EP0145522A1 - Paper sheet, process for producing it, and its applications in particular as a substitute for impregnated glass fibre mats - Google Patents

Paper sheet, process for producing it, and its applications in particular as a substitute for impregnated glass fibre mats Download PDF

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Publication number
EP0145522A1
EP0145522A1 EP84401977A EP84401977A EP0145522A1 EP 0145522 A1 EP0145522 A1 EP 0145522A1 EP 84401977 A EP84401977 A EP 84401977A EP 84401977 A EP84401977 A EP 84401977A EP 0145522 A1 EP0145522 A1 EP 0145522A1
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Prior art keywords
fibers
sheet according
epichlorohydrin
latex
solution
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EP84401977A
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German (de)
French (fr)
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EP0145522B1 (en
Inventor
Pierre Fredenucci
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ArjoWiggins SAS
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Arjomari Prioux SA
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Priority to AT84401977T priority Critical patent/ATE33156T1/en
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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
    • D21H23/00—Processes or apparatus for adding material to the pulp or to the paper
    • D21H23/02—Processes or apparatus for adding material to the pulp or to the paper characterised by the manner in which substances are added
    • D21H23/04—Addition to the pulp; After-treatment of added substances in the pulp
    • D21H23/06—Controlling the addition
    • D21H23/14—Controlling the addition by selecting point of addition or time of contact between components
    • 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
    • D21H13/00—Pulp or paper, comprising synthetic cellulose or non-cellulose fibres or web-forming material
    • D21H13/36—Inorganic fibres or flakes
    • D21H13/38—Inorganic fibres or flakes siliceous
    • D21H13/40—Inorganic fibres or flakes siliceous vitreous, e.g. mineral wool, glass fibres
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/33—Synthetic macromolecular compounds
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/33—Synthetic macromolecular compounds
    • D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds

Definitions

  • the present invention relates to the field of substitutes for impregnated glass veils.
  • the invention relates to sheet products obtained by the papermaking process, with a high content of latex precipitated in the mass.
  • the product obtained also has a good foldability.
  • These products do not contain fillers, but can contain up to 2/3 by weight of latex.
  • the non-cellulosic fibers will preferably be glass fibers, or else also other mineral or synthetic fibers such as rock wool, polyester fibers and similar fibers. Their main role is to provide dimensional stability to the support with respect to water and to temperature variations, these two properties being essential for the applications envisaged.
  • cellulosic fibers which are weakly refined, in particular between 15 and 35 ° S.R.
  • Cellulosic fibers refined at 20 ° SR were used, and glass fibers about 3 or 4 mm in length and 10-11 ⁇ m in diameter.
  • glass fibers of length between 3 and 12 mm, preferably 3 and 6 mm, and of diameter between 5 and 15 ⁇ m.
  • 'A ratio of 40 to 60 parts by dry weight approximately of mineral fibers per 100 parts of cellulose fibers will preferably be chosen, in particular when these mineral fibers are glass fibers whose length is between 4 and 6 mm.
  • a ratio of 40 to 60 parts by dry weight approximately of mineral fibers per 100 parts of cellulose fibers will preferably be chosen.
  • reinforcing fibers to increase the wet mechanical strength.
  • polyvinyl alcohol fibers or polyolefins in proportions known to those skilled in the art and corresponding to the desired objective.
  • the amount of latex to be introduced in bulk is dependent on the nature of the filler used in the formulation.
  • the nature of the flocculants, their dose, as well as the number and place of introduction may vary depending on the nature of the latex used, the material, the contact time between the products; the total dose of flocculants, which itself depends on the nature of these flocculants (in particular the molecular weight of the ionicity, etc.) will preferably be between 2 and 20 parts by dry weight, per 100 parts by weight of the dry latex.
  • compositions used as well as the results of the tests are collated in Tables IV to XV below; these examples are of course not limiting.
  • the alumina hydroxide which gives satisfactory results will be suitable for the manufacture of flame retardant supports.
  • a second aspect of the tests which have been carried out has been to demonstrate that it was possible to approach, or even achieve, the dimensional stability of the impregnated glass webs, using compositions with higher rates of fibers. of glass ( tables X , XI , XIV and XV) .
  • Such a treatment therefore makes it possible, for comparable dimensional stability, to substantially reduce the proportion of glass fibers in the support.
  • tests MP 19474 and 19487 show the loss of dimensional stability when the amount of latex goes from 42.5 parts by weight (MP 19474) to 37 parts by weight (MP 19487) per 100 parts by weight of mixture of based.
  • stage 2 To combat the rolling of plastisol coated products on one side on the front, it is preferable to carry out a treatment of stage 2 on the back side.
  • stage 2 treatments can be coating, impregnation, surfacing operations, aiming to deposit chemical components on the surface or at the core (by spraying, size-press, coater with blades or rollers, etc.). Mention may in particular be made of the addition of latex or of plasticizer by size-press.
  • thermal and / or mechanical treatments such as smoothing or calendering cold or hot.
  • the product will generally be deposited at a rate of 10 to 100 g / m2 (wet state), or 2 to 40 g / m 2 after drying (preferably 2 to 20 g / m) in the case of a treatment on a single side, and 3 to 60 g / m 2 in the case of a treatment on both sides.
  • VETROTEX fibers 4.5 mm long and 10 ⁇ m in diameter Glass fibers
  • B VETROTEX fibers 3 mm long and 7 ⁇ m in diameter Calcium carbonate PR.4 Calcium carbonate from BLANCS MINERAUX DE PARIS average particle size 3 ⁇ m.
  • OMYALITE 60 calcium carbonate OMYA calcium carbonate average particle size 1.5 ⁇ m.
  • - Test references F Formettes MP Pilot machines E Industrial tests

