US2657187A - Dilute alkali dispersible hot melt bookbinding adhesives - Google Patents

Dilute alkali dispersible hot melt bookbinding adhesives Download PDF

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Publication number
US2657187A
US2657187A US131908A US13190849A US2657187A US 2657187 A US2657187 A US 2657187A US 131908 A US131908 A US 131908A US 13190849 A US13190849 A US 13190849A US 2657187 A US2657187 A US 2657187A
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US
United States
Prior art keywords
adhesive
hot melt
parts
vinyl acetate
paper
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 - Lifetime
Application number
US131908A
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English (en)
Inventor
Evans John Lloyd
Micucci Dominic Donald
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EIDP Inc
Original Assignee
EI Du Pont de Nemours and Co
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Filing date
Publication date
Priority to BE499917D priority Critical patent/BE499917A/xx
Application filed by EI Du Pont de Nemours and Co filed Critical EI Du Pont de Nemours and Co
Priority to US131908A priority patent/US2657187A/en
Priority to US131900A priority patent/US2657189A/en
Priority to GB29347/50A priority patent/GB689715A/en
Priority to FR1036600D priority patent/FR1036600A/fr
Priority to CH300599D priority patent/CH300599A/de
Application granted granted Critical
Publication of US2657187A publication Critical patent/US2657187A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J131/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid, or of a haloformic acid; Adhesives based on derivatives of such polymers
    • C09J131/02—Homopolymers or copolymers of esters of monocarboxylic acids
    • C09J131/04—Homopolymers or copolymers of vinyl acetate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
    • C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
    • C08L2666/24—Graft or block copolymers according to groups C08L51/00, C08L53/00 or C08L55/02; Derivatives thereof
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S526/00—Synthetic resins or natural rubbers -- part of the class 520 series
    • Y10S526/935—Hot melt adhesive
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T156/00—Adhesive bonding and miscellaneous chemical manufacture
    • Y10T156/10—Methods of surface bonding and/or assembly therefor
    • Y10T156/1002—Methods of surface bonding and/or assembly therefor with permanent bending or reshaping or surface deformation of self sustaining lamina
    • Y10T156/1034—Overedge bending of lamina about edges of sheetlike base

