CA1287706C - Invert size for the pulp sizing and surface sizing of paper - Google Patents
Invert size for the pulp sizing and surface sizing of paperInfo
- Publication number
- CA1287706C CA1287706C CA000546146A CA546146A CA1287706C CA 1287706 C CA1287706 C CA 1287706C CA 000546146 A CA000546146 A CA 000546146A CA 546146 A CA546146 A CA 546146A CA 1287706 C CA1287706 C CA 1287706C
- Authority
- CA
- Canada
- Prior art keywords
- rosin
- parts
- invert
- size according
- weight
- 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 - Fee Related
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Classifications
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/20—Macromolecular organic compounds
- D21H17/21—Macromolecular organic compounds of natural origin; Derivatives thereof
- D21H17/22—Proteins
-
- 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
-
- 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
Abstract
Abstract of the disclosure An invert size for the engine and tub sizing of paper. It contains an aqueous dispersion of a fortified, unfortified, hydrogenated, or disproportionated and optionally esterified rosin or mixture of such rosins and of a dispersant that contains digested casein or an emulsifier of the general formula [R-(OCH2CH2)n-O-A]? Mx+ (I) wherein R is an alkylphenyl, alkyl, or alkenyl group or a cycloalkyl group with condensed rings, A is a group with the formula -CH2COO or -SO3, Mx+ is a cation, x is 1 or 2, and n is a number such that approximately 21 to 76% of the molecu-lar weight of the anion is in the -OCH2CH2 group. To allow sizing control, the dispersant also contains cationic starch.
Description
7~)6 INVE~T SIZE FOR T~IE ENGINE AND TUB SIZING OF PAP~
The inven-tion concerrls the invert size for the engi.r,e and tub sizing of paper.
The internal sizing of paper wlth rosin and with fortified rosin is described by Casey in ~ulp and Paper, 2nd edition, Volume 2: Papermaking, Chap-ter XIII, pages 1043 to 1066.
Fortified rosins can be prepared by reacting maleic anhy-dride or other dienophilic compounds with rosin while increasing the number of carboxylic-acid groups. A typical fortified size can contain approximately 1 to 30~ maleino-pinaric anhydride.
It is generally recognized that a size wi-th a high level of free rosin results in better sizing and demands less alum.
It is simultaneously possible to use a protective colloid to produce a very stable size containing up to 90% free rosin.
The sewoid process results in a size with a hi.gh percentage of free rosin tha-t contains rosin dispersed in a small amount of rosin soap and stabllized with approximately 2 casein or another protein. The casein is employed as a protective colloid -to prevent the particles of rosin from growing and to keep them finely divided. Irl the Bewoid process the rosin is mechanically divided in the presence of approximately 1 to 2% sodium hydroxide and approximately 2%
casein. The solid rosin is heated and subjec-ted to mechan-lcal shearing strains until it is broken up into small particles. A small amount of sodium hydroxi.de (1.6 parts to 100 part. of rosin) is then added to the molten rosin to partly saponify it, followed by casein (2.0 parts dispersed 7~
in 0.2 parts oE NaO~I) to stabilize -the dispersed particles of rosin. The dissolved casein is worked into the molten rosin while being powerfully stirred, subsecluellt to which a little more (0.2 parts) of NaOH is added, or the ho-t rosin melt is in~ected into water that contains casein. Finally, water is added to obtain a finished dispersion wi~h approxi-mately 45~ solid particles, which is used in that form. This process is also called the "inversion method of manufactur-ing rosin size" and the resulting size "invert size."
The inversion method is employed in US Patent 2 393 179 to produce a size with free rosin, but wi-th an alkaline dis-persant, a sulfonated higher fatty alcohol for example, used instead of the sodium hydroxide. The rosin is mel-ted, and the desired amount of dispersant added, accompanied by enough stirring to produce a homogeneous molten mass. A
practically neutral or weakly acidic aqueous solution or dispersion of a protective colloid, casein for example, is then added gradually and accompanied by rapid stirring, resulting in a paste-like dispersion with a high solids content, which is then diluted Witil water to a solids content of 40 to 60% by weight.
In the Prosize method of producing a pro-tected size with a high percentage of free rosin the particles of rosin are prevented from growing into large aggregates by the presence of a surface-active protein, soybean protein for example.
The sizes containing free rosin disclosed in German Pa-tent l 131 3~8 were dispersions of unsaponified resin acids with a specific percentage of resin soaps. The dispersions were obtained by the inversion method. They were usually employed with 60 to 95~ free rosin plus auxiliary emulsiEiers and stabilizers such as stearates, trie-thanolamine, casein, and waxes.
The fortified rosins in German Patent 1 131 343 have not untll now been appropriate ~or producing dispersions because they usually had too high a melting point, tended to crys-tallize, or formed fine crusts that led to sedimentation when they dispersed. The patent describes a paper size and a method of manufacturing it in the form of an aqueous disper-sion wi-th a high content of free rosin wherein fortified rosin is mixed at elevated temperatures with fatty acids, mixtures of fatty acids, and/or naphthenic acids and the dispersion is carried out in a known way. The method was employed in the form of an inversion.
German OS 2 426 03~ discloses a method of producing a practically stable aqueous dispersion of a material based on rosin and appropriate for sizing pulp-like fibers in,-the manufacture of paper, whereby an unstable aqueous dispersion that contained at least 5% solids consisting of 0 to 95~
rosin and 100 to 5% of a reaction product of rosin with an acidic compound containing the group~-C=C-C'=O, with the amount of the acidic compound bound in the form of an adduct being about 1 to 20% of the total solids weight, was homog-enized at a pressure of approximately 1~2 to 563 bar and at a temperature of approximately 150 -to 195C in the presence of an anionic dispersan~. The dispersants were materials ~7~ 23251-59 based on saponified rosin, sodium alXylbenæene sulfonate, sodium naphthalene sulEonic acid, sodiusn laury:l su:lEate, or the ammonium salt of the sul~ate ester of an alkylphenoxy(poly-ethyleneoxy)ethanol.
U.S. Patent 4,157,982 describes a practically stable aqueous dispersion consisting essentially of water, of rosin material, and of an alkali-metal alkylbenzene sulfonate to stabilize the rosin material. The dispersions are obtained by passing a previously prepared mixture of the components through a homogenizer.
U.S. Patent 3,906,142 discloses an agent for sizing paper without using aluminum sulfate that contained a stable aqueous dispersion of a rosin fortified by reac-ting with an ~,~-unsaturated carboxylic acid or corresponding anhydride, a protective colloid, casein for example, and a volatile base, ammonia for example, whereby at least 90~ of the fortified rosin was unsaponified. This agent was prepared with the inversion method, with the fortified rosin initially melted in a vessel equipped with a stirring and heating mechanismO A
combination dispersant and stabilizer was then prepared in another vessel by dissolving measured amounts of a protective colloid, casein for example, and oE a volatile base, ammonia for example, in water. The prepared dispersant and stabilizer was then rapidly added to the molten rosin, whereby high-speed stirring or another intensive method of blending was employed during and after the addition. Finally, -the solids content of the resulting aqueous rosin X
~7~70!6 dispersion was adjusted by adding a calculated amount o:E
water.
An invert size for the engine sizing of paper i.s known from German OS 2 654 496. It contained an aqueous dispersion of a fortified rosin with a dispersant that yielded in solution anions of the formulas -~R ~ ( H2CH2O)nso3J (II) and ~R'-o(cH2cH2o)nso3~ (III) wherein R was an n- or branched al]cyl radical with 4 to 18 carbon atoms, R' was an alkyl, alkenyl, or cycloalkyl radical with condensed rinys with lO to 20 carhon atoms, and n was a number such that approximately 27 to 75% of the molecular weight was i.n the C~12CH20 groups. Protective cclloids, casein ~or example were no-t supposed to be necessary to manufacture this known paper size, although the inversion water had to be hot.
German OS 2 845 091 discloses an invert size for the enyine and vat sizing o~ paper that c.ontained dispersants in the aqueous resin dispersion in the form of compounds that yielded in solution or dispersion anions of the formulas ~7 L - (oc~l2c~ OCi-l coo ( ~v and/or R (OC 2CH2)n OCH2COO~ (V) wherein R is an n- or branched alkyl group with 8 or 9 carbon atoms, R1 is an n- or branched alkyl or alkenyl group with 12 to 20 carbon atoms, and n is a number such that approxima-tely 21 -to 76% of the rnolecular weight is in the OcH2cH2 groups-The aforesaid sizing agents were employed at a pH of 4.5 to6 and required relatively large amounts of aluminum sulfate to fix them to the fibers, contamina-ting the effluent. When up to now it was desired to size paper at a pH of ~ to ~, it was necessary to employ synthetic sizing agen-ts, diketone derivatives for example, instead of rosins. Controlled sizing, however, was impossible with these synthetic sizing agents.
Thus the present invention seeks ko provide the engine and vat sizing of paper, containing an aqueous rC dispersion of a fortified, ~r-~i~1~1, hydrogenated, or disprcportiona-ted and optionally esterified rosin or mixture of such rosins along with a dispersant that contains digest-ed casein or an emulsifier of the general formula [ ( 2 2)n ]x (I) wherein R is an alkylphelly]., alkyl, or alkenyl group or a eyeloalkyl group with eondensed rings, A is a group of the formula -CH2COO or -SO3, Mx is a ca-tlon, x is l or 2, and n is a number sueh that approximately 21 to 76% of the molecu-lar w~ight of the anion is in the -OCH2CH2 groups, practical cor sizing paper over a wider pH range of 4 to S, ancl without the drawbaeks of synthetie sizing agents, meaning that the sizing can be controlled.
