EP0014520B1 - Verfahren zur Leimung von Papier - Google Patents

Verfahren zur Leimung von Papier Download PDF

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Publication number
EP0014520B1
EP0014520B1 EP80300078A EP80300078A EP0014520B1 EP 0014520 B1 EP0014520 B1 EP 0014520B1 EP 80300078 A EP80300078 A EP 80300078A EP 80300078 A EP80300078 A EP 80300078A EP 0014520 B1 EP0014520 B1 EP 0014520B1
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EP
European Patent Office
Prior art keywords
starch
ester
paper
web
sizing
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Expired
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EP80300078A
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English (en)
French (fr)
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EP0014520A1 (de
Inventor
Roland William Best
Robert Jeseph Sherwin
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Primary Products Ingredients Americas LLC
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Tate and Lyle Ingredients Americas LLC
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Publication of EP0014520A1 publication Critical patent/EP0014520A1/de
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    • 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
    • D21H17/24—Polysaccharides
    • D21H17/28—Starch

Definitions

  • This invention relates to a method of sizing paper.
  • rosin a natural product from pine trees
  • Conventional high-grade, water-resistant papers are made by adding rosin (a natural product from pine trees) at the wet-end of the papermaking process.
  • the rosin is barely water-dispersible, and in the presence of alum, it precipitates in the fibre web as the paper sheet is being formed.
  • Variations in the composition of the paper-making furnish can have an adverse effect on the amount of rosin which precipitates on the papermaking wire.
  • the usual commercial practice to compensate for such variations is to add an excess amount of rosin to the furnish to ensure sufficient pickup to make a paper having the desired level of water-resistance.
  • United States Patent 3,279,975 describes a method of surface sizing using the reaction product of an unsaturated acid and petroleum resin.
  • Various other materials are disclosed in the literature for use as sizing agents for the surface treatment of paper. Such materials include emulsions of the reaction product of an unsaturated dibasic acid or anhydride of the acid with, for example, a maleated petroleum resin, alkyl ketene dimers, alkali-soluble styrene copolymers, chromium complexes of fluorocarbon chemicals, and others.
  • Such materials have not attained widespread use because of costs, or control problems, such as the "gum up" phenomena, or drying problems.
  • United States Patents, 2,613,206; 2,461,139 and 3,091,567 disclose certain hydrophobic starch acid-esters and various uses for these starch derivatives.
  • a method of making these starch acid-esters and their combination with multivalent metal ions such as aluminium is disclosed in United States Patent 2,613,206, and the hydrophobic character of the starch is set forth.
  • the industrial uses suggested for the resulting starch derivative do not include paper sizing.
  • the mentioned uses include: anti-offset spray for preventing ink transfer between freshly printed sheets: insecticide carriers, delustering agent in the manufacture of cellulose acetate rayons, delustering agent in lacquer- type paints and coatings; rubber finishing agent; and textile sizing and finishing agent.
  • United States Patent 2,461,139 describes a method of making starch ester derivatives by reacting starch, in the presence of moisture, with organic acid anhydrides to obtain an inhibited starch having a reduced tendency to gel.
  • the patent states that an alkaline reaction medium (pH 7-11) is essential to the practice of the inventive method.
  • "An amazing increase in water absorptive powers" is shown by starch treated with succinic anhydride. Papermaking is mentioned (Column 3, lines 31-34), but the starch derivative is only described as a replacement for tuber starches in papermaking for its non- gelling nature and its superior cohesiveness.
  • the application under consideration was that of a binder in the wet-end, or furhish, of the paper machine.
  • Examples 4 and 5 of the subject patent describe making a so-called "thin-boiling" starch, but only with maleic and acetic anhydride.
