EP0106763A1 - Composition and process for coating paper and board, process for preparing the composition and paper and board thus obtained - Google Patents
Composition and process for coating paper and board, process for preparing the composition and paper and board thus obtained Download PDFInfo
- Publication number
- EP0106763A1 EP0106763A1 EP83401993A EP83401993A EP0106763A1 EP 0106763 A1 EP0106763 A1 EP 0106763A1 EP 83401993 A EP83401993 A EP 83401993A EP 83401993 A EP83401993 A EP 83401993A EP 0106763 A1 EP0106763 A1 EP 0106763A1
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- EP
- European Patent Office
- Prior art keywords
- starch
- pigment
- depolymerized
- paper
- coating composition
- 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.)
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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
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- 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 consists 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 microns, 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 formed by the layer thus put in place are extremely thin, these are micro-capillaries with a width of the order of 2 to 5 microns.
- the ink pigments which are larger than the channels of the layer, remain on the surface while the ink pigment support which is made up of oils and solvents is easily absorbed by micro-capillaries, which improves the quality of the print.
- 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 sulphate, satin white (S0 4C a + Al 2 O 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 the salts of 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.
- non-depolymerized starch in coating compositions, in particular because of the difficulty of obtaining, from an unpolymerized starch ,. a correct colloidal solution, 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 bedding are depolymerized either by acid or enzymatic hydrolysis, or by oxidation, or by dextrinification, some of these degradations (enzymatic or oxidative) can also 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, carbonization, hydroxyethylenation or hydroxypropylenation for example).
- etherification or esterification acetylation, carbonization, 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 so-called "fluidifying" agent chosen from the group consisting of hydrogenated sugars comprising sorbitol ,. mannitol, maltital, 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 the group comprising casein and soy proteins.
- 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 above, these starches may have been etherified, esterified or crosslinked in order to modify some of their properties, 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 makes it possible to remedy all the drawbacks described above, attached to the use of degraded starches, and in particular makes it possible to obtain a higher binding power, better layer resistance, better retention of 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 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.
- Dislocation of particle clusters. linked by Van der Waals-type forces is designated by the term “deflocculation”. This phenomenon is reversible. This reversibility is prevented by introducing chemicals into the pigment system that act on the particle surfaces so that they repel each other.
- 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 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” seems 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 dispersion of pigments, which the starch glue and the dispersion of pigments are mixed, and an effective proportion of fluidifying agent chosen from the group consisting of hydrogenated sugars including in particular sorbitol, mannitol, maltitol, xylitol, lactitol and hydrogenated starch hydrolysates, by addition either in the water used for the preparation of starch glue and / or the dispersion of pigments, or in starch glue, or in the pigment dispersion, either in the mixture of the two or in the final coating preparation.
- a non-depolymerized starch glue is prepared
- a dispersion of pigments which the starch glue and the dispersion of pigments are mixed
- an effective proportion of fluidifying agent chosen from the group consisting of hydrogenated sugars including in particular sorb
- 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 "Jet Cooker” type well known to starch manufacturers, in which the cooking of the starch is obtained by ' intro duction of water vapor 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 viscosity development 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 en 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.
- binder For the constitution of the binder, use may be made only of non-depolymerized starches but generally the other conventional binding agents are used at the same time.
- 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 corn starch suspension 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.
- a dispersion of the pigments was prepared from the following constituents: by treating the mixture by passage through a deliter of mark "CELLIER" for 15 minutes.
- the second coating composition 1725 g of a non-depolymerized starch glue having a dry matter of 20% (which is equivalent to 4 parts of starch counted as dry per 100 parts of pigment) was added, to a dispersion of pigments prepared in the same manner as above. Then added 1380 g of latex SB 024 at 50% dry matter, or 8% dry / dry with respect to the pigment.
- 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 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.
- the filtration of the composition intended for the ridding any possible agglomerates 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.
- the following products were dispersed in 3500 g of water: using a CELLIER type device for 30 minutes.
- 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.
- a corn starch glue not depolymerized to 20% dry matter prepared under the same conditions as in Example 1, the amount added being 2587 g, ie 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 (amount of composition per unit area) of 12 g / m2.
- 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.
- the hydrogenated starch hydrolyzate No. 1 corresponds to that sold by the Applicant Company under the trademark NEOSORB 70 / 70®; it has the following composition, the percentages being expressed on the dry matter:
- the hydrogenated starch hydrolyzate No. 2 obtained by hydrogenation of a starch hydrolyzate of DE equal to 33, has the following composition:
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Abstract
Description
La présente invention a pour objet une composition aqueuse pour le couchage du papier et du carton.The present invention relates to an aqueous composition for coating paper and cardboard.
Elle vise également un. procédé de couchage du papier mettant en oeuvre ladite composition, ainsi qu'un procédé pour la préparer.It also targets a. process for coating paper using said composition, as well as a process for preparing it.
Elle vise enfin les papiers et cartons obtenus, c'est-à-dire "couchés" à l'aide de cette composition.Finally, it relates to the paper and cardboard obtained, that is to say "coated" using this composition.
Par le terme technique de "couchage", on désigne l'opération consistant à déposer sur une ou sur les deux faces d'une feuille support en papier ou carton, une composition de couchage formant un enduit ; cet enduit confère à la feuille traitée un état de surface particulièrement régulier et donc apte à bien recevoir une impression fine, tout en améliorant l'opacité et l'aspect du papier (blancheur, lissé, brillant).The technical term "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).
Une composition de couchage comprend au moins deux constituants, à savoir un pigment et un liant encore appelé adhésif.A coating composition comprises at least two components, namely a pigment and a binder also called an adhesive.
Le premier de ces constituants, le pigment, intervient comme suit lors de l'opération de couchage.The first of these constituents, the pigment, intervenes as follows during the coating operation.
Le papier est constitué de fibres de dimensions variables qui, malgré l'opération habituelle de satinage, laissent subsister, d'une part, en surface des cavités dont les dimensions sont de l'ordre de 50 à 100 microns et, d'autre part, dans l'épaisseur du papier, des canaux plus ou moins larges, désignés par le terme de macro- capillaires. Quand, lors de l'opération de couchage, on recouvre la surface avec un enduit à base de pigments très fins, ceux-ci viennent combler les cavités en nivelant la surface ; les canaux comportés par la couche ainsi mise en place sont extrêmement fins, il s'agit de micro-capillaires d'une largeur de l'ordre de 2 à 5 microns. Lors de l'impression des papiers couchés, les pigments de l'encre, qu.i sont plus gros que les canaux de la couche, restent en surface alors que le support du pigment de l'encre qui est constitué par des huiles et des solvants est facilement absorbé par les micro-capillaires, ce grâce à quoi la qualité de l'impression est améliorée.The paper consists 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 microns, 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. When, during the coating operation, the surface is covered with a coating based on very fine pigments, these fill the cavities by leveling the surface; the channels formed by the layer thus put in place are extremely thin, these are micro-capillaries with a width of the order of 2 to 5 microns. When printing coated papers, the ink pigments, which are larger than the channels of the layer, remain on the surface while the ink pigment support which is made up of oils and solvents is easily absorbed by micro-capillaries, which improves the quality of the print.
