CA1092737A - Starch/latex cast coatings for paper - Google Patents
Starch/latex cast coatings for paperInfo
- Publication number
- CA1092737A CA1092737A CA289,375A CA289375A CA1092737A CA 1092737 A CA1092737 A CA 1092737A CA 289375 A CA289375 A CA 289375A CA 1092737 A CA1092737 A CA 1092737A
- Authority
- CA
- Canada
- Prior art keywords
- maximum
- parts
- angstroms
- composition
- particle size
- 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
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H19/00—Coated paper; Coating material
- D21H19/10—Coatings without pigments
- D21H19/14—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12
- D21H19/20—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12 comprising macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D21H19/22—Polyalkenes, e.g. polystyrene
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H19/00—Coated paper; Coating material
- D21H19/36—Coatings with pigments
- D21H19/38—Coatings with pigments characterised by the pigments
- D21H19/385—Oxides, hydroxides or carbonates
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H19/00—Coated paper; Coating material
- D21H19/36—Coatings with pigments
- D21H19/38—Coatings with pigments characterised by the pigments
- D21H19/40—Coatings with pigments characterised by the pigments siliceous, e.g. clays
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H19/00—Coated paper; Coating material
- D21H19/36—Coatings with pigments
- D21H19/44—Coatings with pigments characterised by the other ingredients, e.g. the binder or dispersing agent
- D21H19/54—Starch
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H19/00—Coated paper; Coating material
- D21H19/36—Coatings with pigments
- D21H19/44—Coatings with pigments characterised by the other ingredients, e.g. the binder or dispersing agent
- D21H19/56—Macromolecular organic compounds or oligomers thereof obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D21H19/58—Polymers or oligomers of diolefins, aromatic vinyl monomers or unsaturated acids or derivatives thereof
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
- D21H21/50—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by form
- D21H21/52—Additives of definite length or shape
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Dispersion Chemistry (AREA)
- Paper (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE
A non-proteinaceous binder is provided for cast coating of paper which comprises three primary components; a modified starch; a styrene-butadiene latex characterized by a particle size of about 800 to about 1300 angstroms, a solids content of between about 45.0 and about 47.0%, a maximum 200 mesh residue of about 0.075 gms./900 mls., a pH of between about 3.8 and 4.8, a maximum Brookfield viscosity of about 100, and a surface tension of between about 43.0 and about 49.0; and a second styrene-butadiene latex characterized by a particle size of about 1350 to about 1650 angstroms, a solids content of between about 47.0 and about 49.0%, a maximum 200 mesh residue of about 0.05 gms./900 mls., a pH of be-tween about 5.5 and 6.5, a maximum Brookfield viscosity of about 300 cps., and a surface tension of between about 49.0 and 55Ø
An aqueous aliquot portion of the composition is coated on a paper substrate, pressed against a chromium heat roll and dried, thereby providing a cast coating paper according to the invention.
A non-proteinaceous binder is provided for cast coating of paper which comprises three primary components; a modified starch; a styrene-butadiene latex characterized by a particle size of about 800 to about 1300 angstroms, a solids content of between about 45.0 and about 47.0%, a maximum 200 mesh residue of about 0.075 gms./900 mls., a pH of between about 3.8 and 4.8, a maximum Brookfield viscosity of about 100, and a surface tension of between about 43.0 and about 49.0; and a second styrene-butadiene latex characterized by a particle size of about 1350 to about 1650 angstroms, a solids content of between about 47.0 and about 49.0%, a maximum 200 mesh residue of about 0.05 gms./900 mls., a pH of be-tween about 5.5 and 6.5, a maximum Brookfield viscosity of about 300 cps., and a surface tension of between about 49.0 and 55Ø
An aqueous aliquot portion of the composition is coated on a paper substrate, pressed against a chromium heat roll and dried, thereby providing a cast coating paper according to the invention.
Description
The present application is directed to an improvement over the binder composition disclosed and claimed in our earlier . application Serial Number 251,795 filed May 4, 1976.
. . .
. In our mentioned application, we have broadly dis-closed components which when combined resulted in a binder com-position particul~rly useful for cast surface coating of paper.
.
The present application discloses specific formNlations of various components w~ich when admixed in the parts by weight . hereinafter disclosed enhances the paper coating process by en- .
