CA1065518A - Adhesive compositions - Google Patents
Adhesive compositionsInfo
- Publication number
- CA1065518A CA1065518A CA237,141A CA237141A CA1065518A CA 1065518 A CA1065518 A CA 1065518A CA 237141 A CA237141 A CA 237141A CA 1065518 A CA1065518 A CA 1065518A
- Authority
- CA
- Canada
- Prior art keywords
- sodium
- solution
- fatty acid
- film
- tendency
- 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
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
- C08K5/098—Metal salts of carboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
Abstract
ABSTRACT OF THE DISCLOSURE
This invention relates to thickened solutions of film forming polymers especially to thickened adhesive compositions.
Solutions of film forming polymers are widely used as adhesives and lacquers but the standard liquid adhesive and lacquer compositions have a number of disadvantages, principally a tendency to run when applied to inclined or vertical surfaces, and a tendency to "tail". "Tailing" is the name given to the tendency of the liquid adhesive or lacquer compositions to form strands or "tails" between the work surface and the application device, whether it be a hand held spreader, a tube or a bottle, as the device is removed from the work surface after application of the adhesive.
Accordingly the invention is based on the discovery that standard liquid adhesive and lacquer compositions can be improved, the tendency to run and "tail" being reduced, by incorporating a thickening or gelling agent in the composition, and provides a method of thickening a solution of a film-forming polymermaterial in a solvent of dielectric constant in the range 5.0 to 50.0, comprising mixing with said solution at a temperature above room tem-perature, an alkali metal salt of a C8-36 fatty acid and allowing the mixture to cool without substantial agitation.
This invention relates to thickened solutions of film forming polymers especially to thickened adhesive compositions.
Solutions of film forming polymers are widely used as adhesives and lacquers but the standard liquid adhesive and lacquer compositions have a number of disadvantages, principally a tendency to run when applied to inclined or vertical surfaces, and a tendency to "tail". "Tailing" is the name given to the tendency of the liquid adhesive or lacquer compositions to form strands or "tails" between the work surface and the application device, whether it be a hand held spreader, a tube or a bottle, as the device is removed from the work surface after application of the adhesive.
Accordingly the invention is based on the discovery that standard liquid adhesive and lacquer compositions can be improved, the tendency to run and "tail" being reduced, by incorporating a thickening or gelling agent in the composition, and provides a method of thickening a solution of a film-forming polymermaterial in a solvent of dielectric constant in the range 5.0 to 50.0, comprising mixing with said solution at a temperature above room tem-perature, an alkali metal salt of a C8-36 fatty acid and allowing the mixture to cool without substantial agitation.
Description
)65~i ;1l8 This invention relates to thickened solutions of film forming polymers t especially to thickened adhesive compositions.
Solutions o film forming polymers are widely used as adhesives and lacquers. They can be applied by the use of a spreading device to spread a portion of the solution in a thin film over a surface or they can be applied by extrusion from a collapsible tube or from a bottle with a rubber application orifice or the like. However, the standard liquid adhesive and lacquer compositions have a number of disadvan.ages, principally a tendency to run when applied to inclined or vertical surfaces, and a tendency to "tail".
ITailing'' is the name given to the tendency of the liquid adhesive or lacquer compositions to form strands or "tails"
~etween the work surface and the application device, whether ~t be a hand held spreader, a tube or a bottle, as the device is removed from the work surface after appllcation of the adhesive. "Tailing" is undesirable because it makes neat application, (essential for model work and many small-scale domestic uses) very difficult.
, A
This in~rention is based on the discovery that standard liquid adhesive and lacquer compositions can be improved~
the ~endency to run and "tail" being reduced, by i incorpoxa-ting a thickening or gelling ayent in the ' composition.
.
6S~
.
Although thickening and gelling agents are commonly used in many areas of industry, the adhesives and lacquer industry is peculiar in that its range o solvents tend to be medium polar solvents such as methylacetate, ethylacetate, butyl-acetate, acetone, methylethylketone and methylisobutylketone.
The standard thickening and gelling agents for highly polar solvents like water and for non-polar hydrocarbon solvents are generally unsuitable for use with medium polar solvents.