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  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Paper (AREA)
  • Reinforced Plastic Materials (AREA)

Abstract

Feuile papetière obtenue essentiellement à partir de (parties en poids sec) <IMAGE> notamment par un procédé de double floculation. Très forte résistance à la délamination. Applications aux revêtements de sols et muraux.Paper sheet obtained essentially from (parts by dry weight) <IMAGE> in particular by a double flocculation process. Very high resistance to delamination. Applications to floor and wall coverings.

Description

La présente invention concerne le domaine des produits de substitution des voiles de verre imprégnés.The present invention relates to the field of substitutes for impregnated glass veils.

Plus précisément, l'invention concerne des produits en feuille obtenus par voie papetière, à forte teneur en latex précipitée dans la masse.More specifically, the invention relates to sheet products obtained by the papermaking process, with a high content of latex precipitated in the mass.

On connaît, selon les demandes de brevet français n° 82-13391 et 82-18624, déposées au nom de la demanderesse, des feuilles papetières à très fort taux de latex, utilisables comme produits de substitution des voiles de verre imprégnés.There are known, according to French patent applications No. 82-13391 and 82-18624, filed in the name of the applicant, paper sheets with very high latex content, usable as substitutes for impregnated glass webs.

Les produits décrits dans ces brevets se caractérisent par un niveau très élevé de résistance à la rupture, tant à froid qu'à chaud.The products described in these patents are characterized by a very high level of breaking strength, both cold and hot.

De plus, il est très difficile, après enduction double face par exemple de plastisol (poudre PVC + plastifiant) suivie d'un traitement thermique à 160-200°C environ, de délaminer le produit composite obtenu.In addition, it is very difficult, after double-sided coating for example of plastisol (PVC powder + plasticizer) followed by a heat treatment at 160-200 ° C. approximately, to delaminate the composite product obtained.

Le produit obtenu présente de plus une bonne aptitude à la pliabilité.The product obtained also has a good foldability.

Ces produits ne contiennent pas de charges, mais peuvent contenir jusqu'à 2/3 en poids de latex.These products do not contain fillers, but can contain up to 2/3 by weight of latex.

L'homme de métier sait par ailleurs que l'incorporation de charges dans un produit du type considéré réduit fortement les propriétés mécaniques et notamment la résistance à la délamination.A person skilled in the art also knows that the incorporation of fillers into a product of the type under consideration greatly reduces the mechanical properties and in particular the resistance to delamination.

Cette dernière propriété étant tout à fait essentielle pour l'application recherchée (produit de substitution des voiles de verre imprégnés dans les applications aux revêtements de sol ou muraux), cette connaissance antérieure explique l'absence de charges dans les formules décrites dans les demandes précitées.This latter property being entirely essential for the desired application (substitute product for impregnated glass veils in applications for floor or wall coverings), this prior knowledge explains the absence of fillers in the formulas described in the aforementioned requests .

Ce préjugé est confirmé par certains essais comparatifs simples montrant que toute tentative d'incorporer des charges est très préjudiciable, notamment à la résistance à la délamination.This prejudice is confirmed by certain simple comparative tests showing that any attempt to incorporate charges is very detrimental, in particular the resistance to delamination.

On trouvera à cet égard dans les tableaux I et II ci-après la comparaison de formulations typiques des demandes de brevets précitées et des mêmes formulations auxquelles on a tenté d'ajouter des charges.In this respect, a comparison of the formulations typical of the requests for applications is given in Tables I and II below. aforementioned patents and the same formulations to which we have tried to add charges.

Le tableau I rassemble les formulations et le tableau II rassemble les résultats.Table I collates the formulations and Table II collates the results.

On tire du tableau II les conclusions suivantes, qui correspondent bien aux connaissances antérieures de l'homme du métier :

  • L'ajout de charge conduit à une chute sensible de la résistance à la délaminatfon.
The following conclusions are drawn from Table II, which correspond well to the prior knowledge of a person skilled in the art:
  • The addition of charge leads to a significant drop in resistance to delaminating.

De plus, la forte perte de main apportée par l'ajout de cette charge annule largement l'avantage économique de cette composition chargée, pour un produit qui est vendu à l'épaisseur.In addition, the large loss of hand brought by the addition of this filler largely cancels the economic advantage of this charged composition, for a product which is sold by the thickness.

On est parvenu à découvrir selon l'invention qu'un certain domaine de compositions de fibres, de charges et de latex permettait d'obtenir des produits contenant un pourcentage élevé de charges (donc très économique) et présentant cependant, ce qui est surprenant, une résistance à la délamination au moins égale à celle des produits antérieurs.We have managed to discover according to the invention that a certain field of compositions of fibers, fillers and latex makes it possible to obtain products containing a high percentage of fillers (therefore very economical) and having however, which is surprising, resistance to delamination at least equal to that of previous products.