  • Example 6 describes thinning a starch maleate ester to obtain a thin-boiling starch.
  • Both Example 8 and 9 describe reacting starch with succinic anhydride, and the general disclosure states that the starch derivatives of any of the examples may be further converted, as by acid hydrolysis, for example. There is no mention of sizing paper, however, and the starch derivative obtained using succinic anhydride is described as a "high water absorptive starch" (column 12, lines 2 and 3 of U.S. Patent 2,461,139).
  • United States Patent 3,091,567 is directed to a starch acid-ester encapsulating agent having controlled water repellency obtained by reacting the starch acid-ester with a compound containing a polyvalent metallic ion.
  • the starch acid-ester may be obtained from the reaction of starch with octenyl succinic acid anhydride.
  • General language in this patent suggests that the starch used to make the described starch acid-ester "may have been previously modified ... by hydrolysis, oxidation ## etc. (Column 3, lines 22-24).
  • This patent discloses only one use of the starch derivative. It is used to encapsulate water-insoluble substances to permit slow, gradual release of the encapsulated material. There is no mention of possible use in a papermaking process.
  • Example 2 of the subject French Specification is 1-octenylsuccinic anhydride as an esterification agent for making Starch "C”. The method of Example 1 was followed to make Starch "C", and the level of substitution was reported to be 0.027 d.s.
  • a starch derivative like the above Starch “C” was used to size a paper web made from bleached kraft pulp containing about 1% alum, based on the pulp dry weight.
  • the dispersed sizing composition contained 5% of a hydrophobic starch (like Starch “C", but with a d.s. of 0.032) and 95% of a non- hydrophobic cationic starch (having about 0.24% by wt. nitrogen content).
  • the dispersion had a solids level of about 4-5%.
  • Sixty pounds of the size dispersion per ton of paper was applied. Rosin was also used in the sample runs (at 12 and 6 kg/metric tonne respectively).
  • the above derivatized starch sizing agent and sizing method differs from the subject sizing composition and method in at least the following important ways:
  • the present invention provides a method of externally sizing a cellulosic web, which contains a multivalent metal ion but not more than 2 kg/tonne rosin, to impart increased water resistance to the web which comprises applying to the web at a temperature of 50°C to 80°C a starch containing aqueous sizing composition having a pH of 4 to 7.5 and a Brookfield viscosity in the range of 10 to 1 50 cps (No.
  • the starch ester obtained by reacting starch with a dicarboxylic acid anhydride having 8 to 22 carbon atoms which an aliphatic, aromatic, alicyclic, or bicyclic aliphatic dicarboxylic acid anhydride, the starch ester having a degree of substitution of the dicarboxylic acid anhydride in the range from 0.005 to 0.023.
  • the starch ester is obtained by reacting starch with 1-octenyl succinic acid anhydride.
  • the starch ester may be a 1-octenylsuccinic acid half ester of cornstarch, the degree of substitution of which is in the range of 0.008 to 0.016, e.g. a 1-octenylsuccinic acid half ester of cornstarch which is slightly oxidized so that the amount of protein remaining in said half ester is less than 0.1 % by weight based on the weight of the starch.
  • the multivalent metal ion which may be aluminium, calcium, magnesium, manganese or barium is in the form of a slightly water-soluble salt, and is added to the aqueous furnish from which the cellulosic web is formed.
  • the multivalent metal ion is aluminium and is obtained from aluminium chloride, aluminium sulphate or sodium aluminate.
  • the multivalent metal salt may be aluminium sulphate which is present in the cellulosic web in an amount of at least 5 kg aluminium sulphate per tonne of fibre in the cellulosic web, or sodium aluminate which is present in the cellulosic web in an amount of at least 1.5 kg per tonne of fibre in the cellulosic web.
  • the reduced viscosity of the starch ester is obtained by acid hydrolysis of the starch ester or by thermal chemical treatment of the starch ester.
  • the substituted starch may have been slightly oxidized, and the reduced viscosity obtained by high temperature thermal treatment, e.g. at 107 to 163°C.
  • the paper web is free of rosin.