Pour constituer le pigment de la composition de couchage, on a généralement recours à une dispersion aqueuse de kaolin ; il est également possible d'utiliser soit séparément, soit le plus souvent en mélange avec le kaolin, d'autres pigments tels que notamment le carbonate de calcium, l'oxyde de titane, le sulfate de calcium, le blanc satin (S04Ca + Al2O3) ou du talc très fin.To constitute the pigment of the coating composition, use is generally made of 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 sulphate, satin white (S0 4C a + Al 2 O 3 ) or very fine talc.
Pour constituer le liant de la composition de couchage, on a généralement recours à des amidons, des protéines comme la caséine ou la protéine de soja, ou à des produits synthétiques comme l'alcool de polyvinyle, l'acétate de polyvinyle, les produits acryliques, les styrène-butadiène ; la composition peut contenir un seul de ces produits, mais souvent on les utilise en mélange. La quantité de liant représente généralement de 5 à 30 X du poids de pigment. Cette quantité est choisie notamment en fonction de la nature du pigment, en fonction du procédé de couchage utilisé et en fonction des qualités recherchées pour le papier ou le carton. A titre d'exemple, on signale qu'il y a lieu de mettre en oeuvre plus de liant dans le cas du carbonate et du blanc satin que dans le cas du kaolin, dans le cas des charges divisées que dans le cas des charges grossières.To constitute the 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 .
Outre le pigment et le liant, une composition de couchage comprend divers agents complémentaires parmi lesquels on peut citer les réducteurs de mousse, les agents de conservation, les colorants, les dispersants ou défloculants comme le tripolyphosphate, le .pyrophosphate ou l'hexamétaphosphate et les sels d'acides polycarboxy- liques qui retardent notamment la sédimentation des suspensions. [ In addition to the pigment and the binder, 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 the salts of polycarboxylic acids which retard in particular the sedimentation of the suspensions. [
La formulation de la composition de couchage varie en fonction de la technique d'application, des qualités du papier support ou des propriétés recherchées, ces dernières étant différentes suivant le mode d'impression (héliogravure, impression typographique, offset, impression flexographique, sérigraphie) auquel les papiers couchés sont destinés.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.
A noter enfin que le simple aspect énergétique conduit à rechercher, pour une viscosité donnée, des compositions de couchage présentant un extrait sec le plus élevé possible, de façon à ce que la dépense énergétique nécessaire à l'obtention d'un papier. couché sec soit la plus faible possible.Finally, it should be noted that the simple energy aspect leads to the search, for a given viscosity, for coating compositions having the highest possible dry extract, so that the energy expenditure necessary for obtaining a paper. lying dry as low as possible.
Les amidons utilisés jusqu'à présent, seuls ou en mélange avec les protéines ou les produits synthétiques susmentionnés pour constituer le liant de la composition de couchage, sont des amidons dépolymérisés, éventuellement modifiés en outre par éthérification ou estérification.The 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.
Il a été en effet très difficile, voire pratiquement impossible, d'avoir recours à l'amidon non dépolymérisé dans des compositions de couchage, notamment en raison de la difficulté d'obtenir, à partir d'un amidon non dépolymérisé,. une solution colloïdale correcte, vu que des sols d'amidon non dépolymérisé cuits pendant 90 minutes au bain-marie présentent encore des granules fortement gonflés. Et même lorsqu'on obtient des sols corrects d'amidon non dépolymérisé, ceux-ci présentent une viscosité excessive, aggravée par la tendance des molécules à la réassociation ou rétrogradation, qui empêche en fait leur application pratique dans des compositions de couchage.It has indeed been very difficult, even practically impossible, to use non-depolymerized starch in coating compositions, in particular because of the difficulty of obtaining, from an unpolymerized starch ,. a correct colloidal solution, 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.
Les amidons actuellement utilisés en couchage sont dépolymérisés soit par hydrolyse acide ou enzymatique, soit par oxydation, soit par dextrinification, certaines de ces dégradations (enzymatique ou oxydante) pouvant d'ailleurs être réalisées directement chez l'utilisateur. C'est pour améliorer certaines propriétés (comme les propriétés de liaison ou de "lissé") des couches contenant de l'amidon en tant que liant, que l'on peut procéder, soit avant, soit après la réaction de dépolymérisation, à des modifications chimiques comme l'éthérification ou l'estérification (acétylation, catio- nisation, hydroxyéthylénation ou hydroxypropylénation par exemple).The starches currently used in bedding are depolymerized either by acid or enzymatic hydrolysis, or by oxidation, or by dextrinification, some of these degradations (enzymatic or oxidative) can also 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, carbonization, hydroxyethylenation or hydroxypropylenation for example).
Il se trouve qu'actuellement les utilisateurs préfèrent diminuer la proportion d'amidon dépolymérisé présente dans le liant constitutif des compositions de couchage au bénéfice des produits synthétiques identifiés plus haut ; ces derniers entrent même seuls dans la constitution des liants utilisés dans les compositions de couchage mises en oeuvre dans certaines installations appropriées.It turns out that currently users prefer to reduce the proportion of depolymerized starch present in the binder constituting the coating compositions in favor of the synthetic products identified above; the latter even enter alone into the constitution of the binders used in the coating compositions used in certain appropriate installations.
Cette désaffection à l'égard des amidons dépolymérisés doit être attribuée entre autres :
- - à leur pouvoir liant relativement peu élevé,
- - à leurs propriétés médiocres de rétention d'eau dues à la taille réduite des molécules d'amidon dépolymérisé, cette taille réduite favorisant par ailleurs la pénétration de l'enduit de couchage dans la feuille traitée en diminuant la solidité et la résistance de la couche.
- - their relatively low binding power,
- - their poor water retention properties due to the reduced size of the depolymerized starch molecules, this reduced size also promoting the penetration of the coating coating into the treated sheet by reducing the strength and resistance of the layer .
De plus, les phénomènes de migration, essentiellement au séchage, sont importants.In addition, migration phenomena, mainly during drying, are important.
Or, le coût des produits synthétiques est très élevé et en tout cas bien supérieur à celui des amidons dépolymérisés et éventuellement modifiés.However, the cost of synthetic products is very high and in any case much higher than that of depolymerized and possibly modified starches.
Il s'ensuit qu'il existe dans l'industrie du papier et du carton le besoin d'un produit pouvant constituer le liant des compositions de couchage qui soit plus économique que les produits synthétiques actuellement de plus en plus utilisés et qui ne présente pas les défauts des amidons dépolymérisés dont les principaux sont rappelés ci-dessus.It follows that there exists in the paper and cardboard industry the need for a product which can constitute the binder of coating compositions which is more economical than the synthetic products currently increasingly used and which does not have the defects of depolymerized starches, the main ones of which are recalled above.
