US3311532A - Ketene dimer paper sizing compositions including acyl compound extender and paper sized therewith - Google Patents

Ketene dimer paper sizing compositions including acyl compound extender and paper sized therewith Download PDF

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US3311532A
US3311532A US440584A US44058465A US3311532A US 3311532 A US3311532 A US 3311532A US 440584 A US440584 A US 440584A US 44058465 A US44058465 A US 44058465A US 3311532 A US3311532 A US 3311532A
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ketene dimer
paper
sizing
acyl compound
weight
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Kulick Russell Joseph
Strazdins Edward
Savina Anthony Ralph
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Wyeth Holdings LLC
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American Cyanamid Co
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Priority to US440584A priority Critical patent/US3311532A/en
Priority to GB8754/67A priority patent/GB1172898A/en
Priority to NL6703280A priority patent/NL6703280A/xx
Priority to BE695270D priority patent/BE695270A/xx
Priority to FR98122A priority patent/FR1513867A/fr
Priority to DE19671546231 priority patent/DE1546231A1/de
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    • 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
    • D21H17/17—Ketenes, e.g. ketene dimers

Definitions

  • the present invention relates to paper-sizing compositions comprising a hydrophobic paper-sizing ketene dimer and an acyl compound which acts as extender therefor.
  • the invention includes the manufacture of sized paper by use of these compositions, and the resulting paper.
  • ketene dimers act as extenders for the ketene dimers; that is, they permit the amount of paper-sizing ketene dimer which has been previously required to achieve a given level of sizing, to be decreased.
  • the amount of ketene dimer in a typical sizing operation can be decreased by about 50%75%. Since suitable acyl compounds are cheap and freely available and since paper-sizing ketene dimers are comparatively expensive, the present invention permits a major decrease in the cost of manufacturing sized paper by the use of ketene dimers.
  • Ketene dimers are outstandingly effective sizes for paper, capable of imparting a very high degree of Water and lactic acid resistance to paper.
  • the present invention achieves an absolute improvement in the amount of ultimate sizing imparted by the paper-sizing ketene dimers.
  • compositions consisting essentially of a paper-sizing ketene dimer and an efiective extending amount, in excess of about 10%, based on the weight thereof, of a hydrophobic substantially water-insoluble, substantially straight-chain acyl compound as extender for the ketene dimer.
  • a hydrophobic substantially water-insoluble, substantially straight-chain acyl compound as extender for the ketene dimer.
  • the invention includes the manufacture of sized paper by use of the aforesaid components, and the present invention broadly consists in the utilization of substantial amounts of an acyl compound (as hereinafter more fully described) in conjunction with one or more paper-sizing ketene dimers in any of the established paper-making processes.
  • the invention is thus essentially an improvement in established paper-making processes. This is an important advantage because the invention does not require any change in established methods for the manufacture of sized paper by the use of ketene dimer as sizing agents.
  • the process comprises depositing a papersizing ketene dimer on cellulose fibers as size together with an effective amount of the acyl compound as extender therefor, followed by heating the fibers to develop the sizing properties of the ketene dimer thereon.
  • the invention does not primarily depend upon the particular means employed for depositing the components of the fibers.
  • the invention also resides in the resulting paper, which is composed of cellulose fibers sized by a uniformly distributed reacted content of a paper-sizing ketene dimer and by an effective uniformly distributed unreacted surface content of the acyl compound in excess of about 10% of the weight of the ketene dimer as extender therefor.
  • the acyl compound is evidently in uniform admixture with the reacted ketene dimer.
  • acyl compounds act as extender
  • the amount of acyl compound present or used is defined in terms of the action of the acyl compounds as extender, and is sometimes designated as effective extending amounts, and it will be understood that this includes in each instance the amount in which the acyl compounds act as accelerator and fortifying agent.
  • the hydrophobic, substantially water-insoluble, saturated, substantially straight-chain acyl compounds used in the present invention are in general the acids, higher fatty acids (i.e., fatty acids which contain 12 carbon atoms or more) and the anhydrides, amides, acid chlorides and aldehydes of these acids.
  • substantially Water-insoluble we mean that the compounds dissolve in water to the extent of less than 1% and preferably less than 0.1%, and by the term substantially straight chain, we mean that the compounds are either precisely straight chain or that whatever branching they contain is of no significant consequence from the point of view of the amount of sizing which is imparted by these compounds.