Additionally, in aeeordanee with the invention in that the dispersant also eontains eati.onic starch.
It has, surprisingly, been eonfirmecl that the 5ize in aeeordance with the invention works satisfactorily over a pll range of 6.0 to 7.5, makes the paper more hydrophobic, and, eompared with other sizes, requires considerably less aluminum sulfate to fix it to the fibers, which accorclingly reduees eontamination of the e~f]uent from -the paper mill.
The effluent will also be less eontamina-ted by this product in that i-t has, as compared with other sizes, a much lower biochemical and chemieal oxygen demand.
The inver-t size in aeeordanee with the invention preferably.
eorltains in the aqueous dispersion 5 to 50% by weight of rosin or a mlxture of rosins and 1 -to 15~ by weight and espeeially 6 to 12 % by weight of dispersant in terms of the rosin or mixture of rosins, with the remainder consisting of water, up to 100% by weight, whereby the ratio of the weight ~2~Y~
of the casein or emulsifier of Formula I to the cationic starch in tlle dispersant ranges from 20:~0 to ~0:20.
The invert size in accorclance with the invention also contains a cationic starch in the dispersant in addition to the known casein or the known emulsifier of Formula I, which comprises known emulsifiers of Formulas II through V. The cationic starch replaces some of the previousl.y employed casein or emulsifier of Formula I, makes the paper more hydrophobic within the neutral range, especially at a pH
range from 6 to 7.5, promotes the action of the protective colloid, and improves the retention of the ,size or mineral fillers to the fibers. Since the cationic starch does not by itself act as a protective colloid, it was surprising to discover that it promotes the protective-colloid action of the casein. An especially preferred ratio for the weight of the casein or emulsifier of Formula I to the cationic starch in the dispersant ranges from 36:65 -to 65:35. Outstanding results for example are obtained at a weight ratio of 50:50, Cationic starches that can be employed in accordance with the invention are in themselves known and commercially available. They can be obtalned :Eor e.xample by cationizing starch, potato starch or corn starch :Eor example, with a known cationizer, glycidyltrimethylammonium chloride, 3-chloro-2-hydroxypropyl-trimethylammonium chloride, or the corresponding triethyl compounds for example. The cationization binds positively charged anion groups to the starch molecule throuqh ether bridges.
Cationic starches are already employed apart from paper size as flocculants and retention agents in papermakin~. This known use of cationic starch is admittedly accompallied by a sliqht improvemen-t in the hydrophobicity of the paper. ~hen, however, the cationic starch ls employed in the dispersant in the invert siæe in accordance with the invention, its hydrophobicity-improving effect on the paper is surprisingly about 100 times as powerful.
The rosin employed in the invert size in accordance with -the invention can be any commercially availahle type of rosin--root rosin, balsamic resin, tall oil, or mixtures of two or more of these rosins in the raw or refined state ror exam-ple. Rosins that tend to crystallize can be treated at elevated temperatures with formaldehyde or paraformaldehyde in the presence of an acid catalyst, toluene-~-sulphonic acid for example, in a way that is known to one of skill in the art. Thus, rosin treated wi-th formaldehyde can be employed and is to be considered a rosin in the sense employed herein.
An adduct-reac-tion product of rosin wlth an acidic compound containing the raclical C=C~~=O that has been obtained by reacting the rosin with -the acidic compound at elevated temperatures, usually 150 to 210 C, is employed as a fortified rosin. Enough of the acidic compound will be employed to obtain a for-tified rosin containing appro~imate-ly 1 to approximately 30% by weight and preferably approxi-mately 5 to approximately 12% by weight of the added acidic compound based on the fortified rosin. Methods of o~
preparing fortified rosins are described in ~S Patents 2 62 918 and 2 68~ 300.
Examples of acidic compounds with a ~=C-C=O radical that can be employed to prepare the fortified rosin are the unsaturated organic acids and their readily available anhydrides, particularly fumaric acid, maleic acid, acrylic acid, acrylamide, maleic anhydride, itaconic acid, itaconic anhydride, citraconic acid, and citraconic anhydride. The preferred adduct-forming acid is fumaric acid. Mixtures of acids can optionally be employed to prepare the fortified rosin. Mixtures of different fortified rosins can also be employed. Thus, for example, a mixture of the acrylic acid adduct to rosin and of the fumaric acid adduct to rosin can be employed to prepare the invert sizes in accordance with the invention. Finally, the esters of the aforesaid rosins with amino alcohols-- triethanolamine, triisopropanolamine, or tributanolamine for instance-- or with glycerine, glycol, or polyglycols, are appropri.ate for preparing the invert size in accordance with the invention. When a polyglycol is employed as an esteriflcati.on agent, polyethyleneglycols with molecular weights of 190 to 1050 are preferably em-ployed.
The rosin can optionally be mixed with known loaders--waxes, especially paraffin and microcrystalline wax, hydro-carbon resins, including those derived from petroleum hydrocarbons and terpenes, spindle oils, or polyglycols for example. This can be done in the mel-t or in solution, with up to approximately 100~ by weight and preferably 30 to o~
50% by weigilt of the loader mixed in based on we1cJht of the rosin. Some of the rosin can also be replacecl with an extender. Tall oil deriva-tives for instance can be employed as an extender, which can be employed in amounts o~ apprGxi-mately 30 to 50% by weight based on the weight of the the rosin.
The invention can also be carried ou-t with mixtures of fortified and unfortified, hydrogenated, or disproportionat-ed rosins and with mixtures of fortified rosin, extenders, and/or loaders and unfortified, hydrogenated, or dispropor-tionated rosins.
Mixtures of fortified, unfortified, hydrogenated or dispro-portionated rosins will contain approximately O to 100~
fortified rosin and approxirnately 100 -to 0~ unfortified, hydrogenated, or disproportiona-ted rosin. Mixtures of fortified rosin, rosin and rosin extenders will contain approximately 25 to ~9% forti~ied rosin and approximately O
to 25% extenders for the fortified rosin.
If a mixture of rosins is ernployed, -the mixture can contain any of the foregoing rosins, fortified or unfortified, and optionally also partly or practically completely esterified, hydrogenated or disproportionated, or even polymerized.
In preparing the invert size in accordance with the in-vention an aqueous solution or dispersion of the dispersan-t is initially prepared. The casein or the emulsifier of Formula I, the cationic starch, and an acidic or basic 3~2~
digesting a~ent such as formic acid, an amlno alcohol such as triethanolamine, potassium hydroxide solution, sodium hydroxide solution, ammonia or borax are mixed with water and heated. It is pre~erable -to -take wa-ter, stir in the digesting agent, and then add ~he casein or ~lormula ~
emulsifier and the cationic s-tarch, subsequent to which the mixture is heated to 80C for example. As previously mentioned herein the Formula T emulsifier can be one of the known emulsifiers of Formulas II through V. The Mx cation in Formula I can for example be an al~ali metal ion such as Na or K , a hydro~en ion, an ammonia ion or a triethanolammonium ion.
The action of the the cationic starch can optionally be augmented by also adding a cationic resin to the dispersant, which can also be considered a protective colloid. One example of an appropriate cationic resin is a urea-formal-dehyde cationized with 3-chloro-2--hydroxypropyl-trirne-thyl-ammonium chloride, 3-chloro-2-hydroxypropyl-tri.ethylammonium chloride, or another ~nown cationizing agent.
The resulting aqueous solution or dispersion of the disper-sant or pro-tective col].oid is then added to the rosin or mixture of rosins, which has previ.ously been melted and saponified by adding smal.l amounts of a saponifier such as sodium hydroxide solution, potassi.um hydroxi.de solu-tion or triethanolamine. The rosin or mix-ture of rosins is pref-erably melted at approximately 160C and cooled subsequent to saponification to approximately 120C before -the disper-sant is added. Once the saponified rosin has been mixed with the protective collo~d, the mix-ture is diluted with water -to the desired level, inducing the inversion.
The invention wlll now be described with reference to the accompanyin~ drawing, which is a plot of ink flota~ion tlme versus content of size for several dif~erent size compositions, in conjunction with the following illustrative examples wherein parts are by weight unless otherwise expressed.
_xample _ A. Preparation of a rosin fortlfied with maleic anhydride A mixture of 91 parts of tall oil and 9 parts of maleic anhydride was stirred and heated to 190C. Once the reaction was complete the batch was cooled to room temperature.
B. Preparation _ the protective colloid solution 1 part of formic acid was stirred into 80 parts of water.
10 parts of casein and 10 parts of a starch cationized with 3-chloro-2-hydroxypropyl-trimethylammonium chloride (Cato Starch) were added. The mix-ture was heated to 80C.
C. Preparation of the inverted size 200 parts of the rosin from ~ were heated to 160C and treated with 6 parts of 25% sodium hydroxide solution. The batch was cooled to 120C, 60 parts of -the protective colloid solution from B were added, and the ba-tch was diluted to the desired percentage with water.
Example 2 A. A rosin fortified with maleic anhydride and fumaric acid was prepared as describcd in Example lA from 100 parts of tall oil, 3.5 parts of maleic anhydride, and 5.8 parts of fumaric acid at 210C.
B. A protective colloid solution was prepared as described ln Example lB from 82.6 parts of water, 1.2 parts of triethanolamine, 8.7 parts of casein, and 8.7 part~ of Cato Starch.