Selon l'invention, différentes compositions ont été essayées et permettent d'établir les limites suivantes :

Figure imgb0001
[mélange de base : 100 partiesAccording to the invention, different compositions have been tried and allow the following limits to be established:
Figure imgb0001
 [basic mixture: 100 parts

Ces limites peuvent fluctuer en raison de la nature des ingrédients composant le produit et du grammage des produits. La variation de ces paramètres dépendra notamment de l'application et de l'utilisation du produit tant chez les transformateurs que chez les clients. Nous citerons par exemple la nécessité d'éviter le cloquage ("blistering") des couches de chlorure de polyvinyle déposées par enduction, ou la nécessité de ne pas affecter les propriétés mécaniques.These limits may fluctuate due to the nature of the ingredients making up the product and the grammage of the products. The variation of these parameters will depend in particular on the application and use of the product both for processors and customers. We will cite for example the need to avoid blistering (layers) of polyvinyl chloride layers deposited by coating, or the need not to affect the mechanical properties.

A la lecture de la présente description et des exemples de réalisation, l'homme de métier saura adapter l'enseignement de l'invention à chaque cas particulier.On reading this description and the exemplary embodiments, the skilled person will be able to adapt the teaching of the invention to each particular case.

Les fibres non cellulosiques seront de préférence des fibres de verre, ou bien aussi d'autres fibres minérales ou synthétiques telles que laine de roche, fibres de polyester et fibres analogues. Leur rôle principal est d'apporter la stabilité dimensionnelle au support par rapport à l'eau et aux variations de température, ces deux propriétés étant indispensables aux applications envisagées.The non-cellulosic fibers will preferably be glass fibers, or else also other mineral or synthetic fibers such as rock wool, polyester fibers and similar fibers. Their main role is to provide dimensional stability to the support with respect to water and to temperature variations, these two properties being essential for the applications envisaged.

Etant donné que pour les applications visées l'invention recherche un haut niveau de stabilité dimensionnelle, il est préférable d'utiliser des fibres cellulosiques faiblement raffinées notamment entre 15 et 35° S.R.Since for the intended applications the invention seeks a high level of dimensional stability, it is preferable to use cellulosic fibers which are weakly refined, in particular between 15 and 35 ° S.R.

On a utilisé dans les essais des fibres cellulosiques raffinées à 20° SR, et des fibres de verre de longueur environ 3 ou 4 mm et de diamètre 10-11 um.Cellulosic fibers refined at 20 ° SR were used, and glass fibers about 3 or 4 mm in length and 10-11 µm in diameter.

On pourra cependant utiliser des fibres de verre de longueur comprise entre 3 et 12 mm, de préférence 3 et 6 mm, et de diamètre compris entre 5 et 15 µm.However, it is possible to use glass fibers of length between 3 and 12 mm, preferably 3 and 6 mm, and of diameter between 5 and 15 μm.

'On choisira de préférence un rapport de 40 à 60 parties en poids sec environ de fibres minérales pour 100 parties de fibres de cellulose, notamment lorsque ces fibres minérales sont des fibres de verre dont la longueur est comprise entre 4 et 6 mm.'A ratio of 40 to 60 parts by dry weight approximately of mineral fibers per 100 parts of cellulose fibers will preferably be chosen, in particular when these mineral fibers are glass fibers whose length is between 4 and 6 mm.

Il peut être intéressant pour améliorer la formation de la feuille d'utiliser un mélange contenant des fibres minérales courtes. Dans ce cas, pour obtenir la stabilité requise, il sera nécessaire d'augmenter la quantité de fibres minérales par rapport aux fibres cellulosiques. Notamment, lorsque ces fibres minérales courtes sont des fibres de verre de longueur inférieure à 4mm, on choisira de préférence un mélange contenant 40 à 90 parties en poids de fibres de verre pour 100 parties en poids de fibres cellulosiques.It may be advantageous to improve the formation of the sheet to use a mixture containing short mineral fibers. In this case, to obtain the required stability, it will be necessary to increase the amount of mineral fibers compared to the cellulosic fibers. In particular, when these short mineral fibers are glass fibers of length less than 4 mm, a mixture preferably containing 40 to 90 parts by weight of glass fibers will be chosen per 100 parts by weight of cellulosic fibers.

D'autre part, l'Homme du métier sait que certains traitements chimiques des fibres cellulosiques du support permettent d'améliorer la stabilité dimensionnelle (consulter brevets EP 0018961 de ROCKWOOL, US 4.291.101 de NIPPON OILS AND FATS ou l'article de "Papier, Cartons, Films, complexes" de Juin 1979 page 16, colonne 2, paragraphe 2).On the other hand, those skilled in the art know that certain chemical treatments of the cellulosic fibers of the support make it possible to improve the dimensional stability (see patents EP 0018961 from ROCKWOOL, US 4.291.101 from NIPPON OILS AND FATS or the article from "Paper, Cardboard, Films, Complexes" from June 1979 page 16, column 2, paragraph 2).

Appliquant de tels traitements chimiques sur le support, l'Homme du métier pourra en particulier réduire les quantités de fibres de verre nécessaires à la stabilité dimensionnelle.Applying such chemical treatments to the support, a person skilled in the art can in particular reduce the quantities of glass fibers necessary for dimensional stability.

