US2772966A - Cationic rosin sizes - Google Patents
Cationic rosin sizes Download PDFInfo
- Publication number
- US2772966A US2772966A US446396A US44639654A US2772966A US 2772966 A US2772966 A US 2772966A US 446396 A US446396 A US 446396A US 44639654 A US44639654 A US 44639654A US 2772966 A US2772966 A US 2772966A
- Authority
- US
- United States
- Prior art keywords
- rosin
- water
- polyalkylenepolyamine
- size
- fibers
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
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- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 title claims description 41
- 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 title claims description 41
- 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 title claims description 41
- 125000002091 cationic group Chemical group 0.000 title description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 25
- 239000000835 fiber Substances 0.000 claims description 21
- 239000007795 chemical reaction product Substances 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 6
- 159000000021 acetate salts Chemical group 0.000 claims description 5
- 238000001246 colloidal dispersion Methods 0.000 claims description 3
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen(.) Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims 2
- 235000010985 glycerol esters of wood rosin Nutrition 0.000 description 21
- 238000000034 method Methods 0.000 description 20
- 239000002253 acid Substances 0.000 description 18
- 238000006243 chemical reaction Methods 0.000 description 18
- 125000004433 nitrogen atom Chemical group N* 0.000 description 15
- 239000000463 material Substances 0.000 description 13
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 11
- 238000004513 sizing Methods 0.000 description 10
- 239000006185 dispersion Substances 0.000 description 8
- 239000012458 free base Substances 0.000 description 8
- 150000003839 salts Chemical class 0.000 description 8
- 239000000203 mixture Substances 0.000 description 7
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 238000009835 boiling Methods 0.000 description 5
- 150000002148 esters Chemical class 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 5
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- 229960000583 acetic acid Drugs 0.000 description 4
- 239000000945 filler Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 229940037003 alum Drugs 0.000 description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 description 3
- 239000000839 emulsion Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 230000003381 solubilizing effect Effects 0.000 description 3
- 150000005846 sugar alcohols Polymers 0.000 description 3
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- 239000007900 aqueous suspension Substances 0.000 description 2
- 239000011436 cob Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 239000000344 soap Substances 0.000 description 2
- UFTFJSFQGQCHQW-UHFFFAOYSA-N triformin Chemical compound O=COCC(OC=O)COC=O UFTFJSFQGQCHQW-UHFFFAOYSA-N 0.000 description 2
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- YHRUOJUYPBUZOS-UHFFFAOYSA-N 1,3-dichloropropane Chemical compound ClCCCCl YHRUOJUYPBUZOS-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229920003043 Cellulose fiber Polymers 0.000 description 1
- 229920002261 Corn starch Polymers 0.000 description 1
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229920000161 Locust bean gum Polymers 0.000 description 1
- ZTHYODDOHIVTJV-UHFFFAOYSA-N Propyl gallate Chemical compound CCCOC(=O)C1=CC(O)=C(O)C(O)=C1 ZTHYODDOHIVTJV-UHFFFAOYSA-N 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910000329 aluminium sulfate Inorganic materials 0.000 description 1
- 235000011128 aluminium sulphate Nutrition 0.000 description 1
- 239000011260 aqueous acid Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910021538 borax Inorganic materials 0.000 description 1
- 230000009172 bursting Effects 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- GBAOBIBJACZTNA-UHFFFAOYSA-L calcium sulfite Chemical compound [Ca+2].[O-]S([O-])=O GBAOBIBJACZTNA-UHFFFAOYSA-L 0.000 description 1
- 235000010261 calcium sulphite Nutrition 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- MIAKRAULTMFNJM-UHFFFAOYSA-K calcium;magnesium;carbonate;hydroxide Chemical compound [OH-].[Mg+2].[Ca+2].[O-]C([O-])=O MIAKRAULTMFNJM-UHFFFAOYSA-K 0.000 description 1
- 239000005018 casein Substances 0.000 description 1
- BECPQYXYKAMYBN-UHFFFAOYSA-N casein, tech. Chemical compound NCCCCC(C(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(CC(C)C)N=C(O)C(CCC(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(C(C)O)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(COP(O)(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(N)CC1=CC=CC=C1 BECPQYXYKAMYBN-UHFFFAOYSA-N 0.000 description 1
- 235000021240 caseins Nutrition 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 description 1
- 230000001143 conditioned effect Effects 0.000 description 1
- 239000008120 corn starch Substances 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- VAYGXNSJCAHWJZ-UHFFFAOYSA-N dimethyl sulfate Chemical compound COS(=O)(=O)OC VAYGXNSJCAHWJZ-UHFFFAOYSA-N 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- GKIPXFAANLTWBM-UHFFFAOYSA-N epibromohydrin Chemical compound BrCC1CO1 GKIPXFAANLTWBM-UHFFFAOYSA-N 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 239000000711 locust bean gum Substances 0.000 description 1
- 235000010420 locust bean gum Nutrition 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000011505 plaster Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001592 potato starch Polymers 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 230000009290 primary effect Effects 0.000 description 1
- 235000018102 proteins Nutrition 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000007790 scraping Methods 0.000 description 1
- 239000004328 sodium tetraborate Substances 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 239000003784 tall oil Substances 0.000 description 1
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 230000003313 weakening effect Effects 0.000 description 1
- 229940100445 wheat starch Drugs 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 239000011787 zinc oxide Substances 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
- D21H17/62—Rosin; Derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09F—NATURAL RESINS; FRENCH POLISH; DRYING-OILS; OIL DRYING AGENTS, i.e. SICCATIVES; TURPENTINE
- C09F1/00—Obtaining purification, or chemical modification of natural resins, e.g. oleo-resins
- C09F1/04—Chemical modification, e.g. esterification
Definitions
- the present invention relates to a novel cationic rosin size and to paper and other cellulosic webs sized therewith.