Les propriétés bien connues des amidons non dépolymérisés font que ces derniers répondraient au susdit besoin si les difficultés pratiquement insurmontables de préparation de sols corrects de viscosité acceptable à base de ces amidons non dépolymérisés n'en interdisaient l'application.The well-known properties of 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.
Or, la Société Demanderesse a eu le mérite de trouver que, de façon surprenante et inattendue, il était possible d'utiliser des amidons non dépolymérisés dans la constitution des liants pour compositions de couchage dès lors que ces amidons non dépolymérisés étaient mis en oeuvre en même temps qu'une proportion efficace d'au moins un agent dit "fluidifiant" choisi dans le groupe constitué par les sucres hydrogénés comprenant le sorbitol,. le mannitol, le maltital, le xylitol, le lactitol et les hydrolysats d'amidon hydrogénés.However, 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 so-called "fluidifying" agent chosen from the group consisting of hydrogenated sugars comprising sorbitol ,. mannitol, maltital, xylitol, lactitol and hydrogenated starch hydrolysates.
La composition aqueuse de couchage conforme à l'invention est donc caractérisée par le fait qu'elle comprend, outre le pigment :
- .- un ou plusieurs agents fluidifiants choisis dans le groupe constitué par les sucres hydrogénés comprenant notamment le sorbitol, le mannitol, le maltitol, le xylitol, le lactitol et les hydrolysats d'amidon hydrogénés, la proportion d'agent fluidifiant étant de 0,40 à 20 parties en poids pour 100 parties de pigment, et
- - à titre de liant, un ou plusieurs amidons non dépolymérisés, éventuellement modifiés par éthérification, estérification ou réticulation.
- one or more thinning agents chosen from the group consisting of hydrogenated sugars comprising in particular sorbitol, mannitol, maltitol, xylitol, lactitol and hydrogenated starch hydrolysates, the proportion of thinning agent being 0, 40 to 20 parts by weight per 100 parts of pigment, and
- - as a binder, one or more non-depolymerized starches, possibly modified by etherification, esterification or crosslinking.
Généralement, cette composition comprend également un ou plusieurs produits synthétiques du groupe comprenant notamment l'alcool de polyvinyle, l'acétate de polyvinyle, les produits acryliques, les styrène-butadiène, les copolymères synthétiques et/ou une ou plusieurs protéines choisies notamment dans le groupe comprenant la caséine et les protéines de soja.Generally, 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 the group comprising casein and soy proteins.
Par l'expression "amidons non dépolymérisés", on désigne les amidons n'ayant pas subi de traitement de dépolymérisation tel que notamment les hydrolyses acide ou enzymatique, la dégradation oxydante ou la dextrinification. Ils peuvent être choisis parmi les amidons de toute provenance et notamment parmi les amidons de mais, éventuellement hybrides, l'amidon de blé et de riz, la fécule de pomme de terre, la fécule de manioc. En outre, comme déjà mentionné précédemment, ces amidons peuvent avoir été éthérifiés, estérifiés ou réticulés afin de modifier certaines de leurs propriétés comme par exemple leur stabilité en solution.The expression “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 above, these starches may have been etherified, esterified or crosslinked in order to modify some of their properties, for example their stability in solution.
La présence des agents fluidifiants permet de conférer à la composition de couchage une viscosité et une texture parfaitement adaptées au couchage du papier.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.
L'utilisation des amidons non dépolymérisés permet -de remédier à tous les inconvénients précédemment décrits, attachés à l'emploi des amidons dégradés, et permet notamment d'obtenir un pouvoir liant plus élevé, une meilleure résistance de la couche, une meilleure rétention d'eau et une meilleure homogénéité de la surface.The use of non-depolymerized starches makes it possible to remedy all the drawbacks described above, attached to the use of degraded starches, and in particular makes it possible to obtain a higher binding power, better layer resistance, better retention of and better homogeneity of the surface.
Il convient de souligner que l'effet des agents fluidifiants utilisés conformément à l'invention est très différent de l'effet des agents dispersants ou défloculants communément utilisés dans les dispersions de pigments et dont il va être question.It should be emphasized that the effect of the thinning agents used in accordance with the invention is very different from the effect of the dispersing or deflocculating agents commonly used in pigment dispersions and which will be discussed.
Un pigment donné est essentiellement caractérisé, non seulement par sa composition chimique, mais également par la taille et la disposition de ses.particules constitutives.A given pigment is essentially characterized, not only by its chemical composition, but also by the size and arrangement of its constituent particles.
En général, celles-ci sont accolées les unes aux autres, et le nombre des possibilités d'assemblage est illimité; elles peuvent ainsi être groupées en "grappes" rassemblant peu ou beaucoup de particules individuelles plus ou moins serrées les unes contre les autres.In general, these are attached to each other, and the number of assembly possibilities is unlimited; they can thus be grouped into "clusters" gathering little or a lot of individual particles more or less tightly packed against each other.
La description. du comportement des particules dans la grappe est également importante : nombre de particules, mobilité ou manque de mobilité, résistance à la rupture ou au réarrangement de la grappe et état de surface de la grappe.The description. 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.
Il est admis que l'on réalise la dispersion du pigment lorsqu'on réalise la rupture des grappes de particules de pigments.It is recognized that the dispersion of the pigment is carried out when the clusters of pigment particles are ruptured.
Les particules constitutives de la grappe peuvent être liées les unes aux autres par des liaisons chimiques aux points de contact, donnant aux grappes une résistance à peu près égale à celle des particules individuelles de même taille ; elles peuvent également être assez faiblement liées les unes aux autres comme si elles étaient attirées par des forces magnétiques ou de gravitation (force de Van der Waals), ces arrangements particuliers pouvant être "dérangés" ou rompus par l'application d'une force.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.
La dislocation des grappes de particules liées par des liaisons chimiques à leurs points de contact est désignée par le terme "désagrégation". Après désagrégation ou séparation des particules, les liens ne sont pas reformés, le processus de désagrégation étant donc irréversible.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.
La dislocation des grappes de particules. liées par des forces de type Van der Waals est désignée par le terme "défloculation". Ce phénomène est réversible. On empêche cette réversibilité en introduisant dans le système de pigments des produits chimiques qui agissent sur les surfaces de particules pour que celles-ci se repoussent mutuellement.Dislocation of particle clusters. linked by Van der Waals-type forces is designated by the term "deflocculation". This phenomenon is reversible. This reversibility is prevented by introducing chemicals into the pigment system that act on the particle surfaces so that they repel each other.
L'utilisation d'agents dispersants est donc une partie essentielle du processus de dispersion qui rend efficace l'emploi de l'énergie mécanique et qui diminue la viscosité de la suspension des pigments.The use of 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 pigments.
