US2665206A - Sizing of fibrous materials and compositions useful for sizing and for other purposes - Google Patents

Sizing of fibrous materials and compositions useful for sizing and for other purposes Download PDF

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Publication number
US2665206A
US2665206A US33218A US3321848A US2665206A US 2665206 A US2665206 A US 2665206A US 33218 A US33218 A US 33218A US 3321848 A US3321848 A US 3321848A US 2665206 A US2665206 A US 2665206A
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United States
Prior art keywords
sizing
naphthenic
acid
naphthenate
emulsion
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US33218A
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English (en)
Inventor
Theodore F Bradley
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Shell Development Co
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Shell Development Co
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Publication date
Priority to NL72781D priority Critical patent/NL72781C/xx
Application filed by Shell Development Co filed Critical Shell Development Co
Priority to US33218A priority patent/US2665206A/en
Priority to DEP45604A priority patent/DE886409C/de
Priority to FR988219D priority patent/FR988219A/fr
Priority to GB15935/49A priority patent/GB678561A/en
Application granted granted Critical
Publication of US2665206A publication Critical patent/US2665206A/en
Anticipated expiration legal-status Critical
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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
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/62—Rosin; Derivatives thereof
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/02—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with hydrocarbons
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/01—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with natural macromolecular compounds or derivatives thereof
    • D06M15/17—Natural resins, resinous alcohols, resinous 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
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/03—Non-macromolecular organic compounds
    • D21H17/04—Hydrocarbons
    • 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
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/03—Non-macromolecular organic compounds
    • D21H17/05—Non-macromolecular organic compounds containing elements other than carbon and hydrogen only
    • D21H17/14—Carboxylic acids; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
    • C09K23/34—Higher-molecular-weight carboxylic acid esters