~ 10 suring drum release of the coatings without impairing the print-~ ing quality of the paper, its press performance, its sheet .,~ .
. gloss, its water resistance or folding properties.
`~ With the foregoing in mind, we provide in accordance with the invention a composition of matter comprising a modified ~ lS starch of an acid hydrolyzed hydroxyethyl ether cornstarch, à
- dispersed styrene-butadiene polymer having a particle size of from 800 to about 1300 angstroms and a solids content of between ` about 45.0 and about 47.0%, a maximum 200 mesh residue of about 0.075 gms./900 mls., a pH of about 3.8 to about 4.8, a maximum Brookfield viscosity of about 100 cps. and a surface tension of about 43.0 to about 49.0, and a dispersed styrene-buta-diene polymer having a particle size of from about 1350 to - .` . : ......... ..
. '' .~
;~ .
., . : : .
lO9Z73'7 about 1650 angstroms and a solids content of between about 47.0 and about 49.0%, a maximum 200 mesh residue of about 0.05 gms./ 900 mls., a pH of between about 5.5 and about 6.5, a maximum Brookfield viscosity of about 300 cps., and a sur-face tension of from about 49.0 to about 55.0; said starch and said two latexes being included in relative proportions of about 1:2:2 dry weight basis on said composition.
We have now determined that an acid hydrolyzed ` hydroxyethyl ether cornstarch is suited to a cast coating composition because it has reduced tendency to gel or retro-; grade and because of its hydrophilic character. Preferably, between about 3 and about 5 parts of the starch are included i in the composition, calculated on a dry weight basis. The starch is commercially available from American Maize Products .~ .
Co.
Both latexes employed in the coating composition include dispersed styrene-butadiene polymer. The particle size of styrene-butadiene in one latex varies from about 800 to about 1300 angstroms, and the latex is characterized by a solids content of between about 45.0 and about 47.0%, a maxi-mum 200 mesh residue of about 0.075 gms./900 mls., a pH of ~` about 3.8 to about 4.8, a maximum Brookfield viscosity of about -100, and a surface tension of about 43.0 to about 49Ø Styrene-~ butadiene latices and their preparation are well known, and one ;- 25 such latex having the character and properties described herein ~ is a commercially available product of Dow Chemical Company.
s~ Preferably, from about 6 to about 8 parts of this latex are employed in the coating composition, calculated on a dry weight basis.
.. .
.
. -3-~. .
lO9'~q37 Tlle other latex includes dispersed styrene-butadiene ; polymer having a particle size varying from about 1350 to about 1650 angstroms. This latex is characterized by a solids content of about 47.0 to about 49.0%, a maximum 200 mesh residue of about 0.05 gms./900 mls., a pH of between about 5.5 and about 6.5, a maximum Broo~field viscosity of about 300 cps., and a surface tension of from about 49.0 to about 55Ø The coating composition preferably includes from about 6 to about 8 parts of this latex, calculated on the dry weight basis.
As in our earlier application, the preferred form of the coating composition includes an insoluble filler, an inorganic polyphosphate dispersant, an organic dispersant; i.e. a poly-acrylate dispersant, an oleaginous release agent and rosin which promotes adhesion of the coating to a paper web, without deleterious effect. The preferred insoluble filler is described in our earlier application as constituting about 85 parts calcium carbonate and about 15 parts #2 coating clay.
Preferred inorganic polyphosphate dispersants employed herein are the hexametaphosphates. Among the st preferred hexa-metaphosphates are sodium hexametaphosphate and zinc substituted sodium hexametaphosphate which are respectively commercially avail-able from Calgon Corporation and from Merck & Company. Preferably, .~ . .
-` about 0.5 parts, calculated on the dry weight basis, of the in-organic polyphosphate dispersant are employed in the composition.
As the .! ' organic dispersant we use an aqueous solution of sodium polyacrylate which is the preferred polyacrylate.
Preferably about 0.7 parts, calculated on the dry weight basis, ; are employed. The sodium polyacrylate dispersants herein contem-` plated are available from Rohm & Haas Company, Dow Chemical Com-pany and Allied Colloids.
-..
. , .. . : :
lO9Z737 The preferred oleaginous release agent for our im-proved composition is sulfonated castor oil. From about 1.5 to about 1.75 parts, calculated on the dry weight basis, of the oleaginous release agent are preferably employed in the coating composition.