However, we have discovered that the addition of an al]cali metal salt of a C8_36(preferably C12_22~ y ferably as a solution in a lower aliphatic alcohol (e.g.
methanol or ethanol), to standard liquid lacquer and adhesive ; compositions (e.g. to about 5-50% by weight of the total composition) produces a thickened composition which has a reduced tendency to run and "tail".
Accordingly, the present invention provides a method of thickening a solution of a film-forming polymer material in a solvent of dielectric constant in the range 570 to 50.0, comprising mixing with said solution at a temperature above room temperature, an alkali metal salt of a C8 36 fatty acid and allowing the mixture to cool without sub-stantial agitation. The invention provides also a film forming composition produced by this mekhod.
~/
,, The degree of thickening achieved will naturally be related to the concentration of fatty acid salt (:hereinafter called "the soap") added.
~06S~8 In ~encral the soap may comprise from 0.05 to 5~ by weight of the total thickened composition.
The soap is pre~erably an alkali metal salt o~ a C12 22 fatty acid, most preferably a sodium salt. Sodium stearate is a preferred soap.
.
Preferably the soap is mixed with the solution o~ the film-forming polymer as a solution in a lower aliphatic alcohol, especially methancl or ethanol. The temperature at which the alcoholic soap solution is mixed with the so]ution o~
film-formex may be in the range 30C-80C depending on the volatility of the sol~ents used. It m~y sometimes be pos~ible to form the soap in situ by neutralising an added fatty acid.
The solvent of a dielectric constant in the range 5.0 to 50.0 may be selected from the standard medium polarity solvents used in the past for adhesive and lacquer compositions, usually low molecular wei~ht esters and ketones and mixtures thereof, sometimes with small amounts of lo~er alcohols. E~amples of sllch solvents include methylacetate, ethylacetate, butylacetata~ dibutylphthalate, cyclohexanone, acetone, methylethylketone and methylisobutyl ketone. Methyl and ethyl alcohol may be mixed in ~ninor proportions with these ester and ketone solvents. The solvent is usually a blend of individual solvents, chosen to gi-re the desired rate of evaporation. Normal3y the dielectric constant will be in ihe range 5.0 to 30.0, e.g. 10.0 to 25Ø
1~)6S~ 8 The film-forming polymer material may be any of those used in the past for adhesive and lacquer compositions, for example, polyvinyl acetate, po:Lyv:Lnyl alcohol, polyvinyl chloride, polyurethane, polyacrylate or polymethacrylate or their esters/ polyvinylpyrrolidone, or copolymers of these materials, as well as cellulose nitrate, cellulose ethers and esters.
If desired, small amounts of water may be included in the compositions of this invention, eirher as part of normal moisture content of the organic solvents or as added water. The water gives the thickened or gelled composition an attractive translucent-appearance.
Although the compositions of this invention are generally satisfactory in that they have a reduced tendency to run and tail, we have found that with some film-forming agents, e.g.
polyvinylace~ate, especially in compositions containing water, ~he stability cï the total thic]ened or gelled composition is rather less than that o the same composition without the soap or water and that occasionally metal surface adhesion properties may be worse. However, we find that in instanc~s where the stability is u~satisfactory, the adc~ition of buffers o keep the pH of the composition in the range fxom a~out 7.0 to about 9.0 ~preferably inorganic salts ~e.g. sodium salts) of weak oraanic or inorganic acids, as or exa~lple sodium tetraborale (borax), sodium acetate, sodium-p-hydroxybenzoicacid methylester, sodium iodate;
sodium formate and sodium succinatej,in an amount of fxom 0005~ to 20% b~ wei~ht o the whole composition ~depending -- 4 ~
, ... . ... .. ... ... ...
-~g655~
on the pH required) restores stability with little or no adverse e~ect on the adhesi.ve or lacquering properties of the composition. The bu~fer substance m~y be incorporated in the solution as a saturated solution in water, alcohol, or other solvents. At the same time we surprisingly find that these bufer additives, e.g. borax, sodium acetate, sodium-p-hydroxy-benzoicacid methylester, also tend to improve the metal surface adhesion of the composition.
i The buffer substances also appear to ir.crease the gelliny , temperature of the co~positions of this invention (possibly I due to a "salting out" effect which reduces the solubility of the gelling agent ln its colloidal form). This increase in gelling temperature may also partly explain the stabi].ising effect of the buffers.
I, , .