  • Suitable acyl compounds include lauric, palmitic, stearic, and arachidic acids, their anhydrides, amides, aldehydes and acid chlorides, and mixtures thereof.
  • acyl compounds are most advantageously used alone, but they may be used in admixture with minor amounts of highly branched chain or unsaturated acyl compounds. For example, they may be used in admixture with min-or amounts of oleic acid, oleamide and the branched chain carboxylic acids formed by oxidation of petroleum hydrocarbons, which are tolerated.
  • the invention is illustrated by the drawing, which shows the effect of stearic acid as extender, as accelerator, and as fortifying agent for the sizing action of hexadecyl ketene dimer.
  • the data are presented in the form of curves A and B and point E and were obtained as follows:
  • a series of handsheets was prepared by beater addition of hexadecyl ketene dimer (prepared from commercial stearic acid) alone or in admixture with stearic acid as sizing agents. The agents were added as cationic emulsions. In each instance the weight of the hexadecyl ketene dimer (or hexadecyl ketene dimer-stearic acid mixture) was 0.2% of the dry weight of the fibers; the ratio of stearic acid to the ketene dimer is set forth on the lower abscissa.
  • One set of handsheets was dried for two minutes at 230 F. (corresponding to the cure obtained on a typical paper-making machine), after which the sizing of the sheets was determined by the use of 20% aqueous lactic acid applied at 100 F. under a head of 12". The results were plotted and curve A drawn.
  • the second set of handsheets was dried for /2 hour at 223 R, which developed substantially all the sizing which the additives were capable of imparting.
  • the results were plotted and curve B drawn. Further details of the process are shown in Example 5 below.
  • dotted line C which connects points B1 and B2 of curve B. Since the line is substantially horizontal, it shows that in the runs performed, substantially the same sizing is obtained by the use of a hexadecyl ketene dimer and stearic acid mixture wherein the weight of the stearic acid is 100% of the weight of the ketene dimer (point B2) as is obtained by the use of ketene dimer alone (point B1).
  • the maximum elfective amount of the acyl compound as extender at complete cure has not been ascertained but evidently is substantially in excess of 100% of the weight of the ketene dimer since the dotted position of curve B shows that a substantial amount of sizing is obtained when the weight of the acyl compound is 125 150% of the weight of the ketene dimer. A part of the acyl compound thus evidently acts as inert diluent.
  • Line E shows that substantially as good oif the machine sizing is obtained by use of 0.2 g. of a hexadecyl ketent dimer-stearic acid mixture wherein the weight of the latter is about 233% the weight of the former as is obtained by an equal weight of hexadecyl ketene dimer alone.
  • points A2 and B1 of the drawing show that the presence of about 67% of stearic acid, based on the weight of the ketene dimer, causes 7800 seconds of sizing to develop in 2 minutes at 230 F. (point A2), and that 9650 seconds of sizing are developed by the ketene dimer along after /2 hour at 223 F. (point B1).
  • Curve A shows that close to maximum acceleration of the development of sizing per increment of acyl compound present occurs when the weight of the acyl compound is about %25% of the weight of the ketene dimer and that virtually maximum absolute acceleration 4. is obtained when the weight of the stearic acid is 50% to 75% of the weight of the ketene dimer.
  • Curve B shows that valuable sizing results are obtained even when the wei ht of the acyl compound is in excess of the optimum amounts as extender, accelerator and tortifying agent. The excess amount evidently acts essentially as diluent.
  • the data of the drawing illustrate typical results so far obtained. Somewhat different curves are obtained depending particularly on the particular ketene dimer and acyl compound used, the total Weight of ketene dimer and acyl compound added (based on the dry weight of the fibers), the pH of the paper-making suspension and the electrostatic sign of the emulsions and the particular emulsifying agents present therein. The eifect of these variables cannot be calculated, and in each instance, therefore, the optimum or the maximum effective amount of the acyl compound as extender or activator and the best choice of emulsifiers can best be determined by a series of laboratory trials.
