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
  • D21H17/15—Polycarboxylic acids, e.g. maleic acid
  • D21H17/16—Addition products thereof with hydrocarbons

Definitions

• This invention relates to a process for the sizing of paper and to the improved paper thus prepared. More particularly, this invention relates to novel sizing agents for use in the sizing of paper and paperboard products.
• a further object of this invention involves the use of sizing agents which may be employed with all types or" paper pulp over the complete range of pH conditions which are normally encountered in paper manufacturing.
• An additional object involves the use of sizing agents which are fully compatable with alum and rosin as well as with the various fillers, pigments and other chemicals which may be added to paper.
• paper and paperboard include sheet-like masses and molded products made from fibrous cellulosic materials which may be derived from both natural and synthetic sources. Also included are sheetdike 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.
• Paper and paperboard are often sized with various materials for the purpose of increasing their resistance to Water as well as to other types of aqueous solutions. These materials are referred to as sizes or sizing and they may be introduced during the actual paper making operation wherein the process is known as internal or engine sizing. Or, on the other hand, they may be applied to the surface of the finished web or sheet in which case the process is known as external or surface sizing.
• wateruepellant materials have been utilized as sizing agents. These include rosin, mixtures oirosin with waxes, wax emulsions, ketene dimer emulsions, fluorocarbons, fatty acid complexes of chromium or "aluminum chlorides, long chain thermoplastic copolymers, @as well as some themnosetting condensation type resins. Although all of t ese materials are effective under certain conditions, their use is nonethless subject to one or more limitations.
• rosin although the latter is relatively low in cost and readily available, it has poor resistance to alkaline solutions and cannot be used for the sizing of neutral or alkaline pulps. It is inoperable with the latter since it must be ordinarily used in combination with alum, or an acidic aluminum ion donor, which-is present for the purpose of precipitating and setting the sodium rosinate, i.e. the rosin soap, onto the fibers.
• alum for this purpose is, however, precluded under neutral or alkaline conditions. This is a definite disadvantage since the paper produced from neutral and alkaline pulp has been found to have higher strength, greater stability and superior aging charv aliases Patented Aug.
• a still further advantage of these sizing agents is that they do not detract from the strength of the paper and when used with certain adjuncts will in tact, increase the strength of the finished sheets.
• An additional advantage of our novel sizing agents is that only mild drying or curing conditions are required to develop full sizing value.
• novel sizing agents-of our invention may be described as substituted cyclic dicarboxylic acid anhydrides corresponding to the following structural formula:
• R represents a :dimethylene or trimethylene radical and wherein R a hydrophobic group containing more than 5 carbon atoms which may be selected from the class consisting of alkyl, alkenyl, aralkvl or aralkenyl groups.
• Substituted cyclic dicarboxylic acid anhydrides 3 falling within the above described formula are the substituted succinic and glutaric acid 'anhydrides.
• sizing agents include iso-octadecenyl succinic acid anhydride, n-hexadecenyl s uccinic acid anhydride, dodecenyl succinic acid anhydride, dodecyl succinic acid anhydride, decenyl succinic acid anhydride, octenyl succinic acid anhydride, noneny-l succinic acid anhydride, triisobutenyl succinic acid anhydride, capryloxy succinic acid anhydride, heptyl glutaric acid anhydride, and benzyloxy succinic acid anhydride.
• sizing agents of our invention Another important factor in the effective utilization of the sizing agents of our invention involves their use in conjunction with a material which is either cationic in nature or is, on the other hand, capable of ionizing or dissociating in such a manner as to produce one or more cations or other positively charged moieties.
• cationic agents as they will be hereinafter referred to, have been found useful as a means for aiding in the retention of our sizing agents as Well as for bringing the latter into close proximity to the pulp fibers.
• cationic agents include alum, aluminum chloride, long chain fatty amines, sodium aluminate, polyacrylamide, chromic sulfate, animal glue, cationic thermosetting resins and polyamide polymers.
