US3139373A - Process for the internal sizing of paper with a salt of a substituted succinic acid - Google Patents
Process for the internal sizing of paper with a salt of a substituted succinic acid Download PDFInfo
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- US3139373A US3139373A US200908A US20090862A US3139373A US 3139373 A US3139373 A US 3139373A US 200908 A US200908 A US 200908A US 20090862 A US20090862 A US 20090862A US 3139373 A US3139373 A US 3139373A
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- United States
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- paper
- sizing
- anhydride
- pulp
- size
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- 238000004513 sizing Methods 0.000 title claims description 74
- 238000000034 method Methods 0.000 title claims description 36
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical class OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 title claims description 29
- 230000008569 process Effects 0.000 title claims description 15
- 150000003839 salts Chemical class 0.000 title claims description 12
- 239000001384 succinic acid Substances 0.000 title claims description 12
- 239000003795 chemical substances by application Substances 0.000 claims description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 229920001131 Pulp (paper) Polymers 0.000 claims description 15
- 230000001376 precipitating effect Effects 0.000 claims description 9
- 239000007900 aqueous suspension Substances 0.000 claims description 3
- 230000006872 improvement Effects 0.000 claims description 3
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 33
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 32
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 32
- WVRNUXJQQFPNMN-VAWYXSNFSA-N 3-[(e)-dodec-1-enyl]oxolane-2,5-dione Chemical compound CCCCCCCCCC\C=C\C1CC(=O)OC1=O WVRNUXJQQFPNMN-VAWYXSNFSA-N 0.000 description 21
- 229940037003 alum Drugs 0.000 description 21
- 239000002002 slurry Substances 0.000 description 17
- 239000011436 cob Substances 0.000 description 16
- 159000000000 sodium salts Chemical class 0.000 description 16
- 239000000835 fiber Substances 0.000 description 15
- 239000002253 acid Substances 0.000 description 13
- 150000008064 anhydrides Chemical class 0.000 description 12
- 125000004432 carbon atom Chemical group C* 0.000 description 12
- 229940014800 succinic anhydride Drugs 0.000 description 12
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical class ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 description 11
- 239000004215 Carbon black (E152) Substances 0.000 description 11
- 230000032683 aging Effects 0.000 description 11
- 229930195733 hydrocarbon Natural products 0.000 description 11
- -1 alkene hydrocarbon Chemical class 0.000 description 10
- 238000005259 measurement Methods 0.000 description 10
- 239000013055 pulp slurry Substances 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- QDCPNGVVOWVKJG-VAWYXSNFSA-N 2-[(e)-dodec-1-enyl]butanedioic acid Chemical compound CCCCCCCCCC\C=C\C(C(O)=O)CC(O)=O QDCPNGVVOWVKJG-VAWYXSNFSA-N 0.000 description 8
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 150000002561 ketenes Chemical class 0.000 description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 238000013019 agitation Methods 0.000 description 4
- 150000001336 alkenes Chemical class 0.000 description 4
- 150000001345 alkine derivatives Chemical class 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 125000003710 aryl alkyl group Chemical group 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- RINCXYDBBGOEEQ-UHFFFAOYSA-N succinic anhydride Chemical class O=C1CCC(=O)O1 RINCXYDBBGOEEQ-UHFFFAOYSA-N 0.000 description 4
- HFVMEOPYDLEHBR-UHFFFAOYSA-N (2-fluorophenyl)-phenylmethanol Chemical class C=1C=CC=C(F)C=1C(O)C1=CC=CC=C1 HFVMEOPYDLEHBR-UHFFFAOYSA-N 0.000 description 3
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical class O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- WASQWSOJHCZDFK-UHFFFAOYSA-N diketene Chemical compound C=C1CC(=O)O1 WASQWSOJHCZDFK-UHFFFAOYSA-N 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 230000035515 penetration Effects 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 2
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical group CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 2
- UWERUIGPWOVNGG-MDZDMXLPSA-N 3-[(e)-dec-1-enyl]oxolane-2,5-dione Chemical compound CCCCCCCC\C=C\C1CC(=O)OC1=O UWERUIGPWOVNGG-MDZDMXLPSA-N 0.000 description 2
- URVNZJUYUMEJFZ-BUHFOSPRSA-N 3-[(e)-tetradec-1-enyl]oxolane-2,5-dione Chemical compound CCCCCCCCCCCC\C=C\C1CC(=O)OC1=O URVNZJUYUMEJFZ-BUHFOSPRSA-N 0.000 description 2
- FGQUIQAGZLBOGL-UHFFFAOYSA-N 3-non-1-enyloxolane-2,5-dione Chemical compound CCCCCCCC=CC1CC(=O)OC1=O FGQUIQAGZLBOGL-UHFFFAOYSA-N 0.000 description 2
- 150000008065 acid anhydrides Chemical class 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- PFBBCIYIKJWDIN-UHFFFAOYSA-N 2-tetradec-1-enylbutanedioic acid Chemical compound CCCCCCCCCCCCC=CC(C(O)=O)CC(O)=O PFBBCIYIKJWDIN-UHFFFAOYSA-N 0.000 description 1
- KAYAKFYASWYOEB-ISLYRVAYSA-N 3-[(e)-octadec-1-enyl]oxolane-2,5-dione Chemical compound CCCCCCCCCCCCCCCC\C=C\C1CC(=O)OC1=O KAYAKFYASWYOEB-ISLYRVAYSA-N 0.000 description 1
- BTXXTMOWISPQSJ-UHFFFAOYSA-N 4,4,4-trifluorobutan-2-one Chemical compound CC(=O)CC(F)(F)F BTXXTMOWISPQSJ-UHFFFAOYSA-N 0.000 description 1
- BQACOLQNOUYJCE-FYZZASKESA-N Abietic acid Natural products CC(C)C1=CC2=CC[C@]3(C)[C@](C)(CCC[C@@]3(C)C(=O)O)[C@H]2CC1 BQACOLQNOUYJCE-FYZZASKESA-N 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N Propene Chemical compound CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric Acid Chemical compound [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- HFDVRLIODXPAHB-UHFFFAOYSA-N alpha-tetradecene Natural products CCCCCCCCCCCCC=C HFDVRLIODXPAHB-UHFFFAOYSA-N 0.000 description 1
- 210000000988 bone and bone Anatomy 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 238000010835 comparative analysis Methods 0.000 description 1
- 230000001143 conditioned effect Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- FLISWPFVWWWNNP-BQYQJAHWSA-N dihydro-3-(1-octenyl)-2,5-furandione Chemical compound CCCCCC\C=C\C1CC(=O)OC1=O FLISWPFVWWWNNP-BQYQJAHWSA-N 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 125000001165 hydrophobic group Chemical group 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 239000011268 mixed slurry Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
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
- Rosin size which consists mainly of a body of abietic acid, is currently the most widely employed sizing agent for the internal sizing of paper.
