EP0218110B1 - Storage stable paper size composition containing ethoxylated lanolin - Google Patents

Storage stable paper size composition containing ethoxylated lanolin Download PDF

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Publication number
EP0218110B1
EP0218110B1 EP86112384A EP86112384A EP0218110B1 EP 0218110 B1 EP0218110 B1 EP 0218110B1 EP 86112384 A EP86112384 A EP 86112384A EP 86112384 A EP86112384 A EP 86112384A EP 0218110 B1 EP0218110 B1 EP 0218110B1
Authority
EP
European Patent Office
Prior art keywords
paper
weight
sizing
dicarboxylic acid
acid anhydride
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
Application number
EP86112384A
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German (de)
English (en)
French (fr)
Other versions
EP0218110A1 (en
Inventor
Emil D. Mazzarella
Jeffrey Atkinson
Walter Maliczyszyn
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Ingredion Inc
Original Assignee
National Starch and Chemical Corp
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by National Starch and Chemical Corp filed Critical National Starch and Chemical Corp
Priority to AT86112384T priority Critical patent/ATE40165T1/de
Publication of EP0218110A1 publication Critical patent/EP0218110A1/en
Application granted granted Critical
Publication of EP0218110B1 publication Critical patent/EP0218110B1/en
Expired legal-status Critical Current

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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
    • D21H17/03—Non-macromolecular organic compounds
    • D21H17/05—Non-macromolecular organic compounds containing elements other than carbon and hydrogen only
    • D21H17/14—Carboxylic acids; Derivatives thereof
    • D21H17/15—Polycarboxylic acids, e.g. maleic acid
    • D21H17/16—Addition products thereof with hydrocarbons
    • 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
    • D21H17/60—Waxes
    • 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
    • D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
    • D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
    • D21H21/16—Sizing or water-repelling agents