  • the invention relates to a method of making a water resistant paper by sizing the paper web at the size press with an aqueous solution of a viscosity thinned, hydrophobic starch derivative.
  • the preferred starch derivative is the starch acid-ester of octenyl succinic anhydride.
  • Alum present in the web from the wet-end of the papermaking process reacts with the starch derivative to produce a water-resistant sheet.
  • this starch derivative is applied from a solution at the size press of the papermaking machine, it apparently combined with the alum in a unique way to produce a high level of water resistance concentrated at the surface of the paper.
  • the multivalent metal ion (aluminium) is supplied from the sheet passing through the size press from the wet-end (furnish) of the papermaking machine, or if the wet-end composition does not contain alum, aluminium sulphate may be added to the furnish at the wet-end of the papermaking machine so that it is present in the web at the size press where the thin viscosity octenyl succinate starch acid-ester is applied.
  • the starch acid-ester used in the method of the invention may be made as follows:
  • the acid is allowed to convert the starch at 53°C for approximately five hours to reach a target alkali fluidity value of 56 ml, using a 10 g sample of starch in 90 ml of 0.375N NaOH for determining alkali fluidity value.
  • the pH of the thinned starch slurry is adjusted to 4.5-5.0 with 18° B6 soda ash (sodium carbonate). About 2.8 parts soda ash is required.
  • the slurry is then screened, filtered, and the filter cake washed.
  • the washed filter cake is then reslurried in water to 21-22° Be (at 16°C) and the temperature is adjusted to 32-35°C.
  • the slurry is then agitated vigorously throughout the remaining steps of the process.
  • the slurry is then adjusted to 6.0-6.5 pH with 30° Bé sulphuric acid (about 0.5 parts of 60° Be H 2 SO 4 required).
  • the reacted starch is then screened and filtered.
  • the filter cake is thoroughly washed with water at 43°C maximum.
  • the washed starch derivative is then dried and screened.
  • the moisture content of the dried product should be in the range of 10-13%, and at least 1% by weight, dry solids basis, of 1-octenyl succinic anhydride should have been reacted with the starch.
  • the above starch derivative is then ready to use in the method of the invention and its various embodiments described herein.
  • the starch derivative made according to the above Example 1 has been successfully used as a water resistant size press starch to impart a high degree of water resistance to paper when applied to a paper sheet during the papermaking process.
  • the sheet should contain sufficient alum (sodium aluminate) from the wet-end of the Fourdrinier-type papermaking machine.
  • the addition of this starch derivative at the size press also develops the internal strength properties as efficiently as any conventional size press starches.
  • a trial was conducted at a paper mill which normally includes alum (sodium aluminate) in the wet-end of the papermaking machine. This mill also normally used a fortified rosin in the wet-end and another starch (enzyme converted) at the size press to obtain borderline sizing.
  • Various trial runs were made as described below. The tests indicated that a significant improvement in water resistance can be obtained through application of the subject starch derivative at the size press of a paper-making machine.
  • Table I shows that definite and effective sizing was obtained using the subject starch derivative, applied at the size press. Only borderline sizing was obtained when an enzyme converted pearl starch was used at the size press in combination with a fortified rosin in the wet-end. However, Table I shows that the subject starch derivative not only gave excellent water-resistance size effect to the paper, but the internal fortified rosin size was also reduced by 25%. In addition, the subject starch derivative had no adverse effect on other physical properties of the sheet, such as mullen, tear, wax, pick, opacity and brightness.
  • the pH of the size press dispersion was maintained at about 6 during the tests.
  • the level of alum in the newly formed sheet was about 7.5 to 10 kg per metric tonne expressed as alum.
  • the amount of alum in the sheet was determined by the method set forth below following Example 3.
  • Table II below is a report of the second series of tests conducted at the same paper mill as Example 2 on the same commercial papermaking machine.