- the invention includes methods for manufacturing the size and applying the size in the manufacture of paper, etc.
- rosin sized paper In the past it has been customary to manufacture rosin sized paper by forming an aqueous dispersion of cellulosic papemnaking fibers, adding thereto an aqueous dispersion of rosin size formed by saponifying rosin with sodium or potassium hydroxide or carbonate, and precipitating the rosin on the fibers by the addition of alum. The fibers are then sheeted to form paper.
- the manufacture of rosin sized paper according to the foregoing method has three principal disadvantages.
- the rosin size described is anionic, and the alum is effective as a precipitant only when the pH of the fibrous suspension is acid.
- This acidity has a detrimental corrosive action on papermaking equipment and precludes the addition of an acid-sensitive filler such as calcium carbonate.
- the paper itself has an acid pH, and acidity is known to have a weakening efiect upon cellulosic fibers.
- the rosin on the fibers is resaponified or otherwise rendered ineffective. This precludes the use of the paper for the wrapping of alkaline materials such as cement, plaster, or soap.
- the reaction products formed by heating a major amount of an ester gum (a rosin-polyhydric alcohol ester) with a minor amountof a water-soluble polyalkylenepolyamine, when solubilized by addition of a small amount of acid and dispersed in water, are colloidal, cationic sizing agents which are distinctively different from the heretofore known rosin .sizes of the soap or anionic type.
- the sizes of the present invention are substantive to cellulose fibers on contact therewith in aqueous suspension and therefore do not require the addition ofalum or other material as a precipitant. They are adsorbed by the fibers not only at acid pH values but also at alkaline pH values up to about 9. As a result, alkaline filling materials such as calcium carbonate may be added without harm, and the paper thus manufactured may be used in contact with alkaline materials.
- the sizing agents of the present invention when applied by the beater addition process, are added to a dilute aqueous suspension of cellulosic fibers in amount between about 1% and 5% based on the dry weight of the fibers.
- the agents are strongly cationic and are rapidly and substantively adsorbed by the fibers at any pH, not merely on the acid side down to about pH 4, but also on the alkaline side up to about pH 9.
- the thus sized fibers are formed into paper in the usual manner and the paper is heated between about 100 C. and 150 C. for /2 to 4 minutes to dry the paper and develop the water-resistant properties of the size.
- the sizes of the present invention do not undergo.
- the present invention makes possible the incorporation in the paper of the principal commercially used alkaline fillers including calcium carbonate, calcium silicate, Raffold (calcium carbonate-magnesium hydroxide), and calcium sulfite.
- These fillers are usually added in quantities ranging from about 5% to 100% of the dry weight of the paper fibers in order to obtain paper containing from about 2% to 30% of its weight of filler.
- the present invention permits the "addition of other conventional materials such as wax sizing emul- ICC such as corn starch, potato starch, and wheat starch;
- locust bean gum and other mannogalactans locust bean gum and other mannogalactans; casein and other proteins; and similar gums, if necessary, solubilized with borax or other alkali. All these materials are preferably added after the sizing step has been completed.
- the sizes may also be applied by the tub or impregnation method.
- a preformed cellulosic web is saturated by a direct impregnation or spraying with a dispersion of the size, the amount of the size being predetermined so that the web when dried contains from about 1% to 5% by weight of the material.
- the sizes themselves are formed by a method which has as its principal step the reaction of an ester gum' at a suitable temperature of about 175 250 C. with a water-soluble polyalkylenepolyamine containing at least three nitrogen atoms.
- the reaction is continued at least to the point where a sample of the mixture (hereinafter termed the free base), when converted into a salt suchas the acetic acid salt, becomes dispersible in water.
- a sample of the molten free base is withdrawn, cooled to just above its flow point, and into it is stirred 1-2 mols of glacial acetic acid per mol 'of polyalkylenepolyamine present. to roonrtemperature, powdered, and one part of the powder is slowly added to 20 parts by weight of rapidly rosin nucleus.
- the sizing results obtained increase when the reaction is continued beyond the point at which the free base is barely dispersible when tested as described, and usually the reaction is best continued until the rate of decrease in alkalinity (as determined by titration of the samples of the reaction mixture with aqueous acid) falls to a low value as compared to the initial high value or becomes substantially constant.