Definitions

  • An important object of the present invention is to provide alsizing agent which overcomes the ,foregoing disadvantages of conventional sizeszand which will be more economical .to manufacture -and use.
  • Another important .obj ect . is to provide :a paper sizing composition whichrmay be derived entirely from petroleum.
  • a further object is to provide improved articles of manufacture, :pechicularlysized paperand the like, which are-more water-resistant than :prior products .of a similar :type.
  • Still another object is to provide new emulsifiable compositions which are useful not only as sizing agents but also have other imp a -M srs i l be m fully p ted e hereinafter.
  • 2 pus composition for sizing paper and related fibrous materials comprises a novel mixture of salts of naphthenic acids having acid numbers less than 200 with conventional sizing agents, or preferably with the predominantly cyclic extracts obtainable from mineral oils.
  • the naphthenic acids and naphthenic acid'salts used will be referred to generically hereinafter as naphthenat'es'.
  • the acid numbers of the naphthenic acids as used herein refer to the number of milligrams of potassium hydroxide which will neutralize the acids in a one-gram sample of the naphthenic acids.
  • An especially advantageous source of naphthenates having desirable properties for use in the invention is the n'aphthen'ates produced in the refining of petroleum and its various products, particularly lubricating oil.
  • Methods which are suitable for producing naphthenates which-may be used in the new compositions of the invention provided suitable starting materials are selected and/or the :naphthenic acids are properly treated to insure that the final product will be naphthenates hjaving acid numbers less than 200, preferably acid numbers ofabout to 175, include, for examplefa'lkali treatment of acid-refined petroleum distillates, or the caustic distillation of mineral oils, particularly oils from Texas and California crudes, to obtain oil-containing naphthenates which may be used as such or maybe partially purified'by acidtreatment or more completely deoiled by dispersion in an aqueous medium followed by de-emulsification in the presence of a solventfor-the oil.
  • the chosen naphthenate or naphthenate mixture corresponding to naphthenic acids having acid numbers less than 200 is preferably used in sizing as an aqueous emulsion with a sizing agent, preferably a sizing agent of the hydrocarbon type, most preferably the aromatic extracts of mineral oils previously referred to. It is a special advantage of these naphthenates that they not only improve the sizing but also are capable of forming stable emulsions of the water-in-oil type with hydrocarbon type sizing agents, particularly the cyclic extracts of petroleum which may be readily inverted to emulsions of the oil-in-water'type which are quite stable, yet are precipitable in the presence of paper fibers by the usual paper makers precipitants. This unusual combination of desirable properties makes it feasible. to prepare very cheaply highly effective sizing compositions as concentrated water-in-oil typeemulsions which can be conveniently shipped"'a't' low cost,
  • the sizing may also be carried out in the Jordan machine or at the screens.
  • aecaao 4 solvents may be used for the preparation of such extracts, liquid sulfur dioxide, phenol, cresylic acid, furfural, beta,beta-dichlorethyl ether, nitrobenzene, the sulfolanes and sulfolenes, and the like being typical examples of suitable solvents.
  • aecaao 4 solvents may be used for the preparation of such extracts, liquid sulfur dioxide, phenol, cresylic acid, furfural, beta,beta-dichlorethyl ether, nitrobenzene, the sulfolanes and sulfolenes, and the like being typical examples of suitable solvents.
  • Extracts of heavier petroleum oils such as the lubricating oils and residual stocks are especially useful inthe new sizing compositions of the invention, but other fractions of petroleum or related hydrocarbon products can also be used successfully as sources of the extracts.
  • the ex tracts may be derived, for example, from lubricant distillates-or .bright oils or cylinder stocks which may, for instance, range in gravity from I to 8 API at 60 F. They may be obtained wide range of precipitants may be used for fixing the new sizing compositions on the fibers.
  • Alum, aluminum sulfate, calcium chloride, acids such as sulfuric or hydrochloric acid, and the like are all suitable, but paper makers alum is preferred.
  • the precipitant may be added to the fiber along with the size but generally it is preferred to add it later in the process, thus providing adequate time for uniform distribution of the size before
  • the amount of naphthenate size which it will be most advantageous to employ will dependvon the nature of the fibrous material being treated, the purpose for which it is intended, thetype of naphthenate chosen, and the method of its application. As little as 0.2% based on the dry weight of the paper iseifective but up to 10% or more may be used, the preferred range being usually about 0.5% to about 3%.
  • Oils or waxes such as, for example, mineral waxes such as paraffin,
  • the cyclic extracts used in the new compositions of the invention are the products of predominantly aromatic and naphthenic nature, obtainable by extracting petroleum or related oils, including hydrogenation products of coal-and the like, with solvents which are selective for nonparaffinic constituents.
  • a wide variety of polar from” any mixed type petroleum oil such as Mid- Continent or Coastal or California crude or, in lower yields, from Pennsylvania type oils.
  • extracts boiling above 300 C. at 760 mm. Hg pressure are preferred, and most preferably extracts boiling from about 125 C. to 300 Cat 1 mm. Hg pressure are used.
  • the emulsifying properties of the naphthenate chosen may be supplemented by addition of a small amount, usually about'0.l% to 5% by weight of the naphthenate and hydro.- carbon present, of another emulsifying agent.
  • Soap, higher alkyl sulfate salts, organic sulfonic acid salts, particularly alkyl aryl sulfonates,-sodium rosinate and the like may be usedi-as supplementary emulsifying agents where the naphthenate employed is not itself sufiicient to insure the desired stability in the emulsion, either on account of the acid number of the naphthenic acid used being too high or because an insuflicient amount is used.
  • the mostadvantageous sizing emulsions are those made from naphthenates of acid. number less than 200 without other emulsifying agents.