On choisira de préférence un rapport de 40 à 60 parties en poids sec environ de fibres minérales pour 100 parties de fibres de cellulose.A ratio of 40 to 60 parts by dry weight approximately of mineral fibers per 100 parts of cellulose fibers will preferably be chosen.

De plus, pour faciliter le passage sur machine à papier en partie humide, il est possible si nécessaire (notamment pour les compositions à faible taux de cellulose ou à faible grammage) de rajouter des fibres de renforcement pour augmenter la résistance mécanique humide. A cet effet, on pourra utiliser par exemple des fibres d'alcool de polyvinyle ou de polyoléfines dans des proportions connues de l'homme de métier et correspondant au but recherché. Suivant la teneur de ces fibres de renfort, il est possible de réduire la teneur en cellulose.In addition, to facilitate passage through a partially wet paper machine, it is possible if necessary (in particular for compositions with a low cellulose content or a low grammage) to add reinforcing fibers to increase the wet mechanical strength. For this purpose, it will be possible for example to use polyvinyl alcohol fibers or polyolefins in proportions known to those skilled in the art and corresponding to the desired objective. Depending on the content of these reinforcing fibers, it is possible to reduce the cellulose content.

Les essais effectués sur un nombre important de latex ont montré que les copolymères vinyliques convenaient le mieux.Tests carried out on a large number of latexes have shown that vinyl copolymers are most suitable.

On a également obtenu des résultats convenables avec des copolymères styrène-butadiène et des polymères ou copolymères comportant des motifs acryliques.Convenient results have also been obtained with styrene-butadiene copolymers and polymers or copolymers comprising acrylic units.

Les meilleurs résultats ont été obtenus avec le latex terpolymère suivant (% en poids) :

Figure imgb0002
The best results have been obtained with the following terpolymer latex (% by weight):
Figure imgb0002

La quantité de latex à introduire en masse est dépendante de la nature de la charge utilisée dans la formulation.The amount of latex to be introduced in bulk is dependent on the nature of the filler used in the formulation.

Comme floculants, on pourra notamment utiliser les produits dont la liste est donnée dans les demandes de brevets précitées (cf. tableau III ci-après).As flocculants, it is possible in particular to use the products whose list is given in the aforementioned patent applications (cf. table III below).

On pourra utiliser également, de manière classique, les adjuvants connus dans le domaine papetier, agents antimousse, colorants, agents de collage, de résistance sèche, humide, d'imputrescibilité, etc.It will also be possible to use, conventionally, the adjuvants known in the paper industry, anti-foaming agents, dyes, bonding agents, of dry, wet resistance, rot-proofing, etc.

La nature des floculants, leur dose, ainsi que le nombre et le lieu d'introduction peuvent varier en fonction de la nature du latex utilisé, du matériel, du temps de contact entre les produits; la dose totale de floculants, qui dépend elle-même de la nature de ces floculants (en particulier du poids moléculaire de l'ionicité, etc.) sera comprise de préférence entre 2 et 20 parties en poids sec, pour 100 parties en poids du latex sec.The nature of the flocculants, their dose, as well as the number and place of introduction may vary depending on the nature of the latex used, the material, the contact time between the products; the total dose of flocculants, which itself depends on the nature of these flocculants (in particular the molecular weight of the ionicity, etc.) will preferably be between 2 and 20 parts by dry weight, per 100 parts by weight of the dry latex.

Les tableaux et le mode opératoire ci-après fournissent notamment à ce sujet les indications qui permettront à l'homme du métier d'adapter la technique selon l'invention à une variation de ces paramètres.The tables and the operating mode below provide in particular on this subject the indications which will enable a person skilled in the art to adapt the technique according to the invention to a variation of these parameters.

Le mode opératoire correspondant aux essais présentés dans le tableau IV est le suivant (ajouts dans cet ordre) . mélange fibreux :

Figure imgb0003

  • x est la quantité nécessaire à la précipitation totale. Le mélange est alors suffisamment stable pour être conduit jusqu'à la partie de tête de la machine où l'on effectue le dernier ajout de floculant;
  • x est le pourcentage en poids sec par rapport à la composition totale sèche.
The procedure corresponding to the tests presented in Table IV is as follows (additions in this order). fibrous mixture:
Figure imgb0003
  • x is the quantity necessary for total precipitation. The mixture is then stable enough to be led to the head of the machine where the last addition of flocculant is carried out;
  • x is the percentage by dry weight relative to the total dry composition.

Les compositions utilisées ainsi que les résultats des essais sont rassemblés dans les tableaux IV à XV ci-après ; ces exemples n'ont bien entendu pas de caractère limitatif.The compositions used as well as the results of the tests are collated in Tables IV to XV below; these examples are of course not limiting.

Par une première série d'exemples, on a cherché à montrer l'influence de certains paramètres sur les caractéristiques physiquesde la feuille qui sont intéressantes pour concurrencer le voile de verre imprégné.By a first series of examples, we tried to show the influence of certain parameters on the physical characteristics of the sheet which are interesting to compete with the impregnated glass veil.

On a pu constater (tableaux VI et VII) que la nature de la charge minérale utilisée influence considérablement les caractéristiques physiques qui nous intéressent et, notamment la résistance à la dêlamination du papier enduit sur 2 faces.It has been observed (Tables VI and VII) that the nature of the mineral filler used considerably influences the physical characteristics which interest us and, in particular the resistance to damage of coated paper on 2 sides.