Une composition de couchage comporte des particules de pigment et un liant, en solution aqueuse formant un milieu fluide, dans lequel les particules de pigment sont en suspension. Le milieu fluide ne comprend pas seulement le liant ou adhésif mais également toutes les autres matières dissoutes, en particulier les agents fluidifiants utilisés conformément à l'invention.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.
L'amidon ou caséine, par exemple, quoique en solution colloïdale, sont dans un état de solubilité suffisant pour qu'ils soient nettement, considérés comme une partie du fluide.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.
Le milieu fluide agit comme un lubrifiant entre les particules et leur permet de glisser les unes sur les autres beaucoup plus facilement qu'elles ne pourraient le faire.si elles étaient sèches.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.
La faible dimension des molécules d'agent fluidifiant utilisées conformément à l'invention fait qu'elles présentent une mobilité importante mais, en dépit de cette réalité, il est surprenant de constater que l'addition d'un quelconque de ces agents ou de plusieurs d'entre eux, addition qui conduit à une augmentation de la teneur en matières sèches de l'ensemble, se traduise par une diminution de la viscosité telle que le terme "agent fluidifiant" paraît s'imposer pour désigner les agents entrant, conformément à l'invention, dans la constitution du liant.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" seems to be essential to designate the agents entering, in accordance with the invention, in the constitution of the binder.
Cet effet de diminution de la viscosité n'est pas réalisé par l'augmentation du taux d'agents dispersants ou défloculants communément utilisés dans les dispersions de pigments ; bien au contraire, il est connu que l'augmentation du taux d'incorporation de ces produits entrai- ne, au-delà du taux d'utilisation optimal, une élévation très rapide de la viscosité de la préparation de couchage.This viscosity reduction effect is not achieved by increasing the level of dispersing or deflocculating agents commonly used in pigment dispersions; on the contrary, it is known that increasing the rate of incorporation of these products leads, beyond the optimal rate of use, to a very rapid increase in the viscosity of the coating preparation.
C'est donc bien la sélection des agents fluidifiants utilisés conformément à l'invention qui permet l'utilisation, à titre d'agent liant, des amidons non dépolymérisés.It is therefore the selection of the thinning agents used in accordance with the invention that allows the use, as binding agent, of non-depolymerized starches.
Le procédé de 'couchage du papier ou du carton conforme à l'invention est caractérisé par le fait que l'on applique, sur l'une ou les deux faces du papier et du carton, la composition aqueuse de couchage conforme à l'invention.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 .
Tous les dispositifs et appareillages conventionnels tels que les coucheuses à brosses, les coucheuses CHAMPION, les coucheuses à lame d'air ou à râcle traînante, les coucheuses à rouleaux multiples ou les coucheuses à rouleaux gravés, les coucheuses de type BILL-BLADE et autres peuvent être utilisés pour cette application.All conventional devices and equipment such as brush coater, CHAMPION coater, air knife or trailing-blade coater, multi-roller coater or engraved roller coater, BILL-BLADE coater and others can be used for this application.
Le procédé de préparation de la composition aqueuse de couchage conforme à l'invention est caractérisé par le fait que l'on prépare, d'une part, une colle d'amidon non dépolymérisé, d'autre part, une dispersion de pigments, que l'on réalise le mélange de la colle d'amidon et de la dispersion de pigments, et que l'on introduit une proportion efficace d'agent fluidifiant choisi dans le groupe constitué par les sucres hydrogénés comprenant notamment le sorbitol, le mannitol, le maltitol, le xylitol, le lactitol et les hydrolysats d'amidon hydrogénés, par addition soit dans l'eau servant à la préparation de la colle d'amidon et/ou de la dispersion de pigments, soit dans la colle d'amidon, soit dans la dispersion de pigments, soit dans le mélange des deux ou dans la préparation finale de couchage.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 dispersion of pigments, which the starch glue and the dispersion of pigments are mixed, and an effective proportion of fluidifying agent chosen from the group consisting of hydrogenated sugars including in particular sorbitol, mannitol, maltitol, xylitol, lactitol and hydrogenated starch hydrolysates, by addition either in the water used for the preparation of starch glue and / or the dispersion of pigments, or in starch glue, or in the pigment dispersion, either in the mixture of the two or in the final coating preparation.
La cuisson de l'amidon non dépolymérisé peut être effectuée par toute technique appropriée et notamment par une cuisson dans un appareil à injection de vapeur vive.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.
De préférence, on réalise cette cuisson par passage d'une suspension d'amidon non dépolymérisé dans un appareil du type "Jet Cooker" bien connu des amidonniers, dans lequel la cuisson de l'amidon est obtenue par'introduction de vapeur d'eau à une pression supérieure à la pression atmosphérique. De préférence toujours, la cuisson de l'amidon non dépolymérisé est réalisée à une matière sèche comprise entre 5 % et 30 %, à une température supérieure à 1200C et en un temps généralement supérieur à 20 secondes, ce grâce à quoi on obtient une colle d'amidon non dépolymérisé ne comportant pratiquement plus de granules fortement gonflés mais non éclatés, responsables des développements de viscosité et d'un manque de stabilité.Preferably, this cooking is carried out by passing a suspension of non-depolymerized starch in an apparatus of the "Jet Cooker" type well known to starch manufacturers, in which the cooking of the starch is obtained by ' intro duction of water vapor at a pressure higher than atmospheric pressure. Preferably still, 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 viscosity development and a lack of stability.
Parmi les agents fluidifiants identifiés plus haut, on utilise préférentiellement le sorbitol ou les hydrolysats d'amidon hydrogénés, obtenus par hydrolyse acide et/ou enzymatique de tous amidons suivie d'hydrogénation. Ces hydrolysats d'amidon hydrogénés sont constitués principalement et en des proportions variables selon le mode d'hydrolyse appliqué par du sorbitol, du maltitol, de l'isomaltitol et des oligo- et polysaccharides hydrogénés.Among the fluidizing agents identified above, 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.
Plus préférentiellement encore, on a recours à du sorbitol ou à des hydrolysats d'amidon hydrogénés préparés à partir d'hydrolysats d'amidon présentant un D.E. (Dextrose Equivalent) supérieur à 25 ; on préfère notamment les hydrolysats présentant un pourcentage de sorbitol supérieur à 60 % exprimé sur la matière sèche.Even more preferably, use is made of sorbitol or of hydrogenated starch hydrolysates prepared from starch hydrolysates having a D.E. (Dextrose Equivalent) greater than 25; particularly preferred are hydrolysates having a percentage of sorbitol greater than 60% expressed on the dry matter.
Exprimée en matières sèches par rapport à la quantité de pigments, la proportion d'agent fluidifiant entrant dans la composition de couchage selon l'invention est d'environ 0,40 % à 20 Â en poids, de préférence de 0,50 % à 15 % en poids, et plus préférentiellement encore de 0,50 % à 7,5 % en poids.Expressed as dry matter relative to the amount of pigments, the proportion of fluidifying agent entering into the coating composition according to the invention is approximately 0.40% to 20 en by weight, preferably from 0.50% to 15% by weight, and more preferably still from 0.50% to 7.5% by weight.