- the second part of the method consists in converting the modified rosin into a liquid size. This may be performed in several different ways, all essentially equivalent, each involving conversion of the rosin free base intov a salt. by addition of an acid or an acid-forming material, and dispersing the salt in water.
- an acid or acid-forming material such as epichlorohydrin is added to the molten free base.
- the product is cooled on a water-cooled drum provided with a scraping knife, flakes being obtained, and the flakes pulverized in a hammer. mill.
- the resulting powder is stable and can be shipped inbags.
- the powder is formed into a liquid size by the paper manufacturer by slowly flowing it into a volume of hot water with effective agitation. A creamy dispersion rapidly forms.
- the moltenreaction mixture after addition of the salt 'or salt-forming material may be flowed directly into hot agitated water. An emulsion likewise forms.
- the rosinated polyalkylenepolyamine in molten form is slowly poured into a volume of rapidly agitated boiling water containing 1-2 mols :of acid per mol of combined polyalkylenepolyamine present.
- a similar emulsion forms are also possible.
- the emulsions formed by the. foregoing methods may be filtered to remove any insolubles present, and cooled. They appear to be indefinitely storage stable.
- any of the commercially used rosins may be employed, including wood rosin, gum rosin, and tall oil rosin.
- These rosins are employed in the form of ester gum, that is, in the form of their esters with polyhydric alcohols such as glycol, glycerol, pentaerithritol, etc.
- the ester gums employed are widely known articles of commerce and may contain unreacted alcoholic hydroxyl groups. Such gums as glycol monorosinate and glycerolmonorosinate thereforefa-ll within the scope of the present invention.
- the p'olyalkylenepolyamines employed in the present invention are a well-known class of compounds, preferred members known being the commercially available and readily prepared dieth'ylenetriamine, triethylenetetramine, tetraethylenepentamine, corresponding polypropylenepolyamines and polybutylenepolyamines, and analogues thereof.
- These compounds have the generic formula H2N(C1nH2mNY) CmH2mNHz wherein.
- Y represents H or CmH2mNI-Iz', m is an integer between 2 and 4 inclusive, and p is an integer between 1 and 4.
- polyalkylenepolyamines formed by homopolymerizing low molecular alkyleneimines such as ethyleneirnine may .
- high molecular amines formed by reacting simple polyalkylenepolyamines such as diethylenetria'rn'ine or 3,3-imin'obispropylamine with about 1 mol respectively of 1,3-dichloropropane or 1,2-dichloroethane are water-soluble and basic and are suitable for the practice of the present invention.
- hydrochloric formic, propionic, lactic, chloroacetic, and gly'c'olic acids.
- hydrochloric formic, propionic, lactic, chloroacetic, and gly'c'olic acids.
- coinpounds which release acid radicals in situ such as epichlorohydrin, epibromohydrin, or dimethyl sulfate.
- Acetic acid is preferred, this material forming a salt of sufficiently low melting point as to permit the material to be dispersed in water without need for autoclave equipment while yielding a material which exhibits very satisfactory effectiveness as a size.
- reaction mixtures are where necessary cooled to a temperature just above the point at which they are molten so as to minimize any side reactions which would otherwise take place as exemplified by the dehydration of acetic acid to form an amide.
- Such side reactions usually cause the efiicien'c'y 0f the product as a size to fall off.
- the weight of reagents taken is determined by the ratio of the number of mols of combined rosin in. the ester gum to the number of nitrogen atoms of the polyalkylenep'olyamine.
- the ratio of rosin radicals to nitrogen atoms should be between about 3:7 and 223, a smaller proportion of rosin radicals causing the water-resistance of the finished size cellulosic web to fall off rapidly, while a materially larger proportion results ina product which is quite difiicult to disperse even in boiling water at atmospheric pressure.
- the amount of acetic or other acid which is thereafter added should be at least suflicient to permit ready dispersibility of the product. As little as 0.25 mol of acid per mol of combined polyalkylenepolyamine has been found sufiieient for this purpose, but somewhat more (preferably between about 1 and 2 mols) is more advantageous, these larger amounts doing no harm while avoiding the danger of adding too little.
- the aqueous dispersions are formed at any convenient solids content from the point of view of viscosity. Before use in the manufacture of paper the dispersions are diluted to about l%-3% solids content with water to facilitate uniform distribution of the size among the fibers.
- the sizing agents are produced by reacting an ester gum at about l75250 C. with a water-soluble polyalkylenepolyamine containing at least three nitrogen atoms (the ratio of the rosin radicals in the ester gum tothe nitrogen atoms of the polyalkylenepolyamine being between about 3:7 and 2:3) at least until the reaction product (or its acetate salt) forms a colloidal cationic dispersion when agitated with boiling water, and-adding from about A .toabout 2 mols of an amine. solubilizing acid per mol of polyalkylenepolyamine taken.