  • compositions of the present invention may be present in several forms or states. They may thus be present as a dry blend of discrete papersizing ketene dimer particles and particles of a suitable acyl compound. If desired, the components may be in solution form and for this purpose benzene or chloroform are suitable solvents. Moreover, the components may be in unitary homogeneous state such as in the composition which is formed by melting the lretene dimer and the acyl compound together, and then chilling the resulting solution, so that the acyl compound is present as a solution in the ketene dimer (or vice versa).
  • the dry compositions mayinclude one or more emulsifying agents for the ketene dimer and the acyl compound.
  • the emulsifying agent may be non-ionic, cationic, or anionic.
  • the anionic emulsifying agent may be replaced by an equivalent amount of an alkali metal alkali (for example sodium bicarbonate) so as to convert a portion of the acyl compound to a soap when the composition is emulsified with water.
  • compositions may contain materials customarily employed in the manufacture of paper which are not incompatible therewith. They may thus contain supplementary inert extenders such as silica or silica gel; starch; pigments and dyes; supplementary sizing agents as for example wax size; scents; hydrophobic, cyclic compounds as for example rosin; and mold growth inhibitors.
  • supplementary inert extenders such as silica or silica gel; starch; pigments and dyes; supplementary sizing agents as for example wax size; scents; hydrophobic, cyclic compounds as for example rosin; and mold growth inhibitors.
  • compositions may be prepared for use in the same manner as the paper-sizing ketene dimers have been prepared for use in the past.
  • compositions may be dissolved in a volatile organic solvent to form a solution suitable for use as an impregnant.
  • compositions are more economically prepared for use by conversion to fluid aqueous emulsions.
  • the emulsions are conveniently prepared by intensively agitating the ketene dimer and the acyl compound together in a volume of water containing one or more emulsifying agents.
  • the temperature of the water is preferably above the melting points of the ketene dimer and the acyl compound.
  • the emulsifying agent may be anionic, cationic, or non-ionic.
  • the resulting emulsion may be homogenized, after which the emulsion is rapidly cooled to prevent formation of aggregates.
  • the invention does not depend upon the particular way in which the emulsions are formed. Alternatively, the two components may be emulsified separately and mixed.
  • the cationic emulsions may be prepared as is disclosed in Arlt US. Patent No. 3,046,186.
  • the non-ionic and anionic emulsions may be prepared as is disclosed in Downey US. Patent No. 2,627,477 and in Osberg US. Patent No. 2,785,067. Any of the common cationic, anionic and non-ionic emulsifiers may be used for the preparation of the respective emulsions.
  • Sized paper may be manufactured in any convenient way by use of the solution and emulsions referred to above.
  • Preformed paper may be sized by impregnation with a volatile organic solution or with an aqueous anionic, cationic or non-ionic emulsion of the ketene dimer and the acyl compound, followed by heating the paper to develop the sizing properties of the ketene dimer-acyl compound combination.
  • Sized paper may be manufactured by use of the foregoing emulsion as beater additives.
  • the ketene dimer and the acyl compounds as single or as separate emulsions are added to an aqueous suspension of cellulose paper-making fibers, after which the suspension is sheeted to form a wet web and the web is heated to develop the sizing properties of the additives.
  • the ketene dimer and the acyl compound may be added as a single emulsion which may be cationic, anionic o-r non-ionic.
  • the cationic emulsions are self-substantive, and therefore when this type of emulsion is employed the fibrous suspension may be sheeted immediately thereafter.
  • the anionic emulsions are best employed in conjunction with a water-soluble cationic polymer.
  • the polymer can be added first in sufficient amount to render the fibers cationic, or can be added after the anionic emulsion.
  • ketene dimer it is often advantageous to add the ketene dimer as two separate emulsions, which may be of the same or of opposite electrostatic sign. Where both emulsions are cationic or anionic, the process steps are as have been respectively described above. When they are of opposite electrostatic sign, they act as mutual retention aids.
  • the amount of sizing composition to be added in each instance is most conveniently found by trial because a given amount of the sizing composition produces somewhat difierent sizing depending upon the particular pulp employed, its pH, and the amount and identity of any cationic material present.
  • the most sizing per unit weight of the composition added occurs when the composition is added in the range of 0.2% to 0.4% based on the dry weight of the fibers, so that this range is preferred.
  • valuable sizing results are obtained by the use of smaller amounts and by use of larger amounts, at least up to about 1%.
