EP0224976B1 - Papierleimungsverfahren - Google Patents

Papierleimungsverfahren Download PDF

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Publication number
EP0224976B1
EP0224976B1 EP19860303446 EP86303446A EP0224976B1 EP 0224976 B1 EP0224976 B1 EP 0224976B1 EP 19860303446 EP19860303446 EP 19860303446 EP 86303446 A EP86303446 A EP 86303446A EP 0224976 B1 EP0224976 B1 EP 0224976B1
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EP
European Patent Office
Prior art keywords
acid
sulfonic acid
sizing
chosen
paper
Prior art date
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Application number
EP19860303446
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English (en)
French (fr)
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EP0224976A1 (de
Inventor
Akio Maeda
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Chiyoda Kagaku Kenkyusho KK
Original Assignee
Chiyoda Kagaku Kenkyusho KK
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Publication date
Application filed by Chiyoda Kagaku Kenkyusho KK filed Critical Chiyoda Kagaku Kenkyusho KK
Priority claimed from EP87304389A external-priority patent/EP0291588B1/de
Publication of EP0224976A1 publication Critical patent/EP0224976A1/de
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Publication of EP0224976B1 publication Critical patent/EP0224976B1/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
    • 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

  • the present invention relates to a sizing agent for use in cellulosic paper-making.
  • alkenylsuccinic anhydride based sizing agents in particular undergo hydrolysis with time due to their inherent nature if they are kept in contact with water for a short period of time, thereby losing their sizing effect.
  • the invente has carried out a wide variety of investigations on the sizing effect of alkenylsuccinic acids and their derivatives having various structures, and as a result he has found that unsaturated hydrocarbyl partial esters of alkenylsuccinic acids and the salts thereof are at least self-emulsifiable with water and provide an excellent sizing effect.
  • unsaturated hydrocarbyl diesters of alkenylsuccinic acids not only entail significant difficulties in their synthesis but they also require troublesome procedures for emulsifying similar to conventional sizing agents and further they require additional auxiliaries such as an activator. In addition, they are inferior to unsaturated monohydrocarbyl esters in sizing effect, which makes them useless commercially.
  • saturated partial(mono)- and di- hydrocarbyl esters of alkenylsuccinic acids have substantially no sizing effect, thus they can not be used as a sizing agent.
  • saturated hydrocarbyl mono- and di-esters of alkenylsuccinic acids are not substantially absorbed by paper and also they can only impart poor repellancy to paper.
  • alkenylsuccinic anhydrides per se are readily absorbed by paper and make the resultant paper water repellant thereby exihibiting a sizing effect.
  • alkenylsuccinic anhydrides have drawbacks in that they drastically change their identity in water with time thereby requiring a adequate care.
  • the object of the present invention is to provide a sizing agent which is at least self-emulsifiable and stable in water for a long period of time and which is effective in lower concentration.
  • Another object of the present invention is to provide a sizing agent which can be prepared without any difficulties.
  • the present invention relates to a method of sizing paper utilizing as a sizing agent a composition comprising one or more partial esters of alkenylsuccinic acids represented by the formula: and/or one or more salts thereof, wherein R represents an unsaturated hydrocarbyl group having at least 6 carbon atoms and R' represents an unsaturated hydrocarbyl group having 3 to 18 carbon atoms.
  • the present invention further relates to use of a sizing agent as set out above, in combination with an acid catalyst.
  • the unsaturated hydrocarbyl partial esters of alkenylsuccinic acids not only exhibit strong absorbability towards paper, but they also show no discoloring, and indicate a sustained stable sizing effect over a long period of time. Moreover, the unsaturated hydrocarbyl partial esters of the present invention provide consistently stable sized paper sheets even if said paper is treated with the agent in a low concentration.
  • the alkenylsuccinic anhydride or corresponding acid employed comprises all the alkenylsuccinic acid or anhydride in which the substituting side chain contains six or more than six carbon atoms and these include, for example, hexenyl-, octenyl-, decenyl-, octadecenyl-, dococenyl-, triancotenyl-, eicocenyl- succinic acid and the like and corresponding anhydrides.
  • unsaturated alcohols there may be mentioned all the unsaturated alcohols having 3 to 18 cabon atoms such as allyl-, propargyl-, butenyl-, butyn-, pentenyl-, hexenyl-, octenyl-, decenyl-, laurenyl-, oleyl- alcohols and the like.
  • the unsaturated partial esters of the present invention can be converted to water-soluble products or at least self-emulsifiable products by converting the remaining free carboxyl group into a salt with alkaline metals or water-soluble amine whereby a stable aqueous solution or dispersion can be obtained by adding it to water.
  • a cationic starch, an alkyleneoxide adduct based activator and the like as is conventionally employed in the art to fully assure the benefit of the sizing agent, although such use of an activator is not essential.
  • the unsaturated hydrocarbyl partial esters of alkenylsuccinic acids can be easily synthesized by a conventional esterification technique.
