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 sizing agent for use in paper-making comprising at least one unsaturated hydrocarbyl partial ester of alkenylsuccinic acid of the general formula: wherein R represents an unsaturated hydrocarbyl group having at least six carbon atoms and R ⁇ represents an unsaturated hydrocarbyl group having 3 to 18 carbon atoms, and a water-soluble salt thereof as an active component.
• the present invention further relates to a sizing agent comprising at least one unsaturated hydrocarbyl partial ester of alkenylsuccinic acid set forth above and /or at least one water-soluble salt thereof together with at least one 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 provides 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 abscence 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, diaminotoluene sulfonic acid, aniline disulfonic acid, aniline­trisulfonic acid, diaminobenzene disulfonic acid, ethyltoluidine sulfonic acid, diethylaniline sulfonic acid chlor
• organic phosphoric acid or esters thereof include nitrilotrimethylphosphoric acid, aminodimethylphosphonomonoethyl­phosphoric acid, ethylenediaminethtramethylphosphoric acid, diethlenetriaminepentamethylphosphoric acid, triethylenetetramine­hexamethylphosphoric acid, hydroxyethylidenidiphosphoric acid, hydroxypropylidenediphosphoric acid, 1,2,4-tricarboxybutane-2-­phosphoric acid, 1,2-dicarboxybutane-2-phosphoric acid,1,2,4-­tricarboxyhexane-1-phosphoric acid, ⁇ -chloroethylacidphosphate, bis[(2-hydroxyethyl)-methacrylate]acidphosphate,2-ethylhexyl­acidphosphate, methylacidphosphate, ethylacidphosphate, propylaced­phosphate, butylacidphosphate, octylacidphosphate, decylacid
• 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.
• test coditions were as follows: pulp concentration 0.5% paper-making procedure TAPPI STANDARD MACHINE basis weight 70g/m2 filler heavy calcium carbonate drying 110 °C for 5 minutes sizing test JIS P8122 Stoechigt sizing test
• Cationic starch 10g was boiled with 90 ml of water at 95-97 °C for 15 minutes to which was added 5 g of the sizing agent set forth in Table 2 and resultant product was subjected to the sizing test as set forth in Example 1 in order to measure the degree of sizing achieved by the product.
• the results obtained are reproduced in Table 2 below.
• 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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• 1986
  • 1986-05-07 EP EP19860303446 patent/EP0224976B1/de not_active Expired

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