- An aqueous solution of the sodium salt of this body obtained by dissolving rosin in a solution of an alkali, customarily is added to paper and, by treatment with a soluble aluminum salt, the rosin size is precipitated and deposited upon the fibers.
- rosin size is currently the most Widely used type of paper size, it nevertheless possesses certain undesirable characteristics. More specifically, rosin size in the paper tends to lower the brightness of the paper as well as the burst, tensile, tearing and folding strengths. Furthermore, paper which has been sized with a rosin size tends to lose strength on aging.
- ketene dimers have been suggested as sizing agents. These ketene dimers are added to the paper pulp to convert the hydroxyl groups of the fibers to hydrophobic groups which repel water.
- ketene dimers are added to the paper pulp to convert the hydroxyl groups of the fibers to hydrophobic groups which repel water.
- ketene dimer sizing cannot be obtained with ketene dimers on reworked papers since the majority of these reworked papers contain residual alum from prior sizing processes.
- a further disadvantage of ketene dimer sizing is that the retention of the ketene dimer is poor Whenit is added at the wet end of the process, and consequently, costly additives must be employed to increase the retention of the ketene dimer size by the fibers.
- An object of the present invention is to provide an eiiicient economical method for the internal sizing of paper. Another object of the invention is to provide new sizing agents for internal sizing of paper. A further object of the invention is to provide an improved paper product. Other objects and advantages will become apparent from the following description.
- internal sizing of paper is effected by dispersing a saponified substituted succinic anhydride or its corresponding acid having a hydrocarbon radical of 8 to 15 carbon atoms, inclusive,
- the treated pulp may then be formed into sheets or webs in the conventional manner.
- the new sizing agents of the present invention employ 3,139,373 Patented v June 30, 1964 substituted succinic anhydrides or its corresponding acids having the following formulas ice I RHC-b ⁇ Hie-o b (I rt-nc 3-o-on HgC-(fi-OH O wherein R is a hydrocarbon radical which can be an alkyl,
- alkene, alkyne or aryl alkyl group having 8 to 15 carbon atoms, inclusive, and preferably 10 to 14 carbon atoms.
- the preferred hydrocarbon radical is an alkene hydrocarbon wherein the double bond is adjacent the succinic anhydride group.
- Hydrocarbon radicals containing less than 8 carbon atoms or more than 15 carbon atoms were tried, but gave unsatisfactory results.
- Illustrative of compounds suitable for the present invention are n-octenylsuccinic anhydride and its isomers; nonenylsuccinic anhydride and its isomers; n-decenylsuccinic anhydride; dodecenylsuccinic anhydride and its isomers; n-tetradecenylsuccinic anhydride; n-octadecenylsuccinic anhydride; 3--
- the new sizing agents when used in the internal paper sizing procedure produce sized paper having superior qualities over rosin sized paper with regard to brightness, tensile strength, folding strength and retention of strength on aging of the sized paper; and surprisingly, these superior qualities are attained at appreciably lower concentrations of sizing agent than are required for rosin sizing.
- Effective sizing according to the invention has been accomplished with concentrations of 0. 5% and in some cases as low as 0.2% of the saponified substituted succinic compound, and the sizing eifects obtained with these amounts compare favorably, and in many cases are superior, to the effects obtained with rosin sizes at concentrations of 1 to 3 /2% based on the weight of the paper pulp.
- Another practical advantage of the present invention is that these new sizing agents can replace rosin sizes in whole or in part, since the process of the invention is compatible with equipment and procedures now in operation for rosin sizing.
- internal sizing is accomplished by dispersing a water soluble metal salt of the substituted succinic acid,
- an alkali metal salt of the substituted succinic acid preferably the sodium salt
- a precipitating agent i.e. a metal compound which reacts with the soluble saponified substituted succinic anhydride or acid to form an insoluble metal salt of the substituted succinic acid.
- Aluminum salts, particularly alum have been found to be especially effective as the precipitating agents.
- the pulp, internally sized with the substituted succinic acid salt, is formed into a sheet in a manner conventional in the paper industry.
- a convenient procedure is to dissolve the substituted succinic acid (or anhydride which converts to the acid) in an aqueous solution of an alkaline material such as sodium hydroxide to form the sodium salt of the substituted succinic acid and to add this aqueous solution of saponified substituted succinic acid, with sufficient agitation or stirring to insure thorough mixing, to the aqueous paper pulp slurry.
- Saponified substituted succinic anhydride is synonymous with salt of the substituted succinic acid since treatment of the anhydride with aqueous alkali (saponification) results in converting the anhydride to the salt of the acid.
- a precipitating agent aluminum sulfate, which converts the saponified substituted succinic anhydride to the insoluble form which is deposited upon the fibers.
- An important property of the substituted succinic anhydride sizing agents of the present invention is their compatibility with alum which latter, because of its availability and low cost, is conventionally employed as a precipitating agent. In the manufacture of paper, the pulp frequently has a constituent reworked paper which contains residual alum and for this reason alone it is most important that the internal sizing agent be compatible with alum. Control of pH is an important factor in obtaining good sizing efiiciency.
- initial pH values of the paper slurry prior to the addition of the sizing and precipitating agent may vary considerably, and are usually from about 6 to 8, the final pH, i.e. the pH value after the addition of size and alum to the paper slurry, should be desirably in the range of 4.0 to 5.5 for maximum sizing efficiency.
- the final pH may be conveniently adjusted to within this range by the addition of alkaline or acid mediums such as dilute solutions of sodium carbonate or sulfuric acid.