  • the par ticular amount of the composition employed in any instance is not a principal feature of the invention.
  • EXAMPLE 1 The following illustrates the effect of stearic acid as extender for hexadecyl ketene dimer.
  • the agents are applied as organic solutions to preformed paper.
  • Solution A.-O.2 g. of hexadecyl ketene dimer is dissolved in 100 g. of benzene.
  • Solution B 0.1 g. of hexadecyl ketene dimer and 0.1 g. of stearic acid are dissolved in 100 g. of benzene.
  • a sheet of pure untreated cellulose paper (blotting paper) is immersed in solution A for two minutes, and a similar sheet is immersed in solution B for the same length of time. Both sheets are allowed to dry at room temperature for one hour.
  • the sheet which was dipped in solution A is composed of cellulose fibers at least partly coated with hexadecyl ketene dimer.
  • the sheet which was dipped in solution B is composed of cellulose fibers at least partly coated with a mixture consisting of hexadecyl ketene dimer and stearic acid in 1:1 weight ratio.
  • the sheets are then heated at 230 F. for /2 hour to develop the ultimate sizing properties of the agents therein.
  • Sheet A contains about 0.2% by weight of hexadecyl ketene dimer and sheet B about 0.1% by weight each of hexadecyl ketene dimer and of stearic acid.
  • Both sheets possess substantially equal resistance to penetration by 20% aqueous lactic acid solution.
  • the stearic acid in sheet B consequently acted as extender for the ketene dimer.
  • EXAMPLE 2 The following illustrates the comparative effect of several acidic, hydrophobic substantially water-insoluble, substantially straight-chain acyl compounds as accelerators of the development of the water-resistance imparted by paper-sizing ketene dimers.
  • the agents are applied as non-ionic emulsions to preformed paper.
  • a series of emulsions is prepared as'follows. To 200 g. of Water at C. is added 2 g. of the condensation product of 10 mols of ethylene oxide with 1 mol of p-octylphenol (Triton X). The solution is agitated in a Waring Blender running at top speed, and there is slowly run in 15 g. of molten (80 C.) sizing composition, shown in the table below. After 30' seconds of agitation, 20 g. of the resulting emulsions are removed and are diluted to 0.27% size concentration by addition to 480 g. of cold water.
  • Triton X p-octylphenol
  • the sheets are dried by two passes of one minute each over a laboratory drum drier having a surface temperature of 230 F. From prior experience it is known that this drying does not develop more than a fraction of the sizing properties of hexadecyl ketene dimer, in the absence of an accelerator.
  • the sizing imparted by the emulsions was determined by the Cobb test, wherein the sheets are weighed, contacted on one side with 20% aqueous lactic acid as test fluid at 20 C. for 15 minutes, and reweighed. Sizing is reported as the grams of lactic acid solution which are absorbed per 25 cm? of paper surface.
  • EXAMPLE 3 The following illustrates the manufacture of sized paper in similar manner using a different non-ionic emulsifying agent and an additional acyl compound.
  • a series of four emulsions is prepared by adding in each instance 15 g. of a molten (80 C.95 C.) sizing composition as shown in the table below to 200 cc. of water at 80 C. containing 1 ml. of polyoxyethylene sorbitol hexaoleate (a non-ionic emulsying agent manufactured by Atlas Chemicals Industries) in a Waring Blender operating at full speed. After one minute the resulting emulsions are diluted to 0.42% solids by addition of water at about C.
  • a molten (80 C.95 C.) sizing composition as shown in the table below to 200 cc. of water at 80 C. containing 1 ml. of polyoxyethylene sorbitol hexaoleate (a non-ionic emulsying agent manufactured by Atlas Chemicals Industries) in a Waring Blender operating at full speed. After one minute the resulting emulsions are diluted to 0.42% solids by addition of water at
  • the sheets are reweighed and are found in each instance to contain 0.30% of sizing composition based on the dry weight of the fibers.
  • the sheets are dried by one pass of one minute over a laboratory drum drier having a surface temperature of 230 F.
  • Sizing is determined by the Cobb test, as described above, except that water is used as the test fluid.
  • the procedure is repeated twice, in the first instance 25% (2.25 g.) of the ketene dimer being replaced by myristic acid and in the second instance the same amount of the ketene dimer being replaced with stearic acid.