Grâce au choix de la charge, il est par ailleurs pensable de diminuer la quantité de latex introduit en masse sans affecter sensiblement la résistance à la délamination du papier enduit sur deux faces et la stabilité dimensionnelle (tableaux VIII et IX).Thanks to the choice of filler, it is moreover conceivable to reduce the quantity of latex introduced in mass without appreciably affecting the resistance to delamination of the coated paper on two sides and the dimensional stability (Tables VIII and IX).

Il ressort des essais que le carbonate de calcium est à utiliser de préférence aux autres charges minérales.It appears from the tests that calcium carbonate is to be used in preference to other mineral fillers.

L'hydroxyde d'alumine qui donne des résultats satisfaisants conviendra pour la fabrication de supports ignifugés.The alumina hydroxide which gives satisfactory results will be suitable for the manufacture of flame retardant supports.

D'autres essais (tableaux X à XIII ; tableaux VIII et IX : MP 19454 et 19456) ont permis de mettre en évidence l'influence de la floculation en caisse de tête de la machine (ajout 3 x 2) sur la résistance à la délamination du support enduit sur deux faces.Other tests (Tables X to XIII; Tables VIII and IX: MP 19454 and 19456) made it possible to highlight the influence of flocculation in the headbox of the machine (addition 3 x 2) on the resistance to delamination of the coated support on two sides.

Un deuxième aspect des essais qui ont été menés a été de mettre en évidence qu'il était possible d'approcher, voire d'at- teindre, la stabilité dimensionnelle des voiles de verre imprégnés, en utilisant des compositions à taux plus élevés de fibres de verre (tableaux X, XI, XIV et XV).A second aspect of the tests which have been carried out has been to demonstrate that it was possible to approach, or even achieve, the dimensional stability of the impregnated glass webs, using compositions with higher rates of fibers. of glass ( tables X , XI , XIV and XV) .

Nous rappelons qu'une autre possibilité pour obtenir une meilleure stabilité dimensionnelle est le traitement chimique de la cellulose du support par une size-press appropriée que l'Homme du métier saura adapter en fonction de l'absorption du support et des caractéristiques physiques recherchées.We recall that another possibility to obtain better dimensional stability is the chemical treatment of the cellulose of the support by an appropriate size-press that the skilled person will be able to adapt according to the absorption of the support and the desired physical characteristics.

Un tel traitement permet donc pour une stabilité dimensionnelle comparable de réduire sensiblement la proportion de fibres de verre dans le support.Such a treatment therefore makes it possible, for comparable dimensional stability, to substantially reduce the proportion of glass fibers in the support.

Cette baisse de la proportion de fibres de verre conduit à un support présentant une plus grande densité et par là une meilleure résistance à la délamination qui permet d'envisager une baisse du taux de latex.This drop in the proportion of glass fibers leads to a support having a higher density and thereby better resistance to delamination which makes it possible to envisage a drop in the level of latex.

Ces essais ont par ailleurs fait ressortir qu'une résistance à la délamination de 350 à 400 g/cm pour un support enduit sur deux faces rendait ce dernier suffisamment difficile à délaminer pour être substitué aux voiles de verre imprégnés.These tests also revealed that a resistance to delamination of 350 to 400 g / cm for a support coated on two sides made the latter sufficiently difficult to delaminate to be substituted for impregnated glass webs.

Ces résultats expliquent les possibilités d'orientation vers des formules moins riches en latex.These results explain the possibilities of orientation towards formulas less rich in latex.

Cependant, les essais MP 19474 et 19487 mettent en évidence la perte de stabilité dimensionnelle lorsque la quantité de latex passe de 42,5 parties en poids (MP 19474) à 37 parties en poids (MP 19487) pour 100 parties en poids de mélange de base.However, tests MP 19474 and 19487 show the loss of dimensional stability when the amount of latex goes from 42.5 parts by weight (MP 19474) to 37 parts by weight (MP 19487) per 100 parts by weight of mixture of based.

La stabilité dimensionnelle devient insuffisante pour envisager l'utilisation satisfaisante du support en substitution du voile de verre imprégné.The dimensional stability becomes insufficient to consider the satisfactory use of the support in substitution for the impregnated glass veil.

Selon l'invention, après le "stade 1" décrit ci-dessus, il est intéressant d'effectuer un traitement complémentaire de "stade 2" dans le but d'améliorer encore :

  • - l'état de surface (suppression du peluchage ou extraction des fibres de verre);
  • - les propriétés de "barrière" à l'eau, aux plastifiants;
  • - l'imputrescibilité;
  • - la résistance mécanique;
  • - la rigidité ou la souplesse, donc les caractéristiques de roulage ou de plabilité.
According to the invention, after the "stage 1" described above, it is advantageous to carry out an additional treatment of "stage 2" in order to further improve:
  • - surface condition (elimination of linting or extraction of glass fibers);
  • - the properties of "barrier" to water, to plasticizers;
  • - imputrescibility;
  • - mechanical strength;
  • - stiffness or flexibility, therefore rolling characteristics or pliability.

Pour combattre le roulage des produits enduits de plastisol sur une face au recto, on peut effectuer de préférence un traitement du stade 2 sur la face verso.To combat the rolling of plastisol coated products on one side on the front, it is preferable to carry out a treatment of stage 2 on the back side.

