EP0415385B1 - Verfahren zur Herstellung von Papier - Google Patents

Verfahren zur Herstellung von Papier Download PDF

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Publication number
EP0415385B1
EP0415385B1 EP19900116567 EP90116567A EP0415385B1 EP 0415385 B1 EP0415385 B1 EP 0415385B1 EP 19900116567 EP19900116567 EP 19900116567 EP 90116567 A EP90116567 A EP 90116567A EP 0415385 B1 EP0415385 B1 EP 0415385B1
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EP
European Patent Office
Prior art keywords
starch
weight
paper
phosphorus atoms
granules
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP19900116567
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English (en)
French (fr)
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EP0415385A1 (de
Inventor
Sumiitsu Yoshida
Tomohiro Akita
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.)
Sanwa Starch Co Ltd
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Sanwa Starch Co Ltd
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Publication of EP0415385A1 publication Critical patent/EP0415385A1/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
    • D21H19/00—Coated paper; Coating material
    • D21H19/36—Coatings with pigments
    • D21H19/44—Coatings with pigments characterised by the other ingredients, e.g. the binder or dispersing agent
    • D21H19/54—Starch
    • 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

  • the present invention relates to a method of making paper and paper board using a modified spray starch in order to improve paper surface strength, web strength and/or plybond strength and the like.
  • Fig. 1 is a Brabender Visco-Amylogram which shows the relation between temperature and viscosity to explain the gelatinization temperature of the starch.
  • Spray starch which has been generally used in paper industry, is roughly classified into two kinds.
  • One is raw starch (for example, corn starch, potato starch, tapioca starch and the like) and the other is modified starch (for example, starch urea phosphate, acetylated starch, and the like.).
  • the raw starch has a higher gelatinization temperature than the modified starch and thus cannot be sufficiently gelatinized in paper machines currently used.
  • the raw starch cannot sufficiently increase the plybond strength and thus causes ply separation of multiply paper board.
  • the raw starch granules tend to pass through the web with the process water and hence decrease the retention of the starch granules sprayed in the wet web. As a result, problems have occurred in that sufficient strength can not be given to the paper board, the paper machine being stained, and the load of the waste-water treatment system being increased.
  • the modified starch particularly starch urea phosphate, usually has a gelatinization temperature which has been lowered from its original gelatinization temperature within the range of from 5 to 20 °C and thus can be sufficiently gelatinized in a drying part of prevailing paper machines.
  • the starch urea phosphate contributes to the improvement of strength properties of paper and paper board, since starch urea phosphate sprayed in the wet web is excellently retained.
  • the conventional starch urea phosphate has serious drawbacks. That is to say, the conventional starch urea phosphate frequently causes wire filling on a paper machine and thus leads to serious troubles, such as machine shut-down.
  • starch urea phosphate which is commonly used contains phosphorus atoms chemically bonded to the starch in a quantity of 0.3 to 1.5 % by weight and phosphorus atoms present as cold-water soluble phosphorous compounds in the starch in a quantity of 0.15 to 1.5 % by weight.
  • Modified starches other than starch urea phosphate, for example acetylated starch, having a gelatinization temperature of 35 to 55 °C are sufficiently gelatinized in a dryer part of paper machine, but the starch retention in the wet web is extremely poor and the strength properties of paper and paper board are inferior to that obtained using starch urea phosphate.
  • JP-A-62-116602 discloses an urea-phosphate starch used in a process step for coating colours.
  • the present invention provides a starch urea phosphate for paper making which has a gelatinization temperature of 35 to 55 °C and contains phosphorus atoms chemically bonded to the starch in an amount of at least 0.4 % by weight, and phosphorus atoms present as cold-water soluble phosphorous compounds in the starch in an amount of 0.1% by weight or less.
  • the content of phosphorus atoms chemically bonded with starch is 0.4 % by weight or more.
