EP0106763B1 - Zusammensetzung und Verfahren zum Streichen von Papier und Pappe, Verfahren zur Herstellung der Zusammensetzung und Papier und Pappe, die auf diese Weise erhalten werden - Google Patents

Zusammensetzung und Verfahren zum Streichen von Papier und Pappe, Verfahren zur Herstellung der Zusammensetzung und Papier und Pappe, die auf diese Weise erhalten werden Download PDF

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Publication number
EP0106763B1
EP0106763B1 EP83401993A EP83401993A EP0106763B1 EP 0106763 B1 EP0106763 B1 EP 0106763B1 EP 83401993 A EP83401993 A EP 83401993A EP 83401993 A EP83401993 A EP 83401993A EP 0106763 B1 EP0106763 B1 EP 0106763B1
Authority
EP
European Patent Office
Prior art keywords
starch
pigment
weight
paper
dry
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
EP83401993A
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English (en)
French (fr)
Other versions
EP0106763A1 (de
Inventor
Jean Schneider
Serge Gosset
Pierre Lefer
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.)
Roquette Freres SA
Original Assignee
Roquette Freres SA
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 Roquette Freres SA filed Critical Roquette Freres SA
Priority to AT83401993T priority Critical patent/ATE26138T1/de
Publication of EP0106763A1 publication Critical patent/EP0106763A1/de
Application granted granted Critical
Publication of EP0106763B1 publication Critical patent/EP0106763B1/de
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
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31971—Of carbohydrate
    • Y10T428/31975—Of cellulosic next to another carbohydrate