~ ~ Hence, according to a preferred embodiment of the invention ,~ : there is provided a method of thickening a solution of a ~` film-forming polymer materi.al in a solvent of dielectric constant in the range 5.0 to 50.0 contprising mi~lng with said solution a buffer substance in an amount to ~ontrol the final pH of the total composition within the range 7.0 to 9.0 and an alkali metal salt of a C~ 36 fatty acid, preferably in al.coholic solution, said fatty acid salt being mixed with the solution of film.forming agent at a temperature above room temperature, and allowing the mixture to cool without substantial agitation.
~ ~ .
.
3biS5~8 The ~uffer substance is prefexab].y added in an amount of from 0.05~ to 20~ by welght of the whole compos:ltlon to control the pH at about 8Ø It may be added beore, after or together with an alcohol solution of fatty acid sall~ The temperature at which the bu~fer is added ;.s preferably at or above room temperature, and it may be added as an aqueous solution or in some cases may be formed i.n_situ by the addition of a weak inorganic or organic acid followed by neutralisation e.g. with sodium hydroxide.
,.
The following Examples illustrate the invention:
Plexigum MB 319 30 ~ by wei.ght ~a trade mark of Messrs. Rohm Darmstadt) a copolymerisate of polymethylmethacrylate and polyethylacrylate) Methylacetat.e 45 % by weight Etbyl alcohol 24.7 % by weight Sodium st;earate , _ .3 ~ by we.i~ht 100.0 % by weight Procedul-e:
~ix th~ methy~acetate and ethyl alcohol in a vessel fitted with reflux condenser and add the Plexig~ with stirring at room temperature. After about 1 hour the solution will be homoyeneous.
~ ~!tD6S5~8 Now, ad~ the sodium stearate and continue s-tirring ~or about 15 minutes at room temperature. Ileat to 60C and stir (about 5 minutes) until the composition appears homogeneous. The finished batch is p~nped into containers and the resultant mix allowed to coo]..
Polyvinyl acetate with ~ Mol. 38~ by weight weight of 130,000 Methyl alcohol 10% by weigh1:
Methyl acetate 30% by weic3hJ~
Ethyl alcohol 19.75 % by weigllt Sodium stearate 0.25 % by weight 5% solution of borax in water 2~ gh~
100.00 % by wei.ght Procedure:
, Mix the methyl acetate and ethyl alcohol in a vessel fitted with ~ reflux condenser. Add the polyviny].
acetate with stirring. After aboui 2.5 hours when the solution seems to oe homocJeneous, add the sodium stearate as a heate~ solution in the methyl alcohol and continue stirring for about 15 minutes until it is dispersed. Therl heat the whole mixture to about 50C and add the 5~ solution of borax in water. Allow the resultant ~.ix to cool.
EX~MPLE 3 Linear linked po].yureth~n2 20~ by weight Alkylphenol resin (~,~resen*PA104) 10 % hy weicJIlt Methylethylketone 40~ hy wei.c3h~
* Trade Mark , . . _ ~ .. _ . . . .
~'~t`.'.
s~
Ethanol 29.7 ~ by weight Sodium stearate 0.3 _ ~ by~
; 100.0 ~ by weight Procedure-=
Fill the methylethylketone into a vessel fitted wi.th a reflux condenser; add the linear linked polyurethane with stirring. After about 2.5 hours when the solution seems to be homogeneous add the alkylphenol resin and continue stirring for ~ hour. Then add the hot solution (50C) of sodium stearate in ethanol slowly under stirring and heat the whole mixture to about 60C. After reaching a full.y homogeneous solution allow the resul~ant mix to cool.
.
i:
~ ~ ' - . .
`
,' ~ '' ' ' .
Solutions o film forming polymers are widely used as adhesives and lacquers. They can be applied by the use of a spreading device to spread a portion of the solution in a thin film over a surface or they can be applied by extrusion from a collapsible tube or from a bottle with a rubber application orifice or the like. However, the standard liquid adhesive and lacquer compositions have a number of disadvan.ages, principally a tendency to run when applied to inclined or vertical surfaces, and a tendency to "tail".
ITailing'' is the name given to the tendency of the liquid adhesive or lacquer compositions to form strands or "tails"
~etween the work surface and the application device, whether ~t be a hand held spreader, a tube or a bottle, as the device is removed from the work surface after appllcation of the adhesive. "Tailing" is undesirable because it makes neat application, (essential for model work and many small-scale domestic uses) very difficult.