- the paper and other cellulosic units ofthe present invention are sized by a uniformly distributed content. of the cationic rosin formed. by reacting an ester gum. with a water-soluble polyalkylenepolyamine in the-proportions and at least .to the extent setforth above.
- Example 1 The preparation of a colloidal cationic rosin size according to the present invention is illustrated by the following.
- An ester gum was formed by heating 199 g. of N grade,
- a 60% bleached white-40% bleached soda pulp was beaten to a Green freeness of 340 ml. at a consistency of 2.5%.
- Three aliquots were withdrawn and diluted to 0.6% consistency with water. One was reserved as control.
- T o the remaining two was added 3.5% of the sizing solution of Example 1 (size solids on the dry weight of the fibers), previously diluted .to 1.5% solids by addition of water.
- the pH of the aliquots was then adjusted to the values shown in the table by the addition of aqueous NaOH or HCl as necessary.
- the samples were then stirred gently for five minutes and sheeted at light and heavy 'basis weights. The sheets were dried at 240 F. and conditioned for 24 hours at 73 F.
- the light sheets were tested for their dry tensile strength, dry bur-sting strength (Mullen) and water and ink resistance by the Currier and BKY methods respectively.
- the heavy sheets were tested by the Cobb method (15 minute contact time at 73 F.) to determine 5 Grams water absorbed per 100 cm.
- Example 3 The procedure of Example 2 was repeated for the preparation of their sheets, except that 3% of papermak ers alum (based on the dry weight of the fibers) was added after addition of the size and before adjustment of the pH. Results are as follows:
- a method of producing a rosinated polyalkylenepolyamine suitable for conversion to a cationic rosin sizing wherein Y represents a substituent selected from the group consisting of H and CmH2mNH2, m is an integer between 2 and 4 inclusive, and p is an integer between 1 and 4.
- a method of producing a liquid cationic rosin size which comprises reacting an ester gum at about 250 C. with a Water-soluble polyalkylenepolyamine containing at least three nitrogen atoms, the ratio of the rosin radicals in said ester gum to the nitrogen atoms of said polyalkylenepolyamine being between about 3:7 and 2:3 at least until the reaction product as its acetate salt forms a colloidal dispersion when agitated with boiling water, adding from A to 2 mols of an amine-solubilizing acid per mol of combined polyalkylenepolyamine present, and dispersing the salt thus formed in water.
- a method of producing a liquid cationic rosin size which comprises reacting an ester gum at about 175-250 C. with a water-soluble polyalkylenepolyamine containing at least three nitrogen atoms, the ratio of the rosin radicals in said ester gum to the nitrogen atoms of said polyalkylenepolyamine being between about 3:7 and 2:3, at least until the reaction product as its acetate salt forms a colloidal dispersion when agitated with boiling water, and dispersing the reaction product in water containing from about 1 to 2 mols of an amine-.solubilizing acid per mol of combined polyalkylenepolyamine in said reaction product.
- Paper composed of cellulosic fibers sized by a uniformly distributed content of from about 1% to 5%
- the cationic rosin size formed by reacting an ester gum at about 175- 250 C. with a water-soluble polyalkylenepolyamine containing at least three nitrogen atoms, the ratio of the rosin solids in said ester gum to the nitrogen atoms of UNITED :STATES PATENTS 2,304,369 Morgan te a1. Dec. 8, 1942
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Paper (AREA)
Description
CATIONIC ROSIN SIZES John H. Daniel, Jr., and Sewell T. Moore, Stamford, Conn., asslgnors to American Cyanamid Company, New York, N. Y., a corporation of Maine No Drawing. Applicafion July 28, 1954, Serial No. 446,396
Claims. (Cl. 92-3) The present invention relates to a novel cationic rosin size and to paper and other cellulosic webs sized therewith. The invention includes methods for manufacturing the size and applying the size in the manufacture of paper, etc.
In the past it has been customary to manufacture rosin sized paper by forming an aqueous dispersion of cellulosic papemnaking fibers, adding thereto an aqueous dispersion of rosin size formed by saponifying rosin with sodium or potassium hydroxide or carbonate, and precipitating the rosin on the fibers by the addition of alum. The fibers are then sheeted to form paper.
The manufacture of rosin sized paper according to the foregoing method has three principal disadvantages. In the first place, the rosin size described is anionic, and the alum is effective as a precipitant only when the pH of the fibrous suspension is acid. This acidity has a detrimental corrosive action on papermaking equipment and precludes the addition of an acid-sensitive filler such as calcium carbonate. Secondly, the paper itself has an acid pH, and acidity is known to have a weakening efiect upon cellulosic fibers. Thirdly, when the paper is made alkaline the rosin on the fibers is resaponified or otherwise rendered ineffective. This precludes the use of the paper for the wrapping of alkaline materials such as cement, plaster, or soap.