  • Sized paper is prepared by use of these emulsions by forming an aqueous suspension of a 30:70 bleached hardwood: bleached softwood kraft pulp at a consistency of 0.6% and a pH of 7. Aliquots are taken from this suspension and to each is respectively added sufiicient of the foregoing emulsions to provide 0.12% of sizing composition solids (hexadecyl ketene dimer plus any fatty acid added) on the dry weight of the fibers. There is then added suificient of an aqueous solution of cationic starch to provide 0.4% of cationic starch based on the dry weight of the fibers. The pH of the aliquots is adjusted to 6.3 and the suspensions are sheeted to form handsheets at a basis weight of 100 lbs. (25" x "/500 ream).
  • the handsheets are then dried by two passes of 1 minute each over a laboratory drum drier having a surface temperature of 230 F. From previous experience it is known that this drying is insufiicient in the absence of accelerator to develop more than a small fraction of the ultimate sizing of the hexadecyl ketene dimer.
  • the sizing of the resulting handsheets is determined by the lactic acid drop test, wherein drops of blue-tinted 20% aqueous lactic acid solution are applied to the paper at 20 C. Sizing is reported as the average time required for the drops to be absorbed by the paper.
  • Sizing Composition 1 HKD hexadecyl ketene dimer. Of size to accelerator. Based on dry weight of paper.
  • EXAMPLE 4 shows the comparative effect of two different higher fatty acids as accelerators for hexadecyl ketene dimer as paper size. The following also illustrates the manufacture of sized paper by use of these agents employed as beater additives in aqueous cationic emulsion state.
  • a series of emulsions is prepared by the method of Example 4.
  • the ketene dimer is replaced by successively larger increments of stearic acid, but in each instance the total weight of the sizing composition added (ketene dimer plus stearic acid) is constant.
  • Sized handsheets are prepared by the standard test method of Example 4. One set of handsheets is given a short cure (2 minutes at 230 F.) to simulate commercial machine drying. The second set of thandsheets is given a long cure /2 hour at 223 F.) to develop substantially all the sizing which the composition is capable of imparting. The sizing of the sheets is determined by use of 20% aqueous lactic acid solution, applied by penescope at a temperature of F. under a head of 12".
  • curve powder forms an anionic emulsion when 10 g. is slowly A being a graph of the results obtained with the short cure and curve B being a graph of the results obtained with the long cure.
  • EXAMPLE 6 The following illustrates the preparation of a homogeneous composition according to the present invention consisting essentially of a paper-sizing ketene dimer and a fatty acid as accelerator therefor.
  • a melt of hexadecyl ketene dimer and stearic acid in l:1 /2 Weight ratio having a temperature of 90 C. is flowed upon a rotating drum chiller provided with a doctor blade.
  • the surface temperature of the chiller is 30 C. Homogeneous crisp flakes are obtained.
  • the flakes are powdered by passage through a roller crusher.
  • the resulting powder is free-flowing.
  • Both the flakes and the powder emulsify readily when slowly poured into intensively-agitated water at 90 C. which contains an emulsifying agent.
  • Example 8 The procedure of Example 6 is repeated except that stearamide is employed in place of the stearic acid and the temperature of the melt is about 100 C. A similar composition is obtained.
  • EXAMPLE 9 The following illustrates the preparation of an ionic self-dispersible composition according to the present invention.
  • Example 6 To 100 g. of the homogeneous free-flowing powdery blend of hexadecyl ketene dimer and stearic acid (1: 1 /2 weight ratio) of Example 6 is added 1.5 g. of sodium lignosulfonate and 33 g. of a water-soluble cationic starch, and the mixture is ball-milled for a few minutes. The resulting powder emulsifies when 10 g. of the powder is slowly added with intensive agitation to 100 cc. of water at 90 C.
  • EXAMPLE 10 The following illustrates the preparation of a dry blend of a paper sizing which forms an anionic emulsion.
  • An aqueous suspension of beaten cellulose papermaking fibers is prepared at 0.6% consistency and at pH 7 and to this is added 0.2%, based on the dry weight of the fibers of a 50:50 by weight ratio of the diluted hexadeeyl ketene dimer:steric acid cationic emulsion prepared as described in Example 9 above.