  • alkaline agents may be used in preparing the emulsions. Hydroxides or carbonates of alkali metals or ammonia are suitable; sodium or potassium hydroxides are preferred hydroxides, however, becauseof their relatively low cost. The corresponding, particularly the sodium and potassium, carbonates require higher temperatures and are thus somewhat less preferable. Alkaline earth hydroxides such, for example, as calcium and magnesium hydroxides, etc. may also be used. For certain purposes, neutralization with an organic base such, for example, as aliphatic, alicyclic or aromatic, primary, secondary or tertiary amines or quaternary a1.-- monium bases, is advantageous.
  • Water soluble amines such, for instance, as dimethylamine,-prcpylamine, cyclohexlamine, the ethanolamines, etc. may be used in such cases.
  • the chosen base is preferably employed as an aqueous solution of about 5% to about 30% concentration, most preferably about 5% to concentration.
  • the moststable emulsions are prepared by the use of slightly less than the stoichiometric amount of base, preferably about 85% to 95% of the amount required for neutralization of the naphthenic acids.
  • a pH of about 8 to 13, preferably 10 to 11.5, is advantageous in the final emulsion. If the initial emulsion is too acid or alkaline it can be brought to the desired pH by adding a weak base or acid.
  • the emulsionsizes of the invention made with naphthenates of acid number less than 200 are highly stable compositions which do not coagulate readily in the absence of cellulose fibers.
  • these emulsions occasionally show some phase separation on long standing but can be brought backto a homogeneous state by shaking or stirring. Even this separation can be eliminated by adding small amounts of protective colloids such, for instance, as casein and gums.
  • the invention is, of course, not limited to the method of preparing new emulsion sizes de scribed, asotherprocedures arealso applicable.
  • it is feasible to produce highly effective sizes by mixing together a cyclic extract of lubricating oil, for instance, and previously neutralized naphthenic acids of acid number less than 200, preferably .the sodium naphthenates, followed by dilution with the required amount of water.
  • the emulsions of sodium naphthenates of :-acid number less than 200'and high boiling hydrocarbons obtainedv as bottoms fromzthe refining of petroleum :oils by distillation in the presence of caustic soda are also very suitable for sizing according to the invention.
  • the new sizes of the invention may be used without any other change in the paper-making process. "They are preferably precipitated on the fiber with paper makers alum and a pH of about 4.5 too, depending on the type of pulp, is desirable during precipitation. If necessary, the pI-I may be controlled by adding diluteacid in the beater. About 25 grams of aluminum sulfate per kilogram of dry stuff in the beater gives satisfactory precipitation. Too much aluminum in the paper should be avoided as it adversely affects the permeability to water.
  • the sizes of the invention may be used in making papers filled with kaolin and the like as well as in making unfilled papers.
  • the new sizes also do not give any complications with paper dyestuffs. They are not only cheaper than the usual sizes but also have the advantage that the sizing effect obtained is greater than would be expected from sizing with either of the constituent parts of the product alone.
  • Example I To show the superiority of the compositions of the invention to rosin in emulsion sizes using a furfural extract of a lubricatingoil distillate of California petroleum (motor grade lubricating oil having a viscosity of 200 at 210 F'.,.S. U..S:), four emulsions were prepared-byadding suflicient 10% sodium hydroxide solution to mixtures .of the extract and de-oilednaphthenic acid of :acid number 150 or'rosinto-saponify of the acid. The resulting water-in-oil emulsion was mixed with moderate agitation for 15 minutes. The emulsion was then inverted by addition of water to form a 50 oil-in-Water emulsion. Agitation during inversion was afforded by an Eppenbach homo-mixer using as high a rate of shear as possible without incorporation of air.
  • a furfural extract of a lubricatingoil distillate of California petroleum motor grade lub
  • the size emulsions were diluted to 1% oil-inwater and addedto kraft beaten pulp (2 of size' P t b 'Purgstoty or s y weig weight of naph- Parts by am (if exttheiiicf weight g rac aci o of rosin used l50'acid (mm') (mm'2) number Using a lower boiling fraction" of furfural extract of viscosity 60 at 210 F. instead of that used above, the sizing was not as satisfactory but was still superior in the case of the size containing naphthenate of acid number 150. 5
  • Example II The fluorescent size test was carried out as dedescribed by Van den Akker et al. in the Paper Trade Journal, vol. 109, page 33 (1939), and shows clearly the superiority of the naphthenatearomatic extract mixture.
  • Example IV The superior stability of the emulsion compo-' sitions of the invention is shown by the following results for emulsions of a highly aromatic extract having a viscosity at 210 F. of 2030 obtained from an industrial lubricating oil distillate of California petroleum having a viscosity of 200 at 210 F., S. U. S. All the emulsions were prepared in the same way.
  • Example III Comparative tests were made on the use of an aromatic extract of petroleum having a viscosity at 210 F. of 537 'S. U. S. with naphthenic acids of 150 acid number containing about 3% of oil, on the one hand, and an equal amount 55 of rosin, on the other.
  • the emulsions were prepared by mixing 80 parts of the extract with parts of the naphthenic acid or rosin, 1.9 to 2.1 parts of sodium hydroxide and 100 parts of water in a Waring Blendor for minutes at 0., then adding water to form a 50% emulsion and continuing the mixing for 30 minutes.
  • the emulsions were used to size kraft paper, as described in Example I, with the following re- Composition (parts by weight per parts Stabilit water) y Emulsion particle size 95 lub. oil distillate, 5
  • Emulsion broke could not be measured immediately.
  • Dry indicator test (TAP- PI standard proc dure) 41 sees. for penetration Fluorescent size test seconds The other emulsions were too unstable to warrant size testing.
  • Example V The superiority of the emulsions of aromatic extracts with naphthenates of acid numbers less than 200 compared with similar composition prepared with'high acid number naphthenates is shown by the following results for emulsions containing 50% water, 45.5% of an Edeleanu extract of viscosity 79.8 S. U. S. at 210 F. from a lubricating oil distillate of viscosity 60 S. U. S.