C. An inverted size was prepared as described in Example lC
from 100 parts of the resin from A, 2 parts of stearic acid, 4 parts of triethanolamine, and 60 parts of the protective colloid solution from B and diluted with 199 parts of water.
Employing the resulting size at a ratio of 2% bone-dry based on pulp to size paper at a pH of 7.2 resulted in an ink-flotation time of 1 minute.
Example 3 A. A rosin fortified wi-th maleic anhydride and fumaric acid was prepared as described in Example lA from 120 parts of tall oil, 415 parts of balsamic resin, 23 parts of maleic anhydride, and 35 parts of fumaric acid a-t 210C.
B. A protective colloid solution was prepared as described 7'7~i in Example lB from 81 parts of water, 0.7 parts oE formic acid, 9.5 parts of casein, and 9.5 par-ts oE Calo Starch.
C. An inverted size was prepared as described in Example lC
from 100 parts of the resin Erom A, 2 parts of stearic acid, 4 par-ts of triethanolamine, and 60 parts of the protective-colloid solution from B and diluted wi-th 199 parts of water.
Employing the resulting size a-t a ratio of 2~o bone-dry based on pulp to size paper at a pH of 7. 2 resulted in an ink-flotation time of 3.5 minutes.
Example _ A. A fortified rosin was prepared as described in Example lA from 100 parts of tall oil, 2 . 6 parts of maleic anhydride, and 4.3 parts of fumaric acid at 210C. A mixture of this rosin was stirred and heated -to 200C with 4 par~s of trie-thanolamine. Once the reaction was complete the katch was cooled to room temperature, resulting in a fortified rosin esterified wi-th -triethanolamine.
B. A protective colloid solution was prepared as described in Example lB from 81 parts of water, 0.7 parts of formic acid, 9.5 parts of casein, and 9.5 par-ts of Cato Starch.
77~
C. An inverted size was prepared as described in ExalnE)le I.C
from 100 parts oE the res.in from A, 2 part:s of s-tearic acid, 4 parts of triethanolamine, and 60 parts of the protective-collold solution from B and diluted with 199 par-ts of water.
Employing the resulting size at a ratio of 2~ bone-dry based on pulp to size paper at a pH of 7.2 resulted in an ink-flotation time of 8 minutes.
Example 5 A. A rosin fortified with maleic anhydride, fumaric acid, and acrylamide was prepared as described in Example lA from 100 parts of tall oll, 3.5 parts of maleic anhydride, 5.~
parts of fumaric acid, and 3.3 parts of acrylamide at 210C.
A mixture of this rosin was stirred and heated to 200C with 4 parts of -triethanolamine. Once the reaction was complete the batch was cooled to room temperature, resulting in a fortilied rosin esterified with triethanolamine.
B. A protective colloid solution was prepared as descrihed in Example lB from 81 parts of water, 0.7 par-ts of formic acid, 9.5 parts of casein, and 9.5 parts of Cato Starch.
C. An inverted size was prepared as described in Example lC
)6 from 100 parts of the resin from A, 2 parts of steclric ac:id, 4 parts of triethanolamine, and 60 parts oE the plotective collold solution from B and dilutecl wlth 199 parts of water.
Employing the resulting size at a ratio of 2~ bone-dry based on pulp to size paper at a pH of 7.2 resulted in an nk-flotation time of 13 minutes.
Example 6 . _ A. A fortified rosin was prepared as described in Example lA from 100 parts of tall oil and 9 parts of maleic anhydride and esterified wi-th 5 par-ts of triethanolamine as described in Example 5A.
B. A protective colloid solution was prepared as described in Example lB from 81 parts oE water, 0.7 parts oE formic acid, 9.5 parts of casein, and 9.5 parts of Cato Starch.
C. An inverted size was prepared as described in Example lC
from 100 parts of the resin from A, 2 parts of stearic acid, 4 parts of triethanolamine, and 60 parts of the protective colloid solution from B and diluted with 199 parts of water.
Employing the resulting size at a ratio oE 2~ bone-dry based on pulp to size paper at a pH of 7.2 resulted in an ink-flotation time of 10 rninu-tes.
~77~;
Example 7 A. A rosin was prepared as described in Example ~.
B. A protective colloid solution was preparecl as describe~
in Example lB from 82.6 parts of water, 1.2 parts of triethanolamine, 8.7 parts of casein, and 8.7 parts of Cato Starch.
C. An inverted size was prepared as described in Example lC
~rom 100 parts of the resin from A, 2 parts of stearic acid, 4 parts of triethanolamine, and 60 parts of the protective colloid solution from B and diluted with 199 parts of water.
Employing the resulting size at a ratio of 2~ bone-dry based on pulp to size paper at a pH of 7.2 resulted in an ink-flotation time of 12 minutes.
Exam~le 8 A. A fortifi.ed rosin was prepared as described in Example lA from 500 parts of tall oil, 14 parts of maleic anhydride, and 23 parts of fumaric acid and esteri.fied with 25 parts of triethanolamine as described in Example SA.
B. A protective colloid solution was prepared as described ~2~3770~
in Example lB from 160 parts of wa-ter, 0.66 parts of Cormic acid, 20 parts of casein, and 20 par-ts of Cato Starch.
C. An inverted size was prepared as described in E:cample IC
from 300 parts of the resln Erom A, 6 parts of stearic acicl, 12 parts of triethanolamine, and 180 parts oE the protective colloid solution from B and diluted with 582 parts of water.
Employing the resulting size at a ratio of 2% bone-dry based on pulp to size paper at a pH of 7.2 resulted in an in~-flotation time of 8 minutes.
Example _ A. A rosin was prepared as described in Example 2A.
B. A protective colloid solution was prepared as described in Example lB from 80 parts of water, 0.6 parts of formic acid, 8 parts of casein, and 12 parts o~ Cato Starch.
C. An inverted size was prepared as described in Example lC
from lO0 parts of the resin from A, 2 parts of stearic acid, ~ parts of triethanolamine, and 60 parts of the protective colloid solution from B and dilutecl with 199 parts of water.
77C)~
Employing the resulting size at a ratio of 2% bone-dr~ based on pulp -to si2e paper at a pH oE 7.2 resulted in an ink-flotation time of 4 minutes.
Example 10 A. A rosin was prepared as described in Example 2A.
B. A protective colloid solution was prepared as descri~ed in Example lB from 92 parts of water, 0.5 parts of formic acid, 9 parts of casein, and 9 parts of Cato Starch.
C. An inverted size was prepared as described in Example lC
from 100 parts of the resin from A, 2 parts of stearic acid, 4 parts of triethanolamine, and 60 parts of the protective colloid solution from B and diluted with 200 parts of water.
Employing the result1ng size at a ratio of 2% bone-dry based on pulp to size paper at a pH of 7.2 resulted in an ink-flotation time of 4 minutes.
xample 11 A. A rosin was prepared as described in Example 2A.
~0 ~77~
B. A protective colloid solution was prepared as described in Example lB from 90 parts of water, 0.5 par~s ol forrnic acid, 4 parts o~ triethanolamirle, 4 par-ts of nonylphenolpolyethyleneoxy-carboxylic acid, 4 parts of oleylpolyethylenoxycarboxylic acid, and 12 parts of Cato Starch.
C. An inverted size was prepared as described in Example lC
~rom 100 parts of the resin from A, 2 parts of stearic acid, and 60 parts of the protective colloid solution from B and diluted with 195 parts of water.
Employing the resulting size at a ra-tio of 2% bone-dry based on pulp to size paper at a pH of 6.8 resul-ted in an ink-flo-tation time of 0.42 minutes.
Exam~
A. A rosin was prepared as described in ~xample 2A.
B. A protective colloid solution was prepared as described in Example ls from 90 parts of water, 0.5 parts of formic acid, 4 parts of triethanolamirle, 4 parts of nonylphenolpolyethylenoxycarboxylic acid, 4 parts of oleylpolyethylenox~carboxylic acid, and 12 parts o~ Cato Starch.
7~)6 C. An inverted size was prepared as described ir- Exarnple lC
from 100 parts of the resin from A, 2 parts of stearic acid, and 60 parts of the protective collold solu-tion .Erom B and diluted with 195 parts of water.
Employing the resulting size at a ratio of 2% bone-dry based on pulp to size paper at a pH of 6.8 resulted in an ink-flotation time of 0.5 minutes.
Example 13 A. A rosin was prepared as described ln Example 2A.
B. A protective colloid solution was prepared as descrlbed in Example lB from 82.6 par-ts of water, 0.5 parts of ~5%
KOH, 12 parts of casein, and 6 parts of Cato Starch.
C. An inverted size was prepared as described in Exa,nple lC
from 100 parts of the resin from A, 2 parts of stearic acid, 3.~ parts of 266 KOH, and 60 parts of the protective collGid solution from B and diluted with 195 parts of wa-ter.
Employing the resulting si~e at a ratio of 26 bone-dry based on pul.p to size paper at a pH of 7.2 res~llted in an ink-flotation time of 1.5 rninutes.
3 2~3~71~)~
Example 14 A. ~ rosin foriti~ed with ~umaric acid was prepared b~ stirring and heatin~
to 210C a mixture o~ 91 parts o~ tall oil and 9 parts of fumaric acid and cooling to room temperature upon completion of the reaction.