Definitions

  • This invention relates to improvements inthe In applicationSeriaLNo...593.,099, filed May'li0,
  • Adhesive particles are'furtlier deposited on theliot cylinder drying rollswhere their ad hesiveness may be sufliciently great to cause tear-- ing of the felted paper -web as it passes over the drying rolls.
  • aqueous dilute-alkalisolution.
  • Aiurther. object is to. bind the edges. of. pages of books, catalogs and: the like... without stitching'or stapling using.
  • avinyl acetate copolymer,hotmelt adhesive composition which is. dispersible: inaqueous dilute alkali; Stillanothen object istoprovidea book,
  • hesives being durableand-zresistantto.
  • Water butv which. may: be dispersed. in. aqueous: dilute alkali to facilitateuseof paper. trimmings contaminated therewith, and. volumesv subsequently disposed of asst-rap papers These; objects .are accomplished by means; of. a hot, melt; adhesive composition which consists.
  • liquefying softener is used herein to describe softeners, which alter the properties of the vinyl acetate-crotonic acid copolymer from a thermoplastic resinous material having a gradual softening point to a composite blend having a sharply defined melting range as measured by the ball and ring method, said hot melt composition above its melting point rapidly becoming very liquid and capable of wetting and being adsorbed by the paper edges destined to become the backbone of the book.
  • Example 1 The following components were charged into a polymerization kettle equipped with means for agitation, reflux and temperature control.
  • a suitable polymerization initiator is ma azo his (isobutyronitrile)
  • the mixture was constantly agitated at about 95 R. P. M. for the stirrer and the temperature raised to 70 C. and as the polymerization commenced the temperature increased gradually during about six hours to a temperature plateau at about 94 C. under slow reflux without altering the external source of heat, the temperature increase resulting from the conversion monomers to copolymer.
  • 0.25 part of additional azonitrile polymerization initiator was charged into the kettle and polymerization continued under moderate to fast reflux for five additional hours during which time the temperature increased to a new plateau of about 105 C. Polymerization was then stopped by addition of 0.5 part of Ionol inhibitor, which is a Shell Chemical Company proprietary antioxidant. Ionol is described as one of the trialkyl-substituted hindered phenols having antioxidant properties,
  • each of the said alkyl groups containing not more than 4 carbon atoms. More specifically, it is identified as 2,6 di-tertiary butyl 4 methyl phenol having a molecular weight of 220.3 and a melting point of 70 C.
  • the unpolymerized vinyl acetate was removed by vacuum distillation at 50 mm. of mercury until the temperature of the melt reached 160 C. 86.8 parts of vinyl acetate were recovered as the distillate and the recovered product was 440 parts leaving an unaccountable loss of about 8 parts which apparently was vinyl acetate.
  • the product was calculated as having the following composition:
  • the copolymer is estimated to consist of 93.6 parts vinyl acetate and 6.4 parts crotonic acid.
  • This hot melt adhesive was found to be thermally stable for 96 hours and longer at 160 C.
  • dilute aqueous alkali solutions is meant herein alkalinity of the order of the magnitude of 05% sodium hydroxide or its equivalent.
  • This hot melt adhesive used to bind books as shall be described later yielded an excellently bound volume having a tough, flexible backbone which was waterproof and resistant to deterioration with age and exposure to atmospheric conditions.
  • the monomers may be copolymerized in orthodox solvents and subsequently compounded with the liquefying softener and other desirable components to form the hot melt adhesive composition from which the solvent had been removed by distillation.
  • the following example illustrates this practice.
  • Example 2 The following composition was charged into an agitated polymerization kettle.
  • a suitable polymerization initiator is azo bis (isobutyronitrile).
  • the copolymer was estimated to contain about 5.6 parts of crotonic acid and 94.4 parts vinyl acetate.
  • This hot melt adhesive was equivalent to that of Example 1, exhibiting heat stability for 96 hours and longer at 160 C. without loss of its dispersibility in dilute alkali. Likewise applied in the art of binding books with hot melt adhesives,
  • Othenfields of adhesive application may tolerate sacrifice'in these properties andfin'd utility for hot melt adhesives formulated with copolymers rhavinga higher content "than 10f nrotonic zacid coprolturn-miced
  • hot melts might he used .ior attachment of Elabe'ls :to glass :and metal containers *where it desirable to subsequently remove .the :label by soaking in very dilute aque ous alkali solutions.
  • Di(methyl 'Gel-losolve) 'phthalate and triethyl citrate are particularly useful for ipl'asticizi-ng the vinyl acetate- 90 crotonic acid copolymer adhesive.
  • 'liricresyl phosphate, dicresyl carbitol, butyl'phthallyl butyl 'g'lycollate, ortho-cresyl para-toluene sulfonate and polyethylene glycol di z-ethyl hexoate may also be used.
  • the latter palsticizer shows exceb lent compatibility with polyvinyl acetate, but its compatibility with 'thev inyl acetate-crotonic acid copo'lymer is more limited and in some instances it may not be used to the frill extent-of 10%.
  • the adhesive used for'bind- 'ing pages without the reinforcing action or staples or stitched thread to form the backbone of the volume must be "characterizedby greater toughness, flexibility and'freedom'from cold flow than adhesives used for other binding purposes, such as 'for attaching the-cover'to the said backbone. Consequently, "for purposes of economy, the "adhesive ncrmallyused informing the "backbone may be modified with low cost diluentswhen used as a cover adhesive.