Definitions

  • the present invention relates to an aqueous composition for coating paper and cardboard.
  • coating denotes the operation consisting in depositing on one or both sides of a support sheet of paper or cardboard, a coating composition forming a coating; this coating gives the treated sheet a particularly regular surface condition and therefore capable of receiving a fine impression, while improving the opacity and appearance of the paper (whiteness, smoothness, gloss).
  • a coating composition comprises at least two components, namely a pigment and a binder also called an adhesive.
  • the paper is made up of fibers of variable dimensions which, despite the usual satin-finishing operation, allow cavities, the dimensions of which are of the order of 50 to 100 ⁇ rn, to remain on the surface and, on the other hand , in the thickness of the paper, more or less wide channels, designated by the term of macro-capillaries.
  • the surface is covered with a coating based on very fine pigments, these fill the cavities by leveling the surface; the channels comprised by the layer thus placed are extremely thin, they are micro-capillaries with a width of the order of 2 to 5 ⁇ m.
  • aqueous dispersion of kaolin an aqueous dispersion of kaolin; it is also possible to use either separately, or most often in admixture with kaolin, other pigments such as in particular calcium carbonate, titanium oxide, calcium sulfate, satin white (SO A Ca + A1 2 0 3 ) or very fine talc.
  • binder of the coating composition use is generally made of starches, proteins such as casein or soy protein, or of synthetic products such as polyvinyl alcohol, polyvinyl acetate, acrylic products. , styrene-butadiene; the composition may contain only one of these products, but often they are used as a mixture.
  • the amount of binder generally represents from 5 to 30% of the weight of pigment. This quantity is chosen in particular as a function of the nature of the pigment, as a function of the coating process used and as a function of the qualities sought for paper or cardboard. By way of example, it is pointed out that it is necessary to use more binder in the case of carbonate and satin white than in the case of kaolin, in the case of divided charges than in the case of coarse charges .
  • a coating composition comprises various complementary agents among which mention may be made of foam reducers, preservatives, dyes, dispersants or deflocculants such as tripolyphosphate, pyrophosphate or hexametaphosphate and salts polycarboxylic acids which retard in particular the sedimentation of the suspensions.
  • the formulation of the coating composition varies according to the application technique, the qualities of the backing paper or the desired properties, the latter being different according to the printing mode (rotogravure, letterpress printing, offset, flexographic printing, screen printing) for which coated papers are intended.
  • starches used up to now, alone or in admixture with the above-mentioned proteins or synthetic products to constitute the binder of the coating composition are depolymerized starches, optionally further modified by etherification or esterification.
  • patent FR-A-2447388 describes a product formed of particles comprising a support on which are fixed or retained the constituents of a hydrogenated starch hydrolyzate, said product being able to be used as plasticizer in the paper industry, as indicated in Example 7, but then the support is a white dextin, therefore a depolymerized starch and, moreover, the proportion of hydrolyzate relative to the pigment is of the order of 0.1 part per 100 parts of pigment, c that is to say about four times lower than the lower limit provided in accordance with the invention.
  • non-depolymerized starch in coating compositions, in particular because of the difficulty of obtaining, from an unpolymerized starch, a colloidal solution. correct, since non-depolymerized starch soils cooked for 90 minutes in a water bath still have highly swollen granules. And even when correct non-depolymerized starch soils are obtained, they exhibit excessive viscosity, aggravated by the tendency of molecules to reassociate or retrogradate, which in fact prevents their practical application in coating compositions.
  • the starches currently used in coating are depolymerized either by acid or enzymatic hydrolysis, or by oxidation, or by dextrinification, some of these degradations (enzymatic or oxidizing) being able to be carried out directly at the user. It is to improve certain properties (such as the binding or “smoothness” properties) of the layers containing starch as a binder, that it is possible, either before or after the depolymerization reaction, to chemical modifications such as etherification or esterification (acetylation, cationization, hydroxyethylenation or hydroxypropylenation for example).
  • non-depolymerized starches mean that the latter would meet the aforesaid need if the practically insurmountable difficulties of preparing correct soils of acceptable viscosity based on these non-depolymerized starches prevented their application.
  • the Applicant Company had the merit of finding that, surprisingly and unexpectedly, it was possible to use non-depolymerized starches in the constitution of binders for coating compositions as soon as these non-depolymerized starches were used. at the same time as an effective proportion of at least one agent known as a "fluidizer" chosen from the group consisting of hydrogenated sugars comprising sorbitol, mannitol, maltitol, xylitol, lactitol and hydrogenated starch hydrolysates.
  • a fluidizer chosen from the group consisting of hydrogenated sugars comprising sorbitol, mannitol, maltitol, xylitol, lactitol and hydrogenated starch hydrolysates.
  • this composition also comprises one or more synthetic products from the group comprising in particular polyvinyl alcohol, polyvinyl acetate, acrylic products, styrene-butadiene, synthetic copolymers and / or one or more proteins chosen in particular from group comprising casein and soy protein.
  • non-depolymerized starches denotes starches which have not undergone a depolymerization treatment such as in particular acid or enzymatic hydrolyses, oxidative degradation or dextrinification. They can be chosen from starches from all sources and in particular from corn starches, optionally hybrid, wheat and rice starch, potato starch, cassava starch. In addition, as already mentioned previously, these starches may have been etherified, esterified or crosslinked in order to modify some of their properties such as for example their stability in solution.
  • the presence of the thinning agents makes it possible to give the coating composition a viscosity and a texture perfectly suited to the coating of paper.
  • non-depolymerized starches overcomes all the drawbacks described above, attached to the use of degraded starches, and in particular allows to obtain a higher binding power, better layer resistance, better retention of water and better homogeneity of the surface.
  • a given pigment is essentially characterized, not only by its chemical composition, but also by the size and arrangement of its constituent particles.
  • the description of the behavior of the particles in the cluster is also important: number of particles, mobility or lack of mobility, resistance to rupture or rearrangement of the cluster and surface condition of the cluster.
  • the constituent particles of the cluster can be linked to each other by chemical bonds at the contact points, giving the clusters a resistance roughly equal to that of individual particles of the same size; they can also be quite weakly linked to each other as if they were attracted by magnetic or gravitational forces (Van der Waals force), these particular arrangements can be "disturbed or broken by the application of a force.