• cationic agents include various cationic starch derivatives including primary, secondary, tertiary or quaternary amine starch derivatives and other cationic nitrogen substituted starch derivatives, as well as cationic sulf-onium 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.
• any of the above noted cationic agents may be added to the stock, i.e. the pulp slurry, either prior to, along with or after the addition of the sizing agent. However, in order to achieve maximum distribution, it is preferable that the cationic agent be added either subsequent to or in direct combination with the sizing agent.
• the actual addition to the stock of either the cationic agent or the sizing agent may take place at any point in the paper making process prior to the ultimate conversion of the wet pulp into a dry web or sheet.
• our sizing agents may be added to the pulp while the latter is in the headbox, beater, hydropulper or stock chest.
• our sizing agents be uniformly dispersed throughout the fiber slurry in as small a particle size as is possible to obtain.
• non-cationic emulsifiers which may be used as emulsifying agents for our sizing agents, one may list such hydrocolloids as ordinary starches, noncationic starch derivatives, dextrines, carboxymethyl cellulose, gum arabic, gelatin and polyvinyl alcohol as well as various surfactants.
• non-cationic emulsifiers it is often desirable to separately add a cationic agent to the pulp slurry after the addition to the latter of the emulsified sizing agent.
• the sizing agent is then introduced along with vigorous agitation. If the sizing agent normally exists as a Waxy solid, it must first be melted prior to its emulsification.
• the sizing agents of our invention may, of course, be successfully utilized for the sizing of paper prepared from all types of both cellulosic and combinations of cellulosic with non-cellulosic fibers.
• the cellulosic fibers which may be used include bleached and unbleached sulfate (kraft), bleached and unbleached sulfite, bleached and unbleached soda, neutral sulfite, semi-chemical, chemigroundwood, ground wood, and any combination of these fibers. These designations refer to wood pulp fibers which have been prepared by means of a variety of processes which are used in the pulp and paper industry. In addition, synthetic fibers of the viscose rayon or regenerated cellulose type can also be used.
• pigments and fillers may be added to the paper which is to be sized with our novel sizing agents.
• Such materials include clay, talc, titanium dioxide, calcium carbonate, calcium sulfate, and diatomaccous earths.
• Other additives, including alum, as well as other sizing agents can also be used with our sizing agents.
• our sizing agents may be employed in amounts ranging from about 0.05 to about 5.0% of the dry weight of the pulp in the finished sheet or web. Within this range the precise amount which is to be used will, of course, depend for the most part upon the type of pulp which is being utilized, the specific operating conditions, as well as the particular end use for which the paper is destined. Thus, for example, paper which will require good water resistance or ink holdout will necessitate the use of a higher concentration of sizing agent than paper which will be used in applications where excessive sizing is not needed. These same factors also apply in relation to the amount of cationic agent which may be used in conjunction with our sizing agents.
• our reagents have been found to provide a degree of water resistance which is comparable, and in many cases superior, to the results obtained with other heretofore employed sizing agents. Moreover, our sizing agents impart a resistance to acid and alkali which is often unattainable with other sizing agents.
• Example I This example illustrates the use of our sizing agents in the form of aqueous emulsions wherein the emulsifier used is a tertiary amine cationic starch derivative.
• the use of our sizing agents in combination with alum is also illustrated.
• the water resistance of the resulting paper is compared with that of paper which had been sized with mixtures of fortified rosin and alum.
• IODSA aqueous emulsion of iso-octadecenyl succinic acid anhydride which for purposes of brevity will hereinafter be referred to as IODSA, was prepared by first cooking 7.5 parts of the beta-diethyl amino ethyl chloride hydrochloride ether of corn starch, whose preparation is described in Example I of US. Patent 2,813,093, in 85 parts of water which was heated in a boiling water bath. After being cooked for 20 minutes, the dispersion of the cationic starch derivative was cooled to room temperature and transferred to a high speed agitator whereupon 7.5 parts of IODSA were slowly added to the agitated dispersion.
• both the cationic agent and the IODS A were both the cationic agent and the IODS A.
• the basis weight of these sheets was 55 lbs./ ream (24 x 36"500 sheets).
