WO1986002677A1 - Hydrophobing agent for cellulosic fibers, method of preparing the agent, and use of the agent for stock hydrophobation - Google Patents

Hydrophobing agent for cellulosic fibers, method of preparing the agent, and use of the agent for stock hydrophobation Download PDF

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Publication number
WO1986002677A1
WO1986002677A1 PCT/SE1985/000405 SE8500405W WO8602677A1 WO 1986002677 A1 WO1986002677 A1 WO 1986002677A1 SE 8500405 W SE8500405 W SE 8500405W WO 8602677 A1 WO8602677 A1 WO 8602677A1
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Prior art keywords
agent
acid
fatty acid
resin
stock
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PCT/SE1985/000405
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English (en)
French (fr)
Inventor
Kjell Rune Andersson
Nils Ebbe Lyrmalm
Original Assignee
Eka Nobel Aktiebolag
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Application filed by Eka Nobel Aktiebolag filed Critical Eka Nobel Aktiebolag
Priority to DE8585905341T priority Critical patent/DE3570471D1/de
Priority to JP60504785A priority patent/JPH0713358B2/ja
Priority to BR8507006A priority patent/BR8507006A/pt
Priority to AT85905341T priority patent/ATE43378T1/de
Publication of WO1986002677A1 publication Critical patent/WO1986002677A1/en
Priority to FI862646A priority patent/FI80312C/fi
Priority to NO862484A priority patent/NO166805C/no

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Classifications

    • DTEXTILES; PAPER
    • D21PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21HPULP 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
    • D21H17/00Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20Macromolecular organic compounds
    • D21H17/21Macromolecular organic compounds of natural origin; Derivatives thereof
    • D21H17/24Polysaccharides
    • D21H17/28Starch
    • D21H17/29Starch cationic
    • DTEXTILES; PAPER
    • D21PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21HPULP 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
    • D21H17/00Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/03Non-macromolecular organic compounds
    • D21H17/05Non-macromolecular organic compounds containing elements other than carbon and hydrogen only
    • D21H17/14Carboxylic acids; Derivatives thereof
    • DTEXTILES; PAPER
    • D21PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21HPULP 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
    • D21H17/00Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20Macromolecular organic compounds
    • D21H17/21Macromolecular organic compounds of natural origin; Derivatives thereof
    • D21H17/24Polysaccharides
    • D21H17/25Cellulose
    • DTEXTILES; PAPER
    • D21PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21HPULP 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
    • D21H17/00Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20Macromolecular organic compounds
    • D21H17/21Macromolecular organic compounds of natural origin; Derivatives thereof
    • D21H17/24Polysaccharides
    • D21H17/31Gums
    • D21H17/32Guar or other polygalactomannan gum
    • DTEXTILES; PAPER
    • D21PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21HPULP 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
    • D21H17/00Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20Macromolecular organic compounds
    • D21H17/33Synthetic macromolecular compounds
    • D21H17/34Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H17/37Polymers of unsaturated acids or derivatives thereof, e.g. polyacrylates
    • DTEXTILES; PAPER
    • D21PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21HPULP 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
    • D21H17/00Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20Macromolecular organic compounds
    • D21H17/33Synthetic macromolecular compounds
    • D21H17/34Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H17/37Polymers of unsaturated acids or derivatives thereof, e.g. polyacrylates
    • D21H17/375Poly(meth)acrylamide
    • DTEXTILES; PAPER
    • D21PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21HPULP 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
    • D21H17/00Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20Macromolecular organic compounds
    • D21H17/33Synthetic macromolecular compounds
    • D21H17/46Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H17/54Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen
    • D21H17/55Polyamides; Polyaminoamides; Polyester-amides
    • DTEXTILES; PAPER
    • D21PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21HPULP 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
    • D21H17/00Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20Macromolecular organic compounds
    • D21H17/33Synthetic macromolecular compounds
    • D21H17/46Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H17/54Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen
    • D21H17/56Polyamines; Polyimines; Polyester-imides
    • DTEXTILES; PAPER
    • D21PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21HPULP 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
    • D21H17/00Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/62Rosin; Derivatives thereof
    • DTEXTILES; PAPER
    • D21PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21HPULP 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
    • D21H17/00Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/63Inorganic compounds
    • D21H17/66Salts, e.g. alums
    • DTEXTILES; PAPER
    • D21PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21HPULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H21/00Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
    • D21H21/14Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
    • D21H21/16Sizing or water-repelling agents