B. A protective colloid solution was prepared as described in Example lB
from 81 parts of water, 4 parts of triethanolamine, 10 par-ts of casein and 10 parts of Cato S-tarch.
C. An inverted size was prepared as described in Example lC ~rom 200 parts o~ the resin from A, 4 parts triethanolamine and 60 parts of the protective colloid solution ~rom B.
~ A--7~
Exam~ 15 A. A rosin fortified with acrylamicle was prepaLed by stirring and heatincJ to 200C a mixture of 91 parts of tall oil and 9 parts of acrylamide and cooling -to roorn temperature upon completion of tl~e reaction.
B. A protective colloid solution was prepared by stirring 4 parts of triethanolamine followed by 3 parts of a urea-form-aldehyde resin cationized with 3-chloro-2-hydroxypropyl-triethylammonium chloride into 81 parts of water. 10 parts of casein, and 6 parts of Cato Starch were then added and the mixture heated to 80C.
C. An inverted size was prepared as described in Example lC
from 200 parts of the resin from A, 4 parts of triethanol-amine, and 60 parts of the protective colloid solution from B.
Example _ A fortified rosin esterified with glycerine was preparecl by stirring and heatincJ a mi.xture of 91 parts of -the rosin frol-n Example lA or 14 A ancl 9 parts of glycerine to 200C and cooling the batch -to room -temperature once the reac-tion was complete. An inverted size was prepared as described in Example lC from 200 parts each of -the foregoing esteri.fied rosins, 6 parts of 25% ~aOEI or I~OII or 4 parts of 77~
triethanolamine, and 60 par-ts oE the protect.ive col.loid solutlon from either Example lB, Example l~B, or Example 15B.
Example 17 A fortified rosin esterified with glycol was prepared by s~irr.ing and heating a mixture of 91 parts of the rosin from Example lA or 14 A and 9 parts of glycol to 200C and cooling the batch to room temperature once the reaction was complete. An inverted size was prepared as described in Example lC from 200 parts each of the foregoing esterified rosins, 6 parts of 25~ NaOH or KOH or 4 parts of triethanol-amine, and 60 parts of the protective colloid solution from either Example lB, Example 14B, or Example 15B.
Example _ A fortified rosin esterified with polye-thylene glycol was prepared by stirring and hea-ting a mixture of 91 parts of the rosin from Example lA or 1~ A and 9 parts oE pol.yethyl~
ene glycol ~with a mean molecular weight of ~00) to 200C
and cooling the batch to room temperature once -the reaction was complete. An inverted size was prepared as described i.n Example lC from 200 parts each of the foregoing esterified rosins, 6 parts of 25% NaOH or KOH or 4 parts of trie-tharlol amine, and 60 parts of the protective colloid solution from either Example lB, Example 14B, or Example 15B.
~2~77~
Example 19 ( o~a _son) This reference example represents -the prepara-~:ion oE an invert size with a protective-colloid solution that contains only casein and no cationic s-tarch.
A. A rosin was prepared as described in Example 2A.
B. A protec-tive colloid solution was prepared as descriE~ed in Example lB from 158 parts of water, 4.8 parts of 45% KOEI, and 29 parts of casein.
C. An inverted size was prepared as described in Example lC
from 600 parts of the resin from A, 2 parts of s-tearic acid, 18 parts of 26% ~OH, and 180 parts of the protective collolcl solution from B.
Employing the resulting size at a ratio of 2% bone-dry based on pulp to size paper at a pEI of 7.2 resulted in an ink-flotation time of 0.1 minutes.
The drawing is a graph of the ink-flotation -times of sdm21es of pulp sized with the sizes from Examples 2 through 7 and with the comparison size from Example l9 as a function of the percent of size added, based on dry weight.
The chemical (COD) and biochemica] (BOD5) oxygen demands were also determined for the sizes Erom Example 7 and Comparison ExaMple 19. The COD was determinecl in accordance with DIN 38 409, Part 14 and the BOD5 in accordance wi.~h DIM
38 409, Part 51. The ~ollowing results were obtainecl:
Size COD BOD5 Example l9 (comparison~ 745 g/1 474 g/l Example 7 l91 g/1 5~ g/l The size in accordance with Example 7 oE the invention accordingly exhibited considerably lower chemical and biochemical oxygen demands than the size from Reference Example 19.
It will be appreciated that the instan-t specification and claims are set forth by way of illustration and not limitation, and that various modifications and changes may be made without departing frorn the spirit and scope of the present invention.
The inven-tion concerrls the invert size for the engi.r,e and tub sizing of paper.
The internal sizing of paper wlth rosin and with fortified rosin is described by Casey in ~ulp and Paper, 2nd edition, Volume 2: Papermaking, Chap-ter XIII, pages 1043 to 1066.
Fortified rosins can be prepared by reacting maleic anhy-dride or other dienophilic compounds with rosin while increasing the number of carboxylic-acid groups. A typical fortified size can contain approximately 1 to 30~ maleino-pinaric anhydride.
It is generally recognized that a size wi-th a high level of free rosin results in better sizing and demands less alum.
It is simultaneously possible to use a protective colloid to produce a very stable size containing up to 90% free rosin.
The sewoid process results in a size with a hi.gh percentage of free rosin tha-t contains rosin dispersed in a small amount of rosin soap and stabllized with approximately 2 casein or another protein. The casein is employed as a protective colloid -to prevent the particles of rosin from growing and to keep them finely divided. Irl the Bewoid process the rosin is mechanically divided in the presence of approximately 1 to 2% sodium hydroxide and approximately 2%
casein. The solid rosin is heated and subjec-ted to mechan-lcal shearing strains until it is broken up into small particles. A small amount of sodium hydroxi.de (1.6 parts to 100 part. of rosin) is then added to the molten rosin to partly saponify it, followed by casein (2.0 parts dispersed 7~
in 0.2 parts oE NaO~I) to stabilize -the dispersed particles of rosin. The dissolved casein is worked into the molten rosin while being powerfully stirred, subsecluellt to which a little more (0.2 parts) of NaOH is added, or the ho-t rosin melt is in~ected into water that contains casein. Finally, water is added to obtain a finished dispersion wi~h approxi-mately 45~ solid particles, which is used in that form. This process is also called the "inversion method of manufactur-ing rosin size" and the resulting size "invert size."
The inversion method is employed in US Patent 2 393 179 to produce a size with free rosin, but wi-th an alkaline dis-persant, a sulfonated higher fatty alcohol for example, used instead of the sodium hydroxide. The rosin is mel-ted, and the desired amount of dispersant added, accompanied by enough stirring to produce a homogeneous molten mass. A
practically neutral or weakly acidic aqueous solution or dispersion of a protective colloid, casein for example, is then added gradually and accompanied by rapid stirring, resulting in a paste-like dispersion with a high solids content, which is then diluted Witil water to a solids content of 40 to 60% by weight.
In the Prosize method of producing a pro-tected size with a high percentage of free rosin the particles of rosin are prevented from growing into large aggregates by the presence of a surface-active protein, soybean protein for example.
The sizes containing free rosin disclosed in German Pa-tent l 131 3~8 were dispersions of unsaponified resin acids with a specific percentage of resin soaps. The dispersions were obtained by the inversion method. They were usually employed with 60 to 95~ free rosin plus auxiliary emulsiEiers and stabilizers such as stearates, trie-thanolamine, casein, and waxes.
The fortified rosins in German Patent 1 131 343 have not untll now been appropriate ~or producing dispersions because they usually had too high a melting point, tended to crys-tallize, or formed fine crusts that led to sedimentation when they dispersed. The patent describes a paper size and a method of manufacturing it in the form of an aqueous disper-sion wi-th a high content of free rosin wherein fortified rosin is mixed at elevated temperatures with fatty acids, mixtures of fatty acids, and/or naphthenic acids and the dispersion is carried out in a known way. The method was employed in the form of an inversion.
German OS 2 426 03~ discloses a method of producing a practically stable aqueous dispersion of a material based on rosin and appropriate for sizing pulp-like fibers in,-the manufacture of paper, whereby an unstable aqueous dispersion that contained at least 5% solids consisting of 0 to 95~
rosin and 100 to 5% of a reaction product of rosin with an acidic compound containing the group~-C=C-C'=O, with the amount of the acidic compound bound in the form of an adduct being about 1 to 20% of the total solids weight, was homog-enized at a pressure of approximately 1~2 to 563 bar and at a temperature of approximately 150 -to 195C in the presence of an anionic dispersan~. The dispersants were materials ~7~ 23251-59 based on saponified rosin, sodium alXylbenæene sulfonate, sodium naphthalene sulEonic acid, sodiusn laury:l su:lEate, or the ammonium salt of the sul~ate ester of an alkylphenoxy(poly-ethyleneoxy)ethanol.
U.S. Patent 4,157,982 describes a practically stable aqueous dispersion consisting essentially of water, of rosin material, and of an alkali-metal alkylbenzene sulfonate to stabilize the rosin material. The dispersions are obtained by passing a previously prepared mixture of the components through a homogenizer.
U.S. Patent 3,906,142 discloses an agent for sizing paper without using aluminum sulfate that contained a stable aqueous dispersion of a rosin fortified by reac-ting with an ~,~-unsaturated carboxylic acid or corresponding anhydride, a protective colloid, casein for example, and a volatile base, ammonia for example, whereby at least 90~ of the fortified rosin was unsaponified. This agent was prepared with the inversion method, with the fortified rosin initially melted in a vessel equipped with a stirring and heating mechanismO A
combination dispersant and stabilizer was then prepared in another vessel by dissolving measured amounts of a protective colloid, casein for example, and oE a volatile base, ammonia for example, in water. The prepared dispersant and stabilizer was then rapidly added to the molten rosin, whereby high-speed stirring or another intensive method of blending was employed during and after the addition. Finally, -the solids content of the resulting aqueous rosin X
~7~70!6 dispersion was adjusted by adding a calculated amount o:E
water.