  • the maximum content of phosphorus atoms bonded with starch is not specially limited, but an increase of a quantity of phosphoric acid, salts thereof and the like added in a reaction mixture tends to increase the quantity of non-reacted phosphorous compounds in the starch, so that it is natural that the content of phosphorus atoms does not exceed 5 % by weight.
  • the content is less than 0.4 % by weight, sufficient retention of starch granules sprayed in the wet web cannot be achieved and excellent strength properties of paper cannot be given to the paper.
  • the content of phosphorus atoms chemically bonded to the starch is preferably 0.4 to 3 % by weight.
  • the starch urea phosphate contains phosphorus atoms present as cold-water soluble phosphorous compounds in the starch (e.g. sodium-, potassium- or ammonium salt and the like of phosphoric acid, phosphorous acid and the like) in a content of 0.1 % by weight or less. If the content is more than 0.1 % by weight, insoluble substances are formed in the pulp slurry to cause wire filling on the paper machine.
  • cold-water herein is water having a temperature of less than room temperature.
  • the gelatinization temperature of the starch urea phosphate according to the present invention is 35 to 55 °C, preferably 40 to 50 °C. If the gelatinization temperature is lower than 35 °C, the starch granules stored in a storage tank may be unnecessarily gelatinized because the temperature often rises to a value above 35 °C during storage. If the gelatinization temperature is higher than 55 °C, the starch granules do not gelatinize sufficiently during the prevailing drying process of the paper machine.
  • the method of producing the starch urea phosphate according to the present invention is basically conventional.
  • the starch used as raw material in the present invention includes corn starch, tapioca starch, potato starch, sweet-potato starch, wheat starch and the like. In addition, it may be partially and/or perfectly (completely) subjected to a treatment of esterification, etherification, oxidation and the like.
  • phosphoric acid or a phosphate to be used is not specially limited, but phosphoric acid, phosphorous acid and primary, secondary and/or tertiary sodium-, potassium- and/or ammonium salts thereof can be used.
  • acids other than the above described phosphoric acid, salts thereof and the like can be used together with the phosphoric acid and phosphates.
  • hydrochloric acid, sulfuric acid, nitric acid, sulfamic acid, maleic acid, succinic acid and acetic acid and salts thereof can be used.
  • oxidizing agents can be used. For example, hydrogen peroxide, ammonium persulfate and the like can be used.
  • starch urea phosphate according to the present invention When the starch urea phosphate according to the present invention is sprayed onto the wet web, it can be used together with raw starch, polyacrylamide, polyvinyl alcohol, polyethyleneimine, polyethyleneoxide and the like.
  • the starch slurry having a concentration of about 0.1 to 5 % is sprayed onto the paper and paper board web by means of spray nozzles fixed in a spray pipe mounted across the wire. Subsequently, the sprayed wet web is dewatered by suction and pressed to dewater, followed by drying in a dryer to obtain the paper, paper board and the like.
  • pulp slurry of which freeness is adjusted by a laboratory beater is placed in an experimental paper machine and dewatered to make web. A starch slurry is sprayed onto the web.
  • a second wet web is placed on the sprayed side of said wet web.
  • the combined web is dewatered by suction to 80 % water content, pressed for further dewatering, and dried on a drum dryer at a desired temperature to obtain the paper and paper board.
  • the gelatinization temperature is the temperature at which a tangetial line of the temperature/viscosity curve of the Brabender Amylogram left from the base line first makes an angle of 45 ° against the base line, as shown in Fig.1.
  • the starch-concentration is set at 25 % by weight.
  • the present invention provides a starch suitable for paper making.
  • the starch does not deposit insoluble substances on the wire even in a pulp slurry having a low pH, thus effectively preventing wire filling on a paper machine.
  • product A The quantity of phosphorus atoms which are bonded to the starch was 0.66 % by weight based on the dry product and the quantity of phosphorus atoms present as cold-water soluble phosphorous compounds in the starch was 0.08 % by weight, as the result of an elemental analysis.
  • this product is referred to as product A.
  • product B The quantity of phosphorus atoms which are bonded to the starch was 0.51 % by weight (based on the dry product) and the quantity of phosphorous atoms present as cold-water soluble phosphorous compounds in the starch was 0.06 % by weight (based on the dry product) as the result of an elemental analysis.