Definitions

  • the present invention relates generally to a chemical product for use in the sizing of organic cellulosic fibers, especially in papermaking, and above all in stock hydrophobation (sizing) in paper- making.
  • the sizing or hydrophobation of paper is ancient technology which originated in China.
  • absorbent paper was less suitable for the pens and inks of that time.
  • gelatin was therefore added to the paper so as to' obtain a hard and dense, non-absorbent paper. After that, the sizing technique using gelatin and starch has gradually been improved..
  • the resin acid was saponified with caustic soda and diluted prior to dosage.
  • the last-mentioned technique was improved during the 1960 's and 1970's with the introduction of so-called dispersion size. This technique implies that the resin *
  • GB-Al-2,010,352 describes a different stock sizing method in which a resin size which consists of a saponi ⁇ fied resin acid, is added to the stock and then pre- cipitated on the fibers by adding a practically sul ⁇ phate-free aluminium polyhydroxy chloride to the stock mixed with the resin size.
  • the advantage obtained by using this particular precipitant is said to reside in lesser corrosion difficulties as compared with alum as the precipitant.
  • the sizing method uses a two-component system in which the conventional precipitant alum has been replaced by another preci ⁇ pitant in the form of a special aluminium salt.
  • German patent specification 363,668 also indi- cates a two-component system in which a resin size is precipitated with a neutral or basic aluminium chloride.
  • a great disadvantage of prior art sizing methods is that the hydrophobing effect is drastically reduced when the paper systems are neutral or alkaline. This problem is especially pronounced when one wishes to use calcium carbonate instead of clay as a filler because the calcium carbonate is dissolved at low pH.
  • This shortcoming of conventional sizing technique is due to the fact that cations of aluminium are re- quired to precipitate the negatively charged resin acid/fatty acid. In neutral or alkaline systems, alumi ⁇ nium ions are precipitated in the form of aluminium hydroxide which is an inferior precipitant for resin size since it gives a lower sizing degree.
  • the longer time required for the synthetic size implies that the paper directly after its manufacture does not possess wholly water- repellent characteristics after the drying section of the papermaking machine.
  • a longer hardening time is disadvantageous to the surface sizing and/or surface coating of the paper directly after predrying.
  • a low sizing degree when an alkyl ketene dimer is used
  • sizing with such neutral sizing systems may lead to a low paper friction and coating difficulties in diffe ⁇ rent parts of the paper machine system.
  • British patent specification 1,107,717 proposes a sizing system which comprises an emulsion of paraffin wax as the disperse phase and an aqueous solution of a basic aluminium chloride as the continuous phase, the emulsion being stabilised with nonionic emulsifiers and/or nonionic thickeners.
  • hydrophobic materials other than paraffin mention is made of microcrystalline waxes, polyethylene ' and like waxes, high-molecular fatty alcohols and high-molecular fatty amides, although these have not been specified.
  • a further object of the invention is to provide a hydrophobing agent that may be used as a one-component agent without necessitating separate addition of preci ⁇ pitation chemicals.
  • a still further object of the invention is to provide a method of preparing such a new hydrophobing agent, and still another object of the invention is to provide a sizing system that may be used in both acid and neutral or basic stock systems.
  • the invention is based on the surprising discovery that it is possible to produce a stable one-component agent that can be used as a sizing agent and requires no external-precipitant (in contrast to conventional sizes based on resin acid or fatty acid), if one com ⁇ bines certain polyaluminium salts, one or more resin acids and/or -fatty acids, optionally in mixture with a melting point-reducing additive, such as paraffin or other hydrophobic, melting point-reducing agent, and preferably also a cationic organic substance at low pH (below 4).
  • This sizing agent consists of small emulsified (dispersed) and strongly cationised particles that will be directly adsorbed to the negatively charged fibers when dosed to the paper system or applied to other organic fibers.
  • the hydrophobing agent according to the present invention thus consists of resin acid and/or fatty acid that has been emulsified/dispersed in an aqueous phase of water, a polyaluminium salt dissolved in the water, and preferably also a cationic organic compound.
  • the hydrophobing agent is prepared by finely dispersing the resin acid and/or fatty acid in the aqueous phase in the presence of the polyaluminium salt and preferably also the cationic organic compound.
  • the invention also comprises using this hydrophobing agent for stock hydrophobation of cellulosic fibers in papermaking technology.
  • One of the advantages of the invention is that the polyaluminium salt and the resin acid and/or fatty acid are combined at low pH (below 4), resulting in a direct activation when the hydrophobing agent is batched to the stock and a precipitate of a compound of aluminium and resin and/or fatty acid is formed when the emulsion droplet enters the pH range 4-6.
  • the invention provides for intimate contact between the resin acid and/or fatty acid and the polyaluminium salt, such that the aluminium hydroxide, in spite of a high pH, has no time to precipitate during paper ⁇ making before the active resin acid/fatty acid resinate is formed.
  • a further advantage of the hydrophobing agent according to the invention is that the small emulsified/ dispersed particles because of their insignificant size will optimally cover the surface to be hydrophobed.