Les quantités de liants utilisées dans les compositions de couchage selon l'invention sont de 5 à 30 % en poids par rapport au poids des.pigments.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.
Pour la constitution du liant, on peut avoir recours uniquement à des amidons non dépolymérisés mais généralement on utilise en même temps les autres agents liants conventionnels.For the constitution of the binder, use may be made only of non-depolymerized starches but generally the other conventional binding agents are used at the same time.
La proportion d'amidon non dépolymérisé présente dans les compositions de couchage selon l'invention s'établit, les pourcentages étant exprimés sec/sec, entre 0,2 et 30 % et, de préférence, entre 0,5 et 30 % par rapport au poids de pigment.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.
Les compositions de couchage selon l'invention dont le liant est constitué au moins en partie par de l'amidon non dépolymérisé, peuvent être formulées à de très hautes teneurs en matières sèches, de l'ordre de 60 à 70 %, tout en présentant une viscosité compatible avec leur application sur les machines de couchage existantes et tout en n'occasionnant aucune difficulté, par exemple lors de l'opération finale de filtration de la composition de couchage, opération qui consiste à débarrasser la composition notamment des agglomérats qu'elle peut contenir.The coating compositions according to the invention, the binder of which consists at least in part of non-depolymerized starch, 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.
C'est d'ailleurs dans le cas des compositions de couchage présentant une matière sèche élevée, supérieure à environ 53 Â, que l'effet de l'addition des agents fluidifiants utilisés conformément à l'invention se révèle le plus efficace.It is moreover in the case of coating compositions having a high dry matter, greater than approximately 53 Å, that the effect of the addition of the fluidizing agents used in accordance with the invention proves to be most effective.
Un autre avantage inhérent à l'utilisation des compositions de couchage selon l'invention réside dans la meilleure plastification de la couche, apportée par la présence dans les compositions des sucres hydrogénés et plus particulièrement du sorbitol.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.
L'invention pourra être mieux comprise à l'aide des exemples suivants.The invention can be better understood using the following examples.
Comparaison entre deux compositions de couchage selon l'art antérieur comportant comme systèmes liants respectivement un amidon dépolymérisé et un latex pour la première, un amidon non dépolymérisé et un latex pour la deuxième.Comparison between two coating compositions according to the prior art comprising as binding systems respectively a depolymerized starch and a latex for the first, a non-depolymerized starch and a latex for the second.
Les pigments utilisés sont du carbonate de calcium naturel et du kaolin, et le dispersant utilisé est constitué par un polyacrylate, vendu sous la marque "DISPEX N 40" par la Société ALLIED COLLOIDS.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.
La première composition a été préparée à partir d'amidon dépolymérisé par voie enzymatique.The first composition was prepared from enzymatically depolymerized starch.
Pour ce faire, on a traité-une suspension d'amidon de mais dans un convertisseur enzymatique continu tel que construit selon le brevet français N° 1.391.011 et commercialisé par la Société Demanderesse, la transformation enzymatique étant effectuée pendant 30 minutes à 85°C en présence de 1,4 partie d'alpha-amylase pour 1000 parties d'amidon. L'inhibition de l'enzyme a été réalisée sur l'appareil par un flash thermique à 140°C pendant 90 secondes.To do this, a corn starch suspension 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.
Par ailleurs, on a préparé une dispersion des pigments à partir des constituants suivants :
A la dispersion de pigments ainsi obtenue, on a ajouté tout d'abord 2153 g de la susdite colle d'amidon dépolymérisé par voie enzymatique présentant une teneur en matières sèches de 28 %, soit 7 % de "matière sèche/ matière sèche" (ci-après désignée "sec/sec" par souci de simplicité) par rapport au pigment. Puis on a ajouté 1380 g de latex SB 024 (commercialisé par la Société RHONE POULENC) à 50 % de matières sèches, ce qui équivaut à 8 % sec/sec par rapport au pigment.To the pigment dispersion thus obtained, 2153 g of the abovementioned enzymatically depolymerized starch glue was first added, having a dry matter content of 28%, ie 7% of "dry matter / dry matter" ( hereinafter referred to as "dry / dry" for the sake of simplicity) with respect to the pigment. Then 1380 g of SB 024 latex (sold by the company RHONE POULENC) containing 50% dry matter was added, which equals is 8% dry / dry compared to the pigment.
Pour préparer la deuxième composition de couchage, on a ajouté 1725 g d'une colle d'amidon non dépolymérisé présentant une matière sèche de 20 % (ce qui équivaut à 4 parties d'amidon compté en sec pour 100 parties de pigment), à une dispersion de pigments préparée de la même manière que précédemment. On a ajouté ensuite 1380 g de latex SB 024 à 50 % de matières sèches, soit 8 % sec/sec par rapport au pigment.To prepare the second coating composition, 1725 g of a non-depolymerized starch glue having a dry matter of 20% (which is equivalent to 4 parts of starch counted as dry per 100 parts of pigment) was added, to a dispersion of pigments prepared in the same manner as above. Then added 1380 g of latex SB 024 at 50% dry matter, or 8% dry / dry with respect to the pigment.
La colle d'amidon non dépolymérisé a été préparée par passage d'amidon de mais natif sur un Jet-Cooker à une température de 150°C et durant 3 minutes sous une pression de 5 bars.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.
Les viscosités des deux susdites colles d'amidon ont été mesurées sur un viscosimètre BROOKFIELD du type R.V.T., pour une vitesse de 20 tours par minute ; puis elles ont été mesurées une nouvelle fois', les colles d'amidon ayant été maintenues au bain-marie pendant 24 heures à 90°C sans et avec une légère agitation. Ces viscosités enregistrées sont réunies dans le tableau I.
Les viscosités des deux compositions de couchage ont ensuite été mesurées à 30°C, le stockage étant réalisé avec et sans agitation.The viscosities of the two coating compositions were then measured at 30 ° C, storage being carried out with and without stirring.
La rétention d'eau a été mesurée sur une rampe et des filtres de type FANN classiques du genre de ceux utilisés pour l'étude des boues de forage, sous une pression de 6,9 bars. 1 Water retention was measured on a ramp and conventional FANN type filters of the kind used used for the study of drilling muds, at a pressure of 6.9 bars. 1
Dans le tableau II, on a réuni les résultats obtenus.
On constate que la viscosité de la composition de couchage à base d'amidon non dépolymérisé est très supérieure à celle de la composition à base d'amidon dépolymérisé par voie enzymatique. La viscosité HERCULES, très représentative étant donné le cisaillement appliqué, est ainsi pratiquement double de celle obtenue avec amidon dépolymérisé ; une telle viscosité rend pratiquement inapplicable l'utilisation de la composition correspondante pour le couchage du papier et du carton. En.particulier, la filtration de la composition destinée à la débarrasser des agglomérats éventuellement présents est rendue extrêmement difficile.It is found that 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. In particular, the filtration of the composition intended for the ridding any possible agglomerates is made extremely difficult.