  • the subject starch derivative was again applied at the size press in the various combinations described in Table II:
  • the percent starch solids at the size press was about 7.5%, the particular starches comprising the total starch solids were changed as noted from a 50/50 blend of the starch of Example 1 and an enzyme-converted pearl starch to 100% enzyme converted pearl starch and then back to a 50/50 blend of the above starch derivatives.
  • the effect on the H.S.T. #2 INK test results caused by removing the starch derivative of the subject invention from the size press starch blend was dramatic and clear. Excellent water resistance (149 sec) was obtained when a 50/50 blend was used which included the starch derivative of the subject invention.
  • the H.S.T. #2 INK test fell in value by a factor greater than two to a value less than one-half the initial value (61 sec).
  • the level of octenyl succinate groups on the paper web in the range of substitution described is what determines the level of water resistance in the resulting paper, not the amount of starch used, although the starch per se does contribute internal strength to the paper web.
  • a starch derivative having a d.s. of 0.016 can be used in a smaller quantity to obtain the same level of water resistance obtainable from a larger quantity of a starch derivative having a lower level of octenyl succinate groups therein.
  • the substitution level of octenyl succinate groups is 0.016 or lower, it appears to be unnecessary to add any other starch, because enough of the subject starch is then present to provide both water resistance and internal strength to the paper.
  • the lower d.s. levels therefore, greatly simplify the preparation of the sizing composition, since only one starch derivative is needed.
  • Table III below shows the relationship between the percent pick-up of octenyl succinate starch and the effect on sizing that the percent pick-up has.
  • Table III above clearly shows a dramatic increase of water resistance when the amount of pickup of the subject starch derivative is increased. Tripling of the pick-up of the subject starch derivative causes a substantial increase in water resistance of the sheet, as evidenced by the Hercules Sizing Test results (122 seconds). The above sizing effect was obtained without the use of any rosin in the wet-end, but in some applications, it may be desirable to include a small amount (1-1.5 kg rosin/tonne of paper furnish) in the wet-end to aid in controlling size press pick-up.
  • alum aluminium sulphate
  • sodium aluminate be added at the wet-end, so that there is actually a minimum amount of aluminium ion in the paper web as it enters the size press.
  • alum/tonne of fibre in the paper web is the minimum required to obtain effective water-resistant sizing in the finished paper sheet.
  • the subject starch derivative is cooked prior to application to the sheet, either by batch methods, or by a continuous cooking methods, such as jet cooking.
  • the subject starch derivative can be combined with a conventional size press starch (e.g. pearl cornstarch) to increase the strength of the sheet.
  • the application temperature should not fall below 51 °C, and is preferably in the range of 76-82°C.
  • a pH in the wet-end of about 4-6 has been found to be desirable.
  • the subject starch derivative is most useful when added at the size press to develop a high degree of water resistance in a paper web which contains alum, sodium aluminate, or other multivalent metal ion introduced at the wet-end of the papermaking machine.
  • the starch derivative also develops internal strength equivalent to the most efficient of the conventional size press starches. It is also contemplated that the subject starch derivative can be applied to a cellulosic sheet from a kalender stack to efficiently obtain a higher level of water resistance in such sheets.
  • the Brookfield viscosity characteristics of this starch are described below. As the concentration increases from a 2% dsb starch to 12% dsb starch, the Brookfield viscosity increases. For example, at 52°C, the Brookfield viscosity of a 2% dsb aqueous starch sample was about 13 cps. When the concentration was increased to 8%, the Brookfield viscosity was about 45 cps., at 10% concentration, the Brookfield viscosity was about 69 cps and at 12% starch concentration, the Brookfield viscosity was about 97 cps. As the temperature is increased, the viscosity increases with increased solids levels are not as large as they are at lower temperatures. For direct comparison of the temperature effect see the table below: The above Brookfield viscosities are obtained using a #1 spindle at 100 rpm.