The preferred rosin is an acidic thermoplastic pentaerythritol rosin ester, and particularly the sodium salt thereof. Such rosinsare commercially available from Hercules Incorporated. In the most preferred embodiment of the inven-tion about 1.0 parts of the rosin are employed in the composi-tion.
As in our earlier application, the pH of the composi-tion may be adjusted to the desired range by the addition of ammonia thereto. As formulated, the coating composition prefer-ably has a solids content of 55 to about 60%.
In the general preparation of the coating composition,the heretofore disclosed constituents may be added in any appro-priate sequence to a sufficient amount of water to give the desired total solids content and pH thereof.
'I ' .
-;/ 20 The examples that follow are merely exemplary of specific embodiments of the invention, and are not otherwise in-tended to limit the scope thereof. All parts are by dry weight on the composition.
EXAMPLE I
A coating composition is formulated including 3 parts ~ acid hydrolyzed hydroxyethyl ether cornstarch, 8 parts of the ¦ latex including dispersed styrene-butadiene polymer of particle size between 800 and 1300 angstroms, and 8 parts of the latex in-3 cluding dispersed styrene-butadiene polymer of particle size be-j 30 tween 1350 and 1650 angstroms.
-109;~737 EXAMPLE II
A coating composition is formulated including 4 parts - acid hydrolyzed hydroxyethyl ether cornstarch, 8 parts of the . latex including dispersed styrene-butadiene polymer of particle size between 800 and 1300 angstroms, and 6 parts of the latex in-cluding dispersed styrene-butadiene polymer of particle size be-~ tween 1350 and 1650 angstroms.
`~ EXAMPLE III
~' A coating composition is formulated including 5 parts ^ 10 acid hydrolyzed hydroxyethyl ether cornstarch, 6 parts of the :
latex including dispersed styrene-butadiene polymer of particle '~ -~ size between 800 and 1300 angstroms, and 8 parts of the latex in-i.~ ~ cluding dispersed styrene-butadiene polymer of particle size be-. tween 1350 and 1650 angstroms.
The preferred formulation is that of Example III. With that formulation, the drum release of the coatings is at maximum efficiency.
` ~ In employing the formulations in the cast coating of `~ papers, the aqueous coating composition is applied to a paper web and pressed against a rotating heated chromium surface and then dried in the manner described in the above incorporated patents.
By means of the above described coating compositions there are obtained cast coated papers of high printing quality, press per-formance, sheet gloss, water resistance, fold, and freedom from curling.
: `~
, .,;, .
.. ..
. . .
. In our mentioned application, we have broadly dis-closed components which when combined resulted in a binder com-position particul~rly useful for cast surface coating of paper.
.
The present application discloses specific formNlations of various components w~ich when admixed in the parts by weight . hereinafter disclosed enhances the paper coating process by en- .
~ 10 suring drum release of the coatings without impairing the print-~ ing quality of the paper, its press performance, its sheet .,~ .
. gloss, its water resistance or folding properties.
`~ With the foregoing in mind, we provide in accordance with the invention a composition of matter comprising a modified ~ lS starch of an acid hydrolyzed hydroxyethyl ether cornstarch, à
- dispersed styrene-butadiene polymer having a particle size of from 800 to about 1300 angstroms and a solids content of between ` about 45.0 and about 47.0%, a maximum 200 mesh residue of about 0.075 gms./900 mls., a pH of about 3.8 to about 4.8, a maximum Brookfield viscosity of about 100 cps. and a surface tension of about 43.0 to about 49.0, and a dispersed styrene-buta-diene polymer having a particle size of from about 1350 to - .` . : ......... ..
. '' .~
;~ .
., . : : .
lO9Z73'7 about 1650 angstroms and a solids content of between about 47.0 and about 49.0%, a maximum 200 mesh residue of about 0.05 gms./ 900 mls., a pH of between about 5.5 and about 6.5, a maximum Brookfield viscosity of about 300 cps., and a sur-face tension of from about 49.0 to about 55.0; said starch and said two latexes being included in relative proportions of about 1:2:2 dry weight basis on said composition.