  • Acid Aver Ml. of upper phase number age separated from of oilmole- Per- 80 m1, of emulfree cular cent 5 i o n a f t e r Form ofnaphthenate naph weight oil in (hours) thenic of crude acid, ifiiphacid mg. emc KOH/g acid 4 8 20-24 44-48 196 Sodium naphthenate. 118 475 3. 2 2 2.
  • W ile the advanta e of t e ne omp itio 'of the invention in sizing paper and related fibrous materials, particularly cellulose fibers and the like, have been emphasized in the foregoing because of the special importance of this novel application of these products, they have many other advantageous uses.
  • they are particularly suitable as agricultural sprays where a thin, sticky residual film on the plants is desirable to keep the insecticide or fungicide or the like from being blown off after application. They are also useful in aqueous paint emulsions, particularly when, as is preferred, extracts having drying properties are used in their preparation.
  • Such emulsions are advantageously pigmented by adding a separately prepared slurry of pigment, for example, lithopone, zinc oxide, titanium dioxide, ochre, iron oxide or the like, preferably containing glue, to the emulsion with stirring, in the proportions of about 50 to 700 parts of pigment per 100 parts of emulsified extract and naphthenate.
  • pigment for example, lithopone, zinc oxide, titanium dioxide, ochre, iron oxide or the like, preferably containing glue
  • Paper pulp having on the surface thereof a precipitate from an emulsion of a sizing agent comprising cyclic components of a lubricating oil fraction of petroleum soluble in a polar solvent having a preferential solubility for the aromatic and naphthenic components, and having a viscosity of 75 to 5000 S. U. S. at 210 F., together with sodium naphthenate salts derived from naphthenic'acids having an average acid number between 100 and 200, the amount of said naphthenic salts being from about 3% to 75% of the total weight of said salts and said cyclic components.
  • a process of preparing an emulsion of hydrocarbon with water which comprises intimately contacting a liquid cyclic extract of predominantly aromatic and naphthenic nature derived from a mineral oil with 5% to 50% by weight of naphthenic acids having an average acid number between about 100 and 200, reacting the mixture with an aqueous solution of sodium hydroxide of 5% to 15% concentration sufiicient to neutralize 85% to 95% of the naphthenic acid a d. form an muls on o the water n-o t p and diluting said emulsion with'water to bring the total water content of the mixture to 40% to and form an emulsion of said hydrocarboil in water.
  • An emulsion of the water-in-oil type suitable for use as a siz ng agent and for other purposes comprising to parts of a mixture of cyclic components of a lubricating oil fraction of petroleum soluble in a polar solvent having a preferential solubility for the aromatic and naphthenic components, together with a naph thenate salt derived from naphthenic acids having an average acid number between about and 200 in an amount from about 3% to 75% based on the total weight of said cyclic components and said naphthenate salt, and 20 to 40 parts of water.
  • a mixture of a cyclic extract of predominantly aromatic and naphthenic nature obtained by extracting a lubricating oil fraction of petroleum with a polar solvent having a preferential solubility for the aromatic and naphthenic components, together with 3% to 50% of a naphthenate salt derived from naphthenic acids having an average acid number between 100 and 200, said percentage being based on the total weight of said nap-hthenate salt and extract present.
  • Cellulose fibers having the surfaces thereof coated with a precipitate of a cyclic extract of predominantly aromatic and naphthenic nature from a mineral oil, together with from about 3 to 75% of naphthenate salts derived from naphthenic acids having an average acid number of between 100 and 200, said percentage being based on the total weight of naphthenates and extract present.
  • a paper product comprising cellulose fibers having distributed on their surface 0.5% to 5% by weight of the dry fibers of a mixture of a sizing agent made up of a cyclic extract of a mineral oil, which extract is of predominantly aromatic and naphthenic nature, together with a naphthenate salt derived from naphthenic acids having an average acid number between about 100 and 200, said naphthenate salt being present in the amount of 3% to 50% of the total weight of said sizing agent and naphthenate salt.
  • Cellulose fibers having on their surface a sizing agent precipitated thereon from an emulsion of the oil-in-water type essentially comprising at least 40% by weight of Water, a liquid cyclic extract of predominantly aromatic and naphthenic nature derived from petroleum hydrocarbons and having a viscosity of 75 to 5000 S. U. S. at 210 F., together with sodium naphthenate salts derived from naphthenic acids having an average acid number of between about 100 and 200, said sodium naphthenates being present in an amount of 3% to 50% by weight of the total amount of said naphthenate salts and extract.
  • Paper pulp having on the surface thereof a mixture of cyclic components soluble in solvents having a preferential solubility for the arcmatic and naphthenic components extracted, to-
  • An emulsion of the oil-in-water type essentially comprising at least 40% by Weight of water, a liquid mixture of cyclic components of petroleum having a viscosity of 75 to 5000 S. U. S. at 210 F. which are soluble in a polar solvent having a preferential solubility for the aromatic and naphthenic components, and sodium naphthenate salts derived from naphthenic acids having an average acid number between about 100 and 200, said sodium naphthenates being present in an amount of 3% to 50% by Weight of the total amount of naphthenates and said cyclic components.
  • An emulsifiable composition comprising a mixture of cyclic components extracted from petroleum hydrocarbon having a. viscosity of at least 100 S. U. S. at 210 F., and which are soluble in solvents having a preferential solubility for aromatic and naphthenic components, together with sodium naphthenate salts derived from naphthenic acids having an average acid number between 100 and 175.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Paper (AREA)
  • Liquid Carbonaceous Fuels (AREA)
  • Materials Applied To Surfaces To Minimize Adherence Of Mist Or Water (AREA)
US33218A 1948-06-15 1948-06-15 Sizing of fibrous materials and compositions useful for sizing and for other purposes Expired - Lifetime US2665206A (en)