Definitions

  • This invention relates to a paper size comprising a self-emulsifiable mixture of 80 to 99 parts by weight of a cyclic dicarboxylic acid anhydride having hydrophobic substitution and 1 to 20 parts by weight of an alkoxylated compound, an improved method for sizing paper and a paper or paperboard prepared therewith.
  • Paper and paperboard are often sized with various hydrophobic materials including, for example, rosin, wax emulsions, mixtures of rosin waxes, ketene dimers, isocyanate derivatives, fatty acid complexes, fluorocarbons, certain styrene-maleic anhydride copolymers, as well as the substituted cyclic dicarboxylic acid anhydrides more particularly described hereinafter.
  • hydrophobic materials including, for example, rosin, wax emulsions, mixtures of rosin waxes, ketene dimers, isocyanate derivatives, fatty acid complexes, fluorocarbons, certain styrene-maleic anhydride copolymers, as well as the substituted cyclic dicarboxylic acid anhydrides more particularly described hereinafter.
  • These sizes may be introduced during the actual paper making operation wherein the process is known as internal or engine sizing, or they may be applied to the surface of the finished web or sheet in
  • a primary deficiency concerned the necessity of utilizing relatively complex, expensive and heavy equipment capable of exerting high homogenizing shear and/or pressures, together with rigid procedures regarding emulsifying proportions and temperatures, etc., for producing a satisfactory stable emulsion of the particular size. Additionally, the use of many surfactants in conjunction with protective colloids was found to create operational problems in the paper making process such as severe foaming of the stock and/or loss in sizing.
  • a shelf stable paper sizing composition can be provided utilizing alkenyl succinic anhydride (ASA) together with an emulsifier component comprising at least one emulsifier selected from the group consisting of blocked polyoxyalkylenes or sulfur containing anionic surfactants. It is shown that the compositions containing ASA in conjunction with specific blocked polyoxyalkylene compounds provide satisfactory results. According to some examples only unblocked polyoxyalkylene compounds are utilized which provide unsatisfactory emulsifiaction and sizing. Further examples show that sizing compositions can be obtained using the ASA compounds together with unblocked polyoxyalkylene compounds, but only in the presence of further emulsifiers. One example for comparative purposes illustrates that the unblocked compound does not give adequate sizing if the additional sulfur containing surfactant is not employed.
  • ASA alkenyl succinic anhydride
  • a paper size comprising a self-emulsifiable mixture of 80 to 99 parts by weight of a cyclic dicarboxylic acid anhydride having hydrophobic substitution and 1 to 20 parts by weight of an alkoxylated compound, which is characterized in, that the alkoxylated compound is an ethoxylated or propoxylated lanolin containing at least 15 moles ethylene oxide or propylene oxide per mole lanolin.
  • the method for sizing paper products according the invention comprises the steps of
  • the mixture according to the invention is storage stable for extended periods of time, i.e., for at least six months of natural aging, and exhibits excellent sizing properties when emulsified prior to addition to the paper making stock or when added directly to the system and emulsified insitu.
  • the sizing compounds contemplated for use herein are the cyclic dicarboxylic acid anhydrides containing hydrophobic substitution.
  • Those substituted cyclic dicarboxylic acid anhydrides most commonly employed as paper sizes are represented by the following formula: wherein R represents a dimethylene or trimethylene radical and wherein R' is a hydrophobic group containing more than 4 carbon atoms which may be selected from the class consisting of alkyl, alkenyl, aralkyl or aralkenyl groups.
  • Sizing compounds in which R' contains more than twelve carbon atoms are preferred.
  • the substituted cyclic dicarboxylic acid anhydrides may be the substituted succinic and glutaric acid anhydrides of the above described formula including, for example, iso-octadecenyl succinic acid anhydride, n- or iso-hexadecenyl succinic acid anhydride, dodecenyl succinic acid anhydride, dodecyl succinic acid anhydride, decenyl succinic acid anhydride, octenyl succinic acid anhydride, triisobutenyl succinic acid anhydride, etc.
  • the sizing agents may also be those of the above described formula which are prepared employing an internal olefin corresponding to the following general structure: wherein R x is an alkyl radical containing at least four carbon atoms and Ry is an alkyl radical containing at least four carbon atoms and which correspond to the more specific formula: wherein R x is an alkyl radical containing at least 4 carbon atoms and Ry is an alkyl radical containing at least 4 carbon atoms, and R x and Ry are interchangeable.
  • Specific examples of the latter sizing compounds include (1-octyi-2-decenyi)succinic acid anhydride and (1-hexyl-2-octenyl)succinic acid anhydride.
  • the sizing agents may also be prepared employing a vinylidene olefin corresponding to the following general structure wherein R x and Ry are alkyl radicals containing at least 4 carbon atoms in each radical. These compounds correspond to the specific formula: wherein R x is an alkyl radical containing at least 4 carbon atoms and Ry is an alkyl radical containing at least 4 carbon atoms and R x and Ry are interchangeable and are represented by 2-n-hexyl-1-octene, 2-n-octyl-1-dodecene, 2-n-octyl-1-decene, 2-n-dodecyl-1-octene, 2-n-octyl-1-octene, 2-n-octyl-1-non- ene, 2-n-hexyl-decene and 2-n-heptyl-1-octene.
  • the sizing agents may also include those as described above prepared employing an olefin having an alkyl branch on one of the unsaturated carbon atoms or on the carbon atoms contiguous to the unsaturated carbon atoms.