An invert size for the engine sizing of paper i.s known from German OS 2 654 496. It contained an aqueous dispersion of a fortified rosin with a dispersant that yielded in solution anions of the formulas -~R ~ ( H2CH2O)nso3J (II) and ~R'-o(cH2cH2o)nso3~ (III) wherein R was an n- or branched al]cyl radical with 4 to 18 carbon atoms, R' was an alkyl, alkenyl, or cycloalkyl radical with condensed rinys with lO to 20 carhon atoms, and n was a number such that approximately 27 to 75% of the molecular weight was i.n the C~12CH20 groups. Protective cclloids, casein ~or example were no-t supposed to be necessary to manufacture this known paper size, although the inversion water had to be hot.
German OS 2 845 091 discloses an invert size for the enyine and vat sizing o~ paper that c.ontained dispersants in the aqueous resin dispersion in the form of compounds that yielded in solution or dispersion anions of the formulas ~7 L - (oc~l2c~ OCi-l coo ( ~v and/or R (OC 2CH2)n OCH2COO~ (V) wherein R is an n- or branched alkyl group with 8 or 9 carbon atoms, R1 is an n- or branched alkyl or alkenyl group with 12 to 20 carbon atoms, and n is a number such that approxima-tely 21 -to 76% of the rnolecular weight is in the OcH2cH2 groups-The aforesaid sizing agents were employed at a pH of 4.5 to6 and required relatively large amounts of aluminum sulfate to fix them to the fibers, contamina-ting the effluent. When up to now it was desired to size paper at a pH of ~ to ~, it was necessary to employ synthetic sizing agen-ts, diketone derivatives for example, instead of rosins. Controlled sizing, however, was impossible with these synthetic sizing agents.
Thus the present invention seeks ko provide the engine and vat sizing of paper, containing an aqueous rC dispersion of a fortified, ~r-~i~1~1, hydrogenated, or disprcportiona-ted and optionally esterified rosin or mixture of such rosins along with a dispersant that contains digest-ed casein or an emulsifier of the general formula [ ( 2 2)n ]x (I) wherein R is an alkylphelly]., alkyl, or alkenyl group or a eyeloalkyl group with eondensed rings, A is a group of the formula -CH2COO or -SO3, Mx is a ca-tlon, x is l or 2, and n is a number sueh that approximately 21 to 76% of the molecu-lar w~ight of the anion is in the -OCH2CH2 groups, practical cor sizing paper over a wider pH range of 4 to S, ancl without the drawbaeks of synthetie sizing agents, meaning that the sizing can be controlled.
Additionally, in aeeordanee with the invention in that the dispersant also eontains eati.onic starch.
It has, surprisingly, been eonfirmecl that the 5ize in aeeordance with the invention works satisfactorily over a pll range of 6.0 to 7.5, makes the paper more hydrophobic, and, eompared with other sizes, requires considerably less aluminum sulfate to fix it to the fibers, which accorclingly reduees eontamination of the e~f]uent from -the paper mill.
The effluent will also be less eontamina-ted by this product in that i-t has, as compared with other sizes, a much lower biochemical and chemieal oxygen demand.
The inver-t size in aeeordanee with the invention preferably.
eorltains in the aqueous dispersion 5 to 50% by weight of rosin or a mlxture of rosins and 1 -to 15~ by weight and espeeially 6 to 12 % by weight of dispersant in terms of the rosin or mixture of rosins, with the remainder consisting of water, up to 100% by weight, whereby the ratio of the weight ~2~Y~
of the casein or emulsifier of Formula I to the cationic starch in tlle dispersant ranges from 20:~0 to ~0:20.
The invert size in accorclance with the invention also contains a cationic starch in the dispersant in addition to the known casein or the known emulsifier of Formula I, which comprises known emulsifiers of Formulas II through V. The cationic starch replaces some of the previousl.y employed casein or emulsifier of Formula I, makes the paper more hydrophobic within the neutral range, especially at a pH
range from 6 to 7.5, promotes the action of the protective colloid, and improves the retention of the ,size or mineral fillers to the fibers. Since the cationic starch does not by itself act as a protective colloid, it was surprising to discover that it promotes the protective-colloid action of the casein. An especially preferred ratio for the weight of the casein or emulsifier of Formula I to the cationic starch in the dispersant ranges from 36:65 -to 65:35. Outstanding results for example are obtained at a weight ratio of 50:50, Cationic starches that can be employed in accordance with the invention are in themselves known and commercially available. They can be obtalned :Eor e.xample by cationizing starch, potato starch or corn starch :Eor example, with a known cationizer, glycidyltrimethylammonium chloride, 3-chloro-2-hydroxypropyl-trimethylammonium chloride, or the corresponding triethyl compounds for example. The cationization binds positively charged anion groups to the starch molecule throuqh ether bridges.
Cationic starches are already employed apart from paper size as flocculants and retention agents in papermakin~. This known use of cationic starch is admittedly accompallied by a sliqht improvemen-t in the hydrophobicity of the paper. ~hen, however, the cationic starch ls employed in the dispersant in the invert siæe in accordance with the invention, its hydrophobicity-improving effect on the paper is surprisingly about 100 times as powerful.
The rosin employed in the invert size in accordance with -the invention can be any commercially availahle type of rosin--root rosin, balsamic resin, tall oil, or mixtures of two or more of these rosins in the raw or refined state ror exam-ple. Rosins that tend to crystallize can be treated at elevated temperatures with formaldehyde or paraformaldehyde in the presence of an acid catalyst, toluene-~-sulphonic acid for example, in a way that is known to one of skill in the art. Thus, rosin treated wi-th formaldehyde can be employed and is to be considered a rosin in the sense employed herein.
An adduct-reac-tion product of rosin wlth an acidic compound containing the raclical C=C~~=O that has been obtained by reacting the rosin with -the acidic compound at elevated temperatures, usually 150 to 210 C, is employed as a fortified rosin. Enough of the acidic compound will be employed to obtain a for-tified rosin containing appro~imate-ly 1 to approximately 30% by weight and preferably approxi-mately 5 to approximately 12% by weight of the added acidic compound based on the fortified rosin. Methods of o~
preparing fortified rosins are described in ~S Patents 2 62 918 and 2 68~ 300.
Examples of acidic compounds with a ~=C-C=O radical that can be employed to prepare the fortified rosin are the unsaturated organic acids and their readily available anhydrides, particularly fumaric acid, maleic acid, acrylic acid, acrylamide, maleic anhydride, itaconic acid, itaconic anhydride, citraconic acid, and citraconic anhydride. The preferred adduct-forming acid is fumaric acid. Mixtures of acids can optionally be employed to prepare the fortified rosin. Mixtures of different fortified rosins can also be employed. Thus, for example, a mixture of the acrylic acid adduct to rosin and of the fumaric acid adduct to rosin can be employed to prepare the invert sizes in accordance with the invention. Finally, the esters of the aforesaid rosins with amino alcohols-- triethanolamine, triisopropanolamine, or tributanolamine for instance-- or with glycerine, glycol, or polyglycols, are appropri.ate for preparing the invert size in accordance with the invention. When a polyglycol is employed as an esteriflcati.on agent, polyethyleneglycols with molecular weights of 190 to 1050 are preferably em-ployed.
The rosin can optionally be mixed with known loaders--waxes, especially paraffin and microcrystalline wax, hydro-carbon resins, including those derived from petroleum hydrocarbons and terpenes, spindle oils, or polyglycols for example. This can be done in the mel-t or in solution, with up to approximately 100~ by weight and preferably 30 to o~
50% by weigilt of the loader mixed in based on we1cJht of the rosin. Some of the rosin can also be replacecl with an extender. Tall oil deriva-tives for instance can be employed as an extender, which can be employed in amounts o~ apprGxi-mately 30 to 50% by weight based on the weight of the the rosin.
The invention can also be carried ou-t with mixtures of fortified and unfortified, hydrogenated, or disproportionat-ed rosins and with mixtures of fortified rosin, extenders, and/or loaders and unfortified, hydrogenated, or dispropor-tionated rosins.
Mixtures of fortified, unfortified, hydrogenated or dispro-portionated rosins will contain approximately O to 100~
fortified rosin and approxirnately 100 -to 0~ unfortified, hydrogenated, or disproportiona-ted rosin. Mixtures of fortified rosin, rosin and rosin extenders will contain approximately 25 to ~9% forti~ied rosin and approximately O
to 25% extenders for the fortified rosin.
If a mixture of rosins is ernployed, -the mixture can contain any of the foregoing rosins, fortified or unfortified, and optionally also partly or practically completely esterified, hydrogenated or disproportionated, or even polymerized.
In preparing the invert size in accordance with the in-vention an aqueous solution or dispersion of the dispersan-t is initially prepared. The casein or the emulsifier of Formula I, the cationic starch, and an acidic or basic 3~2~
digesting a~ent such as formic acid, an amlno alcohol such as triethanolamine, potassium hydroxide solution, sodium hydroxide solution, ammonia or borax are mixed with water and heated. It is pre~erable -to -take wa-ter, stir in the digesting agent, and then add ~he casein or ~lormula ~
emulsifier and the cationic s-tarch, subsequent to which the mixture is heated to 80C for example. As previously mentioned herein the Formula T emulsifier can be one of the known emulsifiers of Formulas II through V. The Mx cation in Formula I can for example be an al~ali metal ion such as Na or K , a hydro~en ion, an ammonia ion or a triethanolammonium ion.