• comparable sheets were made which contained varying amounts of IODSA as well as several which contained the IODSA in combination with varying amounts of alum.
• the pH of the aqueous pulp slurry was 5.0.
• the water resistance of these sheets was compared with that of sheets prepared from comparable pulp which had been sized with a mixture of rosin and alum.
• the former test involves placing a small amount of uranine dye powder on the upper surface of a swatch of paper which is. then set afloat in distilled water. As the water is absorbed into the paper, the dye is moistened and thus becomes sensitive to ultraviolet light. The time, in seconds, required for this UV sensitivity to occur is thus in direct relation to the water resistance of the paper since a more water resistant paper will, of course, retard the moistening of the dye which has been placed upon its upper surface.
• the ink dip test is a qualitative comparison wherein a swatch of the paper being tested is dipped into a 1:1 mixture of water and blue ink. The swatch is then removed, washed with water and the remaining color evaluated with a colorimeter. Thus, a swatch with a greater degree of water resistance will have a lighter color than a swatch with poor water resistance. For this test an arbitrary color scale of 1-10 was used, with #1 indicating .the least color or the best water resistance, and the #10 indicating the most color or the poorest water resistance. This test also provides a qualitative visual indication of the distribution of the sizing agent in the paper.
• a series of aqueous emulsions of IODSA were prepared by means of the procedure described in Example I wherein the same tertiary amine cationic starch described therein was again used as the emulsifier.
• These emulsions contained varying amounts of both the IODSA and the cationic starch and, with agitation, they were added, at the headbox, to separate batches of bleached sulfate pulp having a fireeness of 500 and a consistency of 0.5
• the pH of the pulp slurry was-8.0 except where rosin was used in which case the resultant pH of the slurry after addition of the alum was 4.5-5.0.
• the basis weight of the resulting paper was 60 lbs/ream. Below are described the compositions of the various sheets which were prepared as well as the results obtained when the Water resistance of these sheets was tested by means of the uranine dye test.
• Example III This example illustrates the use of octenyl succinic acid anhydr-id-e. It also illustrates the importance of using the latter in combination with alum as well as the desirability for the post curing of the sheets sized with this short chain length derivative so as to obtain sizing results which are comparable to those obtained with longer chain derivatives.
• aqueous emulsion of octenyl succinic anhydride was prepared by means of the procedure described in Example I.
• the same cationic starch derivative was used as the emulsifier; however, in this case the derivative was pregelatinized, i.e. put into cold water soluble form, by
• Example I V This example illustrates the use of IODSA in its oily, unemulsified form and demonstrates the improvements obtained when, in one case, a cationic agent is added to the stock after the addition of the unemulsified IODSA; and, in another case, when ordinary corn starch is added to the stock before the addition of the IODSA and a cationic agent, the purpose of the corn starch being to aid in the dispersion of the sizing agent; and, in still another case, where corn starch is added to the stock prior to the addition of only the unemulsified IODSA.
• the basis weight of all of the above described sheets was 55 lbs/ream (24 x 36500 sheets). Below are described the compositions of the various sheets which were prepared as well as the results obtained when the water resistance of these sheets was tested by means of the uranine dye test.
• Example V This example illustrates the use of ordinary corn starch as the emulsifying agent for IODSA.
• Example II An aqueous emulsion of IODSA was prepared using the procedure of Example I; however, in this case, ordinary corn starch rather than the cationic starch derivative was used as the emulsifier. With agitation, this emulsion was added to bleached sulfate pulp having a freeness of 500 and a 1.5% consistency. This was followed by the addition of alum to a pH of 5.5. The finished sheets contained 1.0% of IODSA and 1.0% of corn starch as based upon the dry weight of the pulp and had a basis weight of 60 lbs/ream. Below are described the compositions of the various sheets which were prepared as well as the results obtained when the water resistance of these sheets was tested by means of the uranine dye test. A comparison of sheets which had been sized with fortified rosin and alum is also offered.