The discovery has now been made that the reaction products formed by heating a major amount of an ester gum (a rosin-polyhydric alcohol ester) with a minor amountof a water-soluble polyalkylenepolyamine, when solubilized by addition of a small amount of acid and dispersed in water, are colloidal, cationic sizing agents which are distinctively different from the heretofore known rosin .sizes of the soap or anionic type. The sizes of the present invention are substantive to cellulose fibers on contact therewith in aqueous suspension and therefore do not require the addition ofalum or other material as a precipitant. They are adsorbed by the fibers not only at acid pH values but also at alkaline pH values up to about 9. As a result, alkaline filling materials such as calcium carbonate may be added without harm, and the paper thus manufactured may be used in contact with alkaline materials.
The sizing agents of the present invention, when applied by the beater addition process, are added to a dilute aqueous suspension of cellulosic fibers in amount between about 1% and 5% based on the dry weight of the fibers. The agents are strongly cationic and are rapidly and substantively adsorbed by the fibers at any pH, not merely on the acid side down to about pH 4, but also on the alkaline side up to about pH 9. The thus sized fibers are formed into paper in the usual manner and the paper is heated between about 100 C. and 150 C. for /2 to 4 minutes to dry the paper and develop the water-resistant properties of the size. The sizes of the present invention do not undergo. chemical reaction or polymerization toany significant extent during this brief heating and it is therefore believed that the primary effect of the ited State patento 2,772,966 Patented Dec. 4, 1956 heating is to.soften or melt the particles of adsorbed size and permit them to flow along the fibers, thus greatly extending the fiber area protected. The sizing effect is principally due to the rosin component of the mixture and not to any of the solubilizing acid which may be present. p
The present invention makes possible the incorporation in the paper of the principal commercially used alkaline fillers including calcium carbonate, calcium silicate, Raffold (calcium carbonate-magnesium hydroxide), and calcium sulfite. These fillers are usually added in quantities ranging from about 5% to 100% of the dry weight of the paper fibers in order to obtain paper containing from about 2% to 30% of its weight of filler.
Moreover, the present invention permits the "addition of other conventional materials such as wax sizing emul- ICC such as corn starch, potato starch, and wheat starch;
locust bean gum and other mannogalactans; casein and other proteins; and similar gums, if necessary, solubilized with borax or other alkali. All these materials are preferably added after the sizing step has been completed.
The sizes may also be applied by the tub or impregnation method. in which a preformed cellulosic web is saturated by a direct impregnation or spraying with a dispersion of the size, the amount of the size being predetermined so that the web when dried contains from about 1% to 5% by weight of the material.
The sizes themselves are formed by a method which has as its principal step the reaction of an ester gum' at a suitable temperature of about 175 250 C. with a water-soluble polyalkylenepolyamine containing at least three nitrogen atoms. The reaction is continued at least to the point where a sample of the mixture (hereinafter termed the free base), when converted into a salt suchas the acetic acid salt, becomes dispersible in water. To perform this test, a sample of the molten free base is withdrawn, cooled to just above its flow point, and into it is stirred 1-2 mols of glacial acetic acid per mol 'of polyalkylenepolyamine present. to roonrtemperature, powdered, and one part of the powder is slowly added to 20 parts by weight of rapidly rosin nucleus. V A
agitated water at about the boil. Formation of a creamy, homogeneousemul-sion or dispersion demonstrates that sufficient reaction has taken place. Failure of the mixture to disperse in this manner is evidence that the reaction should be continued somewhat longer.
The sizing results obtained increase when the reaction is continued beyond the point at which the free base is barely dispersible when tested as described, and usually the reaction is best continued until the rate of decrease in alkalinity (as determined by titration of the samples of the reaction mixture with aqueous acid) falls to a low value as compared to the initial high value or becomes substantially constant.
Continuation of the reaction often has the beneficial effect of decreasing the emulsification temperature to the point where water having a temperature as low as C. or lower can be employed, with consequent savings in heat.
From consideration of the above-described decrease in alkalinity and increase in the water-dispersibility of the reaction mixture (as the acetate salt) it is believed that an exchange reaction takes place in which rosin residues are transferred from the polyhydric alcohol component of the ester gum to the polyalkylenepolyamine, the ester linkages being transformed during this. interchange into amide linkages. rosin group in an ester gum to one nitrogen atom in a polyalkylenepolyamine is illustrated by the following theoretical skeleton equation wherein R designates the The sample is cooled The interchange of one- H l l l l n-o-o-ort o 3 no-c in H1] I RC-1TI i I l Ester gum Polyalkylene- Size Polyhydric polyaminc (free base) alcohol The reaction usually does not. and need not go to completion, the extent of the reaction being sufiicient when a sample of the free base, when formed into a salt with acetic acid, etc. is dispersible in hot water. The free base and its salts are thus usually complex mixtures which are conveniently defined by their method of preparation.
The second part of the method consists in converting the modified rosin into a liquid size. This may be performed in several different ways, all essentially equivalent, each involving conversion of the rosin free base intov a salt. by addition of an acid or an acid-forming material, and dispersing the salt in water.