  • the following example is representative of a satisfactory cover adhesive which may be used either in combination'with the hot melt "bound backbone or "alone to attach covers to stitchedior stapled volumes.
  • Polymerization was carried out for about TI hours While the temperature increased lfrom 170 to .91 C. Then .25 part of additional polymerization 10 initiator were charged. into the kettle and the temperature increased from 81 .0. J30 .a -,plateau at .97 'C. in about ,five hours. At this temperature, polymerization was arrested :by additionnf .5 part aQJf (Honor). 220 parts of sulione were charged into the hot nosolution and distillation was-commenced under :50 mm. vacuum to displace the toluene and remove the excess vinyl acetate. Distillation was stopped at 160 C., 200 grams of distillate having been recovered.
  • the examples illustrat the invention using d'ixyly'l su'lfone as the liquefying softener.
  • Other methylated diaryl monosulfones having at least one methyl substituen't on each 'aryl group or mixtures thereof may be substituted i like amount.
  • the various isomeric forms of ditolyl sulfone and :xylyl toly'l sulfone are also particularly useful as the lique'fy'ing softener for the hot-melt adhesives of this invention.
  • Example '3 shows the use of resinous and mineraldiluents. Still other'diluents which are inert, non-volatile and heat stable for periods of 72 hours and longer in the presence of the hot melt composition at C. may be used. Cotton flock, regenerated cellulose flake particles, glass fibers and the like which are generally characterizedby dimensions ofwhich the maximum on the average is about ;12 :inch and the ratio "between'length and diameter or thickness is in the range of 20-100 to 1, may also beused as diluents. Embedded in the applied adhesive, they exhibit reinforcing strength. Obviously due to "matting eifects, the amount of this diluent is limited. 'In the art of binding books and .cover application, it is preferred that the content of this type of diluent does not exceed 7% based on the total adhesive composition.
  • the solvent used as a polymerization medium has an effect on the molecular weight of the polymer .or copolymer.
  • tertiary butanoil was used as solvent in place of toluene, .a higher intrinsi viscosity product was obtained.
  • these .copolymers have viscosities in the .range of commercially .low viscosity vinyl acetate .pclymers.
  • fIhe copolymerization can also be carried out in 'Ihenzene or .ethyl a1- co'hdl.
  • the nature .of the polymerization initiator- also affects the molecular weight .of the .copolymer.
  • Peroxide initiators .such as lauroyl peroxide and benzoyl peroxide, and .azonitrile initiators, such as -d'.,rz' .azo-bisiisobutyronitrile) and 0.,11' azo- -bis.(.alpha-gamma dimethyl') (valeronitrile) give copolymers having melocular weights which are satisfactory for hotmelt adhesives and which are dispersible indilute alkali.
  • any polymerization initiator which is satisfactory for the polymerization of vinyl acetate can be used :for the icopolymerization of vinyl acetate and raretonicacid.
  • Example 4 100 parts by weight or medium viscosity polyvinyl acetate were intimately mixed with parts of phthalic anhydride and melted at a temperature of about 160 C. and with the kettle equipped with a reflux condenser, 10 parts of water were slowly added with continuous agitation of the charge. After 1 hour heating, distillation of the volatiles was commenced and heating continued for four hours. The distillate consisted of acetic acid and water, indicating that some ester interchang occurred between the vinyl acetate polymer and the phthalic acid.
  • This modified polymer was found to be alkali soluble, at caustic soda concentrations of about 1.9% but not at the a desired concentration of 0.1% and less, preferably about parts of this polymer and 50 parts of a iiquciying softener were meltblended at about 160 C. to form a hot melt adhesive.
  • the product was not heat stab-l as evidenced by gelation and charring.
  • Crosslinking of the polycarboxylic phthalic acid by ester interchange in the vinyl acetate polymer presumably accounted for the gelation.
  • Monofunctional acid reacting olefinic unsaturated materials which satisfactorily copolyinerize with vinyl esters, particularly vinyl acetate were also tried.
  • Acrylic acid and metha'crylic acid polymerized in the presence of vinyl acetate yielded polymer compositions of non-uniform quality, apparently constituting mixtures of homopolyrners and copolymers due to the significant difference in relative reactivities of the vinyl acetate and the acrylic and methacryiic acid in copolymerization.
  • the adhesives of the present invention may be used. as other hot-melt adhesives in binding books.
  • the basic design of a machine commer" cially used binding books using glue is the bookibinding covering machine described in the Bredenburg U. 5.
  • the folded signatures subsequently to become pages of the bound vol ume are assembled between fiat metal plates held together under pressure, the position of the gathered signatures being adjusted between the clamping plates to leave about ⁇ -6- to /4 inch of page backbone edge exposed after the cutting operation has trimmed oi? the signature folds to reduce the signatures to a plurality of pages.
  • the assembled clamped signatures are then passed. through cutter to remove the said signature folds.
  • the backbone now having a smooth uniform edge is subjected to roughers which serve the purpose or" opening up the fibers at the edges of the pages to make them more receptive to the adhesive composition to provide better keying action by permitting the composition to penetrate into the interstices.