  • this product is referred to as product B.
  • product D The quantity of phosphorus atoms which are chemically bonded to the starch was 0.42 % by weight (based on the dry product) and the quantity of phosphorus atoms present as cold-water soluble phosphorous compounds in the starch was 0.08 % by weight (based on the dry product) as the result of an elemental analysis.
  • this product is referred to as product D.
  • Aluminium sulfate was added to 375 ml of a 1 % pulp slurry of a needle-leaved tree breached kraft pulp (NBKP) having a freeness (CSF) of 340 ml in a quantity of 1.0 % based on the pulp and the resulting mixture was diluted until 0.03 % in an experimental square type paper machine (25 cm x 25 cm).
  • NNKP needle-leaved tree breached kraft pulp
  • CSF freeness
  • the diluted mixture was dewatered to produce a web and stopped at a point of time when the level of water of the pulp slurry reached 2 cm over the wire, followed by spraying a 1 % slurry of starch shown in Table 1 over the pulp slurry surface, so that the starch will be applied in a quantity of 2 g/m2 based on the dry product. Then, the dewatering was started again to obtain a wet web (having a basis weight of 60 g/m2) as a first ply.
  • test piece (10 cm x 1 cm) was adhered to a metallic plate from which the aimed layer was previously separated by 2 to 3 cm and then pulled in the direction of 90 ° by means of the tensile tester to carry out the separation, whereby measuring the resisting force.
  • the starch having the gelatinization temperature of 60°C or more showed an unsatisfactory value in view of the plybond strength.
  • the starch urea phosphate containing phosphorus atoms bonded with starch in a quantity of 0.36 % or less and having the gelatinization temperature of 42°C, or the starch of which a gelatinization starting temperature was reduced by the acetylation and the like exhibited an improved strength in comparison with the starch having the gelatinization temperature of 60°C or more; it is, however, still insufficient.
  • the starch urea phosphate including starch according to the present invention having the reduced gelatinization temperature and containing phosphorus atoms bonded with starch in a quantity of 0.42 % or more only exhibited the satisfactory plybond strength.
  • potato starch or modified starch therefrom and the starch urea phosphate including starch according to the present invention containing phosphorus atoms bonded with starch in a quantity of 0.42 % or more exhibited the superior value in view of the retention of starch.
  • starch urea phosphate including starch according to the present invention having the reduced gelatinization temperature and containing phosphorus atoms bonded with starch in a quantity of 0.42 % or more exhibits satisfactory results in view of both plybond strength and retention of starch.
  • Starch shown in Table 2 was sprayed between the first ply (pH 4.3) and the second ply (pH 6.5) in a quantity of 2 g/m2 on a cylinder machine (web width: 1,660 mm; paper velocity: 96 m/min) to obtain white paper board having a basis weight of 450 g/m2.
  • Starch shown in Table 3 was sprayed on a pulp slurry having a pH of 4.4 on the wire in a quantity of 0.5 g/m2 on a fourdrinier paper machine (web width: 3,700 mm; paper velocity: 420 m/min) to obtain mechanical paper having a basis weight of 82 g/m2.
  • starch urea phosphate including starch according to the present invention containing phosphorus atoms bonded with starch in a quantity of 0.42 % or more exhibited the superior plybond strength in comparison with cornstarch.
  • the starch urea phosphate of which a cold-water soluble phosphorous compounds contains phosphorus atoms in an amount of 0.14 % by weight or more i.e. the urea-phosphated starch outside the claimed range, brought about the wire filling within 3 to 10 days and therefore the machine had to be stopped and cleaned.
  • the starch according to the present invention did not bring about the wire filling even after the continuous operation of one month or more.
  • the starch according to the present invention can exhibit satisfactory properties in view of both plybond strength and the wire filling and thus it can be said to be the ideal spray starch.
  • Merely product B (having a gelatinization temperature of 45°C and containing phosphorus atoms bonded with starch in a quantity of 0.51 %, of which a cold-water soluble phosphorous compound had phosphorus atoms of 0.06 % by weight), exhibited superior results in various kinds of physical properties shown in Table 3 and did not bring about the wire filling.