According to one method, particularly useful for commercial practice, an acid or acid-forming material such as epichlorohydrin is added to the molten free base. The product is cooled on a water-cooled drum provided with a scraping knife, flakes being obtained, and the flakes pulverized in a hammer. mill. The resulting powder is stable and can be shipped inbags. The powder is formed into a liquid size by the paper manufacturer by slowly flowing it into a volume of hot water with effective agitation. A creamy dispersion rapidly forms. Alternatively, the moltenreaction mixture after addition of the salt 'or salt-forming material may be flowed directly into hot agitated water. An emulsion likewise forms.
According to another method, the rosinated polyalkylenepolyamine in molten form is slowly poured into a volume of rapidly agitated boiling water containing 1-2 mols :of acid per mol of combined polyalkylenepolyamine present. A similar emulsion forms.
The emulsions formed by the. foregoing methods may be filtered to remove any insolubles present, and cooled. They appear to be indefinitely storage stable.
In the foregoing any of the commercially used rosins may be employed, including wood rosin, gum rosin, and tall oil rosin. These rosins are employed in the form of ester gum, that is, in the form of their esters with polyhydric alcohols such as glycol, glycerol, pentaerithritol, etc. The ester gums employed are widely known articles of commerce and may contain unreacted alcoholic hydroxyl groups. Such gums as glycol monorosinate and glycerolmonorosinate thereforefa-ll within the scope of the present invention.
The p'olyalkylenepolyamines employed in the present invention are a well-known class of compounds, preferred members known being the commercially available and readily prepared dieth'ylenetriamine, triethylenetetramine, tetraethylenepentamine, corresponding polypropylenepolyamines and polybutylenepolyamines, and analogues thereof. These compounds have the generic formula H2N(C1nH2mNY) CmH2mNHz wherein. Y represents H or CmH2mNI-Iz', m is an integer between 2 and 4 inclusive, and p is an integer between 1 and 4. Their chain length is not important in terms of results as the high molecular weight polyalkylenepolyamines formed by homopolymerizing low molecular alkyleneimines such as ethyleneirnine may .also be used, as well' as the high molecular amines formed by reacting simple polyalkylenepolyamines such as diethylenetria'rn'ine or 3,3-imin'obispropylamine with about 1 mol respectively of 1,3-dichloropropane or 1,2-dichloroethane. All these and similar polyalkylenepolyaminesare water-soluble and basic and are suitable for the practice of the present invention.
As amine-solubilizing acids there may be employed hydrochloric, formic, propionic, lactic, chloroacetic, and gly'c'olic acids. In place of these may be employed coinpounds which release acid radicals in situ such as epichlorohydrin, epibromohydrin, or dimethyl sulfate. Acetic acid is preferred, this material forming a salt of sufficiently low melting point as to permit the material to be dispersed in water without need for autoclave equipment while yielding a material which exhibits very satisfactory effectiveness as a size. Before addition of these agents the reaction mixtures are where necessary cooled to a temperature just above the point at which they are molten so as to minimize any side reactions which would otherwise take place as exemplified by the dehydration of acetic acid to form an amide. Such side reactions usually cause the efiicien'c'y 0f the product as a size to fall off.
In the principal reaction, the weight of reagents taken is determined by the ratio of the number of mols of combined rosin in. the ester gum to the number of nitrogen atoms of the polyalkylenep'olyamine. In general, the ratio of rosin radicals to nitrogen atoms should be between about 3:7 and 223, a smaller proportion of rosin radicals causing the water-resistance of the finished size cellulosic web to fall off rapidly, while a materially larger proportion results ina product which is quite difiicult to disperse even in boiling water at atmospheric pressure. Thus, when rosin triglyceride ester gum containing three rosin residues per molecule is reacted with diethylenetriamine containing three nitrogen atoms per molecule between about i and /3 mol of the ester gum should be taken per mol of the polyalkylenepolyamine; The ratio of 3:5 is preferred. With one mol of triethylenetetramine we therefore prefer to react 2.4 mols of combined rosin equivalent to 0.8 mol of rosin triglyceride. From. these examples, suitable proportions can readily be worked out for use in conjunction with other ester gums and polyalkylenepolyamines.
The amount of acetic or other acid which is thereafter added should be at least suflicient to permit ready dispersibility of the product. As little as 0.25 mol of acid per mol of combined polyalkylenepolyamine has been found sufiieient for this purpose, but somewhat more (preferably between about 1 and 2 mols) is more advantageous, these larger amounts doing no harm while avoiding the danger of adding too little.
The aqueous dispersions are formed at any convenient solids content from the point of view of viscosity. Before use in the manufacture of paper the dispersions are diluted to about l%-3% solids content with water to facilitate uniform distribution of the size among the fibers.
From the foregoing, it will be seen that broadly the sizing agents are produced by reacting an ester gum at about l75250 C. with a water-soluble polyalkylenepolyamine containing at least three nitrogen atoms (the ratio of the rosin radicals in the ester gum tothe nitrogen atoms of the polyalkylenepolyamine being between about 3:7 and 2:3) at least until the reaction product (or its acetate salt) forms a colloidal cationic dispersion when agitated with boiling water, and-adding from about A .toabout 2 mols of an amine. solubilizing acid per mol of polyalkylenepolyamine taken.