  • Roughing may vary in degree and pattern to produce the desired keying action.
  • the roughened edge is then freed of loose extraneous material by brushing, airblast or vacuum means.
  • the hot melt adhesive is applied to the backbone edge by means or a conventional applicator roll consisting of a fiat surfaced wheel revolving in and about immerse-o. in a hot melt adhesive, such as described in Examples 1 and 2, maintained at a temperature of about 166 C.
  • An adjustable scraper-doctor blade or metering hot spinner removes the excess adhesive, leaving the desired thickness of film on the backbone.
  • the adhesive application may be single stage or by multiple coats applied by subjecting the baclo bone to a series of adhesive applicators.
  • the application of a. priming coat may precede the application of the principal hot melt adhesive.
  • the primer is generally identical with the solvent-free, hot melt adhesive except it is cut with a volatile solvent which reduces the viscous hot melt to a very thin, penetrating liquid.
  • the use of the primer necessitates provision of adequate means of substantially removing the volatile component of the applied primer prior to application of the hot melt.
  • dilute alkali dispersibility is the object of the invention, it is pertinent that the deposited primer, like the principal adhesive, be characterized by that property.
  • an aqueous dispersion of polyvinyl acetate containing a smal percentage of polyvinyl alcohol as the dispersing and stabilizing agent may be used as a primer.
  • the polyvinyl alcohol promotes redispersibility of the deposited primer in aqueous media, although a hot-melt adhesive formulated with vinyl acetate polymer is inadequate y dispersible in dilute aqueous alkali solutions.
  • Example 3 which contains economical diluents is representative of a solvent free hot melt adhesive entirely satisfactory for cover application.
  • the covering machine often is separate from the main bookbinding machine which provides the means of converting the signatures to an uncovered volume having an adhesively bound backbone. Consequently, the covering operation using a hot melt adhesive may be employed in covering magazines, pocketbooks,
  • the waste paper and scrap contaminated with the adhesives of this invention formulated essentially with a copolymer consisting of the polymerization product of 90 to 98 parts vinyl acetate and 10 to 2 parts of crotonic acid and a compatible liquefying softener present no problem to the paper converter inasmuch as the adhesive is solubilized or dispersed in aqueous dilute alkali solution containing .05% sodium hydroxide, although dispersion in .01% caustic has been obtained by lengthening the contact time.
  • the trim or adhesive contaminated waste paper is generally consumed by paper mills in the manufacture of new paper. In some mills, as high as 80% of the furnish is Waste paper with 20% being virgin pulp and the waste paper generally being magazine stock. Such operations involve repulping and de-inking steps which are described briefiy to indicate that alkaline conditions adequate for dispersion of the adhesives of this invention exist in current practices.
  • Repulping or defibering of the waste paper is carried out in a breaker beater or hydrapulper where the waste paper is subject to mechanical action at a consistency of paper and 95% water. During this mechanical operation, chemicals such as alkali, wetting agents, etc. are added for the purpose of de-inking the stock. De-inking is generally carried out at elevated temperatures in the range of110 F. to about 180 F.
  • the paper was repulped at a consistency of 4.5% and for de-inking the temperature was raised to 170 F., with a 6.0% sodium silicate and 1.4% sodium peroxide, on the basis of dry weight paper, being added as the de-inking chemicals.
  • the processing cycle was three hours.
  • the alkalinity is in excess of the .05% suggested as the most suitable concentration for dispersing the hot melt adhesive.
  • a distinct advance in the art of bookbinding, particularly in the art of binding books, magazines, catalogs and the like with a solvent-free, hot melt polymeric resinous adhesive has been made by the use of adhesives comprises essentially of a copolymer consisting of the polymerization product of to 98 parts by weight of vinyl acetate and 10 to 2 parts of crotonic acid and a liquefying softener, the latter being present preferably in the range of /2 to 2 parts for each part of copolymer.
  • hot melt adhesives characterized by dispersibility or solubility in aqueous dilute alkali at concentrations as low as .01% NaOH equivalent, preferably about .05% serves to eliminate a serious disposal problem in reference to use of waste paper contaminated with hot melt polymeric adhesive which heretofor was not dispersible during conventional waste paper processing.
  • a hot melt adhesive which is dispersible in a .05% aqueous alkali solution which comprises one part of a copolymer of from 90 to 98 parts of vinyl acetate and 10 to 2 parts of crotonic acid; and from to 2 parts of a liquefying softener consisting essentially of a methylated diaryl sulfone having at least one but not more than two methyl substituents on each aryl group.
  • composition of claim 1 which contains less than about 10% of a compatible solvent plasticizer.
  • composition of claim 1 in which the liquefying softener is ditolyl sulfone.
  • composition of claim 1 in which the liquefying softener is tolyl Xylyl sulfone.
  • composition of claim 1 in which the liquefying softener is a mixture of isomeric methylated diaryl sulfones.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Adhesives Or Adhesive Processes (AREA)
US131908A 1949-12-08 1949-12-08 Dilute alkali dispersible hot melt bookbinding adhesives Expired - Lifetime US2657187A (en)