, A
This in~rention is based on the discovery that standard liquid adhesive and lacquer compositions can be improved~
the ~endency to run and "tail" being reduced, by i incorpoxa-ting a thickening or gelling ayent in the ' composition.
.
6S~
.
Although thickening and gelling agents are commonly used in many areas of industry, the adhesives and lacquer industry is peculiar in that its range o solvents tend to be medium polar solvents such as methylacetate, ethylacetate, butyl-acetate, acetone, methylethylketone and methylisobutylketone.
The standard thickening and gelling agents for highly polar solvents like water and for non-polar hydrocarbon solvents are generally unsuitable for use with medium polar solvents.
However, we have discovered that the addition of an al]cali metal salt of a C8_36(preferably C12_22~ y ferably as a solution in a lower aliphatic alcohol (e.g.
methanol or ethanol), to standard liquid lacquer and adhesive ; compositions (e.g. to about 5-50% by weight of the total composition) produces a thickened composition which has a reduced tendency to run and "tail".
Accordingly, the present invention provides a method of thickening a solution of a film-forming polymer material in a solvent of dielectric constant in the range 570 to 50.0, comprising mixing with said solution at a temperature above room temperature, an alkali metal salt of a C8 36 fatty acid and allowing the mixture to cool without sub-stantial agitation. The invention provides also a film forming composition produced by this mekhod.
~/
,, The degree of thickening achieved will naturally be related to the concentration of fatty acid salt (:hereinafter called "the soap") added.
~06S~8 In ~encral the soap may comprise from 0.05 to 5~ by weight of the total thickened composition.
The soap is pre~erably an alkali metal salt o~ a C12 22 fatty acid, most preferably a sodium salt. Sodium stearate is a preferred soap.
.
Preferably the soap is mixed with the solution o~ the film-forming polymer as a solution in a lower aliphatic alcohol, especially methancl or ethanol. The temperature at which the alcoholic soap solution is mixed with the so]ution o~
film-formex may be in the range 30C-80C depending on the volatility of the sol~ents used. It m~y sometimes be pos~ible to form the soap in situ by neutralising an added fatty acid.
The solvent of a dielectric constant in the range 5.0 to 50.0 may be selected from the standard medium polarity solvents used in the past for adhesive and lacquer compositions, usually low molecular wei~ht esters and ketones and mixtures thereof, sometimes with small amounts of lo~er alcohols. E~amples of sllch solvents include methylacetate, ethylacetate, butylacetata~ dibutylphthalate, cyclohexanone, acetone, methylethylketone and methylisobutyl ketone. Methyl and ethyl alcohol may be mixed in ~ninor proportions with these ester and ketone solvents. The solvent is usually a blend of individual solvents, chosen to gi-re the desired rate of evaporation. Normal3y the dielectric constant will be in ihe range 5.0 to 30.0, e.g. 10.0 to 25Ø
1~)6S~ 8 The film-forming polymer material may be any of those used in the past for adhesive and lacquer compositions, for example, polyvinyl acetate, po:Lyv:Lnyl alcohol, polyvinyl chloride, polyurethane, polyacrylate or polymethacrylate or their esters/ polyvinylpyrrolidone, or copolymers of these materials, as well as cellulose nitrate, cellulose ethers and esters.
If desired, small amounts of water may be included in the compositions of this invention, eirher as part of normal moisture content of the organic solvents or as added water. The water gives the thickened or gelled composition an attractive translucent-appearance.
Although the compositions of this invention are generally satisfactory in that they have a reduced tendency to run and tail, we have found that with some film-forming agents, e.g.
polyvinylace~ate, especially in compositions containing water, ~he stability cï the total thic]ened or gelled composition is rather less than that o the same composition without the soap or water and that occasionally metal surface adhesion properties may be worse. However, we find that in instanc~s where the stability is u~satisfactory, the adc~ition of buffers o keep the pH of the composition in the range fxom a~out 7.0 to about 9.0 ~preferably inorganic salts ~e.g. sodium salts) of weak oraanic or inorganic acids, as or exa~lple sodium tetraborale (borax), sodium acetate, sodium-p-hydroxybenzoicacid methylester, sodium iodate;
sodium formate and sodium succinatej,in an amount of fxom 0005~ to 20% b~ wei~ht o the whole composition ~depending -- 4 ~
, ... . ... .. ... ... ...