The action of the the cationic starch can optionally be augmented by also adding a cationic resin to the dispersant, which can also be considered a protective colloid. One example of an appropriate cationic resin is a urea-formal-dehyde cationized with 3-chloro-2--hydroxypropyl-trirne-thyl-ammonium chloride, 3-chloro-2-hydroxypropyl-tri.ethylammonium chloride, or another ~nown cationizing agent.
The resulting aqueous solution or dispersion of the disper-sant or pro-tective col].oid is then added to the rosin or mixture of rosins, which has previ.ously been melted and saponified by adding smal.l amounts of a saponifier such as sodium hydroxide solution, potassi.um hydroxi.de solu-tion or triethanolamine. The rosin or mix-ture of rosins is pref-erably melted at approximately 160C and cooled subsequent to saponification to approximately 120C before -the disper-sant is added. Once the saponified rosin has been mixed with the protective collo~d, the mix-ture is diluted with water -to the desired level, inducing the inversion.
The invention wlll now be described with reference to the accompanyin~ drawing, which is a plot of ink flota~ion tlme versus content of size for several dif~erent size compositions, in conjunction with the following illustrative examples wherein parts are by weight unless otherwise expressed.
_xample _ A. Preparation of a rosin fortlfied with maleic anhydride A mixture of 91 parts of tall oil and 9 parts of maleic anhydride was stirred and heated to 190C. Once the reaction was complete the batch was cooled to room temperature.
B. Preparation _ the protective colloid solution 1 part of formic acid was stirred into 80 parts of water.
10 parts of casein and 10 parts of a starch cationized with 3-chloro-2-hydroxypropyl-trimethylammonium chloride (Cato Starch) were added. The mix-ture was heated to 80C.
C. Preparation of the inverted size 200 parts of the rosin from ~ were heated to 160C and treated with 6 parts of 25% sodium hydroxide solution. The batch was cooled to 120C, 60 parts of -the protective colloid solution from B were added, and the ba-tch was diluted to the desired percentage with water.
Example 2 A. A rosin fortified with maleic anhydride and fumaric acid was prepared as describcd in Example lA from 100 parts of tall oil, 3.5 parts of maleic anhydride, and 5.8 parts of fumaric acid at 210C.
B. A protective colloid solution was prepared as described ln Example lB from 82.6 parts of water, 1.2 parts of triethanolamine, 8.7 parts of casein, and 8.7 part~ of Cato Starch.
C. An inverted size was prepared as described in Example lC
from 100 parts of the resin from A, 2 parts of stearic acid, 4 parts of triethanolamine, and 60 parts of the protective colloid solution from B and diluted with 199 parts of water.
Employing the resulting size at a ratio of 2% bone-dry based on pulp to size paper at a pH of 7.2 resulted in an ink-flotation time of 1 minute.
Example 3 A. A rosin fortified wi-th maleic anhydride and fumaric acid was prepared as described in Example lA from 120 parts of tall oil, 415 parts of balsamic resin, 23 parts of maleic anhydride, and 35 parts of fumaric acid a-t 210C.
B. A protective colloid solution was prepared as described 7'7~i in Example lB from 81 parts of water, 0.7 parts oE formic acid, 9.5 parts of casein, and 9.5 par-ts oE Calo Starch.
C. An inverted size was prepared as described in Example lC
from 100 parts of the resin Erom A, 2 parts of stearic acid, 4 par-ts of triethanolamine, and 60 parts of the protective-colloid solution from B and diluted wi-th 199 parts of water.
Employing the resulting size a-t a ratio of 2~o bone-dry based on pulp to size paper at a pH of 7. 2 resulted in an ink-flotation time of 3.5 minutes.
Example _ A. A fortified rosin was prepared as described in Example lA from 100 parts of tall oil, 2 . 6 parts of maleic anhydride, and 4.3 parts of fumaric acid at 210C. A mixture of this rosin was stirred and heated -to 200C with 4 par~s of trie-thanolamine. Once the reaction was complete the katch was cooled to room temperature, resulting in a fortified rosin esterified wi-th -triethanolamine.
B. A protective colloid solution was prepared as described in Example lB from 81 parts of water, 0.7 parts of formic acid, 9.5 parts of casein, and 9.5 par-ts of Cato Starch.
77~
C. An inverted size was prepared as described in ExalnE)le I.C
from 100 parts oE the res.in from A, 2 part:s of s-tearic acid, 4 parts of triethanolamine, and 60 parts of the protective-collold solution from B and diluted with 199 par-ts of water.
Employing the resulting size at a ratio of 2~ bone-dry based on pulp to size paper at a pH of 7.2 resulted in an ink-flotation time of 8 minutes.
Example 5 A. A rosin fortified with maleic anhydride, fumaric acid, and acrylamide was prepared as described in Example lA from 100 parts of tall oll, 3.5 parts of maleic anhydride, 5.~
parts of fumaric acid, and 3.3 parts of acrylamide at 210C.
A mixture of this rosin was stirred and heated to 200C with 4 parts of -triethanolamine. Once the reaction was complete the batch was cooled to room temperature, resulting in a fortilied rosin esterified with triethanolamine.
B. A protective colloid solution was prepared as descrihed in Example lB from 81 parts of water, 0.7 par-ts of formic acid, 9.5 parts of casein, and 9.5 parts of Cato Starch.
C. An inverted size was prepared as described in Example lC
)6 from 100 parts of the resin from A, 2 parts of steclric ac:id, 4 parts of triethanolamine, and 60 parts oE the plotective collold solution from B and dilutecl wlth 199 parts of water.
Employing the resulting size at a ratio of 2~ bone-dry based on pulp to size paper at a pH of 7.2 resulted in an nk-flotation time of 13 minutes.
Example 6 . _ A. A fortified rosin was prepared as described in Example lA from 100 parts of tall oil and 9 parts of maleic anhydride and esterified wi-th 5 par-ts of triethanolamine as described in Example 5A.
B. A protective colloid solution was prepared as described in Example lB from 81 parts oE water, 0.7 parts oE formic acid, 9.5 parts of casein, and 9.5 parts of Cato Starch.
C. An inverted size was prepared as described in Example lC
from 100 parts of the resin from A, 2 parts of stearic acid, 4 parts of triethanolamine, and 60 parts of the protective colloid solution from B and diluted with 199 parts of water.
Employing the resulting size at a ratio oE 2~ bone-dry based on pulp to size paper at a pH of 7.2 resulted in an ink-flotation time of 10 rninu-tes.
~77~;
Example 7 A. A rosin was prepared as described in Example ~.
B. A protective colloid solution was preparecl as describe~
in Example lB from 82.6 parts of water, 1.2 parts of triethanolamine, 8.7 parts of casein, and 8.7 parts of Cato Starch.
C. An inverted size was prepared as described in Example lC
~rom 100 parts of the resin from A, 2 parts of stearic acid, 4 parts of triethanolamine, and 60 parts of the protective colloid solution from B and diluted with 199 parts of water.
Employing the resulting size at a ratio of 2~ bone-dry based on pulp to size paper at a pH of 7.2 resulted in an ink-flotation time of 12 minutes.
Exam~le 8 A. A fortifi.ed rosin was prepared as described in Example lA from 500 parts of tall oil, 14 parts of maleic anhydride, and 23 parts of fumaric acid and esteri.fied with 25 parts of triethanolamine as described in Example SA.
B. A protective colloid solution was prepared as described ~2~3770~
in Example lB from 160 parts of wa-ter, 0.66 parts of Cormic acid, 20 parts of casein, and 20 par-ts of Cato Starch.
C. An inverted size was prepared as described in E:cample IC
from 300 parts of the resln Erom A, 6 parts of stearic acicl, 12 parts of triethanolamine, and 180 parts oE the protective colloid solution from B and diluted with 582 parts of water.
Employing the resulting size at a ratio of 2% bone-dry based on pulp to size paper at a pH of 7.2 resulted in an in~-flotation time of 8 minutes.
Example _ A. A rosin was prepared as described in Example 2A.
B. A protective colloid solution was prepared as described in Example lB from 80 parts of water, 0.6 parts of formic acid, 8 parts of casein, and 12 parts o~ Cato Starch.
C. An inverted size was prepared as described in Example lC
from lO0 parts of the resin from A, 2 parts of stearic acid, ~ parts of triethanolamine, and 60 parts of the protective colloid solution from B and dilutecl with 199 parts of water.
77C)~
Employing the resulting size at a ratio of 2% bone-dr~ based on pulp -to si2e paper at a pH oE 7.2 resulted in an ink-flotation time of 4 minutes.
Example 10 A. A rosin was prepared as described in Example 2A.
B. A protective colloid solution was prepared as descri~ed in Example lB from 92 parts of water, 0.5 parts of formic acid, 9 parts of casein, and 9 parts of Cato Starch.
C. An inverted size was prepared as described in Example lC
from 100 parts of the resin from A, 2 parts of stearic acid, 4 parts of triethanolamine, and 60 parts of the protective colloid solution from B and diluted with 200 parts of water.