• Example VI This example illustrates the use of IODSA for the sizing of paper containing an appreciable quantity of inert pigments.
• An aqueous emulsion of IODSA was prepared using the procedure of Example I. With agitation, portions of this emulsion were added to a series of bleached sulfite pulps having a freeness of 440 and a consistency of 1.5 and which also contained, respectively, 10% of titanium dioxide, 10% of calcium carbonate, and 10% of clay as based upon the dry weight of the pulp.
• the resulting sheets each contained 0.5% of IODSA and 0.5% by weight of the cationic starch derivative as based upon the dry weight of the pulp and had a basis weight of 60 lbs./ ream.
• compositions of the various sheets which were prepared as well as the results obtained when the water resistance of these sheets was tested by means of the uranine dye test. A comparison of pigment containing sheets which had been sized with fortified rosin and alum is also offered.
• Example VII This example illustrates the use of IODSA in its oily, unemulsified form which was, however, added to the pulp in combination with a cationic starch.
• Example II With agitation, separate portions of IODSA and the cationic corn starch derivative described in Example I were added, simultaneously, to a mixture of 73% groundwood and 27% bleached sulfite pulps having a freeness of 350 and a consistency of 1.5%.
• the resulting sheets contained 1.0% of IODSA and 1.0% of the cationic corn starch as based upon the dry weight of the pulp.
• aqueous emulsion of IODSA was prepared by means of the procedure described in Example 1.
• the emulsifier which was used was a corn starch acid ester of octenyl succinic acid as prepared by means of the procedure described in Example H of US. Patent 2,661,349. With agitation, this emulsion along with a quantity of the cationic corn starch derivative described in Example I of this disclosure, were added, at the headbox, to a bleached sulfate pulp having a freeness of 500 and a consistency of 0.5.
• the resulting sheets in this case, contained 1.0% of IODSA, 1.0% of the corn starch acid ester emulsifier, and 1.0% of the cationic starch as based upon the dry weight of the pulp.
• IODSA 1.0% of the corn starch acid ester emulsifier
• cationic starch 1.0% of the cationic starch as based upon the dry weight of the pulp.
• the various emulsifiers used were the tertiary amine, beta-diethyl amino ethyl chloride hydrochloride starch ethers prepared as described in Example I, of US. Patent 2,813,093.
• starch bases including waxy maize, tapioca, potato, a waxy maize starch which was acid converted to a degree known in the trade as fluidity, land a corn starch which was acid converted to a degree known in the trade as 75 fluidity.
• tertiary starch amines were then usedas the emulsifier for the preparation of aqueous emulsions of IODSA. These emulsions were each, in turn, added at the headbox to bleached sulfate pulp having a freeness of 500 and a consistency of 0.5%.
• the resulting sheets in each case contained a 1.0% of IODSA and 1.0% respectively, of the various tertiary amine starches as based upon the dry weight of the pulp.
• the water resistance of these sheets was then evaluated by means of the uranine dye test, as described in Example 1. Additional samples of these sheets were then cured by being heated for 1 hour at a temperature of C. The water resistance of these cured sheets was similarly determined by means of the unanine dye test. The results of these tests are presented in the following table.
• Example XI This example illustrates the use of several of the sizing agents of our invention including n-hexadecenyl succinic acid anhydride, dodecenyl succinic acid anhydride, dodecyl succinic acid anhydride, and a mixture of iso-alkenyl succinic acid anhydrides wherein the alkenyl groups of the mixed anhydrides contained from 18 to 22 carbon atoms.
• aqueous emulsion of each of the above described sizing agents was prepared by means of the procedure described in Example I using, as an emulsifier, the same cationic starch derivative described therein. With agitation, the emulsions of the mixed iso-alkenyl succinic acid anhydrides and the n-hexadecenyl succinic acid anhydride were added, respectively, at the hydropulper to bleached sulfate pulps having a consistency of 1.5% and a freeness of 510.
• the emulsions of dodecenyl succinic acid anhydride and dodecyl succinic acid anhydride were added, at the headbox, to a bleached sulfite pulp having a consistency of 0.5% and a freeness of 500.