  • Representative of the latter olefins are n-ocetene-1; n-dodecene-1; n-octadecene-9; n-hexene-1; 7,8-dimethyl tetradecene-6; 2,2,4,6,6,8,8-heptamethylnone-4; 2,2,4,6,6,8,8-heptamethylnone-3; 2,4,9,11-tetramethyl-5-ethyldodecene-5; 6,7-dimethyldodecene-6; 5-ethyl-6-me- thylundecene-5; 5,6-diethyldecene-5; 8-methyltridecene-6; 5-ethyldodecene-6;
  • the ethoxylated lanolins used herein includes any containing of at least about 15 moles ethylene oxide per mole lanolin. Preferred are those containing 25 to 80 moles ethylene oxide.
  • the lanolin base may be hydrogenated or non-hydrogenated.
  • the alkoxylation of such lanolins with ethylene oxide is well known in the art and the materials useful herein are not limited by their method of preparation. Ethoxylated lanolins containing up to about 80 moles ethylene oxide are available commercially. It is contemplated that the alkoxylation may also be performed using similar levels of propylene oxide however, these adducts are not as readily available and are more expensive.
  • the size mixture is formed by mixing 80 to 99 parts by weight of the aforementioned substituted cyclic dicarboxylic acid anhydride with 1 to 20 parts, preferably less than 10 parts, of the ethoxylated lanolin.
  • the use of the latter component in excess of about 20 parts becomes uneconomical in terms of cost and may be detrimental in terms of the papermaking operation.
  • the use of the lower levels of the ethoxylated lanolin may require greater degrees of emulsification as with a turbine or the addition of emulsifying agents.
  • the mixture of the appropriate amount of the substituted cyclic dicarboxylic acid and the ethoxylated lanolin may be prepared and held in this form for an extended period of time. Testing results run under accelerated aging conditions indicate, to date, the mixture is still stable and effective as a sizing agent after six months at 50 ° C. When use of the mixture is required, it may be readily emulsified either by preemulsifying with water before addition to the paper stock or it may be emulsified in situ at any point in the manufacturing operation where adequate agitation is present.
  • preemulsification of the size mixture it may be readily accomplished by adding the sizing components to water in sufficient quantity so as to yield an emulsion containing the substituted cyclic dicarboxylic acid anhydride in a concentration of from about 0.1 to 20% by weight.
  • the aqueous mixture is thereafter sufficiently emulsified merely by stirring with moderate speed agitation or by passing it through a mixing valve, aspirator or orifice so that the average particle size of the resultant emulsion will be less than about 3 ⁇ m.
  • a mixing valve, aspirator or orifice so that the average particle size of the resultant emulsion will be less than about 3 ⁇ m.
  • Emulsification of the mixture readily occurs at ambient temperatures. Thus, the emulsification will occur directly in cold water and heating of the water prior to addition of the sizing mixture is unnecessary.
  • the thus-prepared emulsion is simply added to the wet end of the paper making machine or to the stock preparation system so as to provide a concentration of the substituted cyclic dicarboxylic acid anhydride of from about 0.01 to about 2.0% based on dry fiber weight.
  • concentration of the substituted cyclic dicarboxylic acid anhydride of from about 0.01 to about 2.0% based on dry fiber weight.
  • the precise amount of size which is to be used will depend for the most part upon the type of pulp which is being treated, the specific operating conditions, as well as the particular end use for which the paper product is destined. For example, paper which will require good water resistance or ink holdout will necessitate the use of a higher concentration of size than paper which will be used in applications where these properties are not critical.
  • the size emulsion may be sprayed onto the surface of the formed web at any point prior to the drying step in the concentrations as prepared so as to provide the required size concentration.
  • the ingredients of the size mixture may also be premixed without water and added to the paper making stock system causing the substituted cyclic dicarboxylic acid anhydride to emulsify in situ in the stock preparation system without the need for prior emulsification in water.
  • the amount of size employed will vary depending on conditions, however, it will generally be within the range of about 0.01 to 2.0% substituted cyclic dicarboxylic acid anhydride based on dry fiber weight.
  • the size mixtures are used in conjunction with a material which is either cationic or is capable of ionizing or dissociating in such a manner as to produce one or more cations or other positively charged moieties.
  • materials which may be employed as cationic agents are long chain fatty amines, amine-containing synthetic polymers (primary, secondary, tertiary or quaternary amine), substituted polyacrylamide, animal glue, cationic thermosetting resins and polyamide-epichlorohydrin polymers.
  • cationic starch derivatives including primary, secondary, tertiary or quarternary amine starch derivatives and other cationic nitrogen substituted starch derivatives as well as cationic sulfonium and phosphonium starch derivatives.
  • Such derivatives may be prepared from all types of starches including corn, tapioca, potato, waxy maize, wheat and rice. Moreover, they may be in their original granule form or they may be converted to pre- gelatinized, cold water soluble products. Amphoteric natural and synthetic polymers containing both anionic and cationic groups may also be used effectively to deposit and retain the sizing agent on the fiber.
  • any of the above noted cationic retention agents may be added to the stock, i.e. the pulp slurry, either prior to, along with or after the addition of the size mixture or size emulsion in conventional amounts of at least about 0.01%, preferably 0.025 to 3.0%, based on dry fiber weight. While amounts in excess of about 3% may be used, the benefits of using increased amounts of retention aid for sizing purposes are usually not economically justified.