- an alkenyl succinic anhydride having 10 to 14 carbon atoms in the alkenyl group preferably dodecenylsuccinic anhydride
- a temperature of about 100 C. is suitable for this purpose.
- the sodium salt of dodecenylsuccinic acid which forms is then dissolved in water to form an aqueous solution, and this solution is added to the paper pulp slurr for example in the beater of a paper making system. This mixture is then agitated to thoroughly mix the two masses.
- the saponified dodecenylsuccinic anhydride is set in the pulp fiber by the addition of about a chemical equivalent quantity of alum.
- the amount of alum employed generally depends on the amount of size, the character of the stock, and the pH of the pulp slurry. As an illustration, about 0.38% alum gives efficient sizing with 0.2% dodecenylsuccinic anhydride in pulp slurries with initial pH values of 6 to 8. Additional amounts of alum, up to 0.75%, may be added without producing any adverse effects.
- the final pH value of the slurry after addition of the sizing agent and alum should be in the range of 4.0 to 5.5 with optimum results being obtainable when the final pH value is about 4 to 5. Addition of controlled amounts of dilute sodium carbonate or sulfuric acid is an effective means of adjusting the pH value.
- the amount of the dodecenylsuccinic anhydride applied to the pulp may be varied depending upon the requiremerits for the sized paper. Results superior to rosin sizing are obtained at concentrations of dodecenylsuccinic anhydride lower than required for similar sizing with rosin sizes. Comparative analysis has indicated that as low as 0.2% saponified dodecenylsuccinic anhydride based on bone dry pulp is as effective as 1% concentration of a superior grade of rosin size. With this concentration of the saponified dodecenylsuccinic anhydride, i.e. 0.2%, it was noted that the sized paper had better resistance to water penetration, and had better aging stability than could be achieved by rosin sizing.
- a feature of the present invention is'that the saponified dodecenylsuccinic anhydride is compatible with rosin sizing procedures and particularly good results are obtained with mixtures of saponified dodecenylsuccinic anhydride and rosin size where it is desired that the paper contain a moderate amount of size.
- the use of saponified dodecenylsuccinic anhydride in combination with rosin size results in a substantial decrease in the amount of rosin size required to produce sized paper of the same quality.
- this feature of the invention is particularly advantageous 41 since a gradual changeover from present rosin sizing procedures may be accomplished.
- the sizing efiiciency of the treated paper may be determined in a variety of ways.
- a particularly suitable procedure and one which has received considerable attention in the paper sizing industry is the Cobb size test, procedure T441 of the Technical Association of the Pulp and Paper Industry (TAPPI); In this procedure, an area of the sheet is defined by clamping it under a metal ring 10 cm. in inside diameter, and then the ring is filled with Water. After a measured interval of time, usually 1 to 5 minutes, the water is poured off, the ring is removed, and the paper is blotted to remove surface Water. The amount of water absorbed is determined from the weights of the paper before and after the exposure, and the Cobb size value is calculated and reported as grams of Water absorbed per square meter of paper. The lower the Cobb value, the better the sizing. For a 3 minute exposure time, a value of 50 g./m. or lower indicates good sizing.
- EXAMPLE '1 The following example shows the sizing eificiency of various substituted succinicanhydrides of the present invention.
- Handsheets containing 0.5 sizing agent were prepared as follows:
- a slurry for each substituted succinic anhydride to be tested was prepared by tearing into small pieces 4.0 grams of 60-brightness pulp which was then placed into a Waring Blendor with 400 ml. of distilled water. The mixture was agitated for 2 minutes and thereafter the required amount of solution of the sodium salt of the substituted succinic acid to give 0.5% based on the weight of the pulp was added and agitation was continued for an additional 1 minute. A solution of alum containing 0.6% alum based on the weight of the pulp was then added, followed by agitation for an additional 1 minute and the pH was adjusted in the range of 4 to 5.5. The action of the Waring Blendor was suflicient for complete disintegration of the pulp sheets and the attainment of a Canadian Standard freeness value of 750 for the pulp.
- Handsheets were formed in a Williamson 8): 8" sheet mold with lSO-mesh stainless steel screen.
- the slurry of the sized pulp was poured into the sheet mold; diluted to 5 liters; and the water was drained off to form a sheet.
- the sheet was removed from the screen on a blotter, pressed between blotters for 1 to 2 minutes at p.s.i., and then dried on an electric dryer at C.
- the sizing efficiency was determined by the Cobb size test according to TAPPI procedure T441, and the results are tabulated 1n Table I. a
- Dodecenylsuccinie anhydride isomer from butylene trimer
- Dodecenylsucciuic anhydride isomer from propylene tetramer
- 7.6 4.
- n-Tetradecenyl-succinic anhydride from l-tetradecene
- the anhydride was mixed with the calculated equivalent quantity of sodium hydroxide; the solids concentration of the salt solution was 0.5%.
- EXAMPLE 2 The following example shows the eifectiveness and uniformity of saponified dodecenylsuccinic anhydride as a paper size at a concentration of 0.2%.
- Two sets of handsheets were prepared, one set containing concentrations of saponified dodecenylsuccinic anhydride of 1% and 0.2%, respectively, and the other set containing concentrations of rosin size of 2 /2%, 1% and 0.2%.
- the handsheets were prepared according to the procedure of Example 1 except that appropriate volumes of the solutions of the sodium salt of dodecenylsuccinic acid and of the rosin size as well as of the alum were used to provide the above concentrations based on the dry pulp.
- the property of the paper that is most affected by aging is the brittleness; therefore, the aged papers were evaluated by measurements of folding endurance. Cobb size measurements were also made on aged and unaged papers. Five measurements of Cobb size values and of folding endurance were made on each sample. The average results from the measurements on aged and unaged paper specimens are shown in the table below.
- the aged and the unaged specimens were conditioned for 48 hours at 72 F. and 50% relative humidity before making measurements.
- Folding endurance was measured with strips of paper 1.5 cm. wide, according to TAPPI standard T4223m.
- An M.I.T. Folding Endurance Tester was used for the measurements.
- EXAMPLE 5 The following example shows the effect of saponified dodecenylsuccinic anhydride when combined with rosin size.
- Papers were prepared with varying amounts of saponified dedecenylsuccinic anhydride and rosin size to determine if the two sizes were compatible and what sizing properties this combination possessed.