Employing the result1ng size at a ratio of 2% bone-dry based on pulp to size paper at a pH of 7.2 resulted in an ink-flotation time of 4 minutes.
xample 11 A. A rosin was prepared as described in Example 2A.
~0 ~77~
B. A protective colloid solution was prepared as described in Example lB from 90 parts of water, 0.5 par~s ol forrnic acid, 4 parts o~ triethanolamirle, 4 par-ts of nonylphenolpolyethyleneoxy-carboxylic acid, 4 parts of oleylpolyethylenoxycarboxylic acid, and 12 parts of Cato Starch.
C. An inverted size was prepared as described in Example lC
~rom 100 parts of the resin from A, 2 parts of stearic acid, and 60 parts of the protective colloid solution from B and diluted with 195 parts of water.
Employing the resulting size at a ra-tio of 2% bone-dry based on pulp to size paper at a pH of 6.8 resul-ted in an ink-flo-tation time of 0.42 minutes.
Exam~
A. A rosin was prepared as described in ~xample 2A.
B. A protective colloid solution was prepared as described in Example ls from 90 parts of water, 0.5 parts of formic acid, 4 parts of triethanolamirle, 4 parts of nonylphenolpolyethylenoxycarboxylic acid, 4 parts of oleylpolyethylenox~carboxylic acid, and 12 parts o~ Cato Starch.
7~)6 C. An inverted size was prepared as described ir- Exarnple lC
from 100 parts of the resin from A, 2 parts of stearic acid, and 60 parts of the protective collold solu-tion .Erom B and diluted with 195 parts of water.
Employing the resulting size at a ratio of 2% bone-dry based on pulp to size paper at a pH of 6.8 resulted in an ink-flotation time of 0.5 minutes.
Example 13 A. A rosin was prepared as described ln Example 2A.
B. A protective colloid solution was prepared as descrlbed in Example lB from 82.6 par-ts of water, 0.5 parts of ~5%
KOH, 12 parts of casein, and 6 parts of Cato Starch.
C. An inverted size was prepared as described in Exa,nple lC
from 100 parts of the resin from A, 2 parts of stearic acid, 3.~ parts of 266 KOH, and 60 parts of the protective collGid solution from B and diluted with 195 parts of wa-ter.
Employing the resulting si~e at a ratio of 26 bone-dry based on pul.p to size paper at a pH of 7.2 res~llted in an ink-flotation time of 1.5 rninutes.
3 2~3~71~)~
Example 14 A. ~ rosin foriti~ed with ~umaric acid was prepared b~ stirring and heatin~
to 210C a mixture o~ 91 parts o~ tall oil and 9 parts of fumaric acid and cooling to room temperature upon completion of the reaction.
B. A protective colloid solution was prepared as described in Example lB
from 81 parts of water, 4 parts of triethanolamine, 10 par-ts of casein and 10 parts of Cato S-tarch.
C. An inverted size was prepared as described in Example lC ~rom 200 parts o~ the resin from A, 4 parts triethanolamine and 60 parts of the protective colloid solution ~rom B.
~ A--7~
Exam~ 15 A. A rosin fortified with acrylamicle was prepaLed by stirring and heatincJ to 200C a mixture of 91 parts of tall oil and 9 parts of acrylamide and cooling -to roorn temperature upon completion of tl~e reaction.
B. A protective colloid solution was prepared by stirring 4 parts of triethanolamine followed by 3 parts of a urea-form-aldehyde resin cationized with 3-chloro-2-hydroxypropyl-triethylammonium chloride into 81 parts of water. 10 parts of casein, and 6 parts of Cato Starch were then added and the mixture heated to 80C.
C. An inverted size was prepared as described in Example lC
from 200 parts of the resin from A, 4 parts of triethanol-amine, and 60 parts of the protective colloid solution from B.
Example _ A fortified rosin esterified with glycerine was preparecl by stirring and heatincJ a mi.xture of 91 parts of -the rosin frol-n Example lA or 14 A ancl 9 parts of glycerine to 200C and cooling the batch -to room -temperature once the reac-tion was complete. An inverted size was prepared as described in Example lC from 200 parts each of -the foregoing esteri.fied rosins, 6 parts of 25% ~aOEI or I~OII or 4 parts of 77~
triethanolamine, and 60 par-ts oE the protect.ive col.loid solutlon from either Example lB, Example l~B, or Example 15B.
Example 17 A fortified rosin esterified with glycol was prepared by s~irr.ing and heating a mixture of 91 parts of the rosin from Example lA or 14 A and 9 parts of glycol to 200C and cooling the batch to room temperature once the reaction was complete. An inverted size was prepared as described in Example lC from 200 parts each of the foregoing esterified rosins, 6 parts of 25~ NaOH or KOH or 4 parts of triethanol-amine, and 60 parts of the protective colloid solution from either Example lB, Example 14B, or Example 15B.
Example _ A fortified rosin esterified with polye-thylene glycol was prepared by stirring and hea-ting a mixture of 91 parts of the rosin from Example lA or 1~ A and 9 parts oE pol.yethyl~
ene glycol ~with a mean molecular weight of ~00) to 200C
and cooling the batch to room temperature once -the reaction was complete. An inverted size was prepared as described i.n Example lC from 200 parts each of the foregoing esterified rosins, 6 parts of 25% NaOH or KOH or 4 parts of trie-tharlol amine, and 60 parts of the protective colloid solution from either Example lB, Example 14B, or Example 15B.
~2~77~
Example 19 ( o~a _son) This reference example represents -the prepara-~:ion oE an invert size with a protective-colloid solution that contains only casein and no cationic s-tarch.
A. A rosin was prepared as described in Example 2A.
B. A protec-tive colloid solution was prepared as descriE~ed in Example lB from 158 parts of water, 4.8 parts of 45% KOEI, and 29 parts of casein.
C. An inverted size was prepared as described in Example lC
from 600 parts of the resin from A, 2 parts of s-tearic acid, 18 parts of 26% ~OH, and 180 parts of the protective collolcl solution from B.
Employing the resulting size at a ratio of 2% bone-dry based on pulp to size paper at a pEI of 7.2 resulted in an ink-flotation time of 0.1 minutes.
The drawing is a graph of the ink-flotation -times of sdm21es of pulp sized with the sizes from Examples 2 through 7 and with the comparison size from Example l9 as a function of the percent of size added, based on dry weight.
The chemical (COD) and biochemica] (BOD5) oxygen demands were also determined for the sizes Erom Example 7 and Comparison ExaMple 19. The COD was determinecl in accordance with DIN 38 409, Part 14 and the BOD5 in accordance wi.~h DIM
38 409, Part 51. The ~ollowing results were obtainecl:
Size COD BOD5 Example l9 (comparison~ 745 g/1 474 g/l Example 7 l91 g/1 5~ g/l The size in accordance with Example 7 oE the invention accordingly exhibited considerably lower chemical and biochemical oxygen demands than the size from Reference Example 19.
It will be appreciated that the instan-t specification and claims are set forth by way of illustration and not limitation, and that various modifications and changes may be made without departing frorn the spirit and scope of the present invention.
Claims (17)
1. In an invert size for the engine and tub sizing of paper, comprising an aqueous dispersion of a fortified, hydrogenated or disproportionated and optionally esterified rosin or mixture of such rosins and of a disper-sant that contains digested casein or an emulsifier of the formula [R-(OCH2CH2)n-O-A]? Mx+ (I) wherein R is an alkylphenyl, alkyl, or alkenyl group or a cycloalkyl group with condensed rings, A is a group of the formula -CH2COO or -SO3, Mx+ is a cation, x is 1 or 2, and n is a number such that approximately 21 to 76% of the molecular weight of the anion is in the -OCH2CH2 groups, the improvement which comprises including cationic starch in the dispersion as a dispersant.
2. An invert size according to Claim 1, wherein the dispersion by weight comprises about 5 to 50% of the rosin or mixture of rosins and 1 to 15% of the dispersant based on the rosin or mixture of rosins, wiht the remainder consisting essentially of water, the ratio of the weight of casein or emulsifier of Formula I to the weight of cationic starch in the dispersant ranging from about 20:80 to 80:20.
3. An invert size according to Claim 2, wherein the dispersion contains 6 to 12% by weight of the dispersant based on the rosin or mixture of rosins.
4. An invert size according to Claim 1, wherein the ratio of the weight of casein or emulsifier of Formula I
to the weight of the cationic starch ranges from about 35.65 to 65:35.
to the weight of the cationic starch ranges from about 35.65 to 65:35.
5. An invert size according to Claim 1, wherein the ratio of the weight of casein or emulsifier of Formula I
to the weight of the cationic starch is about 50:50.
to the weight of the cationic starch is about 50:50.
6. An invert size according to Claim 1, wherein the cationic starch is starch cationized with glycidyltrimethyl-ammonium chloride, 3-chloro-2-hydroxypropyltrimethylammonium chloride, or 3-chloro-2-hydroxypropyltriethylammonium chloride.
7. An invert size according to Claim 1, containing rosin in the form of a rosin fortified with at least one of fumaric acid, maleic anhydride and acrylamide.
8. An invert size according to Claim 1, containing rosin in the form of a rosin esterified with an amino alcohol.
9. An invert size according to Claim 1, containing rosin in the form of a rosin esterified with triethanolamine.
10. An invert size according to Claim 1, containing rosin in the form of a rosin esterified with glycerine, glycol or a polyglycol.