-~g655~
on the pH required) restores stability with little or no adverse e~ect on the adhesi.ve or lacquering properties of the composition. The bu~fer substance m~y be incorporated in the solution as a saturated solution in water, alcohol, or other solvents. At the same time we surprisingly find that these bufer additives, e.g. borax, sodium acetate, sodium-p-hydroxy-benzoicacid methylester, also tend to improve the metal surface adhesion of the composition.
i The buffer substances also appear to ir.crease the gelliny , temperature of the co~positions of this invention (possibly I due to a "salting out" effect which reduces the solubility of the gelling agent ln its colloidal form). This increase in gelling temperature may also partly explain the stabi].ising effect of the buffers.
I, , .
~ ~ Hence, according to a preferred embodiment of the invention ,~ : there is provided a method of thickening a solution of a ~` film-forming polymer materi.al in a solvent of dielectric constant in the range 5.0 to 50.0 contprising mi~lng with said solution a buffer substance in an amount to ~ontrol the final pH of the total composition within the range 7.0 to 9.0 and an alkali metal salt of a C~ 36 fatty acid, preferably in al.coholic solution, said fatty acid salt being mixed with the solution of film.forming agent at a temperature above room temperature, and allowing the mixture to cool without substantial agitation.
~ ~ .
.
3biS5~8 The ~uffer substance is prefexab].y added in an amount of from 0.05~ to 20~ by welght of the whole compos:ltlon to control the pH at about 8Ø It may be added beore, after or together with an alcohol solution of fatty acid sall~ The temperature at which the bu~fer is added ;.s preferably at or above room temperature, and it may be added as an aqueous solution or in some cases may be formed i.n_situ by the addition of a weak inorganic or organic acid followed by neutralisation e.g. with sodium hydroxide.
,.
The following Examples illustrate the invention:
Plexigum MB 319 30 ~ by wei.ght ~a trade mark of Messrs. Rohm Darmstadt) a copolymerisate of polymethylmethacrylate and polyethylacrylate) Methylacetat.e 45 % by weight Etbyl alcohol 24.7 % by weight Sodium st;earate , _ .3 ~ by we.i~ht 100.0 % by weight Procedul-e:
~ix th~ methy~acetate and ethyl alcohol in a vessel fitted with reflux condenser and add the Plexig~ with stirring at room temperature. After about 1 hour the solution will be homoyeneous.
~ ~!tD6S5~8 Now, ad~ the sodium stearate and continue s-tirring ~or about 15 minutes at room temperature. Ileat to 60C and stir (about 5 minutes) until the composition appears homogeneous. The finished batch is p~nped into containers and the resultant mix allowed to coo]..
Polyvinyl acetate with ~ Mol. 38~ by weight weight of 130,000 Methyl alcohol 10% by weigh1:
Methyl acetate 30% by weic3hJ~
Ethyl alcohol 19.75 % by weigllt Sodium stearate 0.25 % by weight 5% solution of borax in water 2~ gh~
100.00 % by wei.ght Procedure:
, Mix the methyl acetate and ethyl alcohol in a vessel fitted with ~ reflux condenser. Add the polyviny].
acetate with stirring. After aboui 2.5 hours when the solution seems to oe homocJeneous, add the sodium stearate as a heate~ solution in the methyl alcohol and continue stirring for about 15 minutes until it is dispersed. Therl heat the whole mixture to about 50C and add the 5~ solution of borax in water. Allow the resultant ~.ix to cool.
EX~MPLE 3 Linear linked po].yureth~n2 20~ by weight Alkylphenol resin (~,~resen*PA104) 10 % hy weicJIlt Methylethylketone 40~ hy wei.c3h~
* Trade Mark , . . _ ~ .. _ . . . .
~'~t`.'.
s~
Ethanol 29.7 ~ by weight Sodium stearate 0.3 _ ~ by~
; 100.0 ~ by weight Procedure-=
Fill the methylethylketone into a vessel fitted wi.th a reflux condenser; add the linear linked polyurethane with stirring. After about 2.5 hours when the solution seems to be homogeneous add the alkylphenol resin and continue stirring for ~ hour. Then add the hot solution (50C) of sodium stearate in ethanol slowly under stirring and heat the whole mixture to about 60C. After reaching a full.y homogeneous solution allow the resul~ant mix to cool.