- EXAMPLE 6 As a check on the reproducibility of sizing with the mixed sizes, a large batch of pulp was prepared and sized with 0.1% saponified dodecenylsuccinic anhydride and 0.2% rosin size by the procedure described in Example 2. Alum (0.6%) was added to set the size, and 10 replicate handsheets were made. The average Cobb size value for the 10 handsheets was 20 and the range of values was from 19 to 24 which is considered to be excellent reproducibility.
- hydrocarbon radical contains 10 to 14, inclusive, carbon atoms.
- a process for the internal sizing of paper which comprises incorporating the sodium salt of dodecenylsuccinic acid in an aqueous paper pulp slurry, adding aluminum sulfate to the slurry to convert the soluble sodium salt of dodecenylsuccinic acid to the insoluble form which deposits upon the fiber, adjusting the pH of said slurry to within the range of about 4.0 to 5.5, and forming the mass into a sheet.
- a process for the internal sizing of paper which comprises incorporating the sodium salt of nonenylsuccinic acid in an aqueous paper pulp slurry, adding aluminum sulfate to the slurry to convert the soluble sodium salt of nonenylsuccinic acid to the insoluble form which deposits upon the fiber, adjusting the pH of said slurry to within the range of about 4.0 to 5.5, and forming the mass into a sheet.
- a process for the. internal sizing of paper which comprises incorporating the sodium salt of 3-methyl-3- (isopropylphenyl)butane-1,2-dicarboxylic acid in an aqueous paper pulp slurry, adding aluminum sulfate to the slurry to convert the soluble sodium salt of B-methyl 3-(isopropyphenyl)butane-1,2-dicarboxylic acid to the insoluble form which deposits upon the fiber, adjusting the pH of said slurry to within the range of about 4.0 to 5.5, and forming the mass into a sheet.
- a process for the internal sizing of paper which comprises incorporating the sodium salt of n-tetradecenyl succinic acid in an aqueous paper pulp slurry, adding aluminum sulfate to the slurry to convert the soluble sodium salt of n-tetradecenylsuccim'c acid to the insoluble form which deposits upon the fiber, adjusting the pH of wherein R is a hydrocarbon radical selected from the group consisting of an alkyl, alkene, alkyne and aryl alkyl having 8 to 15, inclusive, carbon atoms.
- a process for the internal sizing of paper which comprises incorporating saponified rosin and a sodium salt of dodecenylsuccinic acid in an aqueous paper pulp slurry, adding aluminum sulfate to the slurry to convert the soluble sodium salt of dodecenylsuccinic acid to the insoluble form which deposits upon the fiber, adjusting the pH. of said slurry to within the range of about 4.0 to 5.5, and forming the mass into a sheet.
- a sized paper comprising a fibrous cellulosic web which has been internally sized with a salt of a substituted succinic acid having the formula wherein R is a hydrocarbon radical selected from the group consisting of an alkyl, alkene, alkyne and aryl alkyl having 8 to 15, inclusive, carbon atoms.
- A. sized paper comprising a fibrous cellulosic Web which has been internally sized with a salt of a substi:
- tuted succinic acid having the formula wherein R is an alkene hydrocarbon having 10 to 14, inclusive, carbon atoms with the double bond adjacent the succinic anhydride group.
- a sized paper comprising a fibrous cellulosic web which has been internally sized with a salt of dodecenylsuccinic acid.
- a sized paper comprising a fibrous cellulosic web which has been internally sized with saponified rosin and saponified dodecenylsuccinic acid.
Landscapes
- Paper (AREA)
Description
V pulp with agitation;
United States Patent 3,139,373 THE INTERNAL SIZING F PROCESS FOR SUC- This invention relates to the manufacture of paper and more particularly, to a new and improved method of paper sizing.
Current procedures for paper sizing involve two distinct principal methods: (1) internal sizing wherein the sizing agent is mixed with the fiber furnish and thereafter the entire mass is formed into a sheet having a uniform distribution of fibers and sizing agent, and (2) surface sizing which involves the application of a sizing agent to the surface of an already formed paper. This invention is particularly concerned with the internal sizing procedure.
Rosin size, which consists mainly of a body of abietic acid, is currently the most widely employed sizing agent for the internal sizing of paper. An aqueous solution of the sodium salt of this body, obtained by dissolving rosin in a solution of an alkali, customarily is added to paper and, by treatment with a soluble aluminum salt, the rosin size is precipitated and deposited upon the fibers. Although rosin size is currently the most Widely used type of paper size, it nevertheless possesses certain undesirable characteristics. More specifically, rosin size in the paper tends to lower the brightness of the paper as well as the burst, tensile, tearing and folding strengths. Furthermore, paper which has been sized with a rosin size tends to lose strength on aging. More recently, ketene dimers have been suggested as sizing agents. These ketene dimers are added to the paper pulp to convert the hydroxyl groups of the fibers to hydrophobic groups which repel water. Although the use of ketene dimers as paper sizing agents in the internal sizing procedure reduces some of the undesirable characteristics of rosin sizing, unfortunately new problems are created. For example, paper sizing with ketene dimers is inefifective in the presence of alum and therefore presents a serious deterrent to its use since most paper-mill systems in operation today contain alum. Furthermore, sizing cannot be obtained with ketene dimers on reworked papers since the majority of these reworked papers contain residual alum from prior sizing processes. A further disadvantage of ketene dimer sizing is that the retention of the ketene dimer is poor Whenit is added at the wet end of the process, and consequently, costly additives must be employed to increase the retention of the ketene dimer size by the fibers.
An object of the present invention is to provide an eiiicient economical method for the internal sizing of paper. Another object of the invention is to provide new sizing agents for internal sizing of paper. A further object of the invention is to provide an improved paper product. Other objects and advantages will become apparent from the following description.
In accordance with the present invention, internal sizing of paper is effected by dispersing a saponified substituted succinic anhydride or its corresponding acid having a hydrocarbon radical of 8 to 15 carbon atoms, inclusive,
in an aqueous slurry of paper pulp and adding a precipitating agent to convert the saponified substituted succinic anhydride or acid to an insoluble form which is deposited on the fibers of the pulp. The treated pulp may then be formed into sheets or webs in the conventional manner.