11. An invert size according to Claim 1, further containing a cationic resin.
12. An invert size according to Claim 1, wherein the cation Mx+ is chosen from hydrogen, sodium, potassium, ammonium, or triethanolammonium.
13. An invert size according to Claim 12, wherein the cation Mx+ is chosen from sodium, potassium, and triethanolammonium.
14. A method of sizing paper which comprises applying to a dispersion of paper pulp a size according to Claim 1 and a fixing agent, and thereafter forming the pulp into paper.
15. A method according to Claim 14, wherein the size is applied at a pH of from about 4 to about 8.
16. A method according to Claim 15, wherein the size is applied at a pH of from about 6 to about 7.5.
17. Sized paper produced by the process of Claim 14.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP3630268.6 | 1986-09-05 | ||
| DE19863630268 DE3630268A1 (en) | 1986-09-05 | 1986-09-05 | INVERT GLUE FOR MASS SIZING AND SURFACE GLUING OF PAPER |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1287706C true CA1287706C (en) | 1991-08-20 |
Family
ID=6308988
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000546146A Expired - Fee Related CA1287706C (en) | 1986-09-05 | 1987-09-04 | Invert size for the pulp sizing and surface sizing of paper |
Country Status (7)
| Country | Link |
|---|---|
| US (1) | US4983257A (en) |
| EP (1) | EP0259671B1 (en) |
| AT (1) | ATE56993T1 (en) |
| CA (1) | CA1287706C (en) |
| DE (2) | DE3630268A1 (en) |
| ES (1) | ES2017977B3 (en) |
| GR (1) | GR3001023T3 (en) |
Families Citing this family (28)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5192363A (en) * | 1987-05-26 | 1993-03-09 | Eka Nobel Landskrona Ab | Paper sizing compositions |
| JP3072142B2 (en) * | 1991-04-02 | 2000-07-31 | ハリマ化成株式会社 | Sizing composition for papermaking |
| JP3158575B2 (en) * | 1991-10-18 | 2001-04-23 | 日本ピー・エム・シー株式会社 | Rosin emulsion sizing agent for papermaking, sizing paper and sizing method |
| CA2086487C (en) * | 1991-12-31 | 1999-02-16 | Ian A. Pudney | Cationic polyamines useful as drainage aids and stabilizers for rosin-based sizing agents |
| US5830548A (en) | 1992-08-11 | 1998-11-03 | E. Khashoggi Industries, Llc | Articles of manufacture and methods for manufacturing laminate structures including inorganically filled sheets |
| US5631097A (en) | 1992-08-11 | 1997-05-20 | E. Khashoggi Industries | Laminate insulation barriers having a cementitious structural matrix and methods for their manufacture |
| NZ314299A (en) | 1992-08-11 | 1998-08-26 | E | Containers formed from a hydraulically settable mixture including a binder, a rheology-modifying agent, fibres and water |
| US5800647A (en) | 1992-08-11 | 1998-09-01 | E. Khashoggi Industries, Llc | Methods for manufacturing articles from sheets having a highly inorganically filled organic polymer matrix |
| US5453310A (en) | 1992-08-11 | 1995-09-26 | E. Khashoggi Industries | Cementitious materials for use in packaging containers and their methods of manufacture |
| US5641584A (en) | 1992-08-11 | 1997-06-24 | E. Khashoggi Industries | Highly insulative cementitious matrices and methods for their manufacture |
| US5506046A (en) | 1992-08-11 | 1996-04-09 | E. Khashoggi Industries | Articles of manufacture fashioned from sheets having a highly inorganically filled organic polymer matrix |
| US5912306A (en) * | 1992-12-30 | 1999-06-15 | Hercules Incorporated | Cationic compounds useful as drainage aids and stabilizers for rosin-based sizing agents |
| US5292403A (en) * | 1993-03-10 | 1994-03-08 | Betz Paperchem, Inc. | Method for inhibiting the deposition of organic contaminants in pulp and papermaking processes |
| US5556510A (en) * | 1993-03-10 | 1996-09-17 | Betz Laboratories, Inc. | Method for inhibiting the deposition of organic contaminants in polp and papermaking processes |
| US5738921A (en) | 1993-08-10 | 1998-04-14 | E. Khashoggi Industries, Llc | Compositions and methods for manufacturing sealable, liquid-tight containers comprising an inorganically filled matrix |
| DE4412136A1 (en) * | 1994-04-08 | 1995-10-12 | Pts Papiertechnik Beteiligungs | Material for the surface and internal sizing of paper |
| JP3744566B2 (en) * | 1995-04-03 | 2006-02-15 | 荒川化学工業株式会社 | Rosin emulsion sizing agent for papermaking and paper sizing method |
| US6586505B1 (en) * | 1996-02-02 | 2003-07-01 | Eastman Chemical Resins, Inc. | Aqueous resin dispersion |
| GB9610955D0 (en) * | 1996-05-24 | 1996-07-31 | Hercules Inc | Sizing composition |
| GB9721188D0 (en) * | 1997-10-08 | 1997-12-03 | Raisio Chemicals Uk Limited | Rosin emulsion |
| AT406492B (en) * | 1998-01-26 | 2000-05-25 | Krems Chemie Ag | AQUEOUS PAPER SIZING DISPERSIONS AND METHOD FOR THE PRODUCTION THEREOF |
| US6042691A (en) * | 1998-12-08 | 2000-03-28 | Plasmine Technology, Inc. | Cationic dispersions of fortified and modified rosins for use as paper sizing agents |
| FI20011455A (en) * | 2001-07-03 | 2003-01-04 | Metso Paper Inc | Process for making adhesive-coated paper or cardboard |
| FI110443B (en) * | 2001-07-03 | 2003-01-31 | Metso Paper Inc | Method and apparatus for making adhesive-coated paper or cardboard |
| US20050090566A1 (en) * | 2003-10-01 | 2005-04-28 | Nitzman Alan F. | Synthetic resins in casein-stabilized rosin size emulsions |
| US20080190577A1 (en) * | 2007-02-12 | 2008-08-14 | Ehrhardt Susan M | Alkanolamine-stabilized dispersed rosin sizing agents and their preparation |
| ITMI20141842A1 (en) | 2014-10-27 | 2016-04-27 | Gruppo Cordenons Spa | PAPER MATERIAL AND RELATED MANUFACTURING PROCESS |
| ITUA20161829A1 (en) * | 2016-03-18 | 2017-09-18 | Gruppo Cordenons Spa | TISSUE PAPER FOR HYGIENIC AND SANITARY USE AND ITS PROCESS OF PROCESSING |
Family Cites Families (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2393179A (en) * | 1941-12-11 | 1946-01-15 | Hercules Powder Co Ltd | Sizing compositions |
| GB582157A (en) * | 1945-01-05 | 1946-11-08 | Wiggins Teape & Company 1919 L | An improved water dispersible urea-formaldehyde composition and its preparation |
| DE1122200B (en) * | 1960-07-28 | 1962-01-18 | Eisele & Hoffmann K G | Process for the production of particularly stable, finely dispersed resin dispersions with increased sizing power for sizing paper |
| NL268563A (en) * | 1960-08-31 | |||
| US3582464A (en) * | 1967-04-10 | 1971-06-01 | Hercules Inc | Aqueous dispersions of rosin anhydride and their use as sizing agents for paper |
| CA962406A (en) * | 1970-09-08 | 1975-02-11 | Hercules Incorporated | Method of preparing aqueous dispersions of fortified rosin |
| GB1444751A (en) * | 1973-01-22 | 1976-08-04 | Tenneco Chem | Paper sizing |
| AU504229B2 (en) * | 1975-11-17 | 1979-10-04 | A.C. Hatrick Chemicals Pty. Ltd. | Aqueous disperse of fortified rosin |
| DE2845091A1 (en) * | 1978-10-17 | 1980-05-08 | Schultz & Nauth Collodin Kleb | INVERTED PAPER GLUE AND METHOD FOR THE PRODUCTION THEREOF |
| US4263182A (en) * | 1979-09-06 | 1981-04-21 | Hercules Incorporated | Stable dispersions of fortified rosin |
| US4374673A (en) * | 1980-12-31 | 1983-02-22 | Hercules Incorporated | Stable dispersions of fortified rosin |
-
1986
- 1986-09-05 DE DE19863630268 patent/DE3630268A1/en not_active Withdrawn
-
1987
- 1987-08-20 DE DE8787112081T patent/DE3765219D1/en not_active Expired - Fee Related
- 1987-08-20 EP EP87112081A patent/EP0259671B1/en not_active Expired - Lifetime
- 1987-08-20 AT AT87112081T patent/ATE56993T1/en not_active IP Right Cessation
- 1987-08-20 ES ES87112081T patent/ES2017977B3/en not_active Expired - Lifetime
- 1987-09-04 CA CA000546146A patent/CA1287706C/en not_active Expired - Fee Related
-
1989
- 1989-01-09 US US07/294,834 patent/US4983257A/en not_active Expired - Fee Related
-
1990
- 1990-09-27 GR GR90400549T patent/GR3001023T3/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| DE3765219D1 (en) | 1990-10-31 |
| EP0259671B1 (en) | 1990-09-26 |
| EP0259671A1 (en) | 1988-03-16 |
| ATE56993T1 (en) | 1990-10-15 |
| ES2017977B3 (en) | 1991-03-16 |
| GR3001023T3 (en) | 1991-12-30 |
| US4983257A (en) | 1991-01-08 |
| DE3630268A1 (en) | 1988-03-17 |
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