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Claims (6)

  1. Verfahren zur Herstellung von Papier und Pappe, umfassend die Schritte: Aufsprühen einer Aufschlämmung von nicht gelatinierten Stärkekörnern auf eine nasse Papierbahn, Entwässern der Bahn und Erhitzen der Bahn zur Unterstützung der Gelatinierung der Stärkekörner, dadurch gekennzeichnet, daß die Stärkekörner Stärke-Harnstoff-Phosphat-Körner mit einer Gelatinierungstemperatur von 35 -55°C sind, und chemisch an die Stärke gebundene Phosphoratome in einer Menge von mindestens 0,4 Gew.-% und in Form von in kaltem Wasser löslichen Phosphorverbindungen in der Stärke vorliegende Phosphoratome in einer Menge von höchstens 0,1 Gew.-% enthalten.
  2. Verfahren nach Anspruch 1, worin die Menge der chemisch an die Stärke gebundenen Phosphoratome im Bereich von 0,4 bis 3 Gew.-% liegt.
  3. Verfahren nach Anspruch 1, worin die Gelatinierungstemperatur im Bereich von 40 bis 50°C liegt.
  4. Verfahren nach Anspruch 1, worin die Stärkekörner durch Vermischen von 100 Gew.-Teilen Rohstärke mit 2 bis 20 Gew.-Teilen Harnstoff und 1 bis 15 Gew.-Teilen Phosphorsäure oder einem Phosphat und anschließendes Umsetzen für die Dauer von 30 Minuten bis 5 Stunden bei 80 - 150°C hergestellt werden.
  5. Verfahren nach Anspruch 4, worin die Rohstärke ausgewählt ist aus Maisstärke, Tapiokastärke, Kartoffelstärke und Weizenstärke.
  6. Verfahren nach irgendeinem der vorangehenden Ansprüche, worin die Stärkekörner in einer Menge von 0,2 bis 20 g/m² auf die nasse Bahn gesprüht werden.
EP19900116567 1989-08-30 1990-08-29 Verfahren zur Herstellung von Papier Expired - Lifetime EP0415385B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP1223874A JP2788298B2 (ja) 1989-08-30 1989-08-30 抄紙方法
JP223874/89 1989-08-30

Publications (2)

Publication Number Publication Date
EP0415385A1 EP0415385A1 (de) 1991-03-06
EP0415385B1 true EP0415385B1 (de) 1995-11-08

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Family Applications (1)

Application Number Title Priority Date Filing Date
EP19900116567 Expired - Lifetime EP0415385B1 (de) 1989-08-30 1990-08-29 Verfahren zur Herstellung von Papier

Country Status (3)

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EP (1) EP0415385B1 (de)
JP (1) JP2788298B2 (de)
DE (1) DE69023436T2 (de)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102510802A (zh) * 2009-08-03 2012-06-20 乔治亚太平洋法国公司 水崩解性纤维片，制造所述纤维片的方法，所述纤维片用于芯制造的用途