  • the size mixtures are not limited to any particular pH range and may be used in the treatment of neutral and alkaline pulp, as well as acidic pulp.
  • the size mixtures may thus be used in combination with alum, which is very commonly used in making paper, as well as other acid materials. Conversely, they may also be used with calcium carbonate or other alkaline materials in the stock.
  • the web is formed and dried on the paper making machine in the usual manner.
  • full sizing is generally achieved immediately off the paper machine.
  • further improvements in the water resistance of the paper prepared with the size mixtures of this invention may be obtained by curing the resulting webs, sheets, or molded products.
  • This post-curing process generally involves heating the paper at temperatures in the range of from 80 ° to 150 ° C for a period of from 1 to 60 minutes.
  • the size mixtures of the present invention may be successfully utilized for the sizing of paper and paperboard prepared from all types of both cellulosic and combinations of cellulosic with non-cellulosic fiber. Also included are sheet-like masses and molded products prepared from combinations of cellulosic and non-cellulosic materials derived from synthetics such as polyamide, polyester and polyacrylic resin fibers as well as from mineral fibers such as asbestos and glass.
  • the hardwood or softwood cellulosic fibers which may be used include bleached and unbleached sulfate (Kraft) bleached and unbleached sulfite, bleached and unbleached soda, neutral sulfite semi-chemical, groundwood, chemi-groundwood, and any combination of these fibers.
  • synthetic cellulosic fibers of the viscose rayon or regenerated cellulose type can also be used, as well as recycled waste papers from various sources.
  • pigments and fillers may be added in the usual manner to the paper product which is to be sized.
  • Such materials include clay, talc, titanium dioxide, calcium carbonate, calcium sulfate and diatomaceous earths.
  • Stock additives such as defoamers, pitch dispersants, slimicides, etc. as well as other sizing compounds, can also be used with the size mixtures described herein.
  • the size mixtures described herein exhibit extended shelf life, and, when emulsified and used in the paper stock system, yield paper products having superior sizing properties, even after these extended storage periods.
  • This example illustrates the use of a size mixture representative of the size mixtures of this invention utilized in the form of an aqueous emulsion.
  • This emulsion is compared, in terms of particle size and water resistance of the resulting sized paper, with a conventional emulsion made with a mixture of 2 parts of the mixture with 98 parts of a cooked aqueous dispersion of cationic corn starch (containing sufficient starch to provide 0.05% based on dry fiber weight) using a propeller-type agitator at moderate speed (500 rpm) for 10 seconds (Emulsion No. 1).
  • a control was prepared in accordance with U.S.
  • Reissue Patent 29 960 using 93 parts of the same ASA and 7 parts of polyoxyalkylene alkyl-aryl ether wherein the alkyl group contained 9 carbon atoms, the aryl radical was phenol, and the polyoxyalkylene moiety was formed with 9.5 moles of ethylene oxide.
  • the Hercules Size Performance Test was employed to compare the ink resistance of the sheets prepared.
  • the test comprises applying an amount of acid ink (pH 2.3) to the upper paper surface.
  • pH 2.3 an amount of acid ink
  • the underside of the paper is monitored for reflectance.
  • the time it takes for the ink to cause a decrease in reflectance from 100% to 80% is the paper's HST time.
  • the HST of the paper is a measure of the sizing performance of a given size. The longer the HST time, the better the size is.
  • the average particle size (APS) was measured by optical microscopic observation using a calibrated graduated eye piece under 400-600x magnification.
  • Table I presents the average particle size (APS in w m) and internal sizing data (HST in seconds) for the above-described emulsions.
  • This example shows a comparison of direct (unemulsified) addition and preemulsified addition to the stock with both freshly made and three month (accelerated) aged sizing mixtures.
  • the preemulsified product was prepared using the procedure of Emulsion 1 in Example I. With direct addition of the ASA/hydrogenated ethoxylated lanolin mixtures the emulsification occurs in situ due to the shear inherent to the system. In this case, the mixture of Example I was added directly to a slurry of bleached sulfate pulp at 1.5% consistency in a laboratory beater (supplied by Allis Thalmers) and beaten very lightly for a few minutes.
  • Example II The pulp was then diluted to 0.5% consistency, and 0.4% on dry fiber weight of the cationic starch described in Example I was added separately to the slurry to act as a retention aid during sheet formation. Sheets were then formed, conditioned and tested in the HST test as described in Example I.
  • Example II the mixture of hydrogenated ethoxylated lanolin, prepared as in Example I, was compared to four other classes of emulsifiers described in U.S. Reissue Pat. 29 960. Even though these emulsifiers showed improved stability over the polyoxyalkylene alkyl aryl ether emulsifiers, used as a control in Example I, the degree of stability does not approach the level of that achieved by use of ethoxylated lanolin as described herein.
  • the level of ethoxylated lanolin varied from 1-20%, as shown in the table to ascertain the effect of high levels in the sizing mixture.
  • the mixtures and emulsions were prepared in accordance with Example I but varying the relative amounts of ethoxylated lanolin and ASA.
  • the invention is seen to provide the practitioner with a size mixture useful in the manufacture of sized paper products.
  • the size mixture is shelf stable over an extended period of time, and is easily emulsified when desired for use under a wide variety of paper making conditions to provide superior sized paper products.