  • the suspension is stirred briefly to permit adsorption of the size by the fibers to take place, after which the suspension is sheeted to form' handsheets.
  • the handsheets are dried for two minutes at 230 F. and are well sized.
  • EXAMPLE 13 The following illustrates another preferred method for the manufacture of sized paper.
  • the ketene dimer and the acyl compound are added to beater pulp as separate ionic emulsions of opposite electrostatic sign.
  • An aqueous cationic emulsion of hexadecyl ketene dimer is prepared by the method of Example 4.
  • An aqueous anionic emulsion of stearic acid is prepared by intensively agitating 142 g. of stearic acid with 1500 cc. of water at 90 C. containing 0.4 g. of sodium hydroxide.
  • aqueous suspension of cellulose paper-making fibers at pH 7 is added 0.15% of the cationic ketene dimer emulsion (emulsion solids based on the dry weight of the fibers) followed by 0.1% of the stearic acid emulsion, on the same basis.
  • the paper is made into handsheets by customary procedure and is dried for 2 minutes at 230 F. Well-sized paper is obtained.
  • Example 1 The procedure of Example 1 is repeated except that the stearic acid used in Example 1 is replaced by a like amount of hexadecyl aldehyde and chloroform is used as solvent in place of the benzene in Example 1. Similar results are obtained.
  • a composition consisting essentially of a papersizing ketene dimer and an effective extending amount in excess of about based on the Weight thereof, of a hydrophobic substantially water-insoluble saturated substantially straight-chain acyl compound as extender therefor.
  • composition according to claim 1 wherein the acyl compound is stearic acid.
  • composition according to claim 1 wherein the acyl compound is stearamide.
  • composition according to claim 1 wherein the acyl compound is distearic anhydride.
  • a composition consisting essentially of hexadecyl ketene dimer and an effective amount, between about 25% and 100%, based on the weight thereof, of stearic acid as exterior therefor.
  • a composition essentially composed of a paper-sizing ketene dimer and an effective amount within the range of from 10% to about 200%, based on the weight thereof, of a hydrophobic substantially water-insoluble saturated substantially straight-chain acyl compound selected from the group consisting of higherfatty acids and their anhydrides, chlorides, amides and aldehydes as ex tender therefor, and an emulsifying agent for said composition.
  • composition according to claim 6 wherein the acyl compound is stearic acid and the emulsifying agent is an anionic emulsifying agent.
  • Paper composed of cellulose fibers sized by a uniformly distributed reacted content of a paper-sizing ketene dimer and by an effective uniformly distributed unreaoted content, within the range of from. 10% to about 200% of the weight of said ketene dimer, of a hydropho bic substantially water-insoluble saturated substantially straight-chain acyl compound selected from the group consisting of higher fatty acids and their anhydrides, chlorides, amides and aldehydes as extender therefor.
  • Paper composed of cellulose fibers sized by a uniformly distributed reacted content of hexadecyl ketene dimer and by an effective uniformly distributed unreacted content, within the range of from 10% to about 200% of the weight of said ketene dimer, of stearic acid as extender therefor.
  • the improvement which comprises adding to said suspension a small but effective amount'as sizing agent of an aqueous anionic emulsion of a mixture of a paper-sizing ketene dimer and an effective amount within the range of from 10% to about 200%, based on the weight of said ketene dimer, of a hydrophobic substantially water-insoluble saturated straight-chain acyl compound selected from the group consisting of higher fatty acids and their anhydrides, chlorides, amides and aldehydes as extender therefor.
  • ketent should read ketene line 57, "along should read alone Column 10, line 52 "steric should read stearic Column 11, line 28, “exterior” should read extender Column 12, line 23, “extended” should read extender Signed and sealed this 7th day of April 1970.