Ces traitements de stade 2 peuvent être des opérations de couchage, d'imprégnation, de surfaçage, visant à déposer en surface ou à coeur des composants chimiques (par pulvérisation, size-press, coucheuse à lames ou rouleaux, etc.). On citera notamment l'ajout de latex ou de plastifiant par presse-encolleuse ("size-press").These stage 2 treatments can be coating, impregnation, surfacing operations, aiming to deposit chemical components on the surface or at the core (by spraying, size-press, coater with blades or rollers, etc.). Mention may in particular be made of the addition of latex or of plasticizer by size-press.

On pourra aussi effectuer des traitements thermiques et/ou mécaniques, tels que lissage ou calandrage à froid ou à chaud.It is also possible to carry out thermal and / or mechanical treatments, such as smoothing or calendering cold or hot.

L'homme de métier connaît ces techniques et saura choisir les produits à utiliser en fonction de la caractéristique souhaitée.Those skilled in the art know these techniques and will know how to choose the products to be used according to the desired characteristic.

Le produit sera déposé en général à raison de 10 à 100 g/m2 (état humide), soit 2 à 40 g/m 2 après séchage (de préférence 2 à 20 g/m ) dans le cas d'un traitement sur une seule face, et 3 à 60 g/m2 dans le cas d'un traitement sur les deux faces.The product will generally be deposited at a rate of 10 to 100 g / m2 (wet state), or 2 to 40 g / m 2 after drying (preferably 2 to 20 g / m) in the case of a treatment on a single side, and 3 to 60 g / m 2 in the case of a treatment on both sides.

Il pourra être ici particulièrement avantageux d'effectuer un traitement de size-press pour améliorer encore la résistance à la délamination, notamment par ajout d'un latex approprié que l'homme de métier saura choisir en fonction du but recherché.It may be particularly advantageous here to carry out a size-press treatment to further improve the resistance to delamination, in particular by adding an appropriate latex which the skilled person will be able to choose according to the desired goal.

PRODUITS CITES DANS LES TABLEAUXPRODUCTS LISTED IN THE TABLES Fibres de verre AGlass fibers A

Fibres VETROTEX de longueur 4,5 mm et de diamètre 10 µm Fibres de verre B Fibres VETROTEX de longueur 3 mm et de diamètre 7 µm Carbonate de calcium PR.4 Carbonate de calcium de BLANCS MINERAUX DE PARIS granulométrie moyenne 3 µm. Carbonate de calcium OMYALITE 60 Carbonate de calcium de OMYA granulométrie moyenne 1,5 µm. - Références des essais F Formettes MP Machines pilotes E Essais Industriels

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 VETROTEX fibers 4.5 mm long and 10 µm in diameter Glass fibers B VETROTEX fibers 3 mm long and 7 µm in diameter Calcium carbonate PR.4 Calcium carbonate from BLANCS MINERAUX DE PARIS average particle size 3 µm. OMYALITE 60 calcium carbonate OMYA calcium carbonate average particle size 1.5 µm. - Test references F Formettes MP Pilot machines E Industrial tests
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Claims (13)