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  • Paper (AREA)
  • Cosmetics (AREA)
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  • Electrical Control Of Ignition Timing (AREA)
  • Adhesives Or Adhesive Processes (AREA)
EP86112384A 1985-10-03 1986-09-08 Storage stable paper size composition containing ethoxylated lanolin Expired EP0218110B1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT86112384T ATE40165T1 (de) 1985-10-03 1986-09-08 Ethoxyliertes lanolin enthaltende lagerungsstabile papierleimzusammensetzung.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US78390485A 1985-10-03 1985-10-03
US783904 1985-10-03

Publications (2)

Publication Number Publication Date
EP0218110A1 EP0218110A1 (en) 1987-04-15
EP0218110B1 true EP0218110B1 (en) 1989-01-18

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ID=25130771

Family Applications (1)

Application Number Title Priority Date Filing Date
EP86112384A Expired EP0218110B1 (en) 1985-10-03 1986-09-08 Storage stable paper size composition containing ethoxylated lanolin

Country Status (7)

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EP (1) EP0218110B1 (enrdf_load_stackoverflow)
JP (1) JPS6285099A (enrdf_load_stackoverflow)
AT (1) ATE40165T1 (enrdf_load_stackoverflow)
AU (1) AU570856B2 (enrdf_load_stackoverflow)
CA (1) CA1276057C (enrdf_load_stackoverflow)
DE (1) DE3661851D1 (enrdf_load_stackoverflow)
FI (1) FI864026A7 (enrdf_load_stackoverflow)

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL129371C (enrdf_load_stackoverflow) 1961-09-08
US3968005A (en) 1973-10-09 1976-07-06 National Starch And Chemical Corporation Paper sizing process using a reaction product of maleic anhydride with a vinylidene olefin
US3821069A (en) 1973-01-02 1974-06-28 Nat Starch Chem Corp Process of sizing paper with a reaction product of maleic anhydride and an internal olefin
USRE29960E (en) 1976-05-05 1979-04-10 National Starch And Chemical Corp. Method of sizing paper
US4529447A (en) * 1982-06-11 1985-07-16 Sanyo Chemical Industries, Ltd. Sizing composition
JPS59144697A (ja) 1983-02-07 1984-08-18 日本石油化学株式会社 紙サイズ剤
JPH07923A (ja) 1993-06-14 1995-01-06 Katsunori Horikoshi 洗浄装置

Also Published As

Publication number Publication date
FI864026A0 (fi) 1986-10-03
ATE40165T1 (de) 1989-02-15
FI864026L (fi) 1987-04-04
CA1276057C (en) 1990-11-13
FI864026A7 (fi) 1987-04-04
AU570856B2 (en) 1988-03-24
JPS6285099A (ja) 1987-04-18
DE3661851D1 (en) 1989-02-23
AU6302286A (en) 1987-04-09
EP0218110A1 (en) 1987-04-15
JPH0577796B2 (enrdf_load_stackoverflow) 1993-10-27

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