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US440584A US3311532A (en) 1965-03-17 1965-03-17 Ketene dimer paper sizing compositions including acyl compound extender and paper sized therewith
GB8754/67A GB1172898A (en) 1965-03-17 1967-02-23 Paper Sizing
NL6703280A NL6703280A (enrdf_load_stackoverflow) 1965-03-17 1967-02-28
BE695270D BE695270A (enrdf_load_stackoverflow) 1965-03-17 1967-03-09
FR98122A FR1513867A (fr) 1965-03-17 1967-03-09 Nouvelles compositions pour le collage du papier et papier collé à l'aide de ces compositions
DE19671546231 DE1546231A1 (de) 1965-03-17 1967-03-10 Papierleimungsmittel und damit geleimtes Papier

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Cited By (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3931069A (en) * 1972-07-14 1976-01-06 Kemnord Ab Dispersion for sizing cellulose fibres and use thereof
US4017431A (en) * 1973-11-28 1977-04-12 Hercules Incorporated Aqueous dispersions of wax blends and a water-soluble cationic resin and paper sized therewith
US4240935A (en) * 1978-12-22 1980-12-23 Hercules Incorporated Ketene dimer paper sizing compositions
EP0054075B1 (en) * 1980-06-24 1984-08-22 Seiko Kagaku Kogyo Co., Ltd. Cellulose-treating agent and paper products sized therewith
JPS61258098A (ja) * 1985-05-03 1986-11-15 アライド・コロイド・リミテツド サイズ剤組成物
US4659430A (en) * 1981-10-21 1987-04-21 Fuji Photo Film Co., Ltd. Process for making a photographic support
EP0220941A1 (en) * 1985-10-23 1987-05-06 Albright & Wilson Limited Paper sizing composition
US4859244A (en) * 1988-07-06 1989-08-22 International Paper Company Paper sizing
WO1990012921A1 (en) * 1989-04-25 1990-11-01 Roe Lee Paper Chemicals Co., Ltd. Paper sizing compositions
EP0437764A1 (de) * 1990-01-18 1991-07-24 BASF Aktiengesellschaft Stabilisierte wässrige Alkyldiketenemulsionen
US5190584A (en) * 1989-12-14 1993-03-02 Hercules Incorporated Ketene dimer paper sizing agents modified by nonreactive hydrophobes
US5685815A (en) * 1994-02-07 1997-11-11 Hercules Incorporated Process of using paper containing alkaline sizing agents with improved conversion capability
US5725731A (en) * 1995-05-08 1998-03-10 Hercules Incorporated 2-oxetanone sizing agents comprising saturated and unsaturated tails, paper made with the 2-oxetanone sizing agents, and use of the paper in high speed converting and reprographic operations
US5766417A (en) * 1996-03-06 1998-06-16 Hercules Incorporated Process for using alkaline sized paper in high speed converting or reprographics operations
US5846663A (en) * 1994-02-07 1998-12-08 Hercules Incorporated Method of surface sizing paper comprising surface sizing paper with 2-oxetanone ketene multimer sizing agent
US5942588A (en) * 1995-02-20 1999-08-24 Basf Aktiengesellschaft Aqueous alkyldiketene dispersions and their use as size for paper
US6027611A (en) * 1996-04-26 2000-02-22 Kimberly-Clark Worldwide, Inc. Facial tissue with reduced moisture penetration
US6165259A (en) * 1997-02-05 2000-12-26 Akzo Nobel N.V. Aqueous dispersions of hydrophobic material
US20110017417A1 (en) * 2009-07-23 2011-01-27 Ehrhardt Susan M Sizing Composition for Hot Penetrant Resistance
AU2014240282B2 (en) * 2009-07-23 2016-05-12 Solenis Technologies Cayman, L.P. Sizing composition for hot penetrant resistance

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DE3216414A1 (de) * 1982-05-03 1983-11-03 Bayer Ag, 5090 Leverkusen Leimungsmittel auf basis von ketendimeren
GB2252984A (en) * 1991-01-21 1992-08-26 Exxon Chemical Patents Inc Novel compositions and their use for sizing paper

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Cited By (31)

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US3931069A (en) * 1972-07-14 1976-01-06 Kemnord Ab Dispersion for sizing cellulose fibres and use thereof