• the resulting sheets in each case, contained 1.0% of the various sizing agents and 1.0% of the cationic starch as based upon the dry weight of the pulp.
• a comparison of bleached sulfate sheets which had been sized with fortified rosin and alum is also offered.
• Example XII This example illustrates the use of our sizing agents in combination with a variety of cationic agents. It also demonstrates their use in the treatment of paper pulp under a broad range of pH conditions.
• An aqueous emulsion of IODSA was prepared by means of the procedure described in Example I using, as the emulsifier, the corn starch acid ester of octenyl succinic acid prepared by means of the procedure described in Example II of U.S. Patent 2,661,349. With agitation, portions of this emulsion along with a quantity of one or more cationic agents were added to separate bleached sulfate stocks each having a freeness of 510 and a consistency of 0.5% but which were, however, at a variety of pH conditions.
• the resulting sheets in each case, contained 1.0% of IODSA and 1.0%, respectively, of the corn starch acid ester emulsifier and had a basis weight of 55 lbs/ream.
• the water resistance of these sheets was then evaluated by means of the uranine dye test, as described in Example I. The results of these tests as well as the nature of the cationic agents utilized and the pH of each pulp are presented in the following table.
• Example XIII This example illustrates the improved strength which is obtained with the use of our sizing agents as compared with the strength of unsized sheets as well as with sheets sized with mixtures of fortified rosin and alum.
• An aqueous emulsion of IODSA was prepared by means of the procedure described in Example I wherein the same teritiary amine cationic starch described therein was again used as the emulsifier. With agitation, this emulsion was added, at the headbox, to an unbleached sulfate pulp having a freeness of 550 and a consistency of 0.5%.
• the resulting sheets contained 1.0% of both IODSA and the cationic starch as based upon the dry weight of the pulp and had a basis weight of 57 lbs/ream (24" x 36" --500 sheets). The water resistance of these sheets was then evaluated by means of the uranine dye test.
• the strength of these sheets was also determined using the Mullen tester.
• a sheet of the paper is clamped between two ring shaped platens, thus leaving an exposed circular surface of paper under which there is an inflatable rubber diaphragm.
• air is pumped into this diaphragm it expands and comes into contact with the exposed surface of the paper.
• the Mullen factor is then calculated by dividing the latter figure by the basis weight of the paper, a higher Mullen factor thus indicating a stronger paper.
• Example XIV This example illustrates the excellent resistance to acidic and alkaline solutions which is displayed by the paper which has been treated with our novel sizing agents atoms and is selected from the class consisting ttrirnethylene radicals and wherein R is group containing more than five carbon of alkyl,
• pllovlde ⁇ he aluminate polyacrylamide, animal glue, polyamide polyl W ⁇ low/1 812mg f which We Operable mess, primary amine starch derivatives, secondary amine undel a Wide w 0f cofldmons and capable 9 starch derivatives, tertiary amine stanch derivatives and providing paper products which are characterized by their quaternary amine stawh demivativei exceptionally high degree of water resistance.
• the method of sizing paper which comprises the step of intimately dispersing within the wet pulp, prior to the ultimate conversion of said pulp into a dry web, a O sizing agent which comp "ses a cyclic dicarboxylic acid H anhydride corresponding to the structural dormula 5 0 0 H II 0 o R-R 1 wherein R is selectedfrom the class consisting of di- 0 methylene and trinrethylene radicals and wherein R is a hydrophobic group containing more than live carbon wherein R is selected from the class consisting of diatoms and is selected from the class consisting of alkyl,
• alkenyl, aralkyl and aral'kenyl groups (b) at least 0.025%, based on the dry Weight of the pulp, of a cationic :agent.
• said cationic agent is selected from the group consisting of alum, aluminum chloride, long chain fatty amines, sodium aluminate, polyacrylamide, animal glue, polya-mide polymers, primary amine starch derivatives, secondary amine starch derivatives, tertiary amine starch derivatives and quaternary amine starch derivatives.

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