On constate également que l'on obtient, avec la composition à base d'amidon non dépolymérisé, une rétention d'eau très correcte, malgré l'utilisation d'un taux d'amylacé sensiblement moins élevé (4 % au lieu de 7 %).We also note that we obtain, with the non-depolymerized starch-based composition, a very correct water retention, despite the use of a significantly lower starch content (4% instead of 7% ).
Ceci confirme l'intérêt de l'emploi de l'amidon non dépolymérisé, à condition que l'on arrive à réduire la viscosité sans pour autant nuire aux autres caractéristiques.This confirms the advantage of using non-depolymerized starch, provided that the viscosity can be reduced without adversely affecting the other characteristics.
Cet exemple illustre l'effet de l'addition de sorbitol en fonction du moment choisi pour cette addition à une composition de couchage contenant l'amidon non dépolymérisé en tant que liant.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.
Pour préparer la composition de couchage, on a réalisé la dispersion dans 3500 g d'eau des produits suivants :
On a ajouté ensuite à la dispersion environ 1725g d'une colle d'amidon de mais non dépolyrnérisé à 20 % de matières sèches, préparée sur Jet-Cooker dans les. mêmes conditions qu'à l'exemple 1, soit 4 % d'amidon sec par rapport aux pigments.Was then added to the dispersion about 1725 g of a corn starch glue but not depolyrnized to 20% dry matter, prepared on Jet-Cooker in them. same conditions as in Example 1, ie 4% of dry starch relative to the pigments.
On a ajouté enfin 1380 g de latex SB 024, soit 8X en sec par rapport aux pigments.Finally, 1380 g of SB 024 latex was added, or 8X dry relative to the pigments.
A plusieurs échantillons de cette composition, on a ajouté chaque fois 160 g d'une solution de sorbitol NEOSORB 70/02 ® à 70 % de matières sèches, soit 0,7 % de sorbitol sec par rapport à l'ensemble de la composition ou 1,29 % sec/sec par rapport aux pigments, les additions de sorbitol étant effectuées à différentes phases de la préparation, à savoir :
- - addition dans'la dispersion de pigments, après 25 minutes de dispersion (préparation A)
- - addition à la fin de la préparation, après l'introduction du latex (préparation B)
- - addition à la fois dans la dispersion de pigments et dans la préparation finale après l'introduction du latex, en deux parties égales, soit 80 g dans la dispersion et 80 g dans la préparation finale (préparation C).
- - addition in the dispersion of pigments, after 25 minutes of dispersion (preparation A)
- - addition at the end of the preparation, after the introduction of the latex (preparation B)
- - Adding both in the dispersion of pigments and in the final preparation after the introduction of the latex, in two equal parts, ie 80 g in the dispersion and 80 g in the final preparation (preparation C).
Pour la préparation sans sorbitol et pour chacune des autres préparations ainsi réalisées, on a mesuré les viscosités ainsi que la rétention d'eau et on a réuni les chiffres dans le tableau III.
On constate que, quelle que soit la phase d'introduction, l'addition de 0,7 % de sorbitol dans la composition de couchage permet de réduire la viscosité de façon très significative.It is found that, whatever the introduction phase, the addition of 0.7% of sorbitol in the coating composition makes it possible to reduce the viscosity very significantly.
Les caractéristiques de rétention d'eau et de migration ne sont par ailleurs pas affectées par l'addition de sorbitol.The water retention and migration characteristics are also not affected by the addition of sorbitol.
Influence de la proportion (taux croissants) de sorbitol dans une composition de couchage contenant de l'amidon non dépolymérisé comme agent liant.Influence of the proportion (increasing levels) of sorbitol in a coating composition containing starch not depolymerized as a binding agent.
On utilise la formule suivante :
Le kaolin représente donc 70 % de la charge totale et le carbonate de calcium 30 %.Kaolin therefore represents 70% of the total charge and calcium carbonate 30%.
La dispersion des pigments a été effectuée en 15 minutes à grande vitesse sur déliteur CELLIER.The dispersion of the pigments was carried out in 15 minutes at high speed on a CELLIER deliter.
On a ensuite ajouté à la dispersion de pigments ainsi obtenue, une colle d'amidon de mais non dépolymérisé à 20 % de matières sèches, préparée dans les mêmes conditions qu'à l'exemple 1, la quantité ajoutée étant de 2587 g, soit 4 % sec/sec par rapport aux pigments.Then added to the pigment dispersion thus obtained, a corn starch glue not depolymerized to 20% dry matter, prepared under the same conditions as in Example 1, the amount added being 2587 g, ie 4% dry / dry compared to pigments.
A l'ensemble, on a ajouté ensuite 2070 g de latex SB 024, soit 8 % sec/sec.To the whole, 2070 g of latex SB 024, or 8% dry / dry, were then added.
A différents échantillons identiques de la composition ainsi préparée, on a alors ajouté des proportions croissantes de sorbitol sous forme d'une solution à 70 % de matière sèche tel que celui commercialisé par la Société Demanderesse sous la marque NEOSORB 70/02 ®. Le taux d'introduction était de 0 à 2,1 % de sorbitol sec par rapport à l'ensemble de la préparation de couchage.To different identical samples of the composition thus prepared, increasing proportions of sorbitol were then added in the form of a 70% solution of dry matter such as that sold by the Applicant Company under the brand NEOSORB 70/02 ®. The introduction rate was 0 to 2.1% dry sorbitol based on the entire coating preparation.
Les mesures de viscosité sont rassemblées dans le tableau IV.
A l'examen de ces résultats, on constate que l'effet du sorbitol augmente avec le pourcentage introduit, l'action fluidifiante ne passant pas par un maximum. C'est là une différence fondamentale par rapport aux effets enregistrés uniquement sous l'influence d'agents dispersants de pigments.Upon examination of these results, it is found that the effect of sorbitol increases with the percentage introduced, the fluidizing action not passing through a maximum. This is a fundamental difference from the effects recorded only under the influence of pigment dispersing agents.
En particulier, pour un taux de sorbitol de 2,1 X par rapport à l'ensemble de la formule, la viscosité est diminuée de moitié.In particular, for a sorbitol level of 2.1 X relative to the whole of the formula, the viscosity is reduced by half.
Lors de ces mesures, le pH était de 8,8 et la teneur en matière sèche d'environ 62 %.During these measurements, the pH was 8.8 and the dry matter content of about 62%.
On a ensuite étudié sur les mêmes compositions la rétention d'eau en utilisant une rampe et des filtres FANN. La pression était de 6,9 bars, obtenue à l'aide d'air comprimé.Water retention was then studied on the same compositions using a ramp and FANN filters. The pressure was 6.9 bars, obtained using compressed air.