Priority Applications (6)

Application Number Priority Date Filing Date Title
BE499917D BE499917A (https=) 1949-12-08
US131908A US2657187A (en) 1949-12-08 1949-12-08 Dilute alkali dispersible hot melt bookbinding adhesives
US131900A US2657189A (en) 1949-12-08 1949-12-08 Dilute alkali dispersible hot melt bookbinding adhesives
GB29347/50A GB689715A (en) 1949-12-08 1950-11-30 Improvements in and relating to adhesives and their use in book binding
FR1036600D FR1036600A (fr) 1949-12-08 1950-12-05 Adhésifs dispersables dans les alcalis dilués et fusibles à chaud pour reliure
CH300599D CH300599A (de) 1949-12-08 1950-12-07 In der Wärme schmelzendes Klebmittel.

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US131908A US2657187A (en) 1949-12-08 1949-12-08 Dilute alkali dispersible hot melt bookbinding adhesives

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US2657187A true US2657187A (en) 1953-10-27

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BE (1) BE499917A (https=)
CH (1) CH300599A (https=)
FR (1) FR1036600A (https=)
GB (1) GB689715A (https=)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2850471A (en) * 1956-04-09 1958-09-02 Du Pont Water dispersible polymer film composition
WO2018136679A1 (en) * 2017-01-20 2018-07-26 Danimer Bioplastics, Inc. Biodegradable hot melt adhesives

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2806020A (en) * 1952-02-08 1957-09-10 Monsanto Chemicals Copolymers of vinyl acetate and ethylenically unsaturated carboxylic compound havingat least one carboxyl group, compositions prepared from said copolymers and sizing of textile yarns with said compositions
US2715590A (en) * 1952-11-24 1955-08-16 Pont Company Of Canada Ltd Du Process for sizing nylon yarn

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1659401A (en) * 1922-08-16 1928-02-14 Kirschbraun Lester Process of recovering waste fibrous material
US1819159A (en) * 1929-04-11 1931-08-18 Pneumatic Scale Corp Book
US2127400A (en) * 1937-06-25 1938-08-16 Goodrich Co B F Plasticizers
US2249545A (en) * 1939-09-13 1941-07-15 Eastman Kodak Co Polyvinyl acetal resin sheets containing a mixture of dibutyl sulphone and dibutyl phthalate
US2263598A (en) * 1937-04-30 1941-11-25 Gen Aniline & Film Corp Interpolymerization product of vinyl acetate and crotonic acid
US2310725A (en) * 1942-10-10 1943-02-09 Widder & Co J Index directory
US2390695A (en) * 1942-04-25 1945-12-11 Socony Vacuum Oil Co Inc Method of treating paper stock

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1659401A (en) * 1922-08-16 1928-02-14 Kirschbraun Lester Process of recovering waste fibrous material
US1819159A (en) * 1929-04-11 1931-08-18 Pneumatic Scale Corp Book
US2263598A (en) * 1937-04-30 1941-11-25 Gen Aniline & Film Corp Interpolymerization product of vinyl acetate and crotonic acid
US2127400A (en) * 1937-06-25 1938-08-16 Goodrich Co B F Plasticizers
US2249545A (en) * 1939-09-13 1941-07-15 Eastman Kodak Co Polyvinyl acetal resin sheets containing a mixture of dibutyl sulphone and dibutyl phthalate
US2390695A (en) * 1942-04-25 1945-12-11 Socony Vacuum Oil Co Inc Method of treating paper stock
US2310725A (en) * 1942-10-10 1943-02-09 Widder & Co J Index directory

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2850471A (en) * 1956-04-09 1958-09-02 Du Pont Water dispersible polymer film composition
WO2018136679A1 (en) * 2017-01-20 2018-07-26 Danimer Bioplastics, Inc. Biodegradable hot melt adhesives
CN110494521A (zh) * 2017-01-20 2019-11-22 丹尼米尔生物塑料有限公司 可生物降解的热熔粘合剂
CN110494521B (zh) * 2017-01-20 2022-05-03 丹尼米尔生物塑料有限公司 可生物降解的热熔粘合剂

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FR1036600A (fr) 1953-09-09
BE499917A (https=) 1900-01-01
CH300599A (de) 1954-08-15
GB689715A (en) 1953-04-01

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