  • the above viscosity/solids/temperature characteristics are typical of size press starches. It is considered desirable that the subject starch have such viscosity characteristics for convenience of application, particularly when it is applied from the size press in combination with other conventional starches.
  • the subject starch derivative is not effective when subjected to viscosity thinning by means of enzyme conversion. It is possible that the enzyme separates the octenyl groups from the starch ester, so that the hydrophobic properties are lost.
  • starch ester derivatives are also believed to be useful in the method of sizing paper at the size press to obtain high levels of water resistance.
  • additional starch derivatives may be made from substituted cyclic dicarboxylic acid anhydrides and mixed anhydrides which attach to the starch molecule through the ester group, have hydrophobic properties, and are capable of reacting with the multivalent metal ion (aluminium ion) in the paper web as it passes through the size press. It is contemplated that hydrocarbon chain extensions obtainable from CB-Cz4 cyclic dicarboxylic anhydrides are useful for this purpose with the necessary adjustments in concentration of the respective starch derivatives in the size press dispersion. For extremely hydrophobic starch derivatives, less will be required to obtain water resistance, and in those instances a more conventional size press starch is used to obtain internal strength in the paper sheet.
  • cornstarch is slurried in water in about 22.5 Be at 16°C.
  • the slurry temperature is then raised to about 32-35°C, and the pH is adjusted to about 6.5-7.0 with 5% (7.0-7.4° Bé) sodium hydroxide solution.
  • about 2% by weight based on the starch weight of 1- octenylsuccinic anhydride is added to the slurry with agitation (as rapidly as possible).
  • 5% (7.0-7.4° Be) sodium hydroxide is begun, and the pH of the slurry is adjusted to 6.5-7.5.
  • the addition of sodium hydroxide is continued with agitation for about 2f hours with constant agitation while the pH of the slurry is maintained at about 6.5-7.5 with 5% sodium hydroxide.
  • the reaction is continued until the pH remains constant.
  • the degree of substitution at completion of the reaction should be in the range of 0.008 to 0,016.
  • the pH of the derivatized starch slurry is then adjusted to 5.5--6.0 and temperature is adjusted to 43°C.
  • the resulting product is then screened, filtered, washed and dried.
  • the resulting product should have the following characteristics:
  • the above starch derivative is not thinned, but should be, prior to use. It can be thinned at the paper mill at the time of use by thermal-chemical cooking as described in Example 6 below.
  • One hundred parts of cornstarch is slurried in water to a solids level of about 22.5° Be at 16°C.
  • the slurry pH is adjusted to about 7.5 with anhydrous sodium carbonate, and the slurry temperature is adjusted to 49-52°C.
  • the slurry is then subjected to alkaline bleaching for about two hours using about 1.7% by weight of NaOCI, or about 0.5% by weight chlorine (based on the weight of the starch).
  • the alkali fluidity of the bleached starch should be at least 65 ml using a 2.5 g sample, 0.375N and the test procedure described following the examples.
  • the bleaching step is terminated by adding 0.13% by weight, based on the total starch weight, of sodium bisulphite.
  • the slurry temperature is adjusted to about 32-35°C and the pH is maintained in the range of 6.5-7.0. Then about 2% by weight 1-octenylsuccinic anhydride is added while the slurry is vigorously agitated. Then sodium hydroxide is immediately added to adjust the pH to 6.5, and thereafter maintain the pH in the range of 6.5-7.5, and the esterification reaction is continued for about 2t hours to the end point, during which the pH is adjusted with NaOH as needed to maintain the pH in the range of 6.5-7.0.
  • the amount of 1-octenyl succinic anhydride is limited to a total of 3% based on the dry substance weight of the starch.
  • the slurry temperature is then adjusted to 43°C, followed by screening, filtering and drying.