The new sizing agents of the present invention employ 3,139,373 Patented v June 30, 1964 substituted succinic anhydrides or its corresponding acids having the following formulas ice I RHC-b\ Hie-o b (I rt-nc 3-o-on HgC-(fi-OH O wherein R is a hydrocarbon radical which can be an alkyl,
alkene, alkyne or aryl alkyl group having 8 to 15 carbon atoms, inclusive, and preferably 10 to 14 carbon atoms.
and
' The preferred hydrocarbon radical is an alkene hydrocarbon wherein the double bond is adjacent the succinic anhydride group. Hydrocarbon radicals containing less than 8 carbon atoms or more than 15 carbon atoms were tried, but gave unsatisfactory results. Illustrative of compounds suitable for the present invention are n-octenylsuccinic anhydride and its isomers; nonenylsuccinic anhydride and its isomers; n-decenylsuccinic anhydride; dodecenylsuccinic anhydride and its isomers; n-tetradecenylsuccinic anhydride; n-octadecenylsuccinic anhydride; 3--
(ethylphenyl)butane-1,2-dicarboxylic acid anhydride; 3- methy1-3- (isopropylphenyl) -butane,1,2-dicarboxylic acid anhydride. Acids corresponding to the above anhydrides may also be employed.
The new sizing agents when used in the internal paper sizing procedure produce sized paper having superior qualities over rosin sized paper with regard to brightness, tensile strength, folding strength and retention of strength on aging of the sized paper; and surprisingly, these superior qualities are attained at appreciably lower concentrations of sizing agent than are required for rosin sizing. Effective sizing according to the invention has been accomplished with concentrations of 0. 5% and in some cases as low as 0.2% of the saponified substituted succinic compound, and the sizing eifects obtained with these amounts compare favorably, and in many cases are superior, to the effects obtained with rosin sizes at concentrations of 1 to 3 /2% based on the weight of the paper pulp. Another practical advantage of the present invention is that these new sizing agents can replace rosin sizes in whole or in part, since the process of the invention is compatible with equipment and procedures now in operation for rosin sizing.
Basically, internal sizing is accomplished by dispersing a water soluble metal salt of the substituted succinic acid,
. obtained by saponifying a substituted succinic anhydride,
or acid, e.g. an alkali metal salt of the substituted succinic acid, preferably the sodium salt, in an aqueous paper-pulp slurry and converting the saponified substituted succinic anhydride or acid to an insoluble form by treatment with a precipitating agent, i.e. a metal compound which reacts with the soluble saponified substituted succinic anhydride or acid to form an insoluble metal salt of the substituted succinic acid. Aluminum salts, particularly alum, have been found to be especially effective as the precipitating agents. The pulp, internally sized with the substituted succinic acid salt, is formed into a sheet in a manner conventional in the paper industry.
A convenient procedure is to dissolve the substituted succinic acid (or anhydride which converts to the acid) in an aqueous solution of an alkaline material such as sodium hydroxide to form the sodium salt of the substituted succinic acid and to add this aqueous solution of saponified substituted succinic acid, with sufficient agitation or stirring to insure thorough mixing, to the aqueous paper pulp slurry. Saponified substituted succinic anhydride is synonymous with salt of the substituted succinic acid since treatment of the anhydride with aqueous alkali (saponification) results in converting the anhydride to the salt of the acid. Thereafter, to the mixed slurry of paper pulp and saponified substituted succinic anhydride is added a precipitating agent, aluminum sulfate, which converts the saponified substituted succinic anhydride to the insoluble form which is deposited upon the fibers. An important property of the substituted succinic anhydride sizing agents of the present invention is their compatibility with alum which latter, because of its availability and low cost, is conventionally employed as a precipitating agent. In the manufacture of paper, the pulp frequently has a constituent reworked paper which contains residual alum and for this reason alone it is most important that the internal sizing agent be compatible with alum. Control of pH is an important factor in obtaining good sizing efiiciency. Although initial pH values of the paper slurry prior to the addition of the sizing and precipitating agent may vary considerably, and are usually from about 6 to 8, the final pH, i.e. the pH value after the addition of size and alum to the paper slurry, should be desirably in the range of 4.0 to 5.5 for maximum sizing efficiency. The final pH may be conveniently adjusted to within this range by the addition of alkaline or acid mediums such as dilute solutions of sodium carbonate or sulfuric acid.
In a preferred method, an alkenyl succinic anhydride having 10 to 14 carbon atoms in the alkenyl group, preferably dodecenylsuccinic anhydride, is saponified by mixing with sodium hydroxide, and heating until the dodecenylsuccinic anhydride is completely dissolved. A temperature of about 100 C. is suitable for this purpose. The sodium salt of dodecenylsuccinic acid which forms is then dissolved in water to form an aqueous solution, and this solution is added to the paper pulp slurr for example in the beater of a paper making system. This mixture is then agitated to thoroughly mix the two masses. Thereafter the saponified dodecenylsuccinic anhydride is set in the pulp fiber by the addition of about a chemical equivalent quantity of alum. The amount of alum employed generally depends on the amount of size, the character of the stock, and the pH of the pulp slurry. As an illustration, about 0.38% alum gives efficient sizing with 0.2% dodecenylsuccinic anhydride in pulp slurries with initial pH values of 6 to 8. Additional amounts of alum, up to 0.75%, may be added without producing any adverse effects. The final pH value of the slurry after addition of the sizing agent and alum should be in the range of 4.0 to 5.5 with optimum results being obtainable when the final pH value is about 4 to 5. Addition of controlled amounts of dilute sodium carbonate or sulfuric acid is an effective means of adjusting the pH value.
The amount of the dodecenylsuccinic anhydride applied to the pulp may be varied depending upon the requiremerits for the sized paper. Results superior to rosin sizing are obtained at concentrations of dodecenylsuccinic anhydride lower than required for similar sizing with rosin sizes. Comparative analysis has indicated that as low as 0.2% saponified dodecenylsuccinic anhydride based on bone dry pulp is as effective as 1% concentration of a superior grade of rosin size. With this concentration of the saponified dodecenylsuccinic anhydride, i.e. 0.2%, it was noted that the sized paper had better resistance to water penetration, and had better aging stability than could be achieved by rosin sizing. A feature of the present invention is'that the saponified dodecenylsuccinic anhydride is compatible with rosin sizing procedures and particularly good results are obtained with mixtures of saponified dodecenylsuccinic anhydride and rosin size where it is desired that the paper contain a moderate amount of size. The use of saponified dodecenylsuccinic anhydride in combination with rosin size results in a substantial decrease in the amount of rosin size required to produce sized paper of the same quality. Furthermore, this feature of the invention is particularly advantageous 41 since a gradual changeover from present rosin sizing procedures may be accomplished.