  • disintegration The dislocation of clusters of particles linked by chemical bonds to their contact points is called the "disintegration". After disintegration or separation of the particles, the links are not reformed, the disintegration process therefore being irreversible.
  • dispersing agents is therefore an essential part of the dispersion process which makes the use of mechanical energy efficient and which reduces the viscosity of the suspension of the pigments.
  • a coating composition comprises pigment particles and a binder, in aqueous solution forming a fluid medium, in which the pigment particles are in suspension.
  • the fluid medium comprises not only the binder or adhesive but also all the other dissolved materials, in particular the fluidizing agents used in accordance with the invention.
  • Starch or casein for example, although in colloidal solution, are in a state of sufficient solubility for them to be clearly considered as part of the fluid.
  • the fluid medium acts as a lubricant between the particles and allows them to slide over each other much more easily than they could if they were dry.
  • the small size of the fluidizing agent molecules used in accordance with the invention means that they exhibit significant mobility, but, despite this reality, it is surprising to note that the addition of any one of these agents or of several of them, an addition which leads to an increase in the dry matter content of the whole, results in a decrease in viscosity such that the term "fluidifying agent appears to be essential to designate the agents entering, in accordance with the invention, in the constitution of the binder.
  • the process for coating paper or cardboard according to the invention is characterized in that the aqueous coating composition according to the invention is applied to one or both sides of the paper and cardboard.
  • the process for preparing the aqueous coating composition according to the invention is characterized in that, on the one hand, a non-depolymerized starch glue is prepared, on the other hand, a pigment dispersion, which the starch glue and the pigment dispersion are mixed, and an effective proportion of fluidizing agent chosen from the group consisting of hydrogenated sugars comprising in particular sorbitol, mannitol, maltitol, xylitol, lactitol and hydrogenated starch hydrolysates, by addition either in water used for the preparation of the starch glue and / or the dispersion of pigment, either in starch glue, or in the pigment dispersion, or in the mixture of the two or in the final coating preparation.
  • a non-depolymerized starch glue is prepared
  • a pigment dispersion which the starch glue and the pigment dispersion are mixed
  • an effective proportion of fluidizing agent chosen from the group consisting of hydrogenated sugars comprising in particular sorbitol, manni
  • the cooking of the non-depolymerized starch can be carried out by any suitable technique and in particular by cooking in a device with injection of live steam.
  • this cooking is carried out by passing a suspension of non-depolymerized starch in an apparatus of the type known in the art under the expression “Jet Cooker well known to starch manufacturers, in which the cooking of starch is obtained by introduction of steam at a pressure higher than atmospheric pressure.
  • the cooking of the non-depolymerized starch is carried out with a dry matter of between 5% and 30%, at a temperature above 120 ° C and in a time generally greater than 20 seconds, which makes it possible to obtain a non-depolymerized starch glue comprising practically no more highly swollen but unexploded granules, responsible for the development of viscosity and a lack of stability.
  • sorbitol or hydrogenated starch hydrolysates are preferably used, obtained by acid and / or enzymatic hydrolysis of all starches followed by hydrogenation.
  • These hydrogenated starch hydrolysates consist mainly and in variable proportions depending on the mode of hydrolysis applied by sorbitol, maltitol, isomaltitol and hydrogenated oligo- and polysaccharides.
  • D.E. Dextrose Equivalent
  • the proportion of fluidifying agent entering into the coating composition according to the invention is approximately 0.40% to 20% by weight, preferably from 0.50% to 15% by weight, and more preferably still from 0.50% to 7.5% by weight.
  • the amounts of binders used in the coating compositions according to the invention are from 5 to 30% by weight relative to the weight of the pigments.
  • the proportion of non-depolymerized starch present in the coating compositions according to the invention is established, the percentages being expressed dry / dry, between 0.2 and 30% and, preferably, between 0.5 and 30% relative by pigment weight.
  • the coating compositions according to the invention can be formulated at very high dry matter contents, of the order of 60 to 70%, while having a viscosity compatible with their application on existing coating machines and while not causing any difficulty, for example during the final operation of filtration of the coating composition, an operation which consists in ridding the composition in particular of the agglomerates which it can contain.
  • Another advantage inherent in the use of the coating compositions according to the invention lies in the better plasticization of the layer, provided by the presence in the compositions of hydrogenated sugars and more particularly of sorbitol.
  • the pigments used are natural calcium carbonate and kaolin, and the dispersant used consists of a polyacrylate, sold under the brand "DISPEX N 40 by the company ALLIED COLLOIDS.
  • the first composition was prepared from enzymatically depolymerized starch.
  • a suspension of corn starch was treated in a continuous enzymatic converter as constructed according to French patent No. 1,391,011 and marketed by the Applicant Company, the enzymatic transformation being carried out for 30 minutes at 85 ° C. in the presence of 1.4 parts of alpha-amylase per 1000 parts of starch.
  • the inhibition of the enzyme was carried out on the device by a thermal flash at 140 ° C for 90 seconds.
  • the non-depolymerized starch glue was prepared by passing native corn starch over a Jet-Cooker at a temperature of 150 ° C. and for 3 minutes under a pressure of 5 bars.
  • the viscosities of the two coating compositions were then measured at 30 ° C, storage being carried out with and without stirring.
  • the water retention was measured on a ramp and conventional FANN brand filters of the type used for studying drilling muds, under a pressure of 6.9 bars.
  • the viscosity of the coating composition based on non-depolymerized starch is much higher than that of the composition based on enzymatically depolymerized starch.
  • the HERCULES viscosity very representative given the shear applied, is thus practically double that obtained with depolymerized starch; such a viscosity makes practically inapplicable the use of the corresponding composition for coating paper and cardboard.
  • filtration of the composition intended to rid it of any agglomerates present is made extremely difficult.
  • This example illustrates the effect of the addition of sorbitol as a function of the time chosen for this addition to a coating composition containing non-depolymerized starch as a binder.
  • Kaolin therefore represents 70% of the total charge and calcium carbonate 30%.
  • the dispersion of the pigments was carried out in 15 minutes at high speed on a CELLIER deliter.
  • an unpolymerized corn starch glue with 20% dry matter prepared under the same conditions as in Example 1, the amount added being 2,587 g, or 4% dry / dry compared to pigments.
  • compositions according to the invention do not give rise to harmful migration effects.
  • the speed of the coating machine was 140 meters / minute, the temperature of the dryer 170 ° C and the deposit (quantity of composition per unit area) of 12 g / m 2 .
  • the IGT test is also significantly improved.
  • control coating composition The formula and the method of preparation of the control coating composition are the same as in Example 2.