  • an alkenylsuccinic anhydride or the corresponding acids and unsaturated alcohol are heated together to cause a reaction between them in the presence or ab- scence of a catalyst through a ring opening in the case of anhydride, while in the case of acid through a dehydration to form an unsaturated partial ester.
  • the ratio between the acidic starting material to the unsaturated alcohol is such that the amount of the alcohol is sufficient to esterify only one of the carboxyl groups of the acid.
  • the unsaturated hydrocarbyl partial esters of alkenylsuccinic acids of the present invention may be added to paper material in an amount of 0.0001 to 10 parts by weight per 100 parts by weight of paper material (dry base) and preferably 0.01 to 2.0 parts by weight per 100 parts by weight of paper material.
  • the use of the above catalyst can significantly reduce the amount of unsaturated hydrocarbyl partial ester and thus provide great economical advantages.
  • the acid catalyst such as the sulfonic acid, organic phosphoric acid, inorganic acid or Lewis acid excites the unsaturated linkage in the unsaturated hydrocarbyl partial esters, thereby bringing about a state where the double or triple unsaturated bond can be readily broken, so as to promote the etherification reaction with hydroxyl groups contained in cellulose or the esterification reaction by dehydration and that as a result the fixing of the sizing agent to paper is more fully effected in a short period of time.
  • the acid catalyst there may be mentioned sulfonic acid, organic phosphoric acid, inorganic acid, such as phosphoric acid, phosphorous acid, hypophosphorous acid, sulfuric acid, nitric acid, hydrochloric acid or the like, a Lewis acid such as boron fluoride, zinc chloride, aluminium chloride, ferric chloride and the like.
  • sulfonic acid organic phosphoric acid
  • inorganic acid such as phosphoric acid, phosphorous acid, hypophosphorous acid, sulfuric acid, nitric acid, hydrochloric acid or the like
  • a Lewis acid such as boron fluoride, zinc chloride, aluminium chloride, ferric chloride and the like.
  • sulfonic acid catalysts include benzenesulfonic acid, toluene sulfonic acid, dimethylbenzene sulfonic acid, ethylbenzene sulfonic acid, diethylbenzene sulfonic acid, triethylbenzene sulfonic acid, styrene sulfonic acid, dichlorobenzene sulfonic acid, dichlorotoluene sulfonic acid, aniline sulfonic acid, aminotoluene sulfonic acid, dimethylaniline sulfonic acid, diaminobenzene sulfonic acid, diami- notoluene sulfonic acid, aniline disulfonic acid, anilinetrisulfonic acid, diaminobenzene disulfonic acid, ethyltoluidine sulfonic acid, diethylaniline sulfonic acid chloro
  • organic phosphoric acid or esters thereof include nitrilotrimethylphosphoric acid, amin- odimethylphosphonomonoethylphosphoric acid, ethylenediaminethtramethylphosphoric acid, diethlenetri- aminepentamethylphosphoric acid, triethylenetetraminehexamethylphosphoric acid, hydroxyethylidenidi- phosphoric acid, hydroxypropylidenediphosphoric acid, 1,2,4-tricarboxybutane-2-phosphoric acid, 1,2-dicarboxybutane-2-phosphoric acid,1,2,4-tricarboxyhexane-1-phosphoric acid, fi-chloroethylacidphos- phate, bis[(2-hydroxyethyl)-methacrylate]acidphosphate,2-ethylhexylacidphosphate, methylacidphos- phate, ethylacidphosphate, propylacedphosphate, butylacidphosphate, octy
  • the amount of acid catalyst to be used in the sizing agent is 0.0001 to 10.0 parts by weight, preferably 0.001 to 1 parts by weight of the acid catalyst per 100 parts by weight of the sizing agent.
  • a sizing agent was prepared by mixing 10g of cationic starch with 90ml water, boiling the resulting mixture at 95-97 ° C for 15 minutes and then adding 5g of dodecylsuccinic anhydride thereto.
  • a sizing agent was prepared similar to Comparative Example 1 except that octadecenylsuccinic anhydride acid was used in place of dodecylsuccinic anhydride.
  • a sizing agent was prepared by modifying the pH of a commercially available rosin based sizing agent to 4.5 with alum.
  • a sizing agent was prepared by adding cationized cellulose to a commercially available alkylketene dimer based sizing agent in an amount to 25 % by weight of the agent.
  • monoesters hereinafter described were prepared and these monoesters were subjected to a sizing test in the form of amine salts, sodium salts or potassium salts and like.
  • a monoallylester of decenylsuccinic acid was prepared as in Example 3 hereinafter described and the resultant product was modified with cationic starch to form a homogeneous slurry.
  • a monoallylester of octadecenylsuccinic acid was prepared as in Example 3 hereinafter described, but without addition of benzene sulfonic acid.
  • the resultant monoallylester was mixed with cationic starch as in Comparative Example 1 to form a homogeneous slurry.
  • a monoallylester of octadecenylsuccinic acid was sythesized by reacting in a three-necked flask 1 mole of octadecenylsuccinic anhydride and 1 mole of allylalcohol together at 110 ⁇ 5 ° C for two hours.
  • To the resultant monoallylester of octadecenylsuccinic acid was added 0.1% by weight of benzensulfonic acid on the basis of the weight of the monoallylester.
  • the product thus obtained was modified with cationic starch as in Comparative Example 1 to form a homogeneuos slurry (sample No.25).
  • Example 3 and Comparative Examples 1 to 4 set forth above and Comparative Example 5 and 6 were added to a 0.5 % pulp slurry so as to provide sizing agent concentration of 0.05 %, 0.1 %, and 0.2 % on the basis of the pulp solid and then mixed together for 15 minutes.
  • the resulting slurry was subjected to a sizing test. The results obtained are reproduced in Tables 3 and 4.