  • a major advantage of the invention is that its ' execution requires no external precipitant, whereby hydrophobation, especially in papermaking technology, is very much simplified, not only because but one substance need be batched, but also because sizing will be more efficient and uniform since it is easier to optimise the dosing amount using a one-component size according to the invention than using a conven ⁇ tional two-component size.
  • the greatest advantage is deemed to be the high efficiency of the hydrophobing agent according to the invention also at high pH in paper types con ⁇ taining large amounts of calcium carbonate as filler.
  • Still another advantage of the invention is that the hydrophobing agent is made up of raw materials which are far less expensive than the synthetic sizes now available on the market. Resin and fatty acids are available in practically unlimited quantities.
  • the new hydrophobing agent furthermore is superior to synthetic sizes (such as alkyl ketene dimers) for neutral or alkaline paper systems because the hydrophobing agent according to the invention is quick-hardening and thus provides a low-wetting paper already on the paper machine.
  • the present invention implies that a polyaluminium salt, a nonsaponified resin acid and/or fatty acid, optionally in mixture with a melting point- reducing additive, such as paraffin, and preferably also a cationic organic substance are mixed in water under intense agitation, whereby an emulsion/dispersion is obtained which consists of small cationic droplets of the order 0.05-50 ⁇ m, preferably 0.05-25 ⁇ m.
  • the cationic organic substance is included in the size proper.
  • the one-component size i.e. resin acid/fatty acid and the special polyaluminium salt
  • the cationic substance may thus be added separately to the stock, either for sizing or for some other purpose, and the sizing method according to the invention may be combined with known papermaking methods in which a cationic organic substance is added to the stock, for instance the methods as disclosed by European patent specification EP-B1-41,056 and European published patent application EP-Al-80,986.
  • the dispersion/emulsion thus prepared is so stable and highly concentrated, especially if it contains the cationic organic substance, that it can be conveni ⁇ ently distributed to consumers by conventional transport means.
  • the polyaluminium salts that have proved to be best suited for the purpose of the invention are the basic polyaluminium salts, such as polyaluminium sul ⁇ phate or polyaluminium chloride. These salts are cha ⁇ racterised by a high molar ratio of aluminium to coun ⁇ ter-ions (>1) and in that they provide, in aqueous solution, high-charged polyaluminium ions, such as Al 13 O 4 (OH) 26 (H 2 O) 10 5+ .
  • the raw material for the hydrophobing agent accord ⁇ ing to the invention may comprise pure resin acids, pure fatty acids, or combinations of resin acids and fatty acids, although it is also possible to admix melting point-reducing additives, such as paraffins.
  • a typical resin acid composition is abietic acid: 40% neoabietic acid: 4% pimaric acid: 3% isopimaric acid: 6% palustric acid: 7% other acids: 40%
  • a typical composition is ⁇ leic acid: 30% linoleic acid: 65% other acids: 5%
  • the invention makes it possible to use a modified resin acid/fatty acid fortified by reactions with substances that are conventional in the context, such as maleic anhydride, fumaric acid etc.
  • the resin acids and/or fatty acids are present in the uncharged form (nonsaponified form), i.e. a low pH must be maintained, preferably below pH 5. With higher pH, negatively charged carboxylate groups are obtained which detract from the cationic character of the emulsion/dispersion droplets (meaning that the emulsion/dispersion is disrupted).
  • Suitable amounts of the various components are 0.5-90% resin acid/fatty acid and 10-99.5% water.
  • a suitable weight ratio of resin acids/fatty acids to aluminium in the dispersion is between 100:1 and 1:4, preferably 10:1-and 1:2.
  • the cationic organic compound comprised by the aqueous phase may be a surface active agent, starch, guar gum, carboxy methyl cellulose, polyacrylic amide, polyimine, polyamine, polyamide amine, polyethylene imine, or polyacrylate.
  • a suitable weight ratio of resin acids/fatty acids to the cationic organic compound is between 100:0.01 and 100:30.
  • the mixture was then homogenised in a valve homo- geniser (Gualin Lab 60, APV Schroder, L ⁇ beck, Federal Republic of Germany) at an excess pressure of 350 bar.
  • the pH of the resulting emulsion was measured at room temperature and was 3.7. Microscopic examina- tion showed that the size thus prepared had an emulsion droplet size of about 1-2 ⁇ m.
  • the resulting emulsion was stable against phase separation for more than two months.
  • EXAMPLE 2 25 g of a mixture of 55% tall fatty acid and 45% tall resin acid (special fraction from the di- stillation plant at Bergvik Kemi AB; the fraction had been fortified with 10% fumaric acid) were added in the same manner as in Example 1 to a mixture of 24 g polyaluminium chloride (same as in Example 1) and 0.063 g cationic polyacrylic amide ("PERCOL" 181 from COM, Vastra Fr ⁇ lunda, Gothenburg) and 250 ml water. Otherwise the same procedure as in Example 1 was followed, and the result was a stable disper ⁇ sion having a small particle size and a pH of about 2.5.
  • EXAMPLE 3 25 g of a mixture of 55% tall fatty acid and 45% tall resin acid (special fraction from the di- stillation plant at Bergvik Kemi AB; the fraction had been fortified with 10% fumaric acid) were added in the same manner as in Example 1 to a mixture of 24 g polyaluminium
  • a stable dispersion was prepared by adding 1.7 g of unfortified tall resin acid ( "BE- VIROS SG" from Bergvik Kemi AB, S ⁇ derhamn) to 16.7 g of water which contained 0.02 g cationic surface active agent (hexadecyl trimethyl ammonium bromide from Riedel- de Haen AG, Seelze-Hannover, Federal Republic of Ger ⁇ many) and 1.6 g polyaluminium chloride (same as in Example 1) .