The paper and other cellulosic units ofthe present invention are sized by a uniformly distributed content. of the cationic rosin formed. by reacting an ester gum. with a water-soluble polyalkylenepolyamine in the-proportions and at least .to the extent setforth above.
The following examples constitute specific. embodiments of the invention, but are not to be construed as limitations thereon.
Example 1 The preparation ofa colloidal cationic rosin size according to the present inventionis illustrated by the following.
An ester gum was formed by heating 199 g. of N grade,
' heat-treated gum rosin (0.66 mol) and 0.03 gfof zinc oxide as catalyst in a reaction flask equipped with stirrer, thermometer, nitrogen gas inlet tube, and funnel to 260 'C., adding 24.5 g. of glycerol (0.266 mol) at that temperature over a period of three hours, and maintaining the temperature between about 270 C. and 275 C. for about eight additional hours at which point the product had an acid number of 8.4. During the reaction nitrogen :gas was passed through the mixture to sweep out water :as formed and minimize discoloration.
The ester gum thus formed was cooled to 180 C. and 38 g. of triethylenetetramine (0.26 mol) added over a period of ten minutes. (The ratio of rosin groups in the ester gum to the nitrogen atoms in the polyalkylenepoly- :aimine was 0.63.) The mixture was then maintained at 200 C. The course of the reaction was followed byv Example 2 The preparation of sized paper according to the present invention is illustrated by the following.-
A 60% bleached white-40% bleached soda pulp was beaten to a Green freeness of 340 ml. at a consistency of 2.5%. Three aliquots were withdrawn and diluted to 0.6% consistency with water. One was reserved as control. T o the remaining two was added 3.5% of the sizing solution of Example 1 (size solids on the dry weight of the fibers), previously diluted .to 1.5% solids by addition of water. The pH of the aliquots was then adjusted to the values shown in the table by the addition of aqueous NaOH or HCl as necessary. The samples were then stirred gently for five minutes and sheeted at light and heavy 'basis weights. The sheets were dried at 240 F. and conditioned for 24 hours at 73 F. and 50% relative humidity. The light sheets were tested for their dry tensile strength, dry bur-sting strength (Mullen) and water and ink resistance by the Currier and BKY methods respectively. The heavy sheets were tested by the Cobb method (15 minute contact time at 73 F.) to determine 5 Grams water absorbed per 100 cm.
From previous experience with similar sizes prepared by direct reaction of stearic acid with triethylenetetramine, it would have been expected that the application of this quantity of size to the fibers would have decreased the dry tensile and dry burst values of the resulting paper by about 75%. The results show that application of the sizes of the present invention caused only a 22% and 26% decrease in dry tensile strength and only a 29% and 32% decrease in burst. These values are quite acceptable commercially.
The Currier, BKY and Cobb values showed that the papers possessed very satisfactory resistance to water and ink.
. Example 3 p The procedure of Example 2 was repeated for the preparation of their sheets, except that 3% of papermak ers alum (based on the dry weight of the fibers) was added after addition of the size and before adjustment of the pH. Results are as follows:
Per- Sheet Dry Currier BKY Percent Size 1 cent pH 1 Basis Tens. (Slack) Ink, um Weight 1 Secs. Secs.
1 See table of Example 1.
These results in comparison with those of Example 1 show that the addition of alum effected a distinct increase in the Currier and ink-resistance values without significantly affecting the dry tensile values.
We claim:
1. A method of producing a rosinated polyalkylenepolyamine suitable for conversion to a cationic rosin sizing wherein Y represents a substituent selected from the group consisting of H and CmH2mNH2, m is an integer between 2 and 4 inclusive, and p is an integer between 1 and 4.
4. A method according to claim 1 wherein the ratio or rosin radicals to nitrogen atoms is about 3:5.
5. A sizing agent produced by the process of claim 1.
6. A method of producing a liquid cationic rosin size which comprises reacting an ester gum at about 250 C. with a Water-soluble polyalkylenepolyamine containing at least three nitrogen atoms, the ratio of the rosin radicals in said ester gum to the nitrogen atoms of said polyalkylenepolyamine being between about 3:7 and 2:3 at least until the reaction product as its acetate salt forms a colloidal dispersion when agitated with boiling water, adding from A to 2 mols of an amine-solubilizing acid per mol of combined polyalkylenepolyamine present, and dispersing the salt thus formed in water.
7. A size produced by the process of claim 6.
8. A method of producing a liquid cationic rosin size which comprises reacting an ester gum at about 175-250 C. with a water-soluble polyalkylenepolyamine containing at least three nitrogen atoms, the ratio of the rosin radicals in said ester gum to the nitrogen atoms of said polyalkylenepolyamine being between about 3:7 and 2:3, at least until the reaction product as its acetate salt forms a colloidal dispersion when agitated with boiling water, and dispersing the reaction product in water containing from about 1 to 2 mols of an amine-.solubilizing acid per mol of combined polyalkylenepolyamine in said reaction product.