1 - Nouvelle feuille papetière, caractérisée en ce qu'elle contient (parties en poids sec) :1 - New paper sheet, characterized in that it contains (parts by dry weight):
Figure imgb0021
2 - Feuille selon la revendication 1, caractérisée en ce que les fibres non cellulosiques sont choisies parmi les fibres de verre, la laine de roche, les fibres de polyester, les fibres d'alcool polyvinylique, les fibres de polyoléfine, et autres fibres minérales ou synthétiques analogues.
Figure imgb0021
 2 - Sheet according to claim 1, characterized in that the non-cellulosic fibers are chosen from glass fibers, rock wool, polyester fibers, polyvinyl alcohol fibers, polyolefin fibers, and other mineral fibers or analogous synthetics. 3 - Feuille selon la revendication 2, caractérisée en ce que les fibres non cellulosiques sont des fibres de verre.3 - Sheet according to claim 2, characterized in that the non-cellulosic fibers are glass fibers. 4 - Feuille selon la revendication 2 ou 3, caractérisée en ce que les fibres de verre présentent une longueur comprise entre environ 3 et 12 mm, de préférence entre environ 3 et 6 mm, et un diamètre d'environ 5 à 15 µm, de préférence 10-11 µm.4 - Sheet according to claim 2 or 3, characterized in that the glass fibers have a length of between approximately 3 and 12 mm, preferably between approximately 3 and 6 mm, and a diameter of approximately 5 to 15 µm, of preferably 10-11 µm. 5 - Feuille selon l'une quelconque des revendications 1 à 4, caractérisée en ce que la composition destinée à passer sur la machine à papier contient de plus un ou plusieurs floculant(s) dont au moins une partie est ajoutée au mélange après l'ajout du latex, et les adjuvants classiques de la technique papetière.5 - Sheet according to any one of claims 1 to 4, characterized in that the composition intended to pass over the paper machine additionally contains one or more flocculant (s) at least part of which is added to the mixture after addition of latex, and conventional adjuvants in the papermaking technique. 6 - Feuille selon l'une quelconque des revendications 1 à 5, caractérisé en ce que le floculant est choisi parmi les suivants : - sulfate d'aluminium - polychlorure d'aluminium - aluminate de sodium et de calcium - mélange d'acide polyacrylique et de polyacrylamide en solution à 5-30% (poids volume) - polyéthylèneimine en solution à 2-50% (poids/volume) - copolymère d'acrylamide et de P-méthacrylyloxyéthyltriméthylammonium méthylsulfate - résine polyamine-épichlorhydrine et de diamine-propylméthylamine en solution à 2-50% - résine polyamide-épichlorhydrine fabriquée à partir d'épichlorhydrine, d'acide adipique, de caprolactame, de diéthylènetriamine et/ou d'éthylènediamine, en solution à 2-50% - résine polyamide-polyamine-épichlorhydrine fabriquée à partir d'épichlorhydrine, d'ester diméthylique d'acide adipique et de diéthylènetriamine, en solution à 2-50%. - résine polyamide-épichlorhydrine fabriquée à partir d'épichlorhydrine, de diéthylènetriamine, d'acide adipique et d'éthylèneimine - résine polyamide-épichlorhydrine fabriquée à partir d'acide adipique, de diéthylènetriamine et d'un mélange d'épichlorhydrine et de diméthylamine en solution à 2-50% - résine polyamide-polyamine cationique fabriquée à partir de tri- éthylènetriamine - produits de condensation d'acides sulfoniques aromatiques avec le formaldéhyde - acétate d'aluminium - formiate d'aluminium - mélange d'acétate, sulfate et formiate d'aluminium. 6 - Sheet according to any one of claims 1 to 5, characterized in that the flocculant is chosen from the following: - aluminum sulfate - aluminum polychloride - sodium and calcium aluminate - mixture of polyacrylic acid and polyacrylamide in solution at 5-30% (weight by volume) - polyethyleneimine in 2-50% solution (weight / volume) - copolymer of acrylamide and P-methacrylyloxyethyltrimethylammonium methylsulfate - polyamine-epichlorohydrin and diamine-propylmethylamine resin in 2-50% solution - polyamide-epichlorohydrin resin made from epichlorohydrin, adipic acid, caprolactam, diethylenetriamine and / or ethylenediamine, in 2-50% solution - polyamide-polyamine-epichlorohydrin resin made from epichlorohydrin, adipic acid dimethyl ester and diethylenetriamine, in 2-50% solution. - polyamide-epichlorohydrin resin made from epichlorohydrin, diethylenetriamine, adipic acid and ethyleneimine - polyamide-epichlorohydrin resin made from adipic acid, diethylenetriamine and a mixture of epichlorohydrin and dimethylamine in 2-50% solution - cationic polyamide-polyamine resin made from triethylenetriamine - condensation products of aromatic sulfonic acids with formaldehyde - aluminum acetate - aluminum formate - mixture of aluminum acetate, sulfate and formate. 7 - Feuille selon l'une quelconque des revendications 1 à 6, caractérisée en ce que le latex est choisi parmi les copolymères styrène-butadiène, les latex acryliques, de préférence vinyliques.7 - Sheet according to any one of claims 1 to 6, characterized in that the latex is chosen from styrene-butadiene copolymers, acrylic latex, preferably vinyl. 8 - Feuille selon la revendication 7, caractérisée en ce que le latex est un terpolymère d'acétate de vinyle, d'éthylène et de chlorure de vinyle.8 - Sheet according to claim 7, characterized in that the latex is a terpolymer of vinyl acetate, ethylene and vinyl chloride. 9 - Feuille selon-l'une quelconque des revendications 1 à 8, caractérisée en ce que la charge minérale est du carbonate de calcium ou de l'hydroxyde d'aluminium.9 - Sheet according to any one of claims 1 to 8, characterized in that the mineral filler is calcium carbonate or aluminum hydroxide. 10- Feuille selon l'une quelconque des revendications 1 à 9, caractérisée en ce qu'elle est obtenue par une technique papetière à partir d'une des compositions suivantes, en parties en poids sec :
Figure imgb0022
 10- Sheet according to any one of claims 1 to 9, characterized in that it is obtained by a papermaking technique from one of the following compositions, in parts by dry weight:
Figure imgb0022
 11-Feuille papetière selon l'une quelconque des revendications 1 à 10, caractérisée en ce qu'elle subit un traitement de "stade 2" consistant en opération(s) de couchage, imprégnation, surfaçage, par pulvérisation, size-press, coucheuse à lames ou rouleaux, ..., et éventuellement des traitements thermiques et/ou mécaniques, tels que lissage ou calandrage à froid ou à chaud.11-papermaking sheet according to any one of claims 1 to 10, characterized in that it undergoes a "stage 2" treatment consisting of coating operation (s), impregnation, surfacing, by spraying, size-press, coater with blades or rollers, ..., and possibly thermal and / or mechanical treatments, such as smoothing or calendering cold or hot. 12-Applications des feuilles selon l'une quelconque des revendications 1 à 11, notamment comme supports d'enduction pour revêtement de sols et muraux plastiques.12- Applications of the sheets according to any one of claims 1 to 11, in particular as coating supports for covering plastic floors and walls. 13-Procédé de fabrication des feuilles papetières selon l'une quelconque des revendications 1 à 12, caractérisé en ce que l'on prépare une dispersion aqueuse par les ajouts suivants , dans cet ordre : - mélange fibreux : . fibres cellulosiques raffinées entre 15 et 35° SR . fibres de verre et/ou fibres non cellulosiques - charges - ajout du floculant n° 1 - latex choisi parmi les copolymères styrène-butadiène, acryliques et de préférence vinylique, notamment copolymère chlorure de vinyle/éthylène/acétate de vinyle ou copolymère chlorure de vinyle/acrylate plastifié - ajout du floculant (polyacrylamide) . ajout n° 2 (en cuvier) . ajout n° 3 (en tête) et en ce que l'on fait passer cette dispersion aqueuse sur une machine à papier, la feuille papetière obtenue subissant ensuite éventuellement un traitement de "stade 2" consistant en opération(s) de couchage, imprégnation, surfaçage, par pulvérisation, size-press, coucheuse à lames ou rouleaux, ... et éventuellement des traitements thermiques et/ou mécaniques, tels que lissage ou calandrage à froid ou à chaud. 13-A method of manufacturing paper sheets according to any one of claims 1 to 12, characterized in that an aqueous dispersion is prepared by the following additions, in this order: - fibrous mixture: . refined cellulosic fibers between 15 and 35 ° SR . glass fibers and / or non-cellulosic fibers - charges - addition of flocculant n ° 1 - latex chosen from styrene-butadiene, acrylic and preferably vinyl copolymers, in particular vinyl chloride / ethylene / vinyl acetate copolymer or vinyl chloride / plasticized acrylate copolymer - addition of the flocculant (polyacrylamide) . addition n ° 2 (in vat room) . addition n ° 3 (at the top) and in that this aqueous dispersion is passed through a paper machine, the paper sheet obtained then possibly undergoing a "stage 2" treatment consisting of coating (impregnation) operation (s) , surfacing, spraying, size-press, coater with blades or rollers, ... and possibly thermal and / or mechanical treatments, such as smoothing or calendering cold or hot.
EP84401977A 1983-10-06 1984-10-04 Paper sheet, process for producing it, and its applications in particular as a substitute for impregnated glass fibre mats Expired EP0145522B1 (en)