Priority Applications (5)

Application Number Priority Date Filing Date Title
NL72781D NL72781C (de) 1948-06-15
US33218A US2665206A (en) 1948-06-15 1948-06-15 Sizing of fibrous materials and compositions useful for sizing and for other purposes
DEP45604A DE886409C (de) 1948-06-15 1949-06-12 Verfahren zum Leimen von Faserstoffen u. dgl.
FR988219D FR988219A (fr) 1948-06-15 1949-06-13 Procédé et compositions convenant à l'encollage des matières fibreuses
GB15935/49A GB678561A (en) 1948-06-15 1949-06-15 Compositions for sizing and other purposes and processes involving their use

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US33218A US2665206A (en) 1948-06-15 1948-06-15 Sizing of fibrous materials and compositions useful for sizing and for other purposes

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US2665206A true US2665206A (en) 1954-01-05

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US33218A Expired - Lifetime US2665206A (en) 1948-06-15 1948-06-15 Sizing of fibrous materials and compositions useful for sizing and for other purposes

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US (1) US2665206A (de)
DE (1) DE886409C (de)
FR (1) FR988219A (de)
GB (1) GB678561A (de)
NL (1) NL72781C (de)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3008868A (en) * 1957-12-23 1961-11-14 Armstrong Cork Co Drainage rate of cellulosic papermaking slurries
US4349455A (en) * 1979-03-27 1982-09-14 Fuji Photo Film Co., Ltd. Emulsification process
US4956049A (en) * 1984-08-06 1990-09-11 Ciba-Geigy Corporation Process for sizing paper with anionic hydrophobic sizing agents and cationic retention aids
US4996004A (en) * 1982-08-14 1991-02-26 Bayer Aktiengesellschaft Preparation of pharmaceutical or cosmetic dispersions
US5116536A (en) * 1982-08-14 1992-05-26 Bayer Aktiengesellschaft Preparation of pharmaceutical or cosmetic dispersions