.
i:
~ ~ ' - . .
`
,' ~ '' ' ' .
Claims (15)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A method of thickening a solution of a film-forming polymer material in a solvent of dielectric constant in the range 5.0 to 50.0, comprising mixing with said solution at a temperature above room temperature, an alkali metal salt of a C8-36 fatty acid and allow-ing the mixture to cool without substantial agitation.
2. A method as claimed in claim 1 wherein the added fatty acid salt comprises from 0.05 to 5.0% by weight of the total composition.
3. A method as claimed in claim 1 wherein the fatty acid salt is an alkali metal salt of a C12-22 fatty acid.
4. A method as claimed in claim 3 wherein the fatty acid salt is sodium stearate.
5. A method as claimed in claim 1 wherein the fatty acid salt is mixed with the solution of film-forming polymer as a solution is a lower aliphatic alcohol.
6. A method as claimed in claim 5 wherein the alcohol is methanol or ethanol.
7) A method as claimed in claim 1 wherein the film-forming polymer is polyvinyl acetate, polyvinyl alcohol, polyvinyl chloride, polyurethane, polyacrylate or polylmeth-acrylate, polyvinylpyrrolidone, copolymers of the preceding substances, cellulose nitrate, cellulose ethers or cellulose esters.
8) A method as claimed in claim 1 comprising mixing with the said solution of a film-forming polymer a buffer substance in an amount to control the final pH of the total composition within the range 7.0 to 9.0 and the said alkali metal salt of a C12-36 fatty acid, said fatty acid salt being mixed with said solution at a temperature above room temperature, and allowing the mixture to cool without substantial agitation.
9) A method as claimed in claim 8 wherein the buffer substance is added in an amount of from 0.05 to 20% by weight of the whole composition to control the pH at about 8Ø
10) A method as claimed in claim 8 wherein the buffer substance is sodium tetraborate, sodium acetate, sodium-p-hydroxybenzoicacid methyl ester, sodium iodate, sodium formate or sodium succinate.
11. A method as claimed in claim 9 wherein the buffer substance is sodium tetraborate, sodium acetate, sodium-p-hydroxybenzoicacid methyl ester, sodium iodate, sodium formate or sodium succinate.
12. The film forming composition produced by the method of any one of claims 1, 2 or 3.
13. The film forming composition produced by the method of any one of claims 4, 5 or 6.
14. The film forming composition produced by the method of any one of claims 7, 8 or 9.
15. The film forming composition produced by the method of any one of claims 10 or 11.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB44222/74A GB1527596A (en) | 1974-10-11 | 1974-10-11 | Adhesive compositions |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1065518A true CA1065518A (en) | 1979-10-30 |
Family
ID=10432335
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA237,141A Expired CA1065518A (en) | 1974-10-11 | 1975-10-06 | Adhesive compositions |
Country Status (4)
| Country | Link |
|---|---|
| BE (1) | BE834411A (en) |
| CA (1) | CA1065518A (en) |
| GB (1) | GB1527596A (en) |
| ZA (1) | ZA756332B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2775982A1 (en) * | 1998-03-12 | 1999-09-17 | Eastman Kodak Co | NEW COMPOSITION FOR BONDING PHOTOGRAPHIC FILMS |
| GB0606468D0 (en) * | 2006-03-31 | 2006-05-10 | Ici Plc | Improved paint compositions |
| US20230407152A1 (en) | 2020-09-28 | 2023-12-21 | Covestro Deutschland Ag | Solvent-Borne Polyurethane Adhesives with High Molecular Weight, High OH Content and Low Solution Viscosity |
| EP4012002A1 (en) | 2020-12-09 | 2022-06-15 | Covestro Deutschland AG | Hybrid solvent-borne polyurethane adhesives |
-
1974
- 1974-10-11 GB GB44222/74A patent/GB1527596A/en not_active Expired
-
1975
- 1975-10-06 CA CA237,141A patent/CA1065518A/en not_active Expired
- 1975-10-07 ZA ZA00756332A patent/ZA756332B/en unknown
- 1975-10-10 BE BE160865A patent/BE834411A/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| BE834411A (en) | 1976-04-12 |
| ZA756332B (en) | 1976-10-27 |
| GB1527596A (en) | 1978-10-04 |
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