Les résultats sont réunis dans le tableau V.
On constate, au vu de ces résultats, que la rétention d'eau n'est pas perturbée par la présence du sorbitol, même en quantité importante.It is noted, in view of these results, that water retention is not disturbed by the presence of sorbitol, even in large quantities.
De plus, on constate que les compositions selon l'invention ne donnent pas lieu à des effets néfastes de migration.In addition, it is found that the compositions according to the invention do not give rise to harmful migration effects.
Ensuite et toujours à l'aide des susdites compositions, on a procédé à des essais de couchage sur un support papier préalablement surfacé de 70 g/m2.Then and still with the aid of the above compositions, coating tests were carried out on a paper support previously coated with 70 g / m 2 .
La vitesse de la machine de couchage était de 140 mètres/minute, la température du séchoir de 170°C et la dépose (quantité de composition par unité de surface) de 12 g/m2.The speed of the coating machine was 140 meters / minute, the temperature of the dryer 170 ° C and the deposit (amount of composition per unit area) of 12 g / m2.
Les tests auxquels ont été soumis les papiers ainsi "couchés" sont
- - le test dit aux "Cires Dennison" (cf. norme TAPPI T 459 os 75),
- - le test dit "IGT-encre 3805" (cf. norme TAPPI T 499 su 64) et
- - le test dit "IGT humide - encre 3801" (cf. norme TAPPI T 499 su 64).
- - the test known as "Dennison Waxes" (cf. TAPPI standard T 459 os 75),
- - the so-called "IGT-ink 3805" test (cf. TAPPI T 499 su 64 standard) and
- - the so-called "wet IGT - ink 3801" test (see TAPPI T 499 su 64 standard).
Les résultats obtenus dans ces tests sont réunis dans le tableau VI.
On observe que le test aux cires DENNISSON est légèrement amélioré par l'utilisation de sorbitol. Il s'ensuit que la résistance de surface est meilleure.It is observed that the DENNISSON wax test is slightly improved by the use of sorbitol. It follows that the surface resistance is better.
Le test IGT est également sensiblement amélioré.The IGT test is also significantly improved.
Comparaison entre la viscosité d'une composition de couchage à base d'amidon non dépolymérisé ne contenant pas d'agent fluidifiant et les viscosités de différentes compositions de couchage selon l'invention comprenant divers sucres hydrogénés.Comparison between the viscosity of a coating composition based on non-depolymerized starch containing no fluidizing agent and the viscosities of different com sleeping positions according to the invention comprising various hydrogenated sugars.
La formule et le mode de préparation de la composition de couchage témoin sont les mêmes qu'à l'exemple 2.The formula and the method of preparation of the control coating composition are the same as in Example 2.
Le taux d'incorporation des différents agents fluidifiants testés a été dans tous les cas de 1,29 % sec/sec par rapport aux pigments, les agents fluidifiants ayant été ajoutés dans la préparation finale.The incorporation rate of the various fluidizing agents tested was in all cases 1.29% dry / dry with respect to the pigments, the fluidizing agents having been added in the final preparation.
Les agents fluidifiants testés sont :
- - une solution de sorbitol commercialisée sous la marque de fabrique NEOSORB 70/02®,
- - un hydrolysat d'amidon hydrogéné n° 1,
- - un hydrolysat d'amidon hydrogéné n° 2,
- - le mannitol,
- - le xylitol.
- - a sorbitol solution sold under the trademark NEOSORB 70 / 02®,
- - a hydrogenated starch hydrolyzate n ° 1,
- - a hydrogenated starch hydrolyzate No. 2,
- - mannitol,
- - xylitol.
L'hydrolysat d'amidon hydrogéné n° 1 correspond à celui commercialisé par la Société Demanderesse sous la marque de fabrique NEOSORB 70/70®; il présente la composition suivante, les pourcentages étant exprimés sur la matière sèche :
L'hydrolysat d'amidon hydrogéné n° 2, obtenu par hydrogénation d'un hydrolysat d'amidon de D.E. égal à 33, présente la composition suivante :
Les résultats des mesures de viscosité sont réunis dans le tableau VII.
On constate, à l'examen de ces résultats, que les compositions de couchage conformes à l'invention présentent une viscosité très nettement inférieure à la composition témoin, ce qui rend possible leur utilisation dans le couchage du papier.It is found, on examination of these results, that the coating compositions in accordance with the invention have a viscosity very much lower than the control composition, which makes it possible to use them in the coating of paper.
Comme il va de soi et comme il résulte d'ailleurs déjà de ce qui précède, l'invention ne se limite nullement à ceux de ses modes d'application et de réalisation qui ont été plus particulièrement envisagés ; elle en embrasse, au contraire, toutes les variantes.As goes without saying and as it moreover already follows from the above, the invention is in no way limited to those of its modes of application and embodiments which have been more particularly envisaged; on the contrary, it embraces all its variants.