  • Example 3 0.13 g cationic surface active agent (dissolved in 3.5 g ethanol) was added to 50 g of a mixture of fatty acid/resin acid (same fraction as in Example 2) .
  • the cationic surface active agent was the same as in Example 3.
  • the fatty acid/resin acid mixture was added to 148 g water containing 48.4 g polyaluminium chloride (same as in the earlier Examples) and 0.25 g cationic starch having a nitrogen content of 0.4%. Otherwise, the procedure was the same as in Examples 1 and 2. This experiment gave a stable dispersion of pH 2.5 and a viscosity slightly higher than that of the dispersion in the earlier Examples.
  • EXAMPLE 6 1.25 g cationic starch having a nitrogen content of 0.40% and 4.86 g polyaluminium chloride (see the earlier Examples) were dissolved in 250 g water at
  • a stable size emulsion was prepared by adding 25 g tall oil fatty acid ("BEVACID 2") to 250 g water containing 5.6 g cationic starch having a nitrogen content of 0.40%, and 29.2 g polyaluminium chloride. Otherwise, the same conditions were utilised as in Example 1. The pH of resulting emulsion was 2.8.
  • BEVACID 2 tall oil fatty acid
  • EXAMPLE 8 25 g of a special fraction of fatty acid/resin acid (same product as in Example 2) were added in the manner described in Example 1 to a solution con- sisting of 58.3 g polyaluminium chloride (same as in Example 1) and 216.7 ml water. Otherwise, the pro ⁇ cedure of Example 1 was followed, and a stable emulsion/ dispersion of pH 2.8 was obtained.
  • EXAMPLE 9 In this Example, 25 g of a mixture of fatty acid/re ⁇ sin acid (same fraction as in Example 2) were added to a solution of 58.3 g polyaluminium chloride (same as in Example 1) and 91.7 g water, used being made of the same procedure as in Example 1. After cooling . in a water bath, 125 g of a 1% solution of cationic starch (nitrogen content 0.40%) were admixed to the product formed as described above. The result was a stable emulsion/dispersion of pH 2.8.
  • Table 1 shows the results of the evaluation.
  • the dosed amounts of the sizes refer to the amount added (active content), based on dry stock.
  • Table 1 shows that the size according to the invention, in spite of a high pH and high amounts of calcium carbonate, has adequate sizing capacity.
  • a paper stock was prepared in the same manner as in Example 10.
  • the resulting stock had a pH of 7.3. Different sizes according to the present invention were added to the stock.
  • Size prepared in accordance with Example 3 was dosed in different amounts to the suspension of fibers and fillers. Sheets were manufactured according to SCAN 26:67 (basis weight 73 g/m 2 ).
  • the sheets were dried on a drying cylinder at 85°C and then placed in an oven (120°C) for 30 min.
  • EXAMPLE 14 In this experiment, use was made of the same paper stock and the same procedure as in Example 10. However, the hydrophobing agent was a size according to Example 8, which was dosed in different quantities, 0.6% cationic starch (based on dry stock) being added 15 s after size dosing to serve as an external reten ⁇ tion agent. The results of these experiments are shown in Table 5, and it appears that the size according to Example 1 gave an improvement also in the absence of cationic substance, but that the improvement was more pronounced when the cationic substance had been added.
  • EXAMPLE 15 In the experiments according to this Example, use was made of a paper stock prepared in accordance with the procedure stated in Example 10. Sizing was carried out by the same procedure as in Example 10, but in the present Example use was made instead of a size prepared in accordance with Example 9. Adequate sizing was obtained also in this experiment, the result of which is shown in Table 6. TABLE 6
  • the hydrophobing substance used in this Example was a mixture of 42 g tall oil rosin (BEVIROS SG from Bergvik Kemi) and 18 g paraffin wax (melting point 58°C, from Malmsten & Bergvall, Gothenburg). This hydrophobing substance was added under very intense agitation (ULTRA TURRAX from IKA-Werk, Staufen) to a mixture consisting of 3 g cationic starch having a nitrogen content of 0.4%, 144.7 g polyaluminium chloride solution (KLORHYDROL from Reheis Chemical Ltd, Dublin, Al content 12.-5% by weight) and 92.3 g water. The emulsification temperature was 95 C for all of the chemicals included.
  • the emulsion was homogenised for a further 3 min at 10,000 rpm, whereupon it was cooled in a water bath to room temperature.
  • the pH of the product thus prepared was 3.7, and the particle size was about 1-2 ⁇ m.
  • the stability was excellent for more than two months.
  • the birch and pine sulphates were beaten together in a laboratory beater to a beating degree of 200 ml CSF (Canadian Standard Freeness).
  • the calcium carbonate slurried in water) added, and the stock was diluted to 0.5% dry content.
  • the pH of the stock was 8.0.
  • the sizes were dosed in the form of a 1% solution and added to the 0.5% stock under agitation (45 s), whereupon the stock was transferred to a laboratory sheet mould (Finnish mould) having a 100 mesh wire.
  • Table 7 indicates the results of the evaluation.
  • the dosed amounts of size refer to the amount added (active content), based on dry stock.
  • Table 1 indicates that the size according to the in- vention, in spite of a high pH and high amounts of calcium carbonate, has adequate sizing capacity
  • Example 16 was repeated with the same consti ⁇ tuents, but with the following amounts of the diffe ⁇ rent constituents in the size emulsion: 48 g tall oil rosin 12 g paraffin wax 144.7 g polyaluminium chloride solution 3 g cationic starch 92.2 g water The resulting emulsion had a pH of 3.7, a particle size of about 1-2 ⁇ m, and excellent stability for more than two months.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Paper (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Polysaccharides And Polysaccharide Derivatives (AREA)
PCT/SE1985/000405 1984-10-22 1985-10-21 Hydrophobing agent for cellulosic fibers, method of preparing the agent, and use of the agent for stock hydrophobation WO1986002677A1 (en)

