanium butylate.
Claims (7)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A coating composition comprising A) a reaction product of a phenol and comminuted wood, pre-pared in the presence of a minor amount of a mineral acid, B) a crosslinking agent selected from the group consisting of hexamethylenetetramine, a resol, a urea resin and a melamine resin and C) a plasticiser selected from the group consisting of an epoxide resin and a urethane resin.
2. A composition as claimed in claim 1, which also comprises D) a metal alcoholate.
3. A composition as claimed in claim 2 wherein the metal alcoholate is butyl titanate.
4. A composition as claimed in claim 1, 2 or 3 wherein the reaction product A) has been further reacted with a vinyl aromatic hydrocarbon,
5. A composition as claimed in claim 1, 2 or 3 wherein the reaction product A) has been further reacted with styrene.
6. An article comprising a metal, glass or ceramic substrate coated with a composition comprising A) a reaction product of a phenol and comminuted wood, pre-pared in the presence of a minor amount of a mineral acid, B) a crosslinking agent selected from the group consisting of hexamethylenetetramine, a resol, a urea resin and a melamine resin, C) a plasticizer selected from the group consisting of an epoxide resin and a urethane resin and D) a metal alcoholate.
7. An article as claimed in claim 6 wherein the substrate is resistant to a temperature in the range of from 130 to 280°C.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19803023914 DE3023914A1 (en) | 1980-06-26 | 1980-06-26 | METHOD FOR PRODUCING CURABLE BINDERS |
| DEP3023914.6 | 1980-06-26 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1173584A true CA1173584A (en) | 1984-08-28 |
Family
ID=6105504
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000380569A Expired CA1173584A (en) | 1980-06-26 | 1981-06-25 | Process for preparing hardenable binders and the use thereof |
Country Status (6)
| Country | Link |
|---|---|
| EP (1) | EP0043097B1 (en) |
| JP (1) | JPS612697B2 (en) |
| AT (1) | ATE12004T1 (en) |
| CA (1) | CA1173584A (en) |
| DE (2) | DE3023914A1 (en) |
| FI (1) | FI811979L (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1993006153A1 (en) * | 1991-09-19 | 1993-04-01 | Nauchno-Proizvodstvennoe Obiedinenie 'novye Tekhnologii Sibiri' | Modified lignocellulose material, method of obtaining it and composition for obtaining composite material |
| JP4120517B2 (en) * | 2003-07-24 | 2008-07-16 | 株式会社豊田自動織機 | Wood resin for molding on-vehicle components, its manufacturing method, wood resin material for molding on-vehicle components, and on-vehicle components molded therefrom |
| JP2015048360A (en) * | 2013-08-30 | 2015-03-16 | 住友ベークライト株式会社 | Lignin resin composition, resin molded article, and molding material |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US1721315A (en) * | 1924-09-06 | 1929-07-16 | John Stogdell Stokes | Resinous condensation product of phenol and cellulose |
| GB298968A (en) * | 1927-10-18 | 1928-10-16 | Jeno Karpati | Process for the manufacture of new artificial products |
| US1923756A (en) * | 1931-08-22 | 1933-08-22 | Earl C Sherrard | Molding composition and alpha resinous condensation product resulting from its conversion by heat and pressure |
| FR1025074A (en) * | 1950-08-03 | 1953-04-10 | Montedison Spa | Process for preparing phenolic molding powders |
| DE1217528B (en) * | 1960-06-10 | 1966-05-26 | Herbig Haarhaus A G | Water-thinnable stoving varnish |
| US3405053A (en) * | 1964-11-02 | 1968-10-08 | Richardson Co | Two-step steam-heat treated lignocellulose product and process |
| US4182696A (en) * | 1977-12-14 | 1980-01-08 | Union Carbide Corporation | Process for producing particulate filler-containing resole molding compositions from aqueous dispersion |
-
1980
- 1980-06-26 DE DE19803023914 patent/DE3023914A1/en not_active Withdrawn
-
1981
- 1981-06-24 AT AT81104875T patent/ATE12004T1/en not_active IP Right Cessation
- 1981-06-24 FI FI811979A patent/FI811979L/en not_active Application Discontinuation
- 1981-06-24 DE DE8181104875T patent/DE3169132D1/en not_active Expired
- 1981-06-24 EP EP81104875A patent/EP0043097B1/en not_active Expired
- 1981-06-25 CA CA000380569A patent/CA1173584A/en not_active Expired
- 1981-06-25 JP JP56097628A patent/JPS612697B2/ja not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| JPS612697B2 (en) | 1986-01-27 |
| JPS5736113A (en) | 1982-02-26 |
| EP0043097A1 (en) | 1982-01-06 |
| FI811979A7 (en) | 1981-12-27 |
| DE3169132D1 (en) | 1985-04-04 |
| EP0043097B1 (en) | 1985-02-27 |
| FI811979L (en) | 1981-12-27 |
| ATE12004T1 (en) | 1985-03-15 |
| DE3023914A1 (en) | 1982-02-04 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKEX | Expiry |