US4017431A (en) * 1973-11-28 1977-04-12 Hercules Incorporated Aqueous dispersions of wax blends and a water-soluble cationic resin and paper sized therewith
US4240935A (en) * 1978-12-22 1980-12-23 Hercules Incorporated Ketene dimer paper sizing compositions
EP0054075B1 (en) * 1980-06-24 1984-08-22 Seiko Kagaku Kogyo Co., Ltd. Cellulose-treating agent and paper products sized therewith
US4659430A (en) * 1981-10-21 1987-04-21 Fuji Photo Film Co., Ltd. Process for making a photographic support
JPS61258098A (ja) * 1985-05-03 1986-11-15 アライド・コロイド・リミテツド サイズ剤組成物
EP0220941A1 (en) * 1985-10-23 1987-05-06 Albright & Wilson Limited Paper sizing composition
JPS62125094A (ja) * 1985-10-23 1987-06-06 エカ・ノーベル・アクチボラグ 粒子状固体組成物及びその製造方法
US4859244A (en) * 1988-07-06 1989-08-22 International Paper Company Paper sizing
WO1990012921A1 (en) * 1989-04-25 1990-11-01 Roe Lee Paper Chemicals Co., Ltd. Paper sizing compositions
US5190584A (en) * 1989-12-14 1993-03-02 Hercules Incorporated Ketene dimer paper sizing agents modified by nonreactive hydrophobes
EP0437764A1 (de) * 1990-01-18 1991-07-24 BASF Aktiengesellschaft Stabilisierte wässrige Alkyldiketenemulsionen
US5154763A (en) * 1990-01-18 1992-10-13 Basf Aktiengesellschaft Stabilized aqueous alkyldiketene emulsions
US6048392A (en) * 1994-02-07 2000-04-11 Hercules Incorporated Alkaline paper surface sizing agents
US6325893B1 (en) 1994-02-07 2001-12-04 Hercules Incorporated Alkaline paper surface sizing agents, method of use and surface sized paper
US5846663A (en) * 1994-02-07 1998-12-08 Hercules Incorporated Method of surface sizing paper comprising surface sizing paper with 2-oxetanone ketene multimer sizing agent
US5879814A (en) * 1994-02-07 1999-03-09 Hercules Incorporated 2-oxetanone sizing agents made from linoleic acid and their use in paper
US6007906A (en) * 1994-02-07 1999-12-28 Hercules Incorporated Process of using fine paper containing 2-oxetanone sizing agent in high speed precision converting or reprographic operations
US5685815A (en) * 1994-02-07 1997-11-11 Hercules Incorporated Process of using paper containing alkaline sizing agents with improved conversion capability
US6197417B1 (en) 1994-02-07 2001-03-06 Hercules Incorporated 2-oxetanone sizing agents made from linoleic acid and their use in paper
US5942588A (en) * 1995-02-20 1999-08-24 Basf Aktiengesellschaft Aqueous alkyldiketene dispersions and their use as size for paper
US5725731A (en) * 1995-05-08 1998-03-10 Hercules Incorporated 2-oxetanone sizing agents comprising saturated and unsaturated tails, paper made with the 2-oxetanone sizing agents, and use of the paper in high speed converting and reprographic operations
US5766417A (en) * 1996-03-06 1998-06-16 Hercules Incorporated Process for using alkaline sized paper in high speed converting or reprographics operations
US6027611A (en) * 1996-04-26 2000-02-22 Kimberly-Clark Worldwide, Inc. Facial tissue with reduced moisture penetration
US6165259A (en) * 1997-02-05 2000-12-26 Akzo Nobel N.V. Aqueous dispersions of hydrophobic material
US20110017417A1 (en) * 2009-07-23 2011-01-27 Ehrhardt Susan M Sizing Composition for Hot Penetrant Resistance
WO2011011563A1 (en) 2009-07-23 2011-01-27 Hercules Incorporated Sizing composition for hot penetrant resistance
CN102472018A (zh) * 2009-07-23 2012-05-23 赫尔克里士公司 耐受热渗透剂的施胶组合物
US20120282477A1 (en) * 2009-07-23 2012-11-08 Ehrhardt Susan M Aseptic packaging
AU2014240282B2 (en) * 2009-07-23 2016-05-12 Solenis Technologies Cayman, L.P. Sizing composition for hot penetrant resistance
TWI550160B (zh) * 2009-07-23 2016-09-21 英屬開曼群島索理思科技開曼公司 用於抗熱穿透性之上漿組合物

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NL6703280A (enrdf_load_stackoverflow) 1968-08-29
DE1546231A1 (de) 1970-04-16
GB1172898A (en) 1969-12-03
BE695270A (enrdf_load_stackoverflow) 1967-09-11

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