Priority Applications (6)

Application Number Priority Date Filing Date Title
DE8585905341T DE3570471D1 (en) 1984-10-22 1985-10-21 Hydrophobing agent for cellulosic fibers, method of preparing the agent, and use of the agent for stock hydrophobation
JP60504785A JPH0713358B2 (ja) 1984-10-22 1985-10-21 セルロ−ス繊維用疎水化剤とその製造法並びに紙料の疎水化のためのその使用
BR8507006A BR8507006A (pt) 1984-10-22 1985-10-21 Agente de hidrofobizacao de fibras celulosicas,processo para preparar o agente e uso do agente para hidrofobizacao de materia prima celulosica
AT85905341T ATE43378T1 (de) 1984-10-22 1985-10-21 Wasserabweisendes mittel fuer cellulosefasern, dessen herstellung und verwendung zum wasserabweisendmachen von pulpe.
FI862646A FI80312C (fi) 1984-10-22 1986-06-19 Hydrofoberingsmedel foer cellulosafibrer, saett att framstaella detta medel samt anvaendningen av medlet foer maeldhydrofobering.
NO862484A NO166805C (no) 1984-10-22 1986-06-20 Hydrofoberingsmiddel for cellulosefibre, fremgangsmaate ved fremstilling av dette middel samt anvendelse av midlet for massehydrofobering.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
SE8405260-4 1984-10-22
SE8405260A SE8405260L (sv) 1984-10-22 1984-10-22 Hydrofoberingsmedel for organiska fibrer, serskilt cellulosafibrer, sett att framstella detta medel samt anvendningen av medlet for meldhydrofobering