9. A size produced by the process of claim 8.
10. Paper composed of cellulosic fibers sized by a uniformly distributed content of from about 1% to 5%,
based on the dry weight of the fibers, of the cationic rosin size formed by reacting an ester gum at about 175- 250 C. with a water-soluble polyalkylenepolyamine containing at least three nitrogen atoms, the ratio of the rosin solids in said ester gum to the nitrogen atoms of UNITED :STATES PATENTS 2,304,369 Morgan te a1. Dec. 8, 1942
Claims (1)
10. PAPER COMPOSED OF CELLULOSIC FIBERS SIZED BY A UNIFORMLY DISTRIBUTED CONTENT OF FROM ABOUT 1% TO 5%, BASED ON THE DRY WEIGHT OF THE FIBERS, OF THE CATIONIC ROSIN SIZE FORMED BY REACTING AN ESTER GUM AT ABOUT 175*250* C. WITH A WATER-SOLUBLE POLYALKYLENEPOLYAMINE CONTAINING AT LEAST THREE NITROGEN ATOMS, THE RATIO OF THE ROSIN SOLIDS IN SAID ESTER GUM TO THE NITROGEN ATOMS OF SAID POLYALKYLENEPOLYAMINE BEING BETWEEN ABOUT 3:7 AND 2:3, AT LEAST UNTIL THE REACTION PRODUCT AS ITS ACETATE SALT FORMS A COLLOIDAL DISPERSION WHEN AGITATED WITH WATER.
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US446396A US2772966A (en) | 1954-07-28 | 1954-07-28 | Cationic rosin sizes |
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US3027295A (en) * | 1960-08-05 | 1962-03-27 | Michigan Res Lab Inc | Paper of improved dimensional stability |
DE1150865B (en) * | 1958-04-14 | 1963-06-27 | Schweizerische Viscose | Process for the production of cellulose and polyamide-containing flat structures from fiber material using polyamides as binders |
DE1237423B (en) * | 1958-02-11 | 1967-03-23 | Shell Int Research | Process for felling waxy substances onto fiber material |
US4219382A (en) * | 1976-02-19 | 1980-08-26 | American Cyanamid Company | Cationic fortified rosin size |
US4323425A (en) * | 1973-01-22 | 1982-04-06 | Tenneco Chemicals, Inc. | Paper sizing |
US5308441A (en) * | 1992-10-07 | 1994-05-03 | Westvaco Corporation | Paper sizing method and product |
WO1999032718A1 (en) * | 1997-12-22 | 1999-07-01 | International Paper Company | Dimensionally stable paper and paperboard products |
US20050056391A1 (en) * | 2003-09-17 | 2005-03-17 | Huang Yan C. | Papers having borate-based complexing and method of making same |
US10352619B2 (en) * | 2017-05-05 | 2019-07-16 | Exxonmobil Research And Engineering Company | Refractory anchor assembly and method for installing the same |
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US2601597A (en) * | 1946-09-06 | 1952-06-24 | American Cyanamid Co | Application of dispersed coating materials to cellulosic fibers |
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DE1237423B (en) * | 1958-02-11 | 1967-03-23 | Shell Int Research | Process for felling waxy substances onto fiber material |
DE1150865B (en) * | 1958-04-14 | 1963-06-27 | Schweizerische Viscose | Process for the production of cellulose and polyamide-containing flat structures from fiber material using polyamides as binders |
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US4323425A (en) * | 1973-01-22 | 1982-04-06 | Tenneco Chemicals, Inc. | Paper sizing |
US4219382A (en) * | 1976-02-19 | 1980-08-26 | American Cyanamid Company | Cationic fortified rosin size |
US5308441A (en) * | 1992-10-07 | 1994-05-03 | Westvaco Corporation | Paper sizing method and product |
WO1999032718A1 (en) * | 1997-12-22 | 1999-07-01 | International Paper Company | Dimensionally stable paper and paperboard products |
US6416628B1 (en) | 1997-12-22 | 2002-07-09 | International Paper Company | Method of producing dimensionally stable paper and paperboard products |
US6565709B1 (en) | 1997-12-22 | 2003-05-20 | Yan C. Huang | Process for producing dimensionally stable release liner and product produced thereof |
US20050056391A1 (en) * | 2003-09-17 | 2005-03-17 | Huang Yan C. | Papers having borate-based complexing and method of making same |
US7608166B2 (en) * | 2003-09-17 | 2009-10-27 | International Paper Company | Papers having borate-based complexing and method of making same |
US20100043991A1 (en) * | 2003-09-17 | 2010-02-25 | International Paper Company | Papers Having Borate-Based Complexing And Method Of Making Same |
US7815770B2 (en) | 2003-09-17 | 2010-10-19 | International Paper Company | Papers having borate-based complexing and method of making same |
US10352619B2 (en) * | 2017-05-05 | 2019-07-16 | Exxonmobil Research And Engineering Company | Refractory anchor assembly and method for installing the same |
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