We have now determined that an acid hydrolyzed ` hydroxyethyl ether cornstarch is suited to a cast coating composition because it has reduced tendency to gel or retro-; grade and because of its hydrophilic character. Preferably, between about 3 and about 5 parts of the starch are included i in the composition, calculated on a dry weight basis. The starch is commercially available from American Maize Products .~ .
Co.
Both latexes employed in the coating composition include dispersed styrene-butadiene polymer. The particle size of styrene-butadiene in one latex varies from about 800 to about 1300 angstroms, and the latex is characterized by a solids content of between about 45.0 and about 47.0%, a maxi-mum 200 mesh residue of about 0.075 gms./900 mls., a pH of ~` about 3.8 to about 4.8, a maximum Brookfield viscosity of about -100, and a surface tension of about 43.0 to about 49Ø Styrene-~ butadiene latices and their preparation are well known, and one ;- 25 such latex having the character and properties described herein ~ is a commercially available product of Dow Chemical Company.
s~ Preferably, from about 6 to about 8 parts of this latex are employed in the coating composition, calculated on a dry weight basis.
.. .
.
. -3-~. .
lO9'~q37 Tlle other latex includes dispersed styrene-butadiene ; polymer having a particle size varying from about 1350 to about 1650 angstroms. This latex is characterized by a solids content of about 47.0 to about 49.0%, a maximum 200 mesh residue of about 0.05 gms./900 mls., a pH of between about 5.5 and about 6.5, a maximum Broo~field viscosity of about 300 cps., and a surface tension of from about 49.0 to about 55Ø The coating composition preferably includes from about 6 to about 8 parts of this latex, calculated on the dry weight basis.
As in our earlier application, the preferred form of the coating composition includes an insoluble filler, an inorganic polyphosphate dispersant, an organic dispersant; i.e. a poly-acrylate dispersant, an oleaginous release agent and rosin which promotes adhesion of the coating to a paper web, without deleterious effect. The preferred insoluble filler is described in our earlier application as constituting about 85 parts calcium carbonate and about 15 parts #2 coating clay.
Preferred inorganic polyphosphate dispersants employed herein are the hexametaphosphates. Among the st preferred hexa-metaphosphates are sodium hexametaphosphate and zinc substituted sodium hexametaphosphate which are respectively commercially avail-able from Calgon Corporation and from Merck & Company. Preferably, .~ . .
-` about 0.5 parts, calculated on the dry weight basis, of the in-organic polyphosphate dispersant are employed in the composition.
As the .! ' organic dispersant we use an aqueous solution of sodium polyacrylate which is the preferred polyacrylate.
Preferably about 0.7 parts, calculated on the dry weight basis, ; are employed. The sodium polyacrylate dispersants herein contem-` plated are available from Rohm & Haas Company, Dow Chemical Com-pany and Allied Colloids.
-..
. , .. . : :
lO9Z737 The preferred oleaginous release agent for our im-proved composition is sulfonated castor oil. From about 1.5 to about 1.75 parts, calculated on the dry weight basis, of the oleaginous release agent are preferably employed in the coating composition.
The preferred rosin is an acidic thermoplastic pentaerythritol rosin ester, and particularly the sodium salt thereof. Such rosinsare commercially available from Hercules Incorporated. In the most preferred embodiment of the inven-tion about 1.0 parts of the rosin are employed in the composi-tion.
As in our earlier application, the pH of the composi-tion may be adjusted to the desired range by the addition of ammonia thereto. As formulated, the coating composition prefer-ably has a solids content of 55 to about 60%.
In the general preparation of the coating composition,the heretofore disclosed constituents may be added in any appro-priate sequence to a sufficient amount of water to give the desired total solids content and pH thereof.
'I ' .
-;/ 20 The examples that follow are merely exemplary of specific embodiments of the invention, and are not otherwise in-tended to limit the scope thereof. All parts are by dry weight on the composition.
EXAMPLE I
A coating composition is formulated including 3 parts ~ acid hydrolyzed hydroxyethyl ether cornstarch, 8 parts of the ¦ latex including dispersed styrene-butadiene polymer of particle size between 800 and 1300 angstroms, and 8 parts of the latex in-3 cluding dispersed styrene-butadiene polymer of particle size be-j 30 tween 1350 and 1650 angstroms.