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WO1986002677A1 true WO1986002677A1 (en) 1986-05-09

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PCT/SE1985/000405 WO1986002677A1 (en) 1984-10-22 1985-10-21 Hydrophobing agent for cellulosic fibers, method of preparing the agent, and use of the agent for stock hydrophobation

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Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0200002A1 (de) * 1985-04-13 1986-11-05 Chemische Fabrik Brühl Oppermann GmbH Papierleimungsmittel und ihre Verwendung
EP0275851A1 (de) * 1987-01-09 1988-07-27 Eka Nobel Ab Wässerige Dispersionen, ein Verfahren zu ihrer Herstellung und ihre Verwendung als Leimungsmittel
FR2612961A1 (fr) * 1987-03-23 1988-09-30 Atochem Procede de fabrication du papier par adjonction a la suspension fibreuse d'une charge minerale, d'un agent de collage, d'amidon cationique et de polychlorure d'aluminium
FR2612960A1 (fr) * 1987-03-23 1988-09-30 Atochem Procede de fabrication du papier d'emballage et du carton par adjonction a la suspension fibreuse d'amidon cationique et de polychlorure d'aluminium
EP0293119A1 (de) * 1987-05-26 1988-11-30 Eka Nobel Landskrona AB Zusammensetzungen zum Leimen von Papier
AU619260B2 (en) * 1988-03-18 1992-01-23 Eka Nobel Ab Paper sizing methods and compositions
US5192363A (en) * 1987-05-26 1993-03-09 Eka Nobel Landskrona Ab Paper sizing compositions
US5652360A (en) * 1995-01-24 1997-07-29 Japan Corn Starch Co., Ltd Cationic starch composition and process for making same
WO1998024972A1 (en) * 1996-11-30 1998-06-11 Raisio Chemicals Uk Ltd. Rosin emulsion including starch derivative for paper sizing
WO1999037857A1 (de) * 1998-01-26 1999-07-29 Krems Chemie Aktiengesellschaft Stabile, wässrige dispersionen für die papierleimung
US6165259A (en) * 1997-02-05 2000-12-26 Akzo Nobel N.V. Aqueous dispersions of hydrophobic material
US10982391B2 (en) 2016-06-01 2021-04-20 Ecolab Usa Inc. High-efficiency strength program used for making paper in higher charge demand system

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08299495A (ja) * 1995-05-08 1996-11-19 Pin Kuo Hai 張力構造を有する健康維持機器
JP5751412B2 (ja) * 2010-05-28 2015-07-22 荒川化学工業株式会社 製紙用ロジン系エマルジョン型サイズ剤およびこれを用いて得られる紙
US10542773B2 (en) * 2013-07-19 2020-01-28 Philip Morris Products S.A. Hydrophobic paper

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US4147682A (en) * 1976-12-09 1979-04-03 Toagosei Chemical Industry Co., Ltd. Additive composition for use in papermaking
GB2010352A (en) * 1977-12-14 1979-06-27 Sulzer Ag Paper Sizing Process
GB2015614A (en) * 1978-02-27 1979-09-12 Ugine Kuhlmann A process for the production of paper or cardboard
US4246040A (en) * 1978-06-05 1981-01-20 Nihonshikizai Kogyo Co., Ltd. Surface treatment method
US4327017A (en) * 1979-03-08 1982-04-27 Nihonshikizai Kogyo Co., Ltd. Agent of chroma and brightness for pigments
EP0069718A1 (de) * 1981-07-03 1983-01-12 Boliden Aktiebolag Basisches Aluminiumsulfat, seine Herstellung und Verwendung
DE3245390C1 (de) * 1982-12-08 1984-01-26 Giulini Chemie Gmbh, 6700 Ludwigshafen Mittel und Verfahren zur Neutralleimung