Generally the sizing efiiciency of the treated paper may be determined in a variety of ways. A particularly suitable procedure and one which has received considerable attention in the paper sizing industry is the Cobb size test, procedure T441 of the Technical Association of the Pulp and Paper Industry (TAPPI); In this procedure, an area of the sheet is defined by clamping it under a metal ring 10 cm. in inside diameter, and then the ring is filled with Water. After a measured interval of time, usually 1 to 5 minutes, the water is poured off, the ring is removed, and the paper is blotted to remove surface Water. The amount of water absorbed is determined from the weights of the paper before and after the exposure, and the Cobb size value is calculated and reported as grams of Water absorbed per square meter of paper. The lower the Cobb value, the better the sizing. For a 3 minute exposure time, a value of 50 g./m. or lower indicates good sizing.
The following examples illustrate the invention.
EXAMPLE '1 The following example shows the sizing eificiency of various substituted succinicanhydrides of the present invention.
Handsheets containing 0.5 sizing agent were prepared as follows:
A slurry for each substituted succinic anhydride to be tested was prepared by tearing into small pieces 4.0 grams of 60-brightness pulp which was then placed into a Waring Blendor with 400 ml. of distilled water. The mixture was agitated for 2 minutes and thereafter the required amount of solution of the sodium salt of the substituted succinic acid to give 0.5% based on the weight of the pulp was added and agitation was continued for an additional 1 minute. A solution of alum containing 0.6% alum based on the weight of the pulp was then added, followed by agitation for an additional 1 minute and the pH was adjusted in the range of 4 to 5.5. The action of the Waring Blendor was suflicient for complete disintegration of the pulp sheets and the attainment of a Canadian Standard freeness value of 750 for the pulp.
Handsheets were formed in a Williamson 8): 8" sheet mold with lSO-mesh stainless steel screen. For each handsheet, the slurry of the sized pulp was poured into the sheet mold; diluted to 5 liters; and the water was drained off to form a sheet. The sheet was removed from the screen on a blotter, pressed between blotters for 1 to 2 minutes at p.s.i., and then dried on an electric dryer at C. The sizing efficiency was determined by the Cobb size test according to TAPPI procedure T441, and the results are tabulated 1n Table I. a
Table I 0.5% size pH of size Compound solution Final Cobb pH size Nonenylsuccinic anhydride 10. 5 4. 3 31 3-(Ethylphenyl)butane-1,2-dicarboxylie acid anhydride 6. 8 4. 1 44 Oetenylsuoeinic anhydride isomer (from caprylene) 6. 3 4. 0 34 3-Methyl-3-(isopropylphenyl)butane- 1,2-d1carboxylic acid anhydride 6. 8 4. 3 33 Octenylsuccirnc anhydride isomer (from di-isobutylene) 6. 4 4. l 34 n-Octylsuceinic anhydride (from l-octene) 6.5 4.0 36 Nonenylsuecinic anhydride isomer (from tripropylene) 7. 4 4. 4 30 n-Decenylsuccinic anhydride (from 1- decene)... 6.9 4.0 32
Dodecenylsuccinie anhydride isomer (from butylene trimer) 7. 4 4. 0 33 Dodecenylsucciuic anhydride isomer (from propylene tetramer) 7.6 4. 2 33 n-Tetradecenyl-succinic anhydride (from l-tetradecene) 7.8 4. 0
The anhydride was mixed with the calculated equivalent quantity of sodium hydroxide; the solids concentration of the salt solution was 0.5%.
The pH value or the pulp slurry, after addition of size and alum. For 3 minute penetration time.
EXAMPLE 2 The following example shows the eifectiveness and uniformity of saponified dodecenylsuccinic anhydride as a paper size at a concentration of 0.2%.
One pound of sheeted, 60-brightness pulp was torn into small pieces and put into a Valley one-pound pulp beater with 22 liters of water. The pulp was dispersed by running the beater for a few minutes without any weight on the lever arm of the bed plate. Then a 5500 gram weight was hung on the lever arm of the beater and the pulp was lgeaten for 2 hours to a Canadian Standard freeness of A portion of the beaten-pulp slurry (3.9 liters) was diluted with water to make 12 liters. The pulp solids content of the dilute suspension was determined by vacuum filtering the pulp from 500 m1. of the suspension and then drying the pad of pulp to constant weight. The required amount of solution to give 0.2% saponified dodecenylsuccinic anhydride on the weight of pulp was then added to the suspension while the pulp was being stirred with a high speed mixer. The pulp was stirred for 30 minutes after the size was added, then a 1.0% solution of alum was added to give 0.6% alum on the Weight of pulp and the slurry was stirred for a few more minutes.
Ten 4-gram handsheets were formed according to the procedure of Example 1. The Cobb size measurements on handsheets prepared in this manner showed good agreement in values. The average Cobb size value for the 10 sheets was 23 with a maximum of 26 and a minimum of 18.
EXAMPLE 3.
Two sets of handsheets were prepared, one set containing concentrations of saponified dodecenylsuccinic anhydride of 1% and 0.2%, respectively, and the other set containing concentrations of rosin size of 2 /2%, 1% and 0.2%. The handsheets were prepared according to the procedure of Example 1 except that appropriate volumes of the solutions of the sodium salt of dodecenylsuccinic acid and of the rosin size as well as of the alum were used to provide the above concentrations based on the dry pulp.
The handsheets were then evaluated for sizing efficiency by the Cobb test method. The results are indicated below.