  • the dry product should have the following properties:
  • the starch half ester of Example 5 is also thinned prior to use, as described in Example 4, by thermal-chemical cooking, jet cooking, high temperature pressure cooking, acid hydrolysis, or by any conventional method, except enzyme thinning, to produce a thinned viscosity starch having a Brookfield viscosity in the range of 10-150 cps (2-15% solids level; 66°C; No. 1 spindle at 100 rpm).
  • the starch derivative has been bleached, as in Example 5, then chemical conversion at the mill is unnecessary.
  • the bleached product produces better colour in the coated paper, also.
  • the viscosity of the starch composition is adjusted to effect the most desirable pick-up of materials from the size press. There are viscosity differences dictated by particular paper machine apparatus, and also by the particular grade of paper being manufactured. For certain hard-to-size papers, it is believed that it would be desirable to increase the substitution level above the normal upper limit of 0.023, up to about 0.039.
  • Such a starch derivative is then thinned, and can be used alone at the size press without a second, or supplementary, starch sizing agent.
  • the pH range at the wet end may be up to 6, and, at the size press, the pH may range from 4 to 7.5.
  • the subject starch derivatives can be used without any rosin present in the wet end. However, it may be desirable to use about 1-1.5 kg of rosin/tonne of paper in the wet end furnish of the paper making machine to help control size press pick-up and to improve runability of the paper making process.
  • alum aluminium sulphate
  • Sodium aluminate for example can be used to provide multivalent aluminium ion in the paper web as it enters the size press.
  • CaCl z' MgCl z , MnCI 2. , or BaCl z could be used in the wet end furnish to provide a multivalent metal ion in the web of the paper entering the size press.
  • 5 kg alum/tonne of fibre in the paper web is the minimum required to obtain effective sizing.
  • the starch ester derivative made according to Example 4 was tested under laboratory conditions to simulate application to a paper web at the size press of a paper making machine. Six hundred grams of the Example 4 starch derivative was slurried in sufficient water with 0.2% ammonium persulphate based on the starch (dry substance weight) to make a total weight of 4000 g. The above slurry was then cooked at about 157-160°C through a loop type cooker similar to that described in U.S. Patent 3,661,640. The solids level of the cooked starch paste was 13% at a pH of 4.9. The pH was then adjusted to 5.7 with 5% NaOH solution. The solids of the cooked starch paste was adjusted to 10%. The Brookfield viscosity, using a No. 1 spindle at 20 rpm and 66°C was 35 cps.
  • a base sheet containing no rosin and 10 kg alum/tonne of paper was sized with the above starch derivative paste at 10% solids level and a pH of 5.7.
  • the pick-up of sizing calculated to 6.2%, which was considered excellent.
  • the Hercules Size Test for the above sized paper was 49.5, indicating excellent sizing was obtained.
  • the starch ester derivative of Example 5 was also tested in the laboratory as described above in Example 6.
  • the lightly oxidized starch derivative was first subject to thermal cooking (without added ammonium persulphate).
  • a 15% solids slurry of the Example 5 starch derivative was jet cooked at a temperature of about 160°C in a jet cooker (without a loop tube).
  • the solids level of the cooked starch derivative was adjusted to 10% by adding hot water.
  • the Brookfield viscosity was 23 cps (No. 1 spindle; 20 rpm; 66°C).
  • the pick-up of the cooked starch paste was 6.2%.
  • the Hercules Sizing Test value was 85.6, showing unexpectedly superior sizing.
  • the d.s. of octenyl succinate may be measured by determining the carboxyl level of the unsubstituted starch, and subtracting this value from the carboxyl level determined on the reacted and filtered starch. The determination may be made by titrating known samples with standard (0.100N) sodium hydroxide to pH 7.5. The respective samples are thoroughly washed prior to the test, to remove any unreacted reagent from the product test sample, and to subject the control to all the same conditions as the test sample.
  • the alkali fluidity or "inhibition index” test is substantially as described in United States Patent 3,876,629, column 7, lines 33-67 and column 8, lines 1-10.