Claims (6)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AT83401993T ATE26138T1 (en) | 1982-10-12 | 1983-10-12 | COMPOSITION AND PROCESS FOR COATING PAPER AND BOARD, PROCESS FOR MAKING THE COMPOSITION AND PAPER AND BOARD THUS OBTAINED. |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR8217085 | 1982-10-12 | ||
FR8217085A FR2540153B1 (en) | 1982-10-12 | 1982-10-12 | COMPOSITION AND METHOD FOR COATING PAPER AND CARDBOARD, PROCESS FOR PREPARING THE COMPOSITION AND PAPER AND CARDBOARD THUS OBTAINED |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0106763A1 true EP0106763A1 (en) | 1984-04-25 |
EP0106763B1 EP0106763B1 (en) | 1987-03-25 |
Family
ID=9278203
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP83401993A Expired EP0106763B1 (en) | 1982-10-12 | 1983-10-12 | Composition and process for coating paper and board, process for preparing the composition and paper and board thus obtained |
Country Status (6)
Country | Link |
---|---|
US (1) | US4600439A (en) |
EP (1) | EP0106763B1 (en) |
AT (1) | ATE26138T1 (en) |
CA (1) | CA1218480A (en) |
DE (1) | DE3370499D1 (en) |
FR (1) | FR2540153B1 (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0609983A2 (en) * | 1993-02-05 | 1994-08-10 | Cerestar Holding Bv | Starch based material |
EP0667245A1 (en) * | 1994-02-15 | 1995-08-16 | Xerox Corporation | Recording sheets containing alcohols and saccharides |
WO2001092401A2 (en) * | 2000-06-01 | 2001-12-06 | A.E. Staley Manufacturing Co. | Highly flexible starch-based films |
Families Citing this family (20)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4705570A (en) * | 1985-11-05 | 1987-11-10 | American Cyanamid Company | Method of manufacturing a bonded particulate article by reacting a polyol and a meterocyclic compound |
US4921795A (en) * | 1987-03-20 | 1990-05-01 | North American Adhesive Company | Method for producing high solids dextrin adhesives |
US5416181A (en) * | 1989-02-10 | 1995-05-16 | Penford Products Company | Reinforced films made from water soluble polymers |
US4933051A (en) * | 1989-07-24 | 1990-06-12 | Omi International Corporation | Cyanide-free copper plating process |
US5440808A (en) * | 1992-01-30 | 1995-08-15 | Warner-Lambert Company | Disposable shaped article |
FR2777478B1 (en) | 1998-04-17 | 2000-06-16 | Roquette Freres | AQUEOUS PIGMENT (S) AND / OR FILLER (S) DISPERSION CONTAINING A PARTICULAR SACCHARIDE COMPOSITION |
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 |
US20050013847A1 (en) * | 2003-04-14 | 2005-01-20 | Fmc Corporation | Delivery systems of homogeneous, thermoreversible alginate films |
US20050019294A1 (en) * | 2003-04-14 | 2005-01-27 | Fmc Corporation | Homogeneous, thermoreversible alginate films and soft capsules made therefrom |
US20050019295A1 (en) * | 2003-04-14 | 2005-01-27 | Fmc Corporation | Homogeneous, thermoreversible low viscosity polymannan gum films and soft capsules made therefrom |
US20050008677A1 (en) * | 2003-04-14 | 2005-01-13 | Fmc Corporation | Delivery system of homogeneous, thermoreversible gel film containing kappa-2 carrageenan |
US7816341B2 (en) * | 2003-04-14 | 2010-10-19 | Fmc Corporation | Homogeneous, thermoreversible gel containing reduced viscosity carrageenan and products made therefrom |
US20050048185A1 (en) * | 2003-04-14 | 2005-03-03 | Fmc Corporation | Delivery systems of homogeneous, thermoreversible low viscosity polymannan gum films |
US7807194B2 (en) * | 2003-04-14 | 2010-10-05 | Fmc Corporation | Homogeneous, thermoreversible gel film containing kappa-2 carrageenan and soft capsules made therefrom |
US20090314183A1 (en) * | 2008-06-24 | 2009-12-24 | S.D. Warren Company | Multi-component Starch Binder Compositions |
SE542657C2 (en) * | 2018-05-18 | 2020-06-23 | Stora Enso Oyj | Coating composition for paper and paperboard |
SE542658C2 (en) * | 2018-05-18 | 2020-06-23 | Stora Enso Oyj | Coating composition for paper and paperboard |
Citations (5)
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US1733524A (en) * | 1926-11-08 | 1929-10-29 | Champion Coated Paper Company | Coating paper |
US3222220A (en) * | 1963-02-07 | 1965-12-07 | Nat Starch Chem Corp | Water dispersible high amylose starch |
FR2125490A1 (en) * | 1971-02-15 | 1972-09-29 | Hayashibara Ken | |
FR2411866A1 (en) * | 1977-12-15 | 1979-07-13 | Cpc International Inc | PIGMENTED COMPOSITION, BASED ON TREATED STARCH, FOR COATING THE PAPER, ITS PRODUCTION PROCESS AND COATED PAPER OBTAINED |
FR2447388A1 (en) * | 1979-01-23 | 1980-08-22 | Roquette Freres | Hydrogenated starch hydrolysate fixed to carrier - e.g. of starch or protein material, to form solid prod. particles (NL 25.7.80) |
Family Cites Families (4)
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US2287161A (en) * | 1940-01-23 | 1942-06-23 | Du Pont | Coated cellulosic products and method for producing the same |
US3462283A (en) * | 1967-02-28 | 1969-08-19 | Penock & Ford Ltd | Monofunctionally substituted hydrophobic starch and film-forming dispersions prepared therefrom |
US3632786A (en) * | 1968-11-12 | 1972-01-04 | Monsanto Co | Polyvinyl alcohol adhesive composition with high wet tack containing a boron compound and a cis 1 2 polyol compound |
US4173488A (en) * | 1968-12-23 | 1979-11-06 | Champion International Corporation | Oil-in-water emulsions containing hydropholeic starch |
-
1982
- 1982-10-12 FR FR8217085A patent/FR2540153B1/en not_active Expired
-
1983
- 1983-10-12 AT AT83401993T patent/ATE26138T1/en not_active IP Right Cessation
- 1983-10-12 DE DE8383401993T patent/DE3370499D1/en not_active Expired
- 1983-10-12 EP EP83401993A patent/EP0106763B1/en not_active Expired
- 1983-10-12 CA CA000438870A patent/CA1218480A/en not_active Expired
- 1983-10-12 US US06/541,236 patent/US4600439A/en not_active Expired - Lifetime
Patent Citations (5)
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US1733524A (en) * | 1926-11-08 | 1929-10-29 | Champion Coated Paper Company | Coating paper |
US3222220A (en) * | 1963-02-07 | 1965-12-07 | Nat Starch Chem Corp | Water dispersible high amylose starch |
FR2125490A1 (en) * | 1971-02-15 | 1972-09-29 | Hayashibara Ken | |
FR2411866A1 (en) * | 1977-12-15 | 1979-07-13 | Cpc International Inc | PIGMENTED COMPOSITION, BASED ON TREATED STARCH, FOR COATING THE PAPER, ITS PRODUCTION PROCESS AND COATED PAPER OBTAINED |
FR2447388A1 (en) * | 1979-01-23 | 1980-08-22 | Roquette Freres | Hydrogenated starch hydrolysate fixed to carrier - e.g. of starch or protein material, to form solid prod. particles (NL 25.7.80) |
Non-Patent Citations (1)
Title |
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STARCH/STÄRKE, vol. 31, no. 5, mai 1979, pages 163-165, Verlag Chemie, GmbH, Weinheim, DE * |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0609983A2 (en) * | 1993-02-05 | 1994-08-10 | Cerestar Holding Bv | Starch based material |
EP0609983A3 (en) * | 1993-02-05 | 1994-12-21 | Cerestar Holding Bv | Starch based material. |
EP0667245A1 (en) * | 1994-02-15 | 1995-08-16 | Xerox Corporation | Recording sheets containing alcohols and saccharides |
WO2001092401A2 (en) * | 2000-06-01 | 2001-12-06 | A.E. Staley Manufacturing Co. | Highly flexible starch-based films |
WO2001092401A3 (en) * | 2000-06-01 | 2002-05-02 | Staley Mfg Co A E | Highly flexible starch-based films |
Also Published As
Publication number | Publication date |
---|---|
FR2540153B1 (en) | 1987-02-13 |
FR2540153A1 (en) | 1984-08-03 |
CA1218480A (en) | 1987-02-24 |
US4600439A (en) | 1986-07-15 |
DE3370499D1 (en) | 1987-04-30 |
EP0106763B1 (en) | 1987-03-25 |
ATE26138T1 (en) | 1987-04-15 |
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