EP0217202B1 - Ethoxyliertes Rizinusöl enthaltende lagerungsstabile Papierleimzusammensetzung - Google Patents

Ethoxyliertes Rizinusöl enthaltende lagerungsstabile Papierleimzusammensetzung Download PDF

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Publication number
EP0217202B1
EP0217202B1 EP86112650A EP86112650A EP0217202B1 EP 0217202 B1 EP0217202 B1 EP 0217202B1 EP 86112650 A EP86112650 A EP 86112650A EP 86112650 A EP86112650 A EP 86112650A EP 0217202 B1 EP0217202 B1 EP 0217202B1
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EP
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Prior art keywords
castor oil
paper
sizing
weight
dicarboxylic acid
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Expired
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EP86112650A
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English (en)
French (fr)
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EP0217202A1 (de
Inventor
Emil D. Mazzarella
Walter Maliczyszyn
Jeffrey Atkinson
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Ingredion Inc
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National Starch and Chemical Corp
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Priority to AT86112650T priority Critical patent/ATE40164T1/de
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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
    • D21H17/03—Non-macromolecular organic compounds
    • D21H17/05—Non-macromolecular organic compounds containing elements other than carbon and hydrogen only
    • D21H17/14—Carboxylic acids; Derivatives thereof
    • 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
    • D21H17/15—Polycarboxylic acids, e.g. maleic acid
    • D21H17/16—Addition products thereof with hydrocarbons