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US4147682A (en) * 1976-12-09 1979-04-03 Toagosei Chemical Industry Co., Ltd. Additive composition for use in papermaking
GB2010352A (en) * 1977-12-14 1979-06-27 Sulzer Ag Paper Sizing Process
GB2015614A (en) * 1978-02-27 1979-09-12 Ugine Kuhlmann A process for the production of paper or cardboard
US4246040A (en) * 1978-06-05 1981-01-20 Nihonshikizai Kogyo Co., Ltd. Surface treatment method
US4327017A (en) * 1979-03-08 1982-04-27 Nihonshikizai Kogyo Co., Ltd. Agent of chroma and brightness for pigments
EP0069718A1 (de) * 1981-07-03 1983-01-12 Boliden Aktiebolag Basisches Aluminiumsulfat, seine Herstellung und Verwendung
DE3245390C1 (de) * 1982-12-08 1984-01-26 Giulini Chemie Gmbh, 6700 Ludwigshafen Mittel und Verfahren zur Neutralleimung

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Chemical Abstracts Vol. 92 (1983) abstract no. 60652 *
Chemical Abstracts Vol. 98 (1980) abstract no. 74107 *

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0200002A1 (de) * 1985-04-13 1986-11-05 Chemische Fabrik Brühl Oppermann GmbH Papierleimungsmittel und ihre Verwendung
EP0275851A1 (de) * 1987-01-09 1988-07-27 Eka Nobel Ab Wässerige Dispersionen, ein Verfahren zu ihrer Herstellung und ihre Verwendung als Leimungsmittel
FR2612961A1 (fr) * 1987-03-23 1988-09-30 Atochem Procede de fabrication du papier par adjonction a la suspension fibreuse d'une charge minerale, d'un agent de collage, d'amidon cationique et de polychlorure d'aluminium
FR2612960A1 (fr) * 1987-03-23 1988-09-30 Atochem Procede de fabrication du papier d'emballage et du carton par adjonction a la suspension fibreuse d'amidon cationique et de polychlorure d'aluminium
EP0285486A1 (de) * 1987-03-23 1988-10-05 Elf Atochem S.A. Verfahren zur Herstellung von Verpackungspapier und Pappe
EP0285487A1 (de) * 1987-03-23 1988-10-05 Elf Atochem S.A. Papierherstellungsverfahren
EP0293119A1 (de) * 1987-05-26 1988-11-30 Eka Nobel Landskrona AB Zusammensetzungen zum Leimen von Papier
US5192363A (en) * 1987-05-26 1993-03-09 Eka Nobel Landskrona Ab Paper sizing compositions
AU619260B2 (en) * 1988-03-18 1992-01-23 Eka Nobel Ab Paper sizing methods and compositions
US5652360A (en) * 1995-01-24 1997-07-29 Japan Corn Starch Co., Ltd Cationic starch composition and process for making same
WO1998024972A1 (en) * 1996-11-30 1998-06-11 Raisio Chemicals Uk Ltd. Rosin emulsion including starch derivative for paper sizing
US6165259A (en) * 1997-02-05 2000-12-26 Akzo Nobel N.V. Aqueous dispersions of hydrophobic material
WO1999037857A1 (de) * 1998-01-26 1999-07-29 Krems Chemie Aktiengesellschaft Stabile, wässrige dispersionen für die papierleimung
US10982391B2 (en) 2016-06-01 2021-04-20 Ecolab Usa Inc. High-efficiency strength program used for making paper in higher charge demand system

Also Published As

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JPH0713358B2 (ja) 1995-02-15
FI80312C (fi) 1990-05-10
DE3570471D1 (en) 1989-06-29
BR8507006A (pt) 1987-01-06
FI80312B (fi) 1990-01-31
CA1339849C (en) 1998-05-05
SE8405260L (sv) 1986-04-23
NO166805C (no) 1991-09-04
SE8405260D0 (sv) 1984-10-22
NO862484L (no) 1986-06-20
FI862646A (fi) 1986-06-19
NO862484D0 (no) 1986-06-20
EP0200755A1 (de) 1986-11-12
FI862646A0 (fi) 1986-06-19
EP0200755B1 (de) 1989-05-24
NO166805B (no) 1991-05-27
JPS63501224A (ja) 1988-05-12

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