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Claims (6)

1. Wässerige Zusammensetzung zum Gautschen von Papier und Karton, mit einem Gehalt an Pigment und einem Bindemittel, das wenigstens teilweise aus nichtdepolymerisierter Stärke besteht, dadurch gekennzeichnet, daß sie, zusätzlich zu dem Pigment, enthält :
- ein oder mehrere fluidifizierende Mittel, ausgewählt aus der Gruppe, die aus den hydrierten Zuckern, umfassend insbesondere Sorbit, Mannit, Maltit, Xylit, Lactit, und den hydrierten Stärkehydrolysaten gebildet ist, wobei der Anteil an fluidifizierendem Mittel von 0,40 bis 20 Gewichtsteile je 100 Teile Pigment beträgt, und
- eine oder mehrere nicht depolymerisierte Stärken, in gegebenem Falle durch Veretherung, Veresterung oder Vernetzung modifiziert, in einer Menge, entsprechend einem in Trockenmaterial/Trockenmaterial ausgedrückten Prozentsatz, bezogen auf das Gewicht des Pigmentes, zwischen 0,2 und 30 %.
2. Zusammensetzung nach Anspruch 1, dadurch gekennzeichnet, daß das Bindemittel zusätzlich zu der oder den nichtdepolymerisierten Stärken ein oder mehrere synthetische Produkte aus der Gruppe, die insbesondere Polyvinylalkohol, Polyvinylacetat, Acrylprodukte, Styrol-Butadiene, synthetische Copolymere und/oder ein oder mehrere Proteine, ausgewählt insbesondere aus der das Casein und die Sojaproteine umfassenden Gruppe, enthält, wobei das genannte Bindemittel in einer Menge entsprechend einem Prozentsatz von 5 bis 30 Gew.-%, bezogen auf das Gewicht des Pigmentes, vorliegt.
3. Wässerige Zusammensetzung zum Gautschen nach einem der Ansprüche 1 und 2, dadurch gekennzeichnet, daß der Anteil des fluidifizierenden Mittels von 0,50 bis 15 Gew.-% und vorzugsweise von 0,50 bis 7,5 Gew.-%, bezogen auf die Pigmentmenge, beträgt.
4. Wässerige Zusammensetzung zum Gautschen nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, daß der Anteil der nichtdepolymerisierten Stärke von 0,5 bis 30 %, bezogen auf das Gewicht des Pigmentes, beträgt.
5. Verfahren zur Herstellung einer wässerigen Zusammensetzung zum Gautschen gemäß einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, daß man einerseits einen Klebstoff aus nichtdepolymerisierter Stärke und anderseits eine Pigmentdispersion bereitet, daß man das Vermischen des Stärkeklebstoffes und der Pigmentdispersion in solchen Verhältnissen vornimmt, daß die nicht depolymerisierte Stärke einen Anteil, ausgedrückt als Trockenmaterial/Trockenmaterial, bezogen auf das Gewicht des Pigmentes, zwischen 0,2 und 30 % ausmacht, und daß man einen Anteil von 0,40 bis 20 Gewichtsteile je 100 Teile Pigment eines fluidifizierenden Mittels, ausgewählt aus der durch die hydrierten Zucker, umfassend insbesondere Sorbit, Mannit, Maltit, Xylit, Lactit, und die hydrierten Stärkehydrolysate gebildeten Gruppe, durch Zugabe zu dem der Bereitung des Stärkeklebstoffes und/oder der Pigmentdispersion dienenden Wasser, zum Stärkeklebstoff, zur Pigmentdispersion, zum Gemisch dieser beiden oder zum fertigen Gautschpräparat einführt.
6. Verfahren zum Gautschen von Papier und Karton, dadurch gekennzeichnet, daß man auf eine oder beide Seiten des Papiers oder Kartons die wässerige Gautschzusammensetzung gemäß einem der Ansprüche 1 bis 4 aufträgt.
EP83401993A 1982-10-12 1983-10-12 Zusammensetzung und Verfahren zum Streichen von Papier und Pappe, Verfahren zur Herstellung der Zusammensetzung und Papier und Pappe, die auf diese Weise erhalten werden Expired EP0106763B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT83401993T ATE26138T1 (de) 1982-10-12 1983-10-12 Zusammensetzung und verfahren zum streichen von papier und pappe, verfahren zur herstellung der zusammensetzung und papier und pappe, die auf diese weise erhalten werden.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR8217085 1982-10-12
FR8217085A FR2540153B1 (fr) 1982-10-12 1982-10-12 Composition et procede de couchage du papier et du carton, procede de preparation de la composition et papier et carton ainsi obtenus