. Cobb size g.lm. at indicated size concentration Size Saponified dodecenylsuccinicanhydride. Rosin size EXAMPLE 4 The following example shows the effects of prolonged aging on sizing and on the strength of paper sized with saponified dodecenylsuccinic anhydride and compares saponified dodecenylsuccinic anhydride with rosin size. The paper specimens prepared according to Example 1 were heat aged according to TAPPI procedure T453- M48, by heating for 72 hours at 105 C. This accelerated aging is generally considered to be equivalent to about 25 years of normal aging. According to the information given with the TAPPI procedure, the property of the paper that is most affected by aging is the brittleness; therefore, the aged papers were evaluated by measurements of folding endurance. Cobb size measurements were also made on aged and unaged papers. Five measurements of Cobb size values and of folding endurance were made on each sample. The average results from the measurements on aged and unaged paper specimens are shown in the table below.
RESULTS FROM COBB SIZE AND FOLDING ENDURANCE MEASUREMENTS ON PAPER HANDSHEETS BEFORE AND AFTER AGING Cobb size (1 Folds to break min.) Size Percent Before After Before After aging aging in aging Dodeeenylsuccinic anhy- V (iride 0.2 25 20 64 45 Rosin size 1.0 24 20 16 27 2. 5 19 17 13 13 e The handsheets were heated 72 hours at C.
The aged and the unaged specimens were conditioned for 48 hours at 72 F. and 50% relative humidity before making measurements. Folding endurance was measured with strips of paper 1.5 cm. wide, according to TAPPI standard T4223m. An M.I.T. Folding Endurance Tester was used for the measurements.
EXAMPLE 5 The following example shows the effect of saponified dodecenylsuccinic anhydride when combined with rosin size.
Papers were prepared with varying amounts of saponified dedecenylsuccinic anhydride and rosin size to determine if the two sizes were compatible and what sizing properties this combination possessed.
The results of sizing measurements on the papers are given below and show that as little as 041% of the rosin size combined with0.l% of saponified dodecenylsuccinic anhydride gave an excellent sizing effect with a Cobb size value of 27. 1 RESULTS FROM COBB SIZE MEASUREMENTS ON PAPER a With 0.6% alum based on pulp. b For 1 minute penetration time.
EXAMPLE 6 As a check on the reproducibility of sizing with the mixed sizes, a large batch of pulp was prepared and sized with 0.1% saponified dodecenylsuccinic anhydride and 0.2% rosin size by the procedure described in Example 2. Alum (0.6%) was added to set the size, and 10 replicate handsheets were made. The average Cobb size value for the 10 handsheets was 20 and the range of values was from 19 to 24 which is considered to be excellent reproducibility.
Although certain preferred embodiments of the invention have been disclosed for purposes of illustration, it will be evident that various changes and modifications may be made therein without departing from the scope and spirit of the invention.
I claim:
1. In a process for the internal sizing of paper wherein an aqueous suspension of paper pulp is admixed with 7 a sizing agent and a precipitating agent to set the sizing agent on the fiber and the mass formed into a sheet, the improvement comprising incorporating as sizing agent a water soluble salt of a substituted succinic acid having the formula R-Ho-d -53 wherein R is a hydrocarbon radical selected from the group consisting of an alkyl, alkene, alkyne and aryl alkyl having 8 to 15, inclusive, carbon atoms.
2. A process as claimed in claim 1 wherein the water soluble salt of the substituted succinic acid is produced by saponifying the corresponding substituted succinic anhydride.
3. A process as claimed in claim 1 wherein the hydrocarbon radical contains 10 to 14, inclusive, carbon atoms.
4. In a process for the internal sizing of paper wherein an aqueous suspension of paper pulp is admixed with a sizing agent and. a precipitating agent to set the sizing agent on the fiber and the mass formed into a sheet, the improvement comprising incorporating as sizing agent a water soluble salt of a substituted succinic acid having the formula wherein R is an alkene hydrocarbon having 10 to 14, inclusive, carbon atoms with the double bond adjacent the succinic acid group.
5. A process for the internal sizing of paper which comprises incorporating the sodium salt of dodecenylsuccinic acid in an aqueous paper pulp slurry, adding aluminum sulfate to the slurry to convert the soluble sodium salt of dodecenylsuccinic acid to the insoluble form which deposits upon the fiber, adjusting the pH of said slurry to within the range of about 4.0 to 5.5, and forming the mass into a sheet.
6. A process for the internal sizing of paper which comprises incorporating the sodium salt of nonenylsuccinic acid in an aqueous paper pulp slurry, adding aluminum sulfate to the slurry to convert the soluble sodium salt of nonenylsuccinic acid to the insoluble form which deposits upon the fiber, adjusting the pH of said slurry to within the range of about 4.0 to 5.5, and forming the mass into a sheet.
7. A process for the. internal sizing of paper which comprises incorporating the sodium salt of 3-methyl-3- (isopropylphenyl)butane-1,2-dicarboxylic acid in an aqueous paper pulp slurry, adding aluminum sulfate to the slurry to convert the soluble sodium salt of B-methyl 3-(isopropyphenyl)butane-1,2-dicarboxylic acid to the insoluble form which deposits upon the fiber, adjusting the pH of said slurry to within the range of about 4.0 to 5.5, and forming the mass into a sheet.
8. A process for the internal sizing of paper which comprises incorporating the sodium salt of n-tetradecenyl succinic acid in an aqueous paper pulp slurry, adding aluminum sulfate to the slurry to convert the soluble sodium salt of n-tetradecenylsuccim'c acid to the insoluble form which deposits upon the fiber, adjusting the pH of wherein R is a hydrocarbon radical selected from the group consisting of an alkyl, alkene, alkyne and aryl alkyl having 8 to 15, inclusive, carbon atoms.
10. A process for the internal sizing of paper which comprises incorporating saponified rosin and a sodium salt of dodecenylsuccinic acid in an aqueous paper pulp slurry, adding aluminum sulfate to the slurry to convert the soluble sodium salt of dodecenylsuccinic acid to the insoluble form which deposits upon the fiber, adjusting the pH. of said slurry to within the range of about 4.0 to 5.5, and forming the mass into a sheet.
11. A sized paper comprising a fibrous cellulosic web which has been internally sized with a salt of a substituted succinic acid having the formula wherein R is a hydrocarbon radical selected from the group consisting of an alkyl, alkene, alkyne and aryl alkyl having 8 to 15, inclusive, carbon atoms.