Claims (12)

1. Verfahren zum äußeren Leimen eines Zellulosegewebes zur Erhöhung der Wasserfestigkeit desselben, wobei das Gewebe das ion eines mehrwertigen Metalles und Rosinharz, jedoch in einer Menge von nicht mehr als 2 kg/Tonne Rosinharz enthält, dadurch gekennzeichnet, daß dem Gewebe bei einer Temperatur im Bereich von 50-80°C ein stärkehaltiges wässriges Verleimungsprodukt mit einem pH von 4-7,5 und einer Viskosität nach Brookfield im Bereich vc n 10 bis 150 cps (Spindel Nr. 1, 20 U/min bei 66°C) mit einer Zugabe-Menge von 10-100 kg/Tonne Zellulosegewebe zugegeben wird, wobei das wässrige Verleimungsprodukt 2-15 Gew.-% (auf der Basis des Gewichts der Verleimungsproduktes) eines Dicarbonsäurestärkeesters enthält, der durch Umsetzung von Stärke mit einem Dicarbonsäureanhydrid mit 8-22 Kohlenstoffatomen erhalten wurde, wobei das Dicarbonsäureanhydrid ein aliphatisches, aromatisches, alicyclisches oder bicyclisch-aliphatisches Dicarbonsäureanhydrid ist und der Stärkeester einen Grad der Substitution mit dem Dicarbonsäureanhydrid im Bereich von 0,005-0,023 hat.
2. Verfahren gemäß Anspruch 1, dadurch gekennziechnet, daß der Stärkeester durch Umsetzung von Stärke mit dem Anhydrid der 1-Octenylbernsteinsäure erhalten wurde.
3. Verfahren gemäß Anspruch 2, dadurch gekennzeichnet, daß der Stärkeester der 1-Octenylbernsteinsäurehalbester von Maisstärke ist, bei dem der Substitutionsgrad im Bereich von 0,008-0,016 liegt.
4. Verfahren gemäß Anspruch 3, dadurch gekennzeichnet, daß der 1-Octenylbernsteinsäurehalbester der Maisstärke in geringem Umfange oxydiert ist, so daß die im Halbester verbliebene Menge Protein weniger als 0,1 Gew.-% auf der Basis der Stärke beträgt.
5. Verfahren gemäß irgendeinem der Ansprüche 1-4, dadurch gekennzeichnet, daß das lon des mehrwertigen Metalles von Aluminium, Calcium, Magnesium, Mangan oder Barium ist.
6. Verfahren gemäß Anspruch 5, dadurch gekennzeichnet, daß das lon des mehrwertigen Metalles in Form eines wenig wasserlöslichen Salzes vorliegt und dem wässrigen Ausgangsprodukt zugegeben wird, aus dem das Zellulosegewebe Gebildet wird.
7. Verfahren gemäß Anspruch 6, dadurch gekennzeichnet, daß das ion des mehrwerigen Metalles ein Aluminiumion ist und aus Aluminiumchlorid, Aluminiumsulphat oder Natriumaluminat erhalten worden ist.
8. Verfahren gemäß Anspruch 7, dadurch gekennzeichnet, daß das Salz des mehrwertigen Metalles Aluminiumsulphat ist, das in dem Zellulosegewebe in einer Menge von mindestens 5 kg Aluminiumsulphat pro Tonne Fasern Im Zellulosegewebe anwesend ist, oder das Salz des mehrwertigen Metalles Natriumaluminat ist. das im Zellulosegewebe in einer Menge von mindestens 1,5 kg pro Tonne Faserb un Zellulosegewebe anwesend ist.
9. Verfahren nach irgendeinem der Ansprüche 1-8, dadurch gekennzeichnet, daß die verminderte Viskosität des Stärkeesters durch Hydrolyse des Stärkeesters durch thermisch-chemische Behandlung desselben erreicht worden ist.
10. Verfahren nach irgendeinem der Ansprüche 1-8, dadurch gekennzeichnet, daß die substituierte Stärke in geringem Maß oxydiert wurde und die verringerte Viskosität durch thermische Behandlung bei hohen Temperaturen erreicht worden ist.
11. Verfahren gemäß Anspruch 10, dadurch gekennzeichnet, daß die thermische Behandlung bei einer Temperatur im Bereich von 107-163°C durchgeführt wurde.
12. Verfahren nach irgendeinem der Ansprüche 1-11, dadurch gekennzeichnet, daß von einem solchen Papierausgangsprodukt ausgegangen wird, daß das Papiergewebe frei von Rosinharz ist.
EP80300078A 1979-02-05 1980-01-08 Verfahren zur Leimung von Papier Expired EP0014520B1 (de)