Publications (2)

Publication Number Publication Date
EP0106763A1 EP0106763A1 (de) 1984-04-25
EP0106763B1 true EP0106763B1 (de) 1987-03-25

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ID=9278203

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EP83401993A Expired EP0106763B1 (de) 1982-10-12 1983-10-12 Zusammensetzung und Verfahren zum Streichen von Papier und Pappe, Verfahren zur Herstellung der Zusammensetzung und Papier und Pappe, die auf diese Weise erhalten werden

Country Status (6)

Country Link
US (1) US4600439A (de)
EP (1) EP0106763B1 (de)
AT (1) ATE26138T1 (de)
CA (1) CA1218480A (de)
DE (1) DE3370499D1 (de)
FR (1) FR2540153B1 (de)

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GB9302259D0 (en) * 1993-02-05 1993-03-24 Cerestar Holding Bv Starch based material
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FR2777478B1 (fr) 1998-04-17 2000-06-16 Roquette Freres Dispersion aqueuse de pigment(s) et/ou charge(s) contenant une composition saccharidique particuliere
WO2001092401A2 (en) * 2000-06-01 2001-12-06 A.E. Staley Manufacturing Co. Highly flexible starch-based films
US6528088B1 (en) 2000-06-01 2003-03-04 A. E. Staley Manufacturing Co. Highly flexible starch-based films
US6517625B2 (en) 2001-01-03 2003-02-11 Mgp Ingredients, Inc. Protein/starch paper coating compositions and method of use thereof
US6949256B2 (en) 2002-01-18 2005-09-27 Banner Pharmacaps, Inc. Non-gelatin capsule shell formulation
US7887838B2 (en) 2002-01-18 2011-02-15 Banner Pharmacaps, Inc. Non-gelatin film and method and apparatus for producing same
US7816341B2 (en) * 2003-04-14 2010-10-19 Fmc Corporation Homogeneous, thermoreversible gel containing reduced viscosity carrageenan and products made therefrom
US20050008677A1 (en) * 2003-04-14 2005-01-13 Fmc Corporation Delivery system of homogeneous, thermoreversible gel film containing kappa-2 carrageenan
US20050013847A1 (en) * 2003-04-14 2005-01-20 Fmc Corporation Delivery systems of homogeneous, thermoreversible alginate films
US20050019295A1 (en) * 2003-04-14 2005-01-27 Fmc Corporation Homogeneous, thermoreversible low viscosity polymannan gum films and soft capsules made therefrom
JP2007525451A (ja) * 2003-04-14 2007-09-06 エフ　エム　シー　コーポレーション 均一かつ熱可逆性アルギネートフィルムの伝達システム
US20050048185A1 (en) * 2003-04-14 2005-03-03 Fmc Corporation Delivery systems of homogeneous, thermoreversible low viscosity polymannan gum films
US20050019294A1 (en) * 2003-04-14 2005-01-27 Fmc Corporation Homogeneous, thermoreversible alginate films and soft capsules made therefrom
US20090314183A1 (en) * 2008-06-24 2009-12-24 S.D. Warren Company Multi-component Starch Binder Compositions
SE542658C2 (en) * 2018-05-18 2020-06-23 Stora Enso Oyj Coating composition for paper and paperboard
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FR2447388A1 (fr) * 1979-01-23 1980-08-22 Roquette Freres Produit comportant les constituants des hydrolysats d'amidon hydrogenes et notamment le sorbitol, son procede de preparation et ses applications

Also Published As

Publication number Publication date
EP0106763A1 (de) 1984-04-25
FR2540153A1 (fr) 1984-08-03
US4600439A (en) 1986-07-15
ATE26138T1 (de) 1987-04-15
DE3370499D1 (en) 1987-04-30
CA1218480A (en) 1987-02-24
FR2540153B1 (fr) 1987-02-13

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