12. A. sized paper comprising a fibrous cellulosic Web which has been internally sized with a salt of a substi:
tuted succinic acid having the formula wherein R is an alkene hydrocarbon having 10 to 14, inclusive, carbon atoms with the double bond adjacent the succinic anhydride group.
13. A sized paper comprising a fibrous cellulosic web which has been internally sized with a salt of dodecenylsuccinic acid.
' 14. A sized paper comprising a fibrous cellulosic web which has been internally sized with saponified rosin and saponified dodecenylsuccinic acid.
References Cited in the file of this patent UNITED STATES PATENTS 1,996,707 Nathansohn Apr. 2, 1935 2,680,751 Prichard June 8, 1954 3,016,325 Pattiloch ,Jan. 2, 1962 3,022,321 Copenhaver Feb. 20, 1962 3,102,064 Wurzburg et a1. Aug. 27, 1963 FOREIGN PATENTS 804,504 Great Britain Nov. 19, 1958
Claims (1)
1. IN A PROCESS FOR THE INTERNAL SIZING OF PAPER WHEREIN AN AQUEOUS SUSPENSION OF PAPER PULP IS ADMIXED WITH A SIZING AGENT AND A PRECIPITATING AGENT TO SET THE SIZING AGENT ON THE FIBER AND THE MASS FORMED INTO A SHEET, THE IMPROVEMENT COMPRISING INCORPORATING AS SIZING AGENT A WATER SOLUBLE SALT OF A SUBSTITUTED SUCCINIC ACID HAVING THE FORMULA
Priority Applications (3)
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US200908A US3139373A (en) | 1962-06-08 | 1962-06-08 | Process for the internal sizing of paper with a salt of a substituted succinic acid |
DEA43265A DE1262755B (en) | 1962-06-08 | 1963-06-05 | Use of succinic acid salts for sizing paper |
GB22884/63A GB978300A (en) | 1962-06-08 | 1963-06-07 | Improved process for the internal sizing of paper |
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US200908A US3139373A (en) | 1962-06-08 | 1962-06-08 | Process for the internal sizing of paper with a salt of a substituted succinic acid |
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US200908A Expired - Lifetime US3139373A (en) | 1962-06-08 | 1962-06-08 | Process for the internal sizing of paper with a salt of a substituted succinic acid |
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DE (1) | DE1262755B (en) |
GB (1) | GB978300A (en) |
Cited By (13)
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---|---|---|---|---|
US3345252A (en) * | 1965-03-24 | 1967-10-03 | Monsanto Co | Process of sizing cellulosic fibers with gamma-lactones and fibrous product thereof |
US4302283A (en) * | 1978-01-16 | 1981-11-24 | Ethyl Corporation | Sizing process and composition |
US4311767A (en) * | 1980-02-25 | 1982-01-19 | National Gypsum Company | Gypsum wallboard and method for producing same |
DE3231106A1 (en) * | 1981-08-22 | 1983-03-10 | Nippon Petrochemicals Co., Ltd., Tokyo | PAPER SIZING AGENT |
EP0074544A1 (en) * | 1981-09-15 | 1983-03-23 | Hercules Incorporated | Aqueous sizing compositions |
GB2137614A (en) * | 1983-02-07 | 1984-10-10 | Mitsubishi Oil Co | Alkenylsuccinic acid salts of use as paper sizing agents |
US4504576A (en) * | 1983-02-04 | 1985-03-12 | Felix Schoeller Jr. Gmbh & Co., Kg | Photographic support paper having a surface size |
EP0208667A1 (en) * | 1985-07-10 | 1987-01-14 | Eka Nobel Aktiebolag | Aqueous dispersions, a process for their preparation and the use of the dispersions as sizing agents |
US4666746A (en) * | 1985-05-22 | 1987-05-19 | Lannen Tehtaat Oy | Method for the impregnation of water-repellent paper |
EP0224976A1 (en) * | 1985-11-29 | 1987-06-10 | Kabushiki Kaisha Chiyoda Kagaku Kenkyusho | Method of sizing paper |
EP0291588A1 (en) * | 1984-11-14 | 1988-11-23 | Kabushiki Kaisha Chiyoda Kagaku Kenkyusho | Sizing agent |
US5319061A (en) * | 1992-08-07 | 1994-06-07 | The Humphrey Chemical Co., Inc. | Imparting moisture resistance to epoxies |
WO2016106300A1 (en) * | 2014-12-26 | 2016-06-30 | Westrock Mwv, Llc | Improved sizing of paperboard |
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JPS58220789A (en) * | 1982-06-18 | 1983-12-22 | Fuji Photo Film Co Ltd | Pressure-sensitive recording sheet |
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Cited By (17)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3345252A (en) * | 1965-03-24 | 1967-10-03 | Monsanto Co | Process of sizing cellulosic fibers with gamma-lactones and fibrous product thereof |
US4302283A (en) * | 1978-01-16 | 1981-11-24 | Ethyl Corporation | Sizing process and composition |
US4311767A (en) * | 1980-02-25 | 1982-01-19 | National Gypsum Company | Gypsum wallboard and method for producing same |
DE3231106A1 (en) * | 1981-08-22 | 1983-03-10 | Nippon Petrochemicals Co., Ltd., Tokyo | PAPER SIZING AGENT |
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US4504576A (en) * | 1983-02-04 | 1985-03-12 | Felix Schoeller Jr. Gmbh & Co., Kg | Photographic support paper having a surface size |
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EP0224976A1 (en) * | 1985-11-29 | 1987-06-10 | Kabushiki Kaisha Chiyoda Kagaku Kenkyusho | Method of sizing paper |
US5319061A (en) * | 1992-08-07 | 1994-06-07 | The Humphrey Chemical Co., Inc. | Imparting moisture resistance to epoxies |
WO2016106300A1 (en) * | 2014-12-26 | 2016-06-30 | Westrock Mwv, Llc | Improved sizing of paperboard |
US9689115B2 (en) | 2014-12-26 | 2017-06-27 | Westrock Mwv, Llc | Sizing of paperboard |
CN107109798A (en) * | 2014-12-26 | 2017-08-29 | 维实洛克Mwv有限责任公司 | Improved cardboard applying glue |
Also Published As
Publication number | Publication date |
---|---|
DE1262755B (en) | 1968-03-07 |
GB978300A (en) | 1964-12-23 |
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