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EP0014520B1 true EP0014520B1 (de) 1983-05-25

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EP (1) EP0014520B1 (de)
JP (1) JPS55107598A (de)
CA (1) CA1143914A (de)
DE (1) DE3063384D1 (de)
NO (1) NO800284L (de)

Cited By (4)

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US6649262B2 (en) 2001-07-06 2003-11-18 Kimberly-Clark Worldwide, Inc. Wet roll having uniform composition distribution
US6651924B2 (en) 2001-07-06 2003-11-25 Kimberly-Clark Worldwide, Inc. Method and apparatus for making a rolled wet product
US8361571B2 (en) 2008-06-20 2013-01-29 International Paper Company Composition and recording sheet with improved optical properties
US11060044B2 (en) 2016-05-24 2021-07-13 Basf Se Copolymer and use thereof for reducing crystallization of paraffin crystals in fuels

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US4687519A (en) * 1985-12-20 1987-08-18 National Starch And Chemical Corporation Paper size compositions
US4721655A (en) * 1985-12-20 1988-01-26 National Starch And Chemical Corporation Paper size compositions
JP3692419B2 (ja) * 1993-12-03 2005-09-07 エバーコーン インク 紙用表面加工剤
US5595631A (en) * 1995-05-17 1997-01-21 National Starch And Chemical Investment Holding Corporation Method of paper sizing using modified cationic starch
US6521088B1 (en) 1999-11-23 2003-02-18 National Starch And Chemical Investment Holding Corporation Degraded hydrophobic, particulate starches and their use in paper sizing
DE102007005927B4 (de) * 2007-02-06 2011-05-05 Emsland - Stärke GmbH Verfahren zur Herstellung eines hydrophoben Stärkederivats
US8017249B2 (en) 2007-02-13 2011-09-13 Tate & Lyle Ingredients Americas Llc Starch-containing compositions for use in imparting oil or grease resistance to paper
US20100322538A1 (en) * 2009-06-22 2010-12-23 Powell Greg L Flexible bulk containers constructed to be liftable from below by a forklift
US8962092B2 (en) * 2013-01-30 2015-02-24 Corn Products Development, Inc. Paper sizing using an agent containing uniformly bound octenyl succinic anhydride groups made by the reaction of octenyl succinic anhydride onto a dispersed waxy starch
CN116289293A (zh) * 2022-11-14 2023-06-23 华邦古楼新材料有限公司 一种可降解吸管原纸及其制造方法

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AU8592375A (en) * 1975-03-05 1977-04-28 Nalco Chemical Co Fungicidal composition containing phenylazocyanoacetic esters
US4239592A (en) * 1976-11-15 1980-12-16 National Starch And Chemical Corp. Starch blend, process of sizing paper therewith, and product thereof

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6649262B2 (en) 2001-07-06 2003-11-18 Kimberly-Clark Worldwide, Inc. Wet roll having uniform composition distribution
US6651924B2 (en) 2001-07-06 2003-11-25 Kimberly-Clark Worldwide, Inc. Method and apparatus for making a rolled wet product
US8361571B2 (en) 2008-06-20 2013-01-29 International Paper Company Composition and recording sheet with improved optical properties
US8906476B2 (en) 2008-06-20 2014-12-09 International Paper Company Composition and recording sheet with improved optical properties
US11060044B2 (en) 2016-05-24 2021-07-13 Basf Se Copolymer and use thereof for reducing crystallization of paraffin crystals in fuels

Also Published As

Publication number Publication date
NO800284L (no) 1980-08-06
JPS55107598A (en) 1980-08-18
EP0014520A1 (de) 1980-08-20
DE3063384D1 (en) 1983-07-07
CA1143914A (en) 1983-04-05

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