Families Citing this family (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6451121B2 (en) 1993-07-30 2002-09-17 National Starch And Chemical Investment Holding Corporation Thermally-inhibited non-pregelatinized granular starches and flours and process for their preparation
US5720822A (en) * 1995-06-07 1998-02-24 National Starch And Chemical Investment Holding Corporation Thermally-inhibited pregelatinized non-granular starches and flours and process for their production
US5932017A (en) * 1993-07-30 1999-08-03 National Starch And Chemical Investment Holding Corporation Thermally-inhibited non-pregelatinized granular starches and flours and process for their preparation
US6221420B1 (en) 1993-07-30 2001-04-24 National Starch And Chemical Investment Holding Corporation Foods containing thermally-inhibited starches and flours
US5718770A (en) * 1994-08-25 1998-02-17 National Starch And Chemical Investment Holding Corporation Thermally-inhibited pregelatinized granular starches and flours and process for their production
CA2210160A1 (en) * 1995-01-18 1996-07-25 Roger Jeffcoat Cosmetics containing thermally-inhibited starches
US5830884A (en) * 1995-01-18 1998-11-03 National Starch And Chemical Investment Holding Corporation Pharmaceutical products containing thermally-inhibited starches
EP0805898A1 (de) * 1995-01-24 1997-11-12 National Starch and Chemical Investment Holding Corporation Thermisch gehemmte stärken enthaltendes papier
EP0805840A1 (de) * 1995-01-24 1997-11-12 National Starch and Chemical Investment Holding Corporation Wässrige klebstoffe auf basis von thermisch inhibierten stärken
DE19829757A1 (de) 1998-07-03 2000-01-05 Stockhausen Chem Fab Gmbh Wässrige Klebemitteldispersionen und deren Verwendung zur Herstellung von mehrlagigen Papieren
JP4629833B2 (ja) * 2000-05-26 2011-02-09 王子コーンスターチ株式会社 繊維シート状物の層間接着剤及び抄紙方法
JP4585650B2 (ja) * 2000-05-26 2010-11-24 王子コーンスターチ株式会社 繊維シート状物の層間接着剤を用いた抄紙方法
JP4527972B2 (ja) * 2003-12-22 2010-08-18 王子コーンスターチ株式会社 省熱貼合用接着剤
JP4594627B2 (ja) * 2004-02-10 2010-12-08 中外写真薬品株式会社 フッ素含有排水の処理方法。
FR2940331B1 (fr) 2008-12-18 2010-12-17 Georgia Pacific France Procede de fabrication d'une feuille de papier delitable, utilisation de la feuille pour la fabrication d'un mandrin formant support de rouleau, feuille de papier delitable et mandrin constitue d'au moins une desdites feuilles
FR2940330B1 (fr) 2008-12-18 2017-06-23 Georgia-Pacific France Feuille de papier delitable dans l'eau, mandrin pour rouleau de papier constitue d'une telle feuille
EP2744940B1 (de) * 2011-08-19 2020-11-04 Basf Se Harnstoffhaltige wässrige papierstreichfarben, harnstoffhaltige wässrige papierstreichfarbkomponenten und deren verwendung
CN104878648B (zh) * 2014-02-28 2018-03-09 金东纸业（江苏）股份有限公司 纸张的制造方法

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL134024C (de) * 1965-11-17 1900-01-01
JPS62116602A (ja) * 1985-11-18 1987-05-28 Sanwa Denpun Kogyo Kk 尿素・リン酸澱粉の製造方法

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102510802A (zh) * 2009-08-03 2012-06-20 乔治亚太平洋法国公司 水崩解性纤维片，制造所述纤维片的方法，所述纤维片用于芯制造的用途
CN102510802B (zh) * 2009-08-03 2015-07-22 乔治亚太平洋法国公司 水崩解性纤维片,制造所述纤维片的方法,所述纤维片用于芯制造的用途

Also Published As

Publication number Publication date
EP0415385A1 (de) 1991-03-06
JP2788298B2 (ja) 1998-08-20
DE69023436T2 (de) 1996-04-04
DE69023436D1 (de) 1995-12-14
JPH0390695A (ja) 1991-04-16

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