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Application Number Priority Date Filing Date Title
AT84401977T ATE33156T1 (en) 1983-10-06 1984-10-04 PAPER SHEET, PROCESS FOR ITS MANUFACTURE AND POSSIBLE APPLICATIONS IN PARTICULAR AS A REPLACEMENT FOR IMPRESSED GLASS FIBER MATS.

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FR8315926A FR2553121B1 (en) 1983-10-06 1983-10-06 PAPER SHEET, ITS PREPARATION METHOD AND ITS APPLICATIONS, IN PARTICULAR AS A SUBSTITUTION PRODUCT FOR IMPREGNATED GLASS VEILS
FR8315926 1983-10-06

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EP0145522A1 true EP0145522A1 (en) 1985-06-19
EP0145522B1 EP0145522B1 (en) 1988-03-23

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JP (1) JPS6099100A (en)
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CA (1) CA1248712A (en)
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EP0322287A1 (en) * 1987-12-23 1989-06-28 Arjo Wiggins S.A. Wet-laid sheet for use as a coating support
WO1995006776A1 (en) * 1993-08-30 1995-03-09 Arjo Wiggins S.A. Mineral web

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GB2291441A (en) * 1994-07-19 1996-01-24 Congoleum Corp Wet-forming of fibre-reinforced sheet
ATE313607T1 (en) * 1999-07-08 2006-01-15 Hercules Inc COMPOSITION FOR GIVING DESIRED PROPERTIES TO MATERIALS
DE19952395A1 (en) * 1999-10-29 2001-05-03 Torsten Urban Stretch-resistant woodchip
US7317053B1 (en) 2000-07-10 2008-01-08 Hercules Incorporated Compositions for imparting desired properties to materials
US6572736B2 (en) 2000-10-10 2003-06-03 Atlas Roofing Corporation Non-woven web made with untreated clarifier sludge
CA2461127C (en) 2001-09-20 2011-07-12 Tex Tech Industries, Inc. Fireblocking/insulating paper
JP4002200B2 (en) * 2002-03-13 2007-10-31 花王株式会社 Papermaking parts for casting production
JP4471629B2 (en) * 2002-11-13 2010-06-02 花王株式会社 Manufacturing method of parts for casting production
WO2007063888A1 (en) * 2005-11-30 2007-06-07 Kao Corporation Component for casting production and method for producing same
CN102154915B (en) * 2007-02-19 2014-04-23 3M创新有限公司 Flexible fibrous material, pollution control device, and methods of making the same
US10464846B2 (en) * 2017-08-17 2019-11-05 Usg Interiors, Llc Method for production of acoustical panels
CN113445357A (en) * 2020-03-24 2021-09-28 中国制浆造纸研究院有限公司 Method for increasing filling amount of paper product

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EP0322287A1 (en) * 1987-12-23 1989-06-28 Arjo Wiggins S.A. Wet-laid sheet for use as a coating support
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CA1248712A (en) 1989-01-17
US4789430A (en) 1988-12-06
JPS6099100A (en) 1985-06-01
DE3470068D1 (en) 1988-04-28
FR2553121B1 (en) 1986-02-21
ATE33156T1 (en) 1988-04-15
EP0145522B1 (en) 1988-03-23
JPH0536556B2 (en) 1993-05-31
FR2553121A1 (en) 1985-04-12
BR8405047A (en) 1985-08-20

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