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  • Paper (AREA)

Claims (6)

1. Verfahren zum Schlichten von Papier unter Verwendung einer Zusammensetzung als Schlichtmittel, die einen oder mehrere Teilester von Alkenylbernsteinsäure der Formel
Figure imgb0011
und/oder ein oder mehrere Salze davon umfaßt, wobei R einen ungesättigten Kohlenwasserstoffrest mit mindestens 6 Kohlenstoffatomen und R' einen ungesättigten Kohlenwasserstoffrest mit 3 bis 18 Kohlenstoffatomen darstellt.
2. Verfahren nach Anspruch 1, wobei das Salz aus einem wasserlöslichen Aminsalz und/oder einem Alkalimetallsalz ausgewählt ist.
3. Verfahren nach Anspruch 1, wobei ferner ein saurer Katalysator enthalten ist.
4. Verfahren nach Anspruch 3, wobei der Katalysator aus einer Sulfonsäure, einer organischen Phosphorsäure, einer anorganischen Säure oder einer Lewis-Säure ausgewählt ist.
5. Verfahren nach Anspruch 4, wobei die anorganische Säure aus Phosphorsäure, phosphoriger Säure, hypophosphoriger Säure, Schwefelsäure, Salzsäure oder Salpetersäure gewählt ist.
6. Verfahren nach Anspruch 4, wobei die Lewis-Säure aus Borfluorid, Zinkchlorid, Aluminiumchlorid oder Eisen(III)-chlorid gewählt ist.
EP19860303446 1985-11-29 1986-05-07 Papierleimungsverfahren Expired EP0224976B1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP270248/85 1985-11-29
JP27024885 1985-11-29
EP87304389A EP0291588B1 (de) 1984-11-14 1987-05-18 Leimungsmittel

Publications (2)

Publication Number Publication Date
EP0224976A1 EP0224976A1 (de) 1987-06-10
EP0224976B1 true EP0224976B1 (de) 1989-10-18

Family

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Family Applications (1)

Application Number Title Priority Date Filing Date
EP19860303446 Expired EP0224976B1 (de) 1985-11-29 1986-05-07 Papierleimungsverfahren

Country Status (1)

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EP (1) EP0224976B1 (de)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7687477B2 (en) 2002-09-27 2010-03-30 Valtion Teknillinen Tutkimuskeskus Polymer solution and dispersion and a process for the preparation thereof

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS61119798A (ja) * 1984-11-14 1986-06-06 株式会社　千代田化学研究所 サイズ剤

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB448294A (en) * 1934-04-21 1936-06-05 Chem Ind Basel A process and a product for softening textiles, leather, paper and like fibrous materials
US3139373A (en) * 1962-06-08 1964-06-30 Allied Chem Process for the internal sizing of paper with a salt of a substituted succinic acid
BE744193A (fr) * 1970-01-08 1970-06-15 Takahara Masaki Produit de polycondensation acide et fabrication de ce produit
DE2361544C3 (de) * 1973-12-11 1982-07-29 Bayer Ag, 5090 Leverkusen Papierleimungsmittel
US4065349A (en) * 1977-02-28 1977-12-27 Standard Oil Company (Indiana) Paper sizing process
EP0176479A1 (de) * 1984-09-13 1986-04-02 Ciba-Geigy Ag Verfahren zur Herstellung von alkalisch- oder neutralgeleimtem Papier oder Karton mit anionischen, hydrophoben Leimungsmitteln und kationischen Retentionsmitteln

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7687477B2 (en) 2002-09-27 2010-03-30 Valtion Teknillinen Tutkimuskeskus Polymer solution and dispersion and a process for the preparation thereof

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