-109;~737 EXAMPLE II
A coating composition is formulated including 4 parts - acid hydrolyzed hydroxyethyl ether cornstarch, 8 parts of the . latex including dispersed styrene-butadiene polymer of particle size between 800 and 1300 angstroms, and 6 parts of the latex in-cluding dispersed styrene-butadiene polymer of particle size be-~ tween 1350 and 1650 angstroms.
`~ EXAMPLE III
~' A coating composition is formulated including 5 parts ^ 10 acid hydrolyzed hydroxyethyl ether cornstarch, 6 parts of the :
latex including dispersed styrene-butadiene polymer of particle '~ -~ size between 800 and 1300 angstroms, and 8 parts of the latex in-i.~ ~ cluding dispersed styrene-butadiene polymer of particle size be-. tween 1350 and 1650 angstroms.
The preferred formulation is that of Example III. With that formulation, the drum release of the coatings is at maximum efficiency.
` ~ In employing the formulations in the cast coating of `~ papers, the aqueous coating composition is applied to a paper web and pressed against a rotating heated chromium surface and then dried in the manner described in the above incorporated patents.
By means of the above described coating compositions there are obtained cast coated papers of high printing quality, press per-formance, sheet gloss, water resistance, fold, and freedom from curling.
: `~
, .,;, .
.. ..
Claims (5)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A composition of matter comprising a modified starch of an acid hydrolyzed hydroxyethyl ether cornstarch, a dis-persed styrene-butadiene polymer having a particle size of from 800 to about 1300 angstroms and a solids content of be-tween about 45.0 and about 47.0%, a maximum 200 mesh residue of about 0.075 gms./900 mls., a pH of about 3.8 to about 4.8, a maximum Brookfield viscosity of about 100 cps. and a surface tension of about 43.0 to about 49.0, and a dispersed styrene-butadiene polymer having a particle size of from about 1350 to about 1650 angstroms and a solids content of between about 47.0 and about 49.0%, a maximum 200 mesh residue of about 0.05 gms./900mls., a pH of between about 5.5 and about 6.5, a maxi-mum Brookfield viscosity of about 300 cps., and a surface ten-sion of from about 49.0 to about 55.0; said starch and said two latexes being included in relative proportions of about 1:2:2 dry weight basis on said composition.
2. The improved composition of claim 1, which includes 0.5 parts of a hexametaphosphate as an inorganic dispersant.
3. The improved composition of claim 2, wherein said hexametaphosphate is sodium hexametaphosphate or zinc substi-tuted sodium hexametaphosphate.
4. The improved composition of any of claims 1 to 3, which includes 0.7 parts of an aqueous sodium polyacrylate as an organic dispersant.
5. The improved composition according to any one of claims 1 to 3, which includes from 1.5 to 1.7 parts of sulfonated castor oil as the release agent.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US05/762,522 US4109056A (en) | 1975-05-05 | 1977-01-26 | Starch/latex cast coatings for paper |
| US762,522 | 1991-09-18 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1092737A true CA1092737A (en) | 1980-12-30 |
Family
ID=25065308
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA289,375A Expired CA1092737A (en) | 1977-01-26 | 1977-10-24 | Starch/latex cast coatings for paper |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JPS5394367A (en) |
| BE (1) | BE859286R (en) |
| CA (1) | CA1092737A (en) |
| DE (1) | DE2747301A1 (en) |
| GB (1) | GB1590399A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2958664B1 (en) | 2010-04-07 | 2012-10-26 | Coatex Sas | USING STYRENE LATEX WITH A SIZE OF 100 NM AS A RHEOLOGICAL AGENT IN PAPER-SLEEP SAUCE, SAUCE AND PROCESS FOR OBTAINING SAME |
-
1977
- 1977-09-30 BE BE181384A patent/BE859286R/en active
- 1977-10-21 JP JP12669177A patent/JPS5394367A/en active Pending
- 1977-10-21 DE DE19772747301 patent/DE2747301A1/en not_active Withdrawn
- 1977-10-24 CA CA289,375A patent/CA1092737A/en not_active Expired
- 1977-10-25 GB GB4426977A patent/GB1590399A/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| GB1590399A (en) | 1981-06-03 |
| BE859286R (en) | 1978-03-30 |
| DE2747301A1 (en) | 1978-07-27 |
| JPS5394367A (en) | 1978-08-18 |
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| Date | Code | Title | Description |
|---|---|---|---|
| MKEX | Expiry |