Citations (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CH89824A (de) * 1917-01-11 1921-07-01 Phil Paul Martin Prof Dr Klemm Verfahren zum Leimen von Papier.
DE364564C (de) * 1921-01-11 1922-11-27 Carl Jaeger G M B H Verfahren zum Leimen und Wasserfestmachen von Zellulose und aehnlichen Materialien im Hollaender
US1582257A (en) * 1922-04-01 1926-04-27 Union Oil Co Preparing soluble oils
US1678720A (en) * 1926-04-22 1928-07-31 Agasote Millboard Co Sizing fibers
US1958202A (en) * 1931-12-19 1934-05-08 Raybestos Manhattan Inc Method of making sizing material
US2036470A (en) * 1931-10-24 1936-04-07 Standard Oil Co California Emulsifiable oil product and process of making the same
US2214438A (en) * 1938-10-04 1940-09-10 Shell Dev Process for purifying naphthenic acids
US2289536A (en) * 1939-04-01 1942-07-14 Union Oil Co Soluble oil and transparent emulsion
US2340035A (en) * 1940-09-13 1944-01-25 Standard Oil Dev Co Soluble oil
US2347678A (en) * 1941-02-15 1944-05-02 Komel Corp Emulsion
US2399464A (en) * 1944-10-14 1946-04-30 Gulf Research Development Co Dust preventive composition
US2423144A (en) * 1944-10-07 1947-07-01 Shell Dev Emulsifiable hydrocarbon oils and emulsions thereof
US2423619A (en) * 1943-11-10 1947-07-08 Nuodex Products Co Inc Method of preparing copper fungicide solutions
US2447475A (en) * 1945-11-29 1948-08-17 Monsanto Chemicals Emulsifiable oils

Patent Citations (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CH89824A (de) * 1917-01-11 1921-07-01 Phil Paul Martin Prof Dr Klemm Verfahren zum Leimen von Papier.
DE364564C (de) * 1921-01-11 1922-11-27 Carl Jaeger G M B H Verfahren zum Leimen und Wasserfestmachen von Zellulose und aehnlichen Materialien im Hollaender
US1582257A (en) * 1922-04-01 1926-04-27 Union Oil Co Preparing soluble oils
US1678720A (en) * 1926-04-22 1928-07-31 Agasote Millboard Co Sizing fibers
US2036470A (en) * 1931-10-24 1936-04-07 Standard Oil Co California Emulsifiable oil product and process of making the same
US1958202A (en) * 1931-12-19 1934-05-08 Raybestos Manhattan Inc Method of making sizing material
US2214438A (en) * 1938-10-04 1940-09-10 Shell Dev Process for purifying naphthenic acids
US2289536A (en) * 1939-04-01 1942-07-14 Union Oil Co Soluble oil and transparent emulsion
US2340035A (en) * 1940-09-13 1944-01-25 Standard Oil Dev Co Soluble oil
US2347678A (en) * 1941-02-15 1944-05-02 Komel Corp Emulsion
US2423619A (en) * 1943-11-10 1947-07-08 Nuodex Products Co Inc Method of preparing copper fungicide solutions
US2423144A (en) * 1944-10-07 1947-07-01 Shell Dev Emulsifiable hydrocarbon oils and emulsions thereof
US2399464A (en) * 1944-10-14 1946-04-30 Gulf Research Development Co Dust preventive composition
US2447475A (en) * 1945-11-29 1948-08-17 Monsanto Chemicals Emulsifiable oils

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3008868A (en) * 1957-12-23 1961-11-14 Armstrong Cork Co Drainage rate of cellulosic papermaking slurries
US4349455A (en) * 1979-03-27 1982-09-14 Fuji Photo Film Co., Ltd. Emulsification process
US4996004A (en) * 1982-08-14 1991-02-26 Bayer Aktiengesellschaft Preparation of pharmaceutical or cosmetic dispersions
US5116536A (en) * 1982-08-14 1992-05-26 Bayer Aktiengesellschaft Preparation of pharmaceutical or cosmetic dispersions
US4956049A (en) * 1984-08-06 1990-09-11 Ciba-Geigy Corporation Process for sizing paper with anionic hydrophobic sizing agents and cationic retention aids

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Publication number Publication date
GB678561A (en) 1952-09-03
FR988219A (fr) 1951-08-24
NL72781C (de)
DE886409C (de) 1953-08-13

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