Definitions

  • This invention relates to a paper size comprising a self-emulsifiable mixture of 85 to 99 parts by weight of a cyclic dicarboxylic acid anhydride having hydrophobic substitution and as emulsifier 1 to 15 parts by weight of an alkoxylated castor oil containing at least 5 moles alkylene oxide per mole castor oil, an improved method for sizing paper and paperboard produced therewith.
  • Paper and paperboard are often sized with various hydrophobic materials including, for example, rosin, wax emulsions, mixtures of rosin waxes, ketene dimers, isocyanate derivatives, fatty acid complexes, fluorocarbons, certain styrene-maleic anhydride copolymers, as well as the substituted cyclic dicarboxylic acid anhydrides more particularly described hereinafter.
  • hydrophobic materials including, for example, rosin, wax emulsions, mixtures of rosin waxes, ketene dimers, isocyanate derivatives, fatty acid complexes, fluorocarbons, certain styrene-maleic anhydride copolymers, as well as the substituted cyclic dicarboxylic acid anhydrides more particularly described hereinafter.
  • These sizes may be introduced during the actual paper making operation wherein the process is known as internal or engine sizing, or they may be applied to the surface of the finished web or sheet in
  • a primary deficiency concerned the necessity of utilizing relatively complex, expensive and heavy equipment capable of exerting high homogenizing shear and/or pressures, together with rigid procedures regarding emulsifying proportions and temperatures, etc., for producing a satisfactory stable emulsion of the particular size. Additionally, the use of many surfactants in conjunction with protective colloids was found to create operational problems in the paper making process such as severe foaming of the stock and/or loss in sizing.
  • a shelf stable paper sizing composition can be provided utilizing alkenyl succinic anhydride (ASA) together with an emulsifier component comprising at least one emulsifier selected from the group consisting of blocked polyoxyalkylenes or sulfur containing anionic surfactants. It is shown that the compositions containing ASA in conjunction with specific blocked polyoxyalkylene compounds provide satisfactory results. According to some examples only unblocked polyoxyalkylene compounds are utilized which provide unsatisfactory emulsification and sizing. Further examples show that sizing compositions can be obtained using the ASA compounds together with unblocked polyoxyalkylene compounds, but only in the presence of further emulsifiers. One example for comparative purposes illustrates that the unblocked compound does not give adequate sizing if the additional sulfur containing surfactant is not employed.
  • ASA alkenyl succinic anhydride
  • a paper size comprising a self-emulsifiable mixture of 85 to 99 parts by weight of a cyclic dicarboxylic acid anhydride having hydrophobic substitution and as emulsifier 1 to 15 parts by weight of an alkoxylated castor oil containing at least 5 moles alkylene oxide per mole castor oil which is characterized in that the alkoxylated castor oil is an unblocked ethoxylated or propoxylated castor oil and that further emulsifiers are excluded.
  • the method for sizing paper products according to the invention comprises the steps of
  • the mixture according to the invention is storage stable for extended periods of time, i.e., for at least six months of natural aging, and exhibits excellent sizing properties when emulsified prior to addition to the paper making stock or when added directly to the system and emulsified in-situ.
  • the sizing compounds contemplated for use herein are the cyclic dicarboxylic acid anhydrides containing hydrophobic substitution.
  • Those substituted cyclic dicarboxylic acid anhydrides most commonly employed as paper sizes are represented by the following formula: wherein R represents a dimethylene or trimethylene radical and wherein R' is a hydrophobic group containing more than 4 carbon atoms which may be selected from the class consisting of alkyl, alkenyl, aralkyl or aralkenyl groups.
  • Sizing compounds in which R' contains more than twelve carbon atoms are preferred.
  • the substituted cyclic dicarboxylic acid anhydrides may be the substituted succinic and glutaric acid anhydrides of the above described formula including, for example, iso-octadecenyl succinic acid anhydride, n- or iso-hexadecenyl succinic acid anhydride, dodecenyl succinic acid anhydride, dodecyl succinic acid anhydride, decenyl succinic acid anhydride, octenyl succinic acid anhydride, triisobutenyl succinic acid anhydride, etc.
  • the sizing agents may also be those of the above described formula which are prepared employing an internal olefin corresponding to the following general structure: wherein R x is an alkyl radical containing at least four carbon atoms and Ry is an alkyl radical containing at least four carbon atoms, and which correspond to the more specific formula: wherein R x is an alkyl radical containing at least 4 carbon atoms and Ry is an alkyl radical containing at least 4 carbon atoms and R x and Ry are interchangeable.
  • Specific examples of the latter sizing compounds include (1-octyl-2-decenyl) succinic acid anhydride and (1-hexyl-2-octenyl) succinic acid anhydride.
  • the sizing agents may also be prepared employing a vinylidene olefin corresponding to the following general structure .
  • R x and Ry are alkyl radicals containing at least 4 carbon atoms in each radical. These compounds correspond to the specific formula: wherein R x is an alkyl radical containing at least 4 carbon atoms and Ry is an alkyl radical containing at least 4 carbon atoms and R x and Ry are interchangeable and are represented by 2-n-hexyl-1-octene, 2-n-octyl-1-dodecene, 2-n-octyl-1-decene, 2-n-dodecyl-1-octene, 2-n-octyl-1-octene, 2-n-octyl-1-- nonene, 2-n-hexyl-decene and 2-n-heptyl-1-octene.
  • the sizing agents may also include those as described above prepared employing an olefin having an alkyl branch on one of the unsaturated carbon atoms or on the carbon atoms contiguous to the unsaturated carbon atoms.
  • Representative of the latter agents are n-octene-1; n-dodecene-1; n-octadecene-9; n-hexene-1; 7,8-dimethyl tetradecene-6; 2,2,4,6,6,8,8-heptamethylnone-4; 2,2,4,6,6,8,8-heptamethylnone-3; 2,4,9,11-tetramethyl-5-ethyldodecene-5; 6,7-dimethyldodecene-6; 5-ethyl-6-methylun- decene-5; 5,6-diethyidecene-5; 8-methyltridecene-6; 5-ethyldodecene-6; and 6,7-dimethyldode
  • the unblocked ethoxylated castor oils used herein are those containing at least about 5 moles ethylene oxide per mole castor oil. Preferred are those containing 25 to 200 moles ethylene oxide.
  • the castor oil base may be hydrogenated or non-hydrogenated.
  • the alkoxylation of such castor oils with ethylene oxide is well known in the art and the oils useful herein are not limited by their method of preparation. Generally the alkoxylation is carried out at 120-180 ° C and 0-4 atmospheres using alkaline catalysts. Unblocked ethoxylated castor oils containing up to about 200 moles ethylene oxide are available commercially. It is contemplated that the alkoxylation may also be performed using similar levels of propylene oxide however these adducts are not as readily available and are more expensive.
  • the size mixture is formed by mixing 85 to 99 parts by weight of the aforementioned subtituted cyclic dicarboxylic acid anhydride with 1 to 15 parts, preferably less than 10 parts, of the unblocked ethoxylated castor oil.
  • the use of the latter component in excess of about 15 parts becomes uneconomical in terms of cost and may be detrimental in terms of the papermaking operation.
  • the use of the lower levels of the ethoxylated castor oil may require greater degrees of emulsification as with a turbine.
  • the mixture of the appropriate amount of the substituted cyclic dicarboxylic acid and the ethoxylated castor oil may be prepared and held in this form for an extended period of time. Testing results obtained under accelerated aging conditions indicate, to date, the mixture is still stable and effective as a sizing agent after six months at 50 ° C. When use of the mixture is required, it may be readily emulsified either by pre-emulsifying with water before addition to the paper stock or it may be emulsified in-situ at any point in the manufacturing operation where adequate agitation is present.
  • pre-emulsification of the size mixture it may be readily accomplished by adding the sizing components to water in sufficient quantity so as to yield an emulsion containing the substituted cyclic dicarboxylic acid anhydride in a concentration of from about 0.1 to 20% by weight.
  • the aqueous mixture is thereafter sufficently emulsified merely by stirring with moderate speed agitation or by passing it through a mixing valve, aspirator or orifice so that the average particle size of the resultant emulsion will be less than about 3 wm.
  • Emulsification of the mixture readily occurs at ambient temperatures. Thus, the emulsification will occur directly in cold water and heating of the water prior to addition of the sizing mixture is unnecessary.
  • the thus-prepared emulsion is simply added to the wet end of the paper making machine or to the stock preparation system so as to provide a concentration of the substituted cyclic dicarboxylic acid anhydride of from about 0.01 to about 2.0% based on dry fiber weight.
  • concentration of the substituted cyclic dicarboxylic acid anhydride of from about 0.01 to about 2.0% based on dry fiber weight.
  • the precise amount of size which is to be used will depend for the most part upon the type of pulp which is being treated, the specific operating conditions, as well as the particular end use for which the paper product is destined. For example, paper which will require good water resistance or ink holdout will necessitate the use of a higher concentration of size than paper which will be used in applications where these properties are not critical.
  • the size emulsion may be sprayed onto the surface of the formed web at any point prior to the drying step in the concentrations as prepared so as to provide the required size concentration.
  • the ingredients of the size mixture may also be premixed without water and added to the paper making stock system causing the substituted cyclic dicarboxylic acid anhydride to emulsify in situ in the stock preparation system without the need for prior emulsification in water.
  • the amount of size employed will vary depending on conditions, however, it will generally be within the range of about 0.01 to 2.0% substituted cyclic dicarboxylic acid anhydride based on dry fiber weight.
  • the size mixtures are used in conjunction with a material which is either cationic or is capable of ionizing or dissociating in such a manner as to produce one or more cations or other positively charged moieties.
  • materials which may be employed as cationic agents are long chain fatty amines, amine-containing synthetic polymers (primary, secondary, tertiary or quaternary amine), substituted polyacrylamide, animal glue, cationic thermosetting resins and polyamide-epichlorohydrin polymers.
  • cationic starch derivatives including primary, secondary, tertiary or quarternary amine starch derivatives and other cationic nitrogen substituted starch derivatives as well as cationic sulfonium and phosphonium starch derivatives.
  • Such derivatives may be prepared from all types of starches including corn, tapioca, potato, waxy maize, wheat and rice. Moreover, they may be in their original granule form or they may be converted to pregelatinized, cold water soluble products. Amphoteric natural and synthetic polymers containing both anionic and cationic groups may also be used effectively to deposit and retain the sizing agent on the fiber.
  • any of the above noted cationic retention agents may be added to the stock, i.e. the pulp slurry, either prior to, along with or after the addition of the size mixture or size emulsion in conventional amounts of at least about 0.01%, preferably 0.025 to 3.0%, based on dry fiber weight. While amounts in excess of about 3% may be used, the benefits of using increased amounts of retention aid for sizing purposes are usually not economically justified.
  • the size mixtures are not limited to any particular pH range and may be used in the treatment of neutral and alkaline pulp, as well as acidic pulp.
  • the size mixtures may thus be used in combination with alum, which is very commonly used in making paper, as well as other acid materials. Conversely, they may also be used with calcium carbonate or other alkaline materials in the stock.
  • the web is formed and dried on the paper making machine in the usual manner.
  • full sizing is generally achieved immediately off the paper machine.
  • further improvements in the water resistance of the paper prepared with the size mixtures of this invention may be obtained by curing the resulting webs, sheets, or molded products.
  • This post-curing process generally involves heating the paper at temperatures in the range of from 80 ° to 150 ° C for a period of from 1 to 60 minutes.
  • the size mixtures of the present invention may be successfully utilized for the sizing of paper and paperboard prepared from all types of both cellulosic and combinations of cellulosic with non-cellulosic fiber. Also included are sheet- like masses and molded products prepared from combinations of cellulosic and non-cellulosic materials derived from synthetics such as polyamide, polyester and polyacrylic resin fibers as well as from mineral fibers such as asbestos and glass.
  • the hardwood or softwood cellulosic fibers which may be used include bleached and unbleached sulfate (Kraft) bleached and unbleached sulfite, bleached and unbleached soda, neutral sulfite semi-chemical, groundwood, chemi-groundwood, and any combination of these fibers.
  • synthetic cellulosic fibers of the viscose rayon or regenerated cellulose type can also be used, as well as recycled waste papers from various sources.
  • pigments and fillers may be added in the usual manner to the paper product which is to be sized.
  • Such materials include clay, talc, titanium dioxide, calcium carbonate, calcium sulfate and diatomaceous earths.
  • Stock additives such as defoamers, pitch dispersants, slimicides, etc. as well as other sizing compounds, can also be used with the size mixtures described herein.
  • the size mixtures described herein exhibit extended shelf life, and, when emulsified and used in the paper stock system, yield paper products having superior sizing properties, even after these extended storage periods.
  • This example illustrates the use of a size mixture representative of the size mixtures of this invention utilized in the form of an aqueous emulsion.
  • This emulsion is compared, in terms of particle size and water resistance of the resulting sized paper, with a conventional emulsion made with a mixture of substituted cyclic dicarboxylic acid anhydride and a polyoxyalkylene alkyl-aryl ether.
  • a size mixture was prepared by combining 7 parts of unblocked ethoxylated castor oil containing 40 moles ethylene oxide per mole castor oil and 93 parts of alkenyl substituted succinic acid anhydride wherein the alkenyl groups contained 15 to 20 carbon atoms (hereinafter referred to as ASA).
  • the mixture was aged for varying lengths of time at 50°C.
  • the emulsion was formed by agitating 2 parts of the mixture with 98 parts of a cooked aqueous dispersion of cationic corn starch (containing sufficient starch to provide 0.05% based on dry fiber weight) using a propeller-type agitator at moderate speed (500 rpm) for 10 seconds (Emulsion No. 1).
  • a control was prepared in accordance with U.S. Reissue Patent 29 960 using 93 parts of the same ASA and 7 parts of polyoxyalkylene alkyl-aryl ether wherein the alkyl group contained 9 carbon atoms, the aryl radical was phenol, and the polyoxyalkylene moiety was formed with 9.5 moles of ethylene oxide.
  • the Hercules Size Performance Test was employed to compare the ink resistance of the sheets prepared.
  • the test comprises applying an amount of acid ink (pH 2.3) to the upper paper surface.
  • pH 2.3 an amount of acid ink
  • the underside of the paper is monitored for reflectance.
  • the time it takes for the ink to cause a decrease in reflectance from 100% to 80% is the paper's HST time.
  • the HST of the paper is a measure of the sizing performance of a given size. The longer the HST time, the better the size is.
  • the average particle size (APS) was measured by optical microscopic observation using a calibrated graduated eye piece under 400-600x magnification.
  • Table I presents the aberage particle size (APS in 11m) and internal sizing data (HST in seconds) for the above-described emulsions. Both the emulsion quality (shown by particle size) and sizing performance (shown by the HST results) indicate that there is no loss in performance with the use of the size employing the ethoxylated castor oil, whereas after only one month accelerated aging, the control made a poor emulsion with no sizing.
  • This example shows the effect of varying the level of the ethoxylated castor oil in size mixtures prepared as in Example I from 4% to 7%. All four levels showed excellent performance both freshly made and after 2.5 months aging. After 3.5 months aging there was a slight drop in performance using this accelerated aging procedure at 50 ° C.
  • ASA and ethoxylated castor oil were prepared as in Example I with unblocked ethoxylated castor oil of varying levels of ethylene oxide (E.O.) substitution. These mixtures were evaluated (fresh) for emulsification and sizing performance. Five moles of ethylene oxide provided minimally acceptable performance. With 25,40, and 80 moles of ethylene oxide excellent results were obtained. The maximum commercially available level of 200 moles of ethylene oxide provided acceptable sizing; however the emulsion was of poorer quality.
  • E.O. ethylene oxide
  • This example shows a comparison of direct (un-emulsified) addition and pre-emulsified addition to the stock with both freshly made and three month (accelerated) aged sizing mixtures.
  • the pre-emulsified product was prepared using the procedure of Emulsion 1 in Example I. With direct addition of the ASA/unblocked ethoxylated castor oil mixtures the emulsification occurs in-situ due to the shear inherent to the system. In this case, the mixture of Example I was added directly to a slurry of bleached sulfate pulp at 1.5% consistency in a laboratory beater (supplied by Allis Chalmers) and beaten very lightly for a few minutes.
  • Example 1 The pulp was then diluted to 0.5% consistency, and 0.4% on dry fiber weight of the cationic starch described in Example I was added separately to the slurry to act as a retention aid during sheet formation. Sheers were then formed, conditioned and tested in the HST test as described in Example 1. The results show that the ethoxylated castor oil/ASA mixtures provided better sizing and equivalent particle size compared to the control as described in Example I by both pre-emulsion and direct addition and that three months accelerated aging had no adverse effect on the performance of the mixtures.
  • the ethoxylated castor oil was evaluated as an emulsifier for four different cyclical dicar- bolic acid anhydrides prepared as in Example I using 7 parts of the unblocked ethoxylated castor oil and 93 parts of the anhydride. The results show that good performance could be achieved with all four anhydride structures.
  • the level of ethoxylated castor oil varied from 1-20%, as shown in the table to ascertain the effect of high levels in the sizing mixture.
  • the mixtures and emulsions were prepared in accordance with Example I but varying the relative amounts of the ethoxylated castor oil and ASA. This data shows that levels as low as 1% work effectively, and that 10% or more, while acceptable, causes reduced sizing results.
  • Example II shows that the hydrogenated unblocked ethoxylated castor oil works as well as the non-hydrogenated unblocked ethoxylated castor oil when the sizing mixture is freshly made and after three and one-half months accelerated aging.
  • Mixtures and emulsions were prepared and evaluated as in Example I.
  • the invention is seen to provide the practitioner with a size mixture useful in the manufacture of sized paper products.
  • the size mixture is shelf stable over an extended period of time, and is easily emulsified when desired for use under a wide variety of paper making conditions to provide superior sized paper products.

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  • Paper (AREA)
  • Cosmetics (AREA)
  • Sanitary Thin Papers (AREA)
  • Medicines Containing Plant Substances (AREA)
  • Picture Signal Circuits (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Medicinal Preparation (AREA)

Claims (10)

1. Papierleim mit einem Gehalt an einer selbstemulgierbaren Mischung von 85 bis 99 Gewichtsteilen eines cyclischen Dicarbonsäureanhydrids mit hydrophober Substitution und, als Emulgator, 1 bis 15 Gewichtsteilen eines alkoxylierten Rizinusöls, das mindestens 5 Mol Alkylenoxid pro Mol Rizinusöl enthält, dadurch gekennzeichnet, daß das alkoxylierte Rizinusöl ein nicht blockiertes ethoxyliertes oder propoxyliertes Rizinusöl ist und daß weitere Emulgatoren ausgeschlossen sind.
2. Verfahren zum Verleimen von Papierprodukten, das die Maßnahmen umfaßt
a) Bereitstellen eines Papierrohstoffsystems,
b) Ausbilden einer Leimemulsion in Abwesenheit hoher Scherkräfte und unter normalem Druck, die 85 bis 99 Gewichtsteile eines substituierten cyclischen Dicarbonsäureanhydrids mit hydrophober Substitution, 1 bis 15 Gewichtsteile eines alkoxylierten Rizinusöls, das mindestens 5 Mol Alkylenoxid pro Mol Rizinusöl enthält, und Wasser enthält,
c) Ausbilden einer Bahn aus dem Papierrohstoffsystem und
d) Dispergieren der Emulsion in dem Papierrohstoff entweder vor oder nach der Ausbildung der Bahn, jedoch bevor die Bahn durch die Trocknungsstufe des Papierfabrikationsbetriebs tritt, in einer ausreichenden Menge, um eine Konzentration des substituierten cyclischen Dicarbonsäureanhydrids von 0,01 bis 2,0%, bezogen auf das Trockenfasergewicht, einzustellen, dadurch gekennzeichnet, daß das alkoxylierte Rizinusöl ein nicht blockiertes ethoxyliertes oder propoxyliertes Rizinusöl ist und daß weitere Emulgatoren ausgeschlossen sind.
3. Anspruch 1 oder 2, wonach das cyclische Dicarbonsäureanhydrid wiedergegeben wird durch die Formel:
Figure imgb0017
worin R ein Dimethylen- oder Trimethylen-Radikal und R' eine hydrophobe Gruppe mit mehr als 4 Kohlenstoffatomen ist, die aus der aus Alkyl-, Alkenyl-, Aralkyl-, oder Aralkenyl-Gruppen bestehenden Klasse ausgewählt worden ist.
4. Anspruch 3, wonach das cyclische Dicarbonsäureanhydrid aus der Gruppe ausgewählt worden ist, die besteht aus:
Figure imgb0018
worin Rx ein Alkyl-Radikal mit mindestens 4 Kohlenstoffatomen und Ry ein Alkyl-Radikal mit mindestens 4 Kohlenstoffatomen ist und Rx und Ry austauschbar sind,
Figure imgb0019
worin Rx ein Alkyl-Radikal mit mindestens 4 Kohlenstoffatomen und Ry ein Alkyl-Radikal mit mindestens 4 Kohlenstoffatomen ist und Rx und Ry austauschbar sind.
5. Anspruch 1 oder 2, worin das nicht blockierte ethoxylierte Rizinusöl 25 bis 200 Mol Ethylenoxid pro Mol Rizinusöl enthält und in einer Menge von weniger als 10 Gewichtsteilen der Mischung vorliegt.
6. Anspruch 2, wonach die Leimemulsion innerhalb des Papierrohstoffsystems insitu gebildet wird.
7. Anspruch 2, wonach die Leimemulsion vor Einführen in das Papierrohstoffsystem gebildet wird.
8. Anspruch 7, wonach die Leimmischung in einer wäßrigen Dispersion eines kationischen oder amphoteren Retentionsmittels in einer ausreichenden Menge emulgiert wird, um eine Emulsion die das substituierte cyclische Dicarbonsäureanhydrid in einer Konzentration von 0,1 bis 20 Gew.-% der gesamten Emulsion enthält, vor Zugabe zu dem Papierrohstoffsystem zu liefern.
9. Anspruch 2, wonach innerhalb des Papierrohstoffs vor der Überführung des Papierrohstoffs in eine trockene Bahn mindestens 0.01%, bezogen auf das Trockenfasergewicht, eines kationischen Retentionsmittels dispergiert werden.
10. Papier oder Pappe, hergestellt nach dem Verfahren des Anspruchs 2.
EP86112650A 1985-10-03 1986-09-12 Ethoxyliertes Rizinusöl enthaltende lagerungsstabile Papierleimzusammensetzung Expired EP0217202B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT86112650T ATE40164T1 (de) 1985-10-03 1986-09-12 Ethoxyliertes rizinusoel enthaltende lagerungsstabile papierleimzusammensetzung.

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US78390385A 1985-10-03 1985-10-03
US783903 1985-10-03

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AT (1) ATE40164T1 (de)
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CA (1) CA1276056C (de)
DE (1) DE3661850D1 (de)
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JP2651535B2 (ja) * 1987-09-08 1997-09-10 星光化学工業株式会社 製紙工程用抑泡剤及び製紙工程における発泡を抑制する方法
CA2910668C (en) * 2013-06-13 2024-05-28 Ecolab Usa Inc. Water-free surface sizing composition and method for treating a paper substrate with same

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JPS5930993A (ja) * 1982-08-16 1984-02-18 三洋化成工業株式会社 安定な製紙用サイズ剤
US4529447A (en) * 1982-06-11 1985-07-16 Sanyo Chemical Industries, Ltd. Sizing composition

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FI864025A7 (fi) 1987-04-04
AU6302386A (en) 1987-04-09
AU566066B2 (en) 1987-10-08
CA1276056C (en) 1990-11-13
FI864025L (fi) 1987-04-04
JPS6285098A (ja) 1987-04-18
FI864025A0 (fi) 1986-10-03
ATE40164T1 (de) 1989-02-15
EP